EP1062277A1 - Melanges miscibles multiconstituants de nylons a proprietes ameliorees - Google Patents

Melanges miscibles multiconstituants de nylons a proprietes ameliorees

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Publication number
EP1062277A1
EP1062277A1 EP99911086A EP99911086A EP1062277A1 EP 1062277 A1 EP1062277 A1 EP 1062277A1 EP 99911086 A EP99911086 A EP 99911086A EP 99911086 A EP99911086 A EP 99911086A EP 1062277 A1 EP1062277 A1 EP 1062277A1
Authority
EP
European Patent Office
Prior art keywords
nylon
copolymer
weight
composition
amount
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Withdrawn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
EP99911086A
Other languages
German (de)
English (en)
Inventor
Yash P. Khanna
Eric D. Day
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.)
Honeywell International Inc
Original Assignee
AlliedSignal Inc
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
Application filed by AlliedSignal Inc filed Critical AlliedSignal Inc
Publication of EP1062277A1 publication Critical patent/EP1062277A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the present invention relates to nylon blends or more particularly to a method for forming extremely uniform, melt blended mixtures of semi- l o crystalline nylon homopolymers with semi-crystalline nylon copolymers
  • the blends are so uniform that they have essentially a single melting point rather than maintaining the melting points of the individual nylon component parts
  • the blend has a larger difference between its melting temperature and its crystallization temperature than each of the semi-
  • the blend has a melting temperature approximately equal to that of the semi-crystalline nylon homopolymer component.
  • U.S. patent 5,206,309 teaches heat stable films based on melt blends of N6 and N6 / N66, where N66 can be 0.1-99.9%. This patent does not describe the random copolymers in the proportions required to achieve a homogenous, miscible phase according to this invention.
  • U.S. patents 5,053259 and 5,344679 teach blends of an amorphous nylon, a copolyamide of Tm > 145 °C, and optionally 10-30 weight % of a polyamide homopolymer.
  • U.S. patent 4,877,684 claims films based on mixtures of nylon 6 and N6/N66.
  • EP Patent 408,390 discloses the use of any polyamide, any copolyamide, or a mixture of polyamides along with amorphous polyamide or a copolyamide.
  • Japanese patent 115,4752 discloses films based on mixtures of an aliphatic polyamide and a partially aromatic amorphous polyamide along with EVOH.
  • AU Patent 8825700 discloses an aliphatic polyamide, e.g., nylon 6 or N6/66 copolymer and an amorphous polyamide. All of these likewise do not teach random copolymers of nylons in certain proportions to form a homogenous, miscible phase composition according to the invention.
  • patents 4,647483; 4,665135 and 4,683170 show blends ofN6 plus a copolymer of N6/N66 or N6/N12 rich in N6 such that the overall blend contains 2.5- 10%, of N66 or N12.
  • the present invention is more effective than the blends of these patents, since more N66 can be incorporated without adverse effects on homogeneity.
  • the invention provides method for producing a uniformly blended semi- crystalline nylon composition which comprises:
  • the invention also provides a method for producing a uniformly blended semi-crystalline nylon composition which comprises:
  • compositions optionally further comprises a non-crystalline amorphous nylon component. These compositions are useful in producing films by casting or blowing and optionally rhonoaxially or biaxially stretching the nylon compositions.
  • a minor nylon component can be incorporated into a major component (e.g., N66 in N6 or N6 in N66 ) in such a way that the resulting product is a one-component, homogenous material as determined by Differential Scanning Calorimetry (DSC).
  • DSC Differential Scanning Calorimetry
  • the products of this invention are different from conventional blends in view of having only one melting point T m ( as opposed to two T m 's ) and reduced crystallizability at a particular chemical composition.
  • the products of this invention are also different from conventional random 5 copolymers in view of a much higher T m and reduced crystallizability for a particular chemical composition of nylon.
  • the invention allows one to incorporate multi-component polyamides, e.g., N66, N12, and amorphous nylons into N6, without observing non-homogeneity in either crystalline or amorphous phase as determined by DSC.
