CA1147090A - Fast crystallising block copolyester composition - Google Patents
Fast crystallising block copolyester compositionInfo
- Publication number
- CA1147090A CA1147090A CA000360357A CA360357A CA1147090A CA 1147090 A CA1147090 A CA 1147090A CA 000360357 A CA000360357 A CA 000360357A CA 360357 A CA360357 A CA 360357A CA 1147090 A CA1147090 A CA 1147090A
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- Prior art keywords
- composition
- glass
- polyester composition
- weight
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- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
Abstract
ABSTRACT OF THE DISCLOSURE:
A fast crystallising polyester composition comprising a block copolyester containing the repeating polymeric segments A and B wherein A is a polymeric segment of ethylene terephthalate units and A is a polymeric segment having n glass-transition temperature of less than 0°C and preferably less than -20°C, the concentration of the segments of B being between 0.05 and 10 mole % of the block copolyester, and a crystallisation nucleant which is an at least partially neutralised salt, preferably an alkali metal salt, of a polymer containing pendant neutralisable groups.
A fast crystallising polyester composition comprising a block copolyester containing the repeating polymeric segments A and B wherein A is a polymeric segment of ethylene terephthalate units and A is a polymeric segment having n glass-transition temperature of less than 0°C and preferably less than -20°C, the concentration of the segments of B being between 0.05 and 10 mole % of the block copolyester, and a crystallisation nucleant which is an at least partially neutralised salt, preferably an alkali metal salt, of a polymer containing pendant neutralisable groups.
Description
o FAST CRY~TALLISING BLOCK COPOLYESTER COMPOSITION -This invention relates to a fast crystallising polyester composition and more particularly to a block copolyester composition containing a major proportion of polyethylene terephthalate units.
The commercial development of polyethylene terephthalate, hereinafter termed PET, as a moulding powder for use in injection moulding machines has been hampered because the cycle time for moulding of dimensionally stable articles is somewhat longer than that for some other plastics of the engineering type. This is primarily due to the fact that the moulded composition does not reach a crystalline condition as rapidly as the other plastics. Premature ejection from ~he mould of an insufficiently crystalli~ed moulding would meall that the article could continue to crystallise when in service with corresponding volume changes. A further disadvantage of PET is that it requires the mou]ds to be maintained at a temperature of at least 120C in order to achieve satisfactory results. More rec~ntly polyethylene terephthalate compositions have been made available which can be moulded more rapidly and at a lower mould temperature. British Patent Publications GB 2 015 013 and ; 2 015 014 describe such compositions containing a substantial quantity o~ a plasticiser and a polymeric nucleant having pendant carboxyl groups. The plasticiser has the effect of lowering the glass-transition temperature of the PET composition. Added plasticisers may, however, introduce some disadvantages into the composition. For example, the plasticisers may give rise to difficulties during moulding of the composition or may give rise to some deterioriation of the properties of the moulding. In addition the most effective plasticisers, in terms of lowering the glass-transition temperature and increasing the crystallisation rate may be so volatile ~7~9~C~
The commercial development of polyethylene terephthalate, hereinafter termed PET, as a moulding powder for use in injection moulding machines has been hampered because the cycle time for moulding of dimensionally stable articles is somewhat longer than that for some other plastics of the engineering type. This is primarily due to the fact that the moulded composition does not reach a crystalline condition as rapidly as the other plastics. Premature ejection from ~he mould of an insufficiently crystalli~ed moulding would meall that the article could continue to crystallise when in service with corresponding volume changes. A further disadvantage of PET is that it requires the mou]ds to be maintained at a temperature of at least 120C in order to achieve satisfactory results. More rec~ntly polyethylene terephthalate compositions have been made available which can be moulded more rapidly and at a lower mould temperature. British Patent Publications GB 2 015 013 and ; 2 015 014 describe such compositions containing a substantial quantity o~ a plasticiser and a polymeric nucleant having pendant carboxyl groups. The plasticiser has the effect of lowering the glass-transition temperature of the PET composition. Added plasticisers may, however, introduce some disadvantages into the composition. For example, the plasticisers may give rise to difficulties during moulding of the composition or may give rise to some deterioriation of the properties of the moulding. In addition the most effective plasticisers, in terms of lowering the glass-transition temperature and increasing the crystallisation rate may be so volatile ~7~9~C~
- 2 - 30976 that it is difficult to incorporate them in a practical manner. Compositions based on a copolyester of PET have now been developed which will crystallise rapidly at low mould temperatures without the need to include an external plasticiser.
According to the invention there is provided a fast crystallising polyester composition comprising a block copolyester containing the repeating polymeric segments A
and B wherein A is a polymeric segment of ethylene terephthalate units and B is a polymeric segment having a glass-transition temperature of less than 0C and preferably less than -20C, the concentration of the segments of B being between 0.05 and lO mole % preferably from 0.1 to 5 mole ~ of the block copolyester, and a crystallisation nucleant which is an at least partially neutralised salt, preferably an alkali metal salt, of a polymer containing pendant neutralisable groups. The neutralisable groups should be sufficiently basic to react with the carboxylic ester groups in the copolyester to form a metal terephthalate species. Preferably the pendant neutralisable groups are~ carboxylic acid groups.
Suitable salts include salts of copolymers of styrene and maleic anhydride, salts of copolymers of olefins and ethylenically unsaturated carboxylic acids or carboxylic acid anhydrides optionally containing non-conjugated dienes and sa~ts of copolymers of acrylate and methacrylate esters and ethylenically unsaturated carbo~ylic acids or carboxylic acid anhydrides. Suitable ethylenically unsaturated carboxylic acids or anhydrides are, for example acrylic acid, methacrylic acid, maleic anhydride and fumaric anhydride.
The preferred concentration of the polymeric nucleant is between 0.5% and 10% by weight of the total weight of the composition. Concentrations of less than 0.5% of the polymeric nucleants, for example 0.1~, may be used but ~ 3 ~ 30976 will require the presence of additional nucleant of a different type to achieve a useful level of nucleation.
Concentrations above 10~ by weight of the polymeric nucleants used in the invention do not normally show much further improvement in the level of nucleation but the presence of up to 50% of such nucleants may confer additional benefits in other properties such as impact resistance.
The polyesters of the compositions of the invention have a significantly rPduced glass-transition temperature but a melting point which is-reduced by a much lower extent. The compositions develop sufficient crystallinity for form stability, when crystallised at low mould temperatures, at a much faster rate than the polyester not containing the polymeric segments B but do not have a significantly reducecl working temperature in service.
In comparison with the exte~rnally plasticised compositions described in Britis~h Patent Specifications 2 015 013 and 2 015 014 the combirlation of the presence of the low glass transition temper~ture blocks in the copolymer and the neutralised polymeric nucleant results in improved processing in the compounding extruder together with improved impact strength and less discolouration introduced at the moulding stage.
The polymeric segments of type B preferably have a molecular weight in the range 500 to 10,000 and is desirably between 1000 and 5000. The polymer used must be capable of undergoing polycondensation with the segments o~ PET through reactive end groups such as hydroxyl or carboxyl groups or of being linked to PET segments by the use of chain extenders. m ey must be thermally and chemically stable under the conditions necessary to form the block copolymer. Typically suitable as the precursors for the segments of B are polyethylene glycol, o ~ 4 ~ 30976 polyethylene adipate, polypropylene glycol, polybutylene glycol, polybutylene adipate, polycaprolactone, polydecamethylene glycol, polyethylene sebacate, polyethylene azelate and polyoxydiethylene sebacate.
The block copolyester used in the invention may be obtained from monomeric constituents of PET and the precursors of segment B by conventional means. For example, copolymers may be made by heating dimethyl terephthalate, ethylene glycol and the precursor in the presence of an appropriate catalyst at about 200C until ester interchange is complete and th~ereafter heating at 275C to effect the polycondensation. Alternatively, a preformed polymer of the polyester or a polyester diol can be compounded under melt conditions with an appropriate reactive precursor. Chain extenders, such as isocyanates, epoxides, phenyl esters and caxbonates, may also be included in a melt compounding process. The melt compounding process is also useful for preparing block copolyesters having various concentrations of the segment B from copolyesters having a higher concentration of segment B. In this "let-down" process PET may be melt blended, for example, with a copolyester of PET containing 10 mole % of polyethylene oxide segments to give a copolyester containing a polyethylene oxide concentration which has been reduced in proportion to the total concentration of ethylene terephthalate units in the final composition.
As with other crystallisable materials the maximum rate of crystallisation is developed when nucleation sites are present in the crystallising mixture. A wide variety of nucleants are known for this purpose but the polymeric nuclPants specified above are particularly suitable when optimum impact strength is required in the polyester composition. Finely divided inorganic materials give a lower nucleating efficiency than the polymeric nucleants used in the composition of the invention.
7~0 _ 5 _ 30976 The compositions are particularly useful for use in engineering applications when they contain particulate or fibrous fillers because these materials can sign~icantly enhance the mechanical properties of the composition. Of the fibrous fillers, glass fibre is most widely used and are commercially available in a variety o~ types. The most suitable type for giving optimum levels of mechanical properties will depend to a significant extent on the nature of the siæe applied to the glass. Manufacturers of glass fibres appl~ a variety of sizes for promoting bonding between t~he polymer and the glass. The most suitable glass may be chosen by examination of the properties obtained when the glass i9 incorporated in the composition or the advice of the glass fibre manufacturer may be sought to obtain a fibre suitable for use in polyester compositions. Suitable glasses are OCF 277B*or OCF 419AA,* obtainable from Owens Corning Fibreglas. The composition~ may contain from 5 to 80~ by weight of the composition of glass fibre.
The composition may addikionally, or alternatively, contain a variety of mineral fillers such as clays, mica, calcium metasilicate, glass beads, pulverised uel ash and hollow glass spheres and other materials which act not only as cheap fillers but also significantly enhance some mechanical properties of the composition. As with the glass ~ibre it is advantageous to use fillers which have been surface treated with adhesion-promoting materials such as silanes.
Whilst fast crystallising polyester compositions can be obtained in the absence of any external plasticisers, the compositions of the invention include those in which external plasticisers may be present.
In addition the compositions of the invention may include colourants, mould release agents, flame retardants, ultra-violet light stabilisers and stabilisers against thermal or oxidative degradation.
*Trade Mark 7~9~
~ 6 - 30976 The fast crystallising characteristics of the compositions of the invention may be determined by subjecting small samples of the composition to ` differential scanning calorimetry techniques in addition to the practical test of determining the fastest rate at which articles may be injection moulded whilst retaining dimensional stability and good surface propertie~. One technique which may be used on small samples to examine the compositions of the present invention is as follows.
; 10 In order to remove residual crystallinity as far as possible a 10 mg sample of ~he composition (dried overnight at ca. 100C) was first heated significantly above the meltiny point of the polyester for 2 minutes and then quenched in liquid nitrogen. Thus the composition is melt pressed at 300C for 2 minutes prior to quenching in liquid nitrogen. The sample was then heated in a Perkin Elmer DSC-2 machine at 20C/min until a temperature of 300C was reached. After leaving the sample at 300C for 2 minutes it was cooled at 20C/minute. For a control sample of PET homopolymer the trace of the heat changes involved on heating the sample ~3hows a glass-transition temperature (Tg) in the region of 70C, a pronounced exotherm, as crystals tend to form from the glassy state, with a peak just below 150C (Tn) and a marked endotherm aq the polymer melts (Tp) at about 260C, On cooling, the temperature at which crystal growth starts (Ts) is readily observed as the start of an exotherm which has a maximum crystallisation rate at its peak (Tc). By comparison with this trace for polyethylene terephthalate a composition according to the invention would have a value for Tn of less than 120C and desirably less than 110C and Ts and Tc values which differ by less than 15C and desirably less than 10C. In practice it has been found that Tn corresponds closely to the temperature at which the peak in the crystallisation curve is reached within 60 seconds under isothermal conditions.
13'9~
Other variation~ of this test may be used as indicated in the Examples.
The intrinsic viscosity of the polyesters in the compositions of the invention are determined on a 1%
solution of the polyester in o-chlorophenol measured at 25~C.
The invention is further illustrated by reference to the following examples.