  • multi-component polyamides e.g., N66, N12, and amorphous nylons into N6, without observing non-homogeneity in either crystalline or amorphous phase as determined by DSC.
  • Miscibility 0 in blends traditionally has implied one homogenous amorphous phase but the crystalline phases always reveal their characteristic T m 's.
  • this invention provides multi-component miscible blends with just one amorphous phase and just one crystalline phase, as determined by DSC.
  • Figure 1 shows a graph of the melting pattern of melt blended nylon films.
  • Figure 2 shows a graph of the melting pattern of nylon 6/nylon 66 random o copolymer films.
  • Figure 3 shows a graph of the melting pattern of nylon films based on nylon 6 homopolymer plus nylon 6/nylon 66 (84/16) random copolymer blends.
  • Figure 4 shows a graph of melting temperature vs. % nylon 66 in nylon 6 films.
  • Figure 5 shows a graph of super-cooling vs. % nylon 66 in nylon 6 films.
  • Figure 6 shows a graph of the melting pattern of nylon films based on nylon 6 homopolymer plus nylon 6/nylon 66 (75/25) random copolymer blends.
  • Figure 7 shows a graph of the melting pattern of nylon films.
  • a composition is prepared by melt blending a semi-crystalline homopolymer of a nylon A with a semi-crystalline nylon which is a copolymer of nylon A plus at least one different nylon B.
  • the composition optionally also comprises a non-crystalline amorphous nylon copolymer C.
  • the formed composition is determined to have a single significant melting point. For purposes of this invention, having only a single significant point means that a second melting point, if one is observed, is no more than 35% of the main melting peak, more preferably no more than 20% of the main melting peak and most preferably no more than 10% of the main melting peak.
  • the intensity of the second melting peak is determined by known DSC methods. Such methods include analyzing a film to be tested after drying at 25 °C - 45 °C under vacuum for several hours. The intensity of the major and any minor peaks in DSC are determined by heat of fusion integrated over the melting ranges of the individual peaks. Preferably the composition has only one melting point and no other melting point at all.
  • the composition when the nylon components are blended in a first proportion, the composition has a larger difference between its melting temperature and its crystallization temperature than each of nylon homopolymer A and the copolymer.
  • the nylon composition when the nylon components are blended in a second proportion, the nylon composition has a melting temperature which is about equal to the melting temperature of the nylon homopolymer A.
  • a melting temperature which is about equal to the melting temperature of the nylon homopolymer A means within about + 5 °C of the melting temperature of the nylon homopolymer A.
  • the first component of the inventive composition is a semi-crystalline homopolymer of nylon A which may be comprised of any semicrystalline polyamide homopolymer.
  • Polyamides suitable for use in this invention as semi-crystalline homopolymer of nylon A include aliphatic polyamides or aliphatic/aromatic polyamides.
  • aliphatic polyamides are polyamides characterized by the presence of recurring carbonamide groups as an integral part of the polymer chain which are separated from one another by at least two aliphatic carbon atoms.
  • Illustrative of these polyamides are those having recurring monomeric units represented by the general formula:
  • R and R 1 are the same or different and are alkylene groups of at least about two carbon atoms, preferably alkylene groups having from about 2 to about 12 carbon atoms.
  • an "aliphatic/aromatic polyamide” is characterized by the presence of recurring carbonamide groups as an integral part of the polymer chain where the carbonyl moieties are separated by aliphatic moieties having at least two carbon atoms and where the nitrogen groups are separated by aromatic moieties.
  • Illustrative of the aliphatic/aromatic polyamides are those having recurring units of the formula:
  • R 2 and R 3 are different and are alkylene groups having at least 2 carbon atoms, preferably having from 2 to about 12 carbon atoms, or arylene, preferably substituted or unsubstituted phenylene,
  • suitable aliphatic polyamides are polyamide homopolymers formed by the reaction of diamines and diacids such as poly(hexamethylene adipamide) (nylon 6,6), poly(hexamethylene sebacamide) (nylon 6,10), poly(heptamethylene pimelamide) (nylon 7,7), poly(octamethylene suberamide) (nylon 8,8), poly(hexamethylene azelamide) (nylon 6,9), poly(nonamethylene azelamide) (nylon 9,9), poly(decamethylene azelamide) (nylon 10,9), and the like.