EX~MPLE 1 A block copolyester containing blocks of PET and polyethylene oxide was~prepared from a polyethylene glycol having a nominal molecular weight of 4000. The block polymer contained 10 weight % of the poLyethylene oxide segments. This polymer was melt compounded with the various additives listed in Table 1 below. The Table also records the data obtained from the differential scanning calorimetry (DSC) studies, outlined above. For comparison purposes the Table includes dat~ on a PET polymer and the polyethylene glycol (PEG 4000) used to prepare the block copolymer.
* Trade Mark .~
7~
, _.. _ . . .
Differential Scanning Calorimetry : Additive Data (C) : Tg Tn Tp Ts Tc _ _ . . , .. _ ._. __.
1~ 'Mistron 49 113.5 251 216 206 Superfrost'*Talc 5% 'Surlyn'**1601* 48.5 104 251 213 207 30% 91~RS fibr + ¦ 51.5 ¦ 111 250.5 ¦ 217 208 30% glass fibre + 53.5 104 251 216 209.5 5% 'Surlyn'**1601*
None 48 132 250 206 174 Control 80 13J 249 209 190 PET (IV 0.65) . - . .~_ ~*'Surlyn' 1601*- a partially neutralised ethylene/
methacrylic acid copolymer (sodium salt).
These results indicate that the compositions containing talc as nucleant were lesq nucleated than those containing 'Surlyn'*as shown by the lower Tn values of the latter.
In actual moulding of test pieces (melt temperature 280C, mould tamperature 110C) the lower Tn values ~or the 'Surlyn'-containing compositions resulted in smooth glossy mouldings compared with rough, dull mouldings for the talc nucleated compositions.
* Trade Mark ~7~
Composition containing equal parts by weight of the block copolymer used in Example 1 and a polyethylene terephthalate homopolymer having an intrinsic viscosity of 0~65 were blended together and with various additives as listed in Table 2. The results obtained from a DSC study, using the procedure hereinbefore specified, are also included.
Dif~erential Scanning Calorimetry Additive Data (C) _ Tg Tn Tp Ts Tc:
None 61 126 251 210 200 1% 'Mistron 64 119.5 250 215.5 205 Superfrost'*Talc .
5~ 'Surlyn' 1601* 59 10!3 250 214 206 .
A block copolyester containing 2~ by weight of polyethylene oxide units from a polyethylene glycol of nominal molecular weight 1500 (PEG 1500) was melt compounded with the additives listed in Table 3. The results obtained from a DSC study using the procPdure hereinbefore specified are listed in the table.
* Trade Mark ~i ` '~!~. -i~
~ __ -- - . .......................... .
Differential Scanning Calorimetry Additive Data (C) . _ _ . . .. .. _ Tg Tn Tp Ts Tc _. _ . . . ._ , .
1% 'Mistron 58 123.5 250.5 214 203 Superfrost' Talc 5% 'Surlyn' 1601 58 113 250.5 214 206 1% talc ~ 30% 57 117 249.5 214 204.5 glass fibre +
According to the invention there is provided a fast crystallising polyester composition comprising a block copolyester containing the repeating polymeric segments A
and B wherein A is a polymeric segment of ethylene terephthalate units and B is a polymeric segment having a glass-transition temperature of less than 0C and preferably less than -20C, the concentration of the segments of B being between 0.05 and lO mole % preferably from 0.1 to 5 mole ~ of the block copolyester, and a crystallisation nucleant which is an at least partially neutralised salt, preferably an alkali metal salt, of a polymer containing pendant neutralisable groups. The neutralisable groups should be sufficiently basic to react with the carboxylic ester groups in the copolyester to form a metal terephthalate species. Preferably the pendant neutralisable groups are~ carboxylic acid groups.
Suitable salts include salts of copolymers of styrene and maleic anhydride, salts of copolymers of olefins and ethylenically unsaturated carboxylic acids or carboxylic acid anhydrides optionally containing non-conjugated dienes and sa~ts of copolymers of acrylate and methacrylate esters and ethylenically unsaturated carbo~ylic acids or carboxylic acid anhydrides. Suitable ethylenically unsaturated carboxylic acids or anhydrides are, for example acrylic acid, methacrylic acid, maleic anhydride and fumaric anhydride.
The preferred concentration of the polymeric nucleant is between 0.5% and 10% by weight of the total weight of the composition. Concentrations of less than 0.5% of the polymeric nucleants, for example 0.1~, may be used but ~ 3 ~ 30976 will require the presence of additional nucleant of a different type to achieve a useful level of nucleation.
Concentrations above 10~ by weight of the polymeric nucleants used in the invention do not normally show much further improvement in the level of nucleation but the presence of up to 50% of such nucleants may confer additional benefits in other properties such as impact resistance.
The polyesters of the compositions of the invention have a significantly rPduced glass-transition temperature but a melting point which is-reduced by a much lower extent. The compositions develop sufficient crystallinity for form stability, when crystallised at low mould temperatures, at a much faster rate than the polyester not containing the polymeric segments B but do not have a significantly reducecl working temperature in service.
In comparison with the exte~rnally plasticised compositions described in Britis~h Patent Specifications 2 015 013 and 2 015 014 the combirlation of the presence of the low glass transition temper~ture blocks in the copolymer and the neutralised polymeric nucleant results in improved processing in the compounding extruder together with improved impact strength and less discolouration introduced at the moulding stage.
The polymeric segments of type B preferably have a molecular weight in the range 500 to 10,000 and is desirably between 1000 and 5000. The polymer used must be capable of undergoing polycondensation with the segments o~ PET through reactive end groups such as hydroxyl or carboxyl groups or of being linked to PET segments by the use of chain extenders. m ey must be thermally and chemically stable under the conditions necessary to form the block copolymer. Typically suitable as the precursors for the segments of B are polyethylene glycol, o ~ 4 ~ 30976 polyethylene adipate, polypropylene glycol, polybutylene glycol, polybutylene adipate, polycaprolactone, polydecamethylene glycol, polyethylene sebacate, polyethylene azelate and polyoxydiethylene sebacate.
The block copolyester used in the invention may be obtained from monomeric constituents of PET and the precursors of segment B by conventional means. For example, copolymers may be made by heating dimethyl terephthalate, ethylene glycol and the precursor in the presence of an appropriate catalyst at about 200C until ester interchange is complete and th~ereafter heating at 275C to effect the polycondensation. Alternatively, a preformed polymer of the polyester or a polyester diol can be compounded under melt conditions with an appropriate reactive precursor. Chain extenders, such as isocyanates, epoxides, phenyl esters and caxbonates, may also be included in a melt compounding process. The melt compounding process is also useful for preparing block copolyesters having various concentrations of the segment B from copolyesters having a higher concentration of segment B. In this "let-down" process PET may be melt blended, for example, with a copolyester of PET containing 10 mole % of polyethylene oxide segments to give a copolyester containing a polyethylene oxide concentration which has been reduced in proportion to the total concentration of ethylene terephthalate units in the final composition.
As with other crystallisable materials the maximum rate of crystallisation is developed when nucleation sites are present in the crystallising mixture. A wide variety of nucleants are known for this purpose but the polymeric nuclPants specified above are particularly suitable when optimum impact strength is required in the polyester composition. Finely divided inorganic materials give a lower nucleating efficiency than the polymeric nucleants used in the composition of the invention.
7~0 _ 5 _ 30976 The compositions are particularly useful for use in engineering applications when they contain particulate or fibrous fillers because these materials can sign~icantly enhance the mechanical properties of the composition. Of the fibrous fillers, glass fibre is most widely used and are commercially available in a variety o~ types. The most suitable type for giving optimum levels of mechanical properties will depend to a significant extent on the nature of the siæe applied to the glass. Manufacturers of glass fibres appl~ a variety of sizes for promoting bonding between t~he polymer and the glass. The most suitable glass may be chosen by examination of the properties obtained when the glass i9 incorporated in the composition or the advice of the glass fibre manufacturer may be sought to obtain a fibre suitable for use in polyester compositions. Suitable glasses are OCF 277B*or OCF 419AA,* obtainable from Owens Corning Fibreglas. The composition~ may contain from 5 to 80~ by weight of the composition of glass fibre.
The composition may addikionally, or alternatively, contain a variety of mineral fillers such as clays, mica, calcium metasilicate, glass beads, pulverised uel ash and hollow glass spheres and other materials which act not only as cheap fillers but also significantly enhance some mechanical properties of the composition. As with the glass ~ibre it is advantageous to use fillers which have been surface treated with adhesion-promoting materials such as silanes.
Whilst fast crystallising polyester compositions can be obtained in the absence of any external plasticisers, the compositions of the invention include those in which external plasticisers may be present.
In addition the compositions of the invention may include colourants, mould release agents, flame retardants, ultra-violet light stabilisers and stabilisers against thermal or oxidative degradation.
*Trade Mark 7~9~
~ 6 - 30976 The fast crystallising characteristics of the compositions of the invention may be determined by subjecting small samples of the composition to ` differential scanning calorimetry techniques in addition to the practical test of determining the fastest rate at which articles may be injection moulded whilst retaining dimensional stability and good surface propertie~. One technique which may be used on small samples to examine the compositions of the present invention is as follows.
; 10 In order to remove residual crystallinity as far as possible a 10 mg sample of ~he composition (dried overnight at ca. 100C) was first heated significantly above the meltiny point of the polyester for 2 minutes and then quenched in liquid nitrogen. Thus the composition is melt pressed at 300C for 2 minutes prior to quenching in liquid nitrogen. The sample was then heated in a Perkin Elmer DSC-2 machine at 20C/min until a temperature of 300C was reached. After leaving the sample at 300C for 2 minutes it was cooled at 20C/minute. For a control sample of PET homopolymer the trace of the heat changes involved on heating the sample ~3hows a glass-transition temperature (Tg) in the region of 70C, a pronounced exotherm, as crystals tend to form from the glassy state, with a peak just below 150C (Tn) and a marked endotherm aq the polymer melts (Tp) at about 260C, On cooling, the temperature at which crystal growth starts (Ts) is readily observed as the start of an exotherm which has a maximum crystallisation rate at its peak (Tc). By comparison with this trace for polyethylene terephthalate a composition according to the invention would have a value for Tn of less than 120C and desirably less than 110C and Ts and Tc values which differ by less than 15C and desirably less than 10C. In practice it has been found that Tn corresponds closely to the temperature at which the peak in the crystallisation curve is reached within 60 seconds under isothermal conditions.
13'9~
Other variation~ of this test may be used as indicated in the Examples.
The intrinsic viscosity of the polyesters in the compositions of the invention are determined on a 1%
solution of the polyester in o-chlorophenol measured at 25~C.
The invention is further illustrated by reference to the following examples.
EX~MPLE 1 A block copolyester containing blocks of PET and polyethylene oxide was~prepared from a polyethylene glycol having a nominal molecular weight of 4000. The block polymer contained 10 weight % of the poLyethylene oxide segments. This polymer was melt compounded with the various additives listed in Table 1 below. The Table also records the data obtained from the differential scanning calorimetry (DSC) studies, outlined above. For comparison purposes the Table includes dat~ on a PET polymer and the polyethylene glycol (PEG 4000) used to prepare the block copolymer.
* Trade Mark .~
7~
, _.. _ . . .
Differential Scanning Calorimetry : Additive Data (C) : Tg Tn Tp Ts Tc _ _ . . , .. _ ._. __.
1~ 'Mistron 49 113.5 251 216 206 Superfrost'*Talc 5% 'Surlyn'**1601* 48.5 104 251 213 207 30% 91~RS fibr + ¦ 51.5 ¦ 111 250.5 ¦ 217 208 30% glass fibre + 53.5 104 251 216 209.5 5% 'Surlyn'**1601*
None 48 132 250 206 174 Control 80 13J 249 209 190 PET (IV 0.65) . - . .~_ ~*'Surlyn' 1601*- a partially neutralised ethylene/
methacrylic acid copolymer (sodium salt).
These results indicate that the compositions containing talc as nucleant were lesq nucleated than those containing 'Surlyn'*as shown by the lower Tn values of the latter.
In actual moulding of test pieces (melt temperature 280C, mould tamperature 110C) the lower Tn values ~or the 'Surlyn'-containing compositions resulted in smooth glossy mouldings compared with rough, dull mouldings for the talc nucleated compositions.
* Trade Mark ~7~
Composition containing equal parts by weight of the block copolymer used in Example 1 and a polyethylene terephthalate homopolymer having an intrinsic viscosity of 0~65 were blended together and with various additives as listed in Table 2. The results obtained from a DSC study, using the procedure hereinbefore specified, are also included.