  • Illustrative of useful aliphatic polyamides are those formed by polymerization of amino acids and derivatives thereof, as for example lactams.
  • Useful polyamides include poly(4-aminobutyric acid) (nylon 4), poly(6-aminohexanoic acid) (nylon 6, also known as poly(caprolactam)), poly(7-aminoheptanoic acid) (nylon 7), poly(8-aminooctanoic acid)(nylon 8), poly(9-aminononanoic acid) (nylon 9), poly(10-aminodecanoic acid) (nylon 10), ⁇ oly(l l- aminoundecanoic acid) (nylon 11), poly(12-aminododecanoic acid) (nylon 12), as well as nylon 46, nylon 66 and nylon 69 and the like.
  • Blends of two or more aliphatic polyamides may also be employed.
  • Preferred polyamides for use in the semi-crystalline nylon A are poly(caprolactam) and poly(hexamethylene adipamide), with poly(caprolactam) being the most preferred.
  • Aliphatic polyamides used in the practice of this invention may be obtained from commercial sources or prepared in accordance with known preparatory techniques.
  • poly(caprolactam) can be obtained from AlliedSignal Inc., Morristown New Jersey under the tradename CAPRON®.
  • aliphatic/aromatic polyamides are poly(hexamethylene isophthalamide), poly (2,2,2-trimethyl hexamethylene terephthalamide), poly(m-xylylene adipamide) (MXD6), poly(p-xylylene adipamide), poly(hexamethylene terephthalamide), poly(dodecamethylene terephthalamide), and the like. Blends of two or more aliphatic/aromatic polyamides can also be used. The most preferred aliphatic/aromatic polyamide is poly(m-xylyene 5 adipamide). Aliphatic/aromatic polyamides can be prepared by known preparative techniques or can be obtained from commercial sources.
  • the second component of the inventive composition is a semi-crystalline nylon which is a copolymer of nylon A plus at least one different nylon B.
  • the semi-crystalline nylon which is a copolymer of nylon A plus at least one different nylon B may be formed by copolymerizing two different monomers as described above for nylon A. Copolymers formed from recurring units of the above referenced aliphatic polyamides can be used in the fabrication of the polyamide.
  • such aliphatic polyamide copolymers include caprolactam/hexamethylene adipamide copolymer (nylon 6,6/6), hexamethylene adipamide/caprolactam copolymer (nylon 6/6,6), trimethylene adipamide/hexamethylene azelaiamide copolymer (nylon trimethyl 6,2/6,2), hexamethylene o adipamide/hexamethyleneazelaiamide/caprolactam copolymer (nylon
  • the number average molecular weight of nylon A as well as the nylon A/nylon B copolymer may vary widely. Such are sufficiently high to 5 form a free standing film but sufficiently low to allow melt processing of the blend. Such number average molecular weights are well known to those of skill in the film forming art and are usually at least about 5,000 as determined by the formic acid viscosity (FAV) method (ASTM D- 789). In this method, a solution of 11 grams of aliphatic polyamide in 0 100 ml of 90% formic acid at 25°C is used. In the preferred embodiments of the invention, the number average molecular weight of nylon A as well as the nylon A/nylon B ranges from about 5,000 to about 100,000, preferable from about 10,000 to about 60,000 and more preferably from about 20,000 to about 40,000.
  • FAV formic acid viscosity
  • the nylon composition may further contain an optional non-crystalline, non-crystallizable, amorphous nylon component C.
  • Amorphous nylons are well known in the art and are available commercially. Amorphous nylons are typically prepared by the reaction of at least one diamine with at least two different diacids. The result is a non-crystallizable nylon having no determinable melting point. Amorphous nylons are available as Grivory 21 available from EMS of Switzerland and Zytel amorphous nylon from DuPont.