Dif~erential Scanning Calorimetry Additive Data (C) _ Tg Tn Tp Ts Tc:
None 61 126 251 210 200 1% 'Mistron 64 119.5 250 215.5 205 Superfrost'*Talc .
5~ 'Surlyn' 1601* 59 10!3 250 214 206 .
A block copolyester containing 2~ by weight of polyethylene oxide units from a polyethylene glycol of nominal molecular weight 1500 (PEG 1500) was melt compounded with the additives listed in Table 3. The results obtained from a DSC study using the procPdure hereinbefore specified are listed in the table.
* Trade Mark ~i ` '~!~. -i~
~ __ -- - . .......................... .
Differential Scanning Calorimetry Additive Data (C) . _ _ . . .. .. _ Tg Tn Tp Ts Tc _. _ . . . ._ , .
1% 'Mistron 58 123.5 250.5 214 203 Superfrost' Talc 5% 'Surlyn' 1601 58 113 250.5 214 206 1% talc ~ 30% 57 117 249.5 214 204.5 glass fibre +
3% neopentyl glycol dibenzoate 5% 'Surlyn'1601 ~ 57 107 250 214 208 30~ glass fibre +
3% neopentyl glycol dibenzoate None 63 143 250 207 138 A copolyester containing blocks of PET and 5~6 by weight of blocks of polyethylene oxide (derived from polyethylene glycol of nominal molecular weight = 1540) 5 was blended with 30% by weight of 3 mm long glass fibre and various levels of 'Surlyn' 1601 by tumbling. The mixture was compounded in a screw extruder. Ihe crystallisation properties of the product obtained was assessed`by measuring the Tn value of the composition as 10 previously described. Physical properties were measured on test pieces formed from the composition. The results obtained are recorded in Table 4.
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A block co~olyester containing 10~ by weight of blocks of PET and polyethylene oxide was prepared using a polyethylene glycoI of nominal molecular weight 1540. The copolyester was compounded with 30% by weight of 3 mm glass fibres and the various levels of 'Surlyn' 1601 listed below. Table 5 below records values of Tg and Tn obtained from DSC measurements as previously described and other physical properties.
TABLE S
..... . ____ . . .. ,.. _ __ _ _ . _ ,, .
Charpy***
'Surlyn' 1601 impact content DSC results Flexural* Tensile** strength % by weight _. modulus Strength notched of total (1/4 mm composition Tg Tn Izod) _ _ 1 51 106 8.6 150 86 . . 52 9l a .0 144 111 .
* measured according to IS0 Method R 178 ** measured according to IS0 M~3thod R 527 *** measursd according to IS0 Method R 180A
- EXI~MPLE 6 A block copolyester containing 10% by weight of blocks of polytetramethylene oxide units was prepared using polytetramethylene glycol. The copolyester was compounded together with 30% by weight of glass fibres (3 mm) and 5% by weight of 'Surlyn' 1601.
DSC measurements indicated values of Tg and Tn of 47C and 99C respectively.
~7~9~
EX~MPLE 7 In this example a composition (hereinafter termed Comparative Composition A) according to British Patent Publication 2 015 014 containing 30~ by weight of glass fibre, 5~ by weight of a partially neutralised sodium salt of an ethylene/methacrylic acid copolymer, 5.5% by weight of neopentylglycol dibenzoate, 0.2% by weight of tetrabisCmethylene(3,5 di-tert-butyl-4-hydroxyhydrocinnamate~] methana as stabiliser and the balance (59.3% by weight) of PET with an intrinsic viscosity of 0.63-is compar~ed with a similar composition (hereinafter termed Composition B) except in t~at the neopentylglycol dibenzoate was omitted and the PET was replaced with a copolyester of blocks of PET and 5~ by weight of blocks of polyethylene oxide. The polymer content of the second composition was 64.8~ by weight.
The crystallisation properties of the two compositions were assessed by the DSC techniques previously described. The results detailed in Table 6 indicate a slightly lower value of Tn for the composition according to the invention. This difference is shown more clearly when comparing the half crystallisation times under isothermal conditions. Although there is little difference at high temperatures the results indicate that Composition B would crystallise considerably more quicXly at a mould temperature o~ 90C than Comparative Composition A.
~7~9~0 . . _ . .
DSC measurements _ _. . . .
Half crystallisation times (min) Tg Tn at 90C 100C 110C 120C
~ _ ....... _ . ~
Comparative 65 110 10.0 1.2 0.52 0.25 Composition A
Composition B 61 108 2.8 0.7 0.3 0.23 The two compositions were moulded on Ankerwerke A36 injection moulding machine into plaques oi. dimensions 75 mm x 50 mm x 3 mm. The plaques were prepared using a melt temperature in the range 280C to 290C and at mould temperatures of 90C and 110C. Very noticeable fuming was observed during the moulding of Comparative Composition A which was absent in the case of Composition B. Examination of t:he moula surface showed that Comparative Composition A had left a deposit in the mould. The mouldings obtained i.'or Composition B had si~niEicantly better surface finish than Comparative Composition A particularly when moulded at a mould .
temperature in excess of 90C.
The physical properties measured on the mouldings are recorded in Table 7.
. .. __ ~
Moulding Conditions Charpy impact Flexural Composition _ modulus _ Melt Mould ~IS UNIS
temp. (CP) (G~/m2) (kJ/m2) (kJ/m2) Comparative 280 11010.5 10.4 25 Composition 280 90 10.7 9.2 35 Composition 280 110 9.3 10.3 38 B 280 90 9.110.3 52 . ., . _ . . . . . _ As expected the flexural modulus of composition B is lower than that of Comparative Composition A because of the presence of the low Tg blocks in the former. On the other hand unnotched impact strength of composition B was superior to that of Comparative Composition A.
In further comparative mouldings of large dimensions it was observed that under severe conditions Composition B
was less susceptible to degradation (as indicated by the appearance of dark coloured streaks in the moulding) than was Comparative Composition A. This superior thermal stability was confirmed by ageing the compositions in air.
At temperatures in excess of 140C Comparative Composition A became discoloured considerably more quickly than Composition B.
~7~
A block copolyester containing blocks of PET and polyethylene oxide was prepared from a polyethylene glycol having a nominal molecular weight of 4000. The block copolyester contained 30% by weight of the polyethylene oxide se~nents. The copolyester was compounded with 5% by weight of the total composition of 'Surlyn' 1706 (a partially neutralised ethylene/methacrylic acid, zinc salt). The Tn value of the composition was determined as follows. After drying a sample of the product overnight at 100C to 110C in a vacuum oven~a-fi~n (0.375 mm thick) was obtained by pressing the product between PTFE coated stainless steel glazing plates at a pressure of 18 MPa and a temperature of 280C. After 1 minute ~t the required pressure the mould was quenched in an ice-batch. About 10 mg of sample was cut from the film and heated in a Perkin E~ner DSC 2 machine at a rate of 16C/minute. A Tn value of 64C was observed compared with a value of 71C
for the copolyester not containing the 'Surlyn' additive.
3% neopentyl glycol dibenzoate None 63 143 250 207 138 A copolyester containing blocks of PET and 5~6 by weight of blocks of polyethylene oxide (derived from polyethylene glycol of nominal molecular weight = 1540) 5 was blended with 30% by weight of 3 mm long glass fibre and various levels of 'Surlyn' 1601 by tumbling. The mixture was compounded in a screw extruder. Ihe crystallisation properties of the product obtained was assessed`by measuring the Tn value of the composition as 10 previously described. Physical properties were measured on test pieces formed from the composition. The results obtained are recorded in Table 4.
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7~
A block co~olyester containing 10~ by weight of blocks of PET and polyethylene oxide was prepared using a polyethylene glycoI of nominal molecular weight 1540. The copolyester was compounded with 30% by weight of 3 mm glass fibres and the various levels of 'Surlyn' 1601 listed below. Table 5 below records values of Tg and Tn obtained from DSC measurements as previously described and other physical properties.
TABLE S
..... . ____ . . .. ,.. _ __ _ _ . _ ,, .
Charpy***
'Surlyn' 1601 impact content DSC results Flexural* Tensile** strength % by weight _. modulus Strength notched of total (1/4 mm composition Tg Tn Izod) _ _ 1 51 106 8.6 150 86 . . 52 9l a .0 144 111 .
* measured according to IS0 Method R 178 ** measured according to IS0 M~3thod R 527 *** measursd according to IS0 Method R 180A
- EXI~MPLE 6 A block copolyester containing 10% by weight of blocks of polytetramethylene oxide units was prepared using polytetramethylene glycol. The copolyester was compounded together with 30% by weight of glass fibres (3 mm) and 5% by weight of 'Surlyn' 1601.
DSC measurements indicated values of Tg and Tn of 47C and 99C respectively.
~7~9~
EX~MPLE 7 In this example a composition (hereinafter termed Comparative Composition A) according to British Patent Publication 2 015 014 containing 30~ by weight of glass fibre, 5~ by weight of a partially neutralised sodium salt of an ethylene/methacrylic acid copolymer, 5.5% by weight of neopentylglycol dibenzoate, 0.2% by weight of tetrabisCmethylene(3,5 di-tert-butyl-4-hydroxyhydrocinnamate~] methana as stabiliser and the balance (59.3% by weight) of PET with an intrinsic viscosity of 0.63-is compar~ed with a similar composition (hereinafter termed Composition B) except in t~at the neopentylglycol dibenzoate was omitted and the PET was replaced with a copolyester of blocks of PET and 5~ by weight of blocks of polyethylene oxide. The polymer content of the second composition was 64.8~ by weight.
The crystallisation properties of the two compositions were assessed by the DSC techniques previously described. The results detailed in Table 6 indicate a slightly lower value of Tn for the composition according to the invention. This difference is shown more clearly when comparing the half crystallisation times under isothermal conditions. Although there is little difference at high temperatures the results indicate that Composition B would crystallise considerably more quicXly at a mould temperature o~ 90C than Comparative Composition A.
~7~9~0 . . _ . .
DSC measurements _ _. . . .
Half crystallisation times (min) Tg Tn at 90C 100C 110C 120C
~ _ ....... _ . ~
Comparative 65 110 10.0 1.2 0.52 0.25 Composition A
Composition B 61 108 2.8 0.7 0.3 0.23 The two compositions were moulded on Ankerwerke A36 injection moulding machine into plaques oi. dimensions 75 mm x 50 mm x 3 mm. The plaques were prepared using a melt temperature in the range 280C to 290C and at mould temperatures of 90C and 110C. Very noticeable fuming was observed during the moulding of Comparative Composition A which was absent in the case of Composition B. Examination of t:he moula surface showed that Comparative Composition A had left a deposit in the mould. The mouldings obtained i.'or Composition B had si~niEicantly better surface finish than Comparative Composition A particularly when moulded at a mould .
temperature in excess of 90C.
The physical properties measured on the mouldings are recorded in Table 7.
. .. __ ~
Moulding Conditions Charpy impact Flexural Composition _ modulus _ Melt Mould ~IS UNIS
temp. (CP) (G~/m2) (kJ/m2) (kJ/m2) Comparative 280 11010.5 10.4 25 Composition 280 90 10.7 9.2 35 Composition 280 110 9.3 10.3 38 B 280 90 9.110.3 52 . ., . _ . . . . . _ As expected the flexural modulus of composition B is lower than that of Comparative Composition A because of the presence of the low Tg blocks in the former. On the other hand unnotched impact strength of composition B was superior to that of Comparative Composition A.
In further comparative mouldings of large dimensions it was observed that under severe conditions Composition B
was less susceptible to degradation (as indicated by the appearance of dark coloured streaks in the moulding) than was Comparative Composition A. This superior thermal stability was confirmed by ageing the compositions in air.
At temperatures in excess of 140C Comparative Composition A became discoloured considerably more quickly than Composition B.
~7~
A block copolyester containing blocks of PET and polyethylene oxide was prepared from a polyethylene glycol having a nominal molecular weight of 4000. The block copolyester contained 30% by weight of the polyethylene oxide se~nents. The copolyester was compounded with 5% by weight of the total composition of 'Surlyn' 1706 (a partially neutralised ethylene/methacrylic acid, zinc salt). The Tn value of the composition was determined as follows. After drying a sample of the product overnight at 100C to 110C in a vacuum oven~a-fi~n (0.375 mm thick) was obtained by pressing the product between PTFE coated stainless steel glazing plates at a pressure of 18 MPa and a temperature of 280C. After 1 minute ~t the required pressure the mould was quenched in an ice-batch. About 10 mg of sample was cut from the film and heated in a Perkin E~ner DSC 2 machine at a rate of 16C/minute. A Tn value of 64C was observed compared with a value of 71C
for the copolyester not containing the 'Surlyn' additive.