  • the amount of nylon homopolymer A ranges from about 30 % to about 99 % based on the weight of the blended nylon composition, preferably from about 35 % to about 85 % and more preferably from about 40 % to about 60 % based on the weight of the blended nylon composition.
  • the amount of the copolymer of nylon A with nylon B ranges from about 1 % to about 70 % based on the weight of the blended nylon composition, preferably from about 15 % to about 65 % and more preferably from about 40 % to about 60 % based on the weight of the blended nylon composition.
  • the amount of nylon A in the copolymer ranges from about 70 % to about 95 % based on the weight of the copolymer, preferably from about 70 % to about 90 % based on the weight of the
  • the amount of nylon B in the copolymer ranges from about 5% to about 30 % based on the weight of the copolymer, preferably from about 10% to about 30 % and more preferably from about 15% to about 30 % based on the weight of the copolymer.
  • an amorphous nylon When included in the first embodiment of the invention, it is present in the overall composition an amount of from about 1 % to about 30 %, preferably from about 2 % to about 25 % and more preferably from about 5 % to about 20 % based on the weight of the blended nylon composition.
  • the nylon composition also has a single melting temperature.
  • the melting temperature is about equal to the melting temperature of nylon homopolymer A.
  • the amount of nylon homopolymer A ranges from about 30 % to about 99 % based on the weight of the blended nylon composition, preferably about 35 % to about 85 % and more preferably ranges from about 40 % to about 60 % based on the weight of the blended nylon composition.
  • the amount of the copolymer of nylon A with nylon B ranges from about 1 % to about 70 % based on the weight of the blended nylon composition, preferably from about 65 % to about 15 % and more preferably from about 60 % to about 40 % based on the weight of the blended nylon composition.
  • the amount of nylon A in the copolymer ranges from about 5 % to about 95 % based on the weight of the copolymer, preferably from about 10 % to about 90 % and more preferably from about 15 % to about 85 % based on the weight of the copolymer.
  • the amount of copolymer B in the copolymer ranges from
  • an amorphous nylon When included in the second embodiment of the invention, it is present in the overall composition an amount of from about 1% to about 30 % based on the weight of the blended nylon composition, preferably from about 2 % to about 25 %, and more preferably from about 5% to about 20 % based on the weight of the blended nylon composition.
  • the blend may contain additives which are conventionally used in nylon compositions.
  • additives are pigments, dyes, slip additives, fillers, nucleating agents, plasticizers, lubricants, reinforcing agents, antiblocking agents, stabilizers and inhibitors of oxidation, thermal stabilizers and ultraviolet light stabilizers.
  • such may be present in an amount of about 10% or less based on the weight of the composition.
  • the composition may be formed by dry blending solid particles or pellets of each of the nylon components and then melt blending the mixture at a temperature of at least the melting point of the nylon A homopolymer. Typical melting temperatures range from about 175 °C to about 260 °C, preferably from about 215 °C to about 225 °C, and more preferably from about 220 °C to about 223 °C (for nylon 6). Blending may take place in any suitable vessel such as an extruder, a roll mixer, or the like. Blending is conducted for a period of time required to attain a substantially uniform blend. Such may easily be determined by those skilled in the art. If desired, the composition may be cooled and cut into pellets for further processing, or it may be formed into films and optionally uniaxially or biaxially stretched by means well known in the art.
  • Films of this invention may be produced by conventional methods useful in producing films, including extrusion techniques.
  • a melted stream of the polyamide is fed through an extrusion die onto a casting roller or the polyamide may be introduced into a blown film apparatus.
  • the film may be stretched uniaxially in either the direction coincident with the direction of movement of the film being withdrawn from the film forming apparatus, also referred to in the art as the "machine direction", or in as direction which is perpendicular to the machine direction, and referred to in the art as the "transverse direction”, or biaxially in both the machine direction and the transverse direction.
  • the films of the present invention have sufficient dimensional stability to be stretched at least 1.5 and preferably more than three times and more preferably from more than three times to about ten times in either the machine direction or the transverse direction or both.