Claims (7)
1. A fast crystallising polyester composition comprising a block copolyester containing the repeating polymeric segments A and B wherein A is a polymeric segment of ethylene terephthalate units and s is a polymeric segment having a glass-transition temperature of less than 0°C, the concentration of the segments of B being between 0.05 and 10 mole % preferably from 0.1 to 5 mole % of the block copolyester, and a crystalli-sation nucleant which is an at least partially neutralised salt of a polymer containing pendant neutralisable groups.
2. A fast crystallising polyester composition according to Claim 1 wherein the polymeric segment B has a glass-transition temperature of less than -20°C.
3. A fast crystallising polyester composition according to Claim 1 or Claim 2 wherein the pendant neutralisable groups are carboxylic acid groups or carboxylic acid anhydride groups.
4. A fast crystallising polyester composition according to Claim 1 or Claim 2 in which the salt is an alkali metal salt.
5. A fast crystallising polyester composition according to Claim 1 or Claim 2 containing from 0.1 to 50% by weight of the composition of the at least partially neutralised salt of a polymer containing pendant neutralisable groups.
6. A fast crystallising polyester composition according to Claim 1 or Claim 2 containing from 5 to 80% by weight of the composition of glass fibres.
7. A fast crystallising polyester composition according to Claim 1 or Claim 2 in which the molecular weight of the polymeric segment B having a glass-transition temperature of less than 0°C is between 1000 and 5000.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7932818 | 1979-09-21 | ||
| GB7932818 | 1979-09-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1147090A true CA1147090A (en) | 1983-05-24 |
Family
ID=10507992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000360357A Expired CA1147090A (en) | 1979-09-21 | 1980-09-16 | Fast crystallising block copolyester composition |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4322335A (en) |
| EP (1) | EP0029285B1 (en) |
| JP (1) | JPS5655451A (en) |
| AT (1) | ATE7396T1 (en) |
| AU (1) | AU6217980A (en) |
| CA (1) | CA1147090A (en) |
| DE (1) | DE3067764D1 (en) |
| ES (1) | ES8107280A1 (en) |
| ZA (1) | ZA805684B (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3110906A1 (en) * | 1981-03-20 | 1982-10-14 | Akzo Gmbh, 5600 Wuppertal | HYDROPHILE POLYESTER MATERIAL |
| US4365036A (en) * | 1981-12-15 | 1982-12-21 | Plastics Engineering Company | Fast crystallizing polyalkyleneterephthalate resin compositions |
| US4438233A (en) | 1982-09-20 | 1984-03-20 | Plastics Engineering Company | Fast crystallizing polyalkyleneterephthalate resin compositions |
| DE3370489D1 (en) * | 1982-11-11 | 1987-04-30 | Akzo Nv | Thermoplastic block copolyester resin composition containing a nucleating agent and an accelerator |
| US4511527A (en) * | 1982-12-16 | 1985-04-16 | Celanese Corporation | Alkali metal salts of cross-linked polymeric microgels as nucleating agents for polyethylene terephthalate molding compositions and method for molding |
| EP0116673B1 (en) * | 1983-02-18 | 1989-08-09 | Toyo Boseki Kabushiki Kaisha | Improved polyester type block copolymer composition |
| US4558085A (en) * | 1983-10-11 | 1985-12-10 | Plastics Engineering Company | Process for the preparation of fast crystallizing polyalkyleneterephthalate resin compositions |
| US4581410A (en) * | 1984-01-09 | 1986-04-08 | Monsanto Company | Hot melt adhesive compositions |
| EP0174343B1 (en) * | 1984-02-24 | 1992-04-29 | E.I. Du Pont De Nemours And Company | Toughened thermoplastic polyester compositions |
| US4548978A (en) * | 1984-02-24 | 1985-10-22 | E. I. Du Pont De Nemours And Company | Fast crystallizing polyester resin containing three-component crystallization system |
| CA1228186A (en) * | 1984-02-24 | 1987-10-13 | William E. Garrison, Jr. | Fast crystallizing polyester resin containing three- component crystallization system |
| US4778842A (en) * | 1985-02-15 | 1988-10-18 | Kuraray Co., Ltd. | Polyester resin compositions |
| US4806588A (en) * | 1986-04-15 | 1989-02-21 | Toyo Boseki Kabushiki Kaisha | Polyester resin composition |
| US4772652A (en) * | 1986-05-27 | 1988-09-20 | Kuraray Co., Ltd. | Copolyester and polyester resin composition comprising said copolyester |
| JPS63108054A (en) * | 1986-06-05 | 1988-05-12 | Kanegafuchi Chem Ind Co Ltd | Polyethylene terephthalate resin composition for molding |
| EP0285102B1 (en) * | 1987-04-03 | 1993-06-30 | Mitsubishi Kasei Corporation | Polyethylene terephthalate resin composition |
| US5089553A (en) * | 1988-08-30 | 1992-02-18 | Idemitsu Petrochemical Co., Ltd. | Copolymerized polyester compositions |
| WO1991002015A1 (en) * | 1989-08-08 | 1991-02-21 | The Pennsylvania Research Corporation | Hydrodegradable polyesters |
| US5389710A (en) * | 1992-11-23 | 1995-02-14 | Dege; Gerald J. | Crystallization modifier for polyester molding compositions |
| US5414036A (en) * | 1993-04-12 | 1995-05-09 | Enichem S.P.A. | Rapidly crystallizing polyester molding compositions |
| AU7099794A (en) * | 1993-06-22 | 1995-01-17 | Olin Corporation | Polyetherester block copolymer elastomers |
| US5344892A (en) * | 1993-07-02 | 1994-09-06 | Enichem S.P.A. | Polyester compositions with improved crystallization rate |
| DE4333930A1 (en) * | 1993-10-05 | 1995-04-06 | Basf Ag | Process for the production of thermoplastic polyesters |
| DE4401055A1 (en) * | 1994-01-15 | 1995-07-20 | Basf Ag | Process for the preparation of thermoplastic polyesters with a low carboxyl end group content |
| US5733268A (en) * | 1996-11-01 | 1998-03-31 | Denco, Inc. | Medical tubing and containers for use in conveying medical solutions and the like |
| US6348049B1 (en) | 1994-03-30 | 2002-02-19 | Denco, Inc. | Surgical/medical tubing and containers for use in conveying medical solutions and the like |
| US5554120A (en) * | 1994-07-25 | 1996-09-10 | Advanced Cardiovascular Systems, Inc. | Polymer blends for use in making medical devices including catheters and balloons for dilatation catheters |
| US5849846A (en) * | 1994-07-25 | 1998-12-15 | Advanced Cardiovascular Systems, Inc. | Balloons for medical catheters |
| JPH11504371A (en) | 1995-04-26 | 1999-04-20 | アライドシグナル・インコーポレーテッド | Polyester molding composition and articles exhibiting good impact resistance, heat resistance and solvent resistance |
| US5928216A (en) * | 1997-01-30 | 1999-07-27 | Denco, Inc. | Surgical/medical tubing and containers for use in conveying medical solutions and the like |
| US6071690A (en) * | 1998-02-02 | 2000-06-06 | Denco, Inc. | Ionomeric modified poly-ether-ester plastic container for cryogenic fluids |
| US6986864B2 (en) * | 2002-04-30 | 2006-01-17 | David Scott Porter | Polyester compositions |
| WO2004104100A1 (en) * | 2003-05-15 | 2004-12-02 | E.I. Dupont De Nemours And Company | Fast crystallizing polyester compositions |
| US20080103217A1 (en) * | 2006-10-31 | 2008-05-01 | Hari Babu Sunkara | Polyether ester elastomer composition |
| US7279124B2 (en) * | 2004-05-20 | 2007-10-09 | Eastman Chemical Company | Nucleation enhanced polyester and its use in melt-to-mold processing of molded articles |
| US7531593B2 (en) * | 2006-10-31 | 2009-05-12 | E.I. Du Pont De Nemours And Company | Thermoplastic elastomer blend composition |
| US10662325B2 (en) | 2017-07-13 | 2020-05-26 | Exxonmobil Chemical Patents Inc. | Polyester compositions, and process for making articles therefrom |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3435093A (en) * | 1965-12-17 | 1969-03-25 | Du Pont | Polymer blends of polyethylene terephthalate and alpha-olefin,alpha,beta-unsaturated carboxylic acid copolymers |
| US3639527A (en) * | 1967-09-05 | 1972-02-01 | Hoechst Ag | Polyester-ionic copolymer thermoplastic moulding compositions |
| JPS4734839U (en) * | 1971-05-12 | 1972-12-18 | ||
| JPS50109947A (en) * | 1974-02-09 | 1975-08-29 | ||
| CA1195464A (en) | 1974-03-28 | 1985-10-22 | Martin L. Brown | Oriented copolyetherester elastomer |
| DE2507776C2 (en) * | 1975-02-22 | 1983-09-22 | Bayer Ag, 5090 Leverkusen | Rapidly crystallizing poly (ethylene / alkylene) terephthalate |
| JPS6042252B2 (en) * | 1975-03-28 | 1985-09-20 | 帝人株式会社 | Hollow body for blood or infusion |
| BE832445A (en) * | 1975-08-14 | 1975-12-01 | ELASTOMERIC ARTICLES IN ORIENTATED COPOLYETHERS-ESTERS. | |
| AU500523B2 (en) * | 1975-12-08 | 1979-05-24 | General Electric Company | Thermoplastic molding composition |
| US4116925A (en) * | 1976-06-14 | 1978-09-26 | Gaf Corporation | Poly(tetramethylene terephthalate)-polyether block |
| US4130603A (en) * | 1977-02-04 | 1978-12-19 | Toray Industries, Inc. | Thermoplastic linear block copolyether-polyesters as hot melt adhesives for textiles |
| DE2732301C3 (en) * | 1977-07-16 | 1980-12-11 | Roehm Gmbh, 6100 Darmstadt | Process for the production of stabilized carrier-bound proteins |
| JPS5493043A (en) * | 1977-12-29 | 1979-07-23 | Unitika Ltd | Resin composition and its production |
| SE430168B (en) | 1978-02-28 | 1983-10-24 | Du Pont | SUBSTANCE PACKAGING PLASTIC COMPOSITION CONTAINING REINFORCEMENT OR FILLER AND USE OF IT |
| SE430169C (en) | 1978-02-28 | 1985-04-14 | Du Pont | SUBSTANCE PACKAGING PLASTIC COMPOSITION CONTAINING REINFORCEMENT OR FILLER AND USE OF IT |
| JPS54138055A (en) * | 1978-04-18 | 1979-10-26 | Toray Ind Inc | Resin composition for metal coating |
-
1980
- 1980-09-02 DE DE8080303053T patent/DE3067764D1/en not_active Expired
- 1980-09-02 EP EP80303053A patent/EP0029285B1/en not_active Expired
- 1980-09-02 AT AT80303053T patent/ATE7396T1/en active
- 1980-09-08 US US06/184,975 patent/US4322335A/en not_active Expired - Lifetime
- 1980-09-10 AU AU62179/80A patent/AU6217980A/en not_active Abandoned
- 1980-09-15 ZA ZA00805684A patent/ZA805684B/en unknown
- 1980-09-16 CA CA000360357A patent/CA1147090A/en not_active Expired
- 1980-09-19 ES ES495207A patent/ES8107280A1/en not_active Expired
- 1980-09-22 JP JP13084580A patent/JPS5655451A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| US4322335B1 (en) | 1988-04-05 |
| ATE7396T1 (en) | 1984-05-15 |
| JPH0157701B2 (en) | 1989-12-07 |
| EP0029285B1 (en) | 1984-05-09 |
| ZA805684B (en) | 1981-09-30 |
| JPS5655451A (en) | 1981-05-16 |
| DE3067764D1 (en) | 1984-06-14 |
| AU6217980A (en) | 1981-03-26 |
| EP0029285A1 (en) | 1981-05-27 |
| ES495207A0 (en) | 1981-10-01 |
| ES8107280A1 (en) | 1981-10-01 |
| US4322335A (en) | 1982-03-30 |
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