  • the oriented film formed from the composition of the invention are preferably produced at draw ratios of from about 1.5: 1 to about 6: 1, and preferably at a draw ratio of from about 3 : 1 to about 4: 1.
  • the term "draw ratio" as used herein indicates the increase of dimension in the direction of the draw. Therefore, a film having a draw ratio of 2:1 has its length doubled during the drawing process.
  • the film is drawn by passing it over a series of preheating and heating rolls. The heated film moves through a set of nip rolls downstream at a faster rate than the film entering the nip rolls at an upstream location. The change of rate is compensated for by stretching in the film.
  • the film structure may have a thickness which preferably ranges from about 0.3 mils (7.6 ⁇ m) to about 5.0 mils (127.0 ⁇ m) and preferably from about 0.5 mils (12.7 ⁇ m) to about 1.5 mils (37.5 ⁇ m). While such thicknesses are preferred as providing a readily flexible film, it is to be
  • composition produced according to the present invention are found to form extremely uniform films.
  • the starting polymers used were analyzed by Gas Chromatography (GC) using standard procedures. The precision of these measurements is ⁇ 2%.
  • the films were analyzed by Differential Scanning Calorimetry (DSC) using a Seiko RDC-220 thermal analyzer, equipped with a robotics system. About 7.5 ( ⁇ 0.5) mg of the film sample was crimped in an aluminum pan, heated from room temperature to about 280 °C at a heating rate of 10 °C / min., and held there to erase crystalline memory. Subsequently, the sample was cooled from 280 °C to room temperature at a cooling rate of 10 °C and then reheated at the same rate.
  • DSC Differential Scanning Calorimetry
  • the upper temperature in DSC was changed to about 300 °C.
  • the T m reported in the examples is the one obtained upon initial heating cycle, i.e., corresponding to the "as received films" cast under the same conditions.
  • Super-cooling is reported as the difference between the reheat cycle T m and T cc ,i.e., corresponding to the heat history imposed prior to the cooling cycle.
  • the T cc cooling curve representing the crystallizability of a particular sample during the 10 °C / minute cooling cycle, was integrated to obtain the heat of crystallization (DH f , J/g ).
  • a DH f 230 J/g for 100% crystalline nylon 6, was used to calculate the crystallinity developed (Close , % ) during the 10 °C / minute cooling scan.
  • DHf 188 J/g, was used. The temperature and DHf calibrations, were assured through a two-point calibration using indium
  • nylon 6 [8207, AlliedSignal], nylon 6(95)/nylon 66(5) [AlliedSignal], nylon 6 (85)/nylon 66(15) [AlliedSignal], nylon 6(80)/nylon 66(20) [AlliedSignal], nylon 6 (70)/nylon 66 (30) [AlliedSignal], nylon 6
  • This example prepares physical blends of nylon homopolymers, namely nylon 6 and nylon 66 in varying proportions.
  • Dried pellets of nylon 6 and nylon 66 were physically mixed in the weight percents indicated in Table 1.
  • the melt temperature was measured as 267 °C.
  • the resultant film had a total thickness of about 2 mil.
  • the extrusion temperature was raised by about 30 °C.
  • Example 1 shows that the super-cooling of nylon 6 decreases, i.e., the crystallization rate increases, by melt blending it with nylon 66 homopolymer. For purposes of reducing the crystallization rate of nylon 6, blending nylon 66 homopolymer by common processing techniques is, therefore, not a desired route.
  • example 1 The procedure of example 1 is repeated except using commercially available random copolymers of nylon 6/nylon 66 in the proportions indicated in Table 2. These are produced by copolymerizing the nylon 6 and nylon 66 monomeric starting materials. A well known, if not the only
  • a nylon 6/nylon 66 (50/50) copolymer would be made by a polymerization reaction of caprolactam (i.e., monomer for nylon 6) and hexamethylenediamine-adipic acid salt (i.e., monomer for nylon 66 ) in a 50 : 50 proportion.
  • caprolactam i.e., monomer for nylon 6
  • hexamethylenediamine-adipic acid salt i.e., monomer for nylon 66
  • the DT for nylon 6 is 38.4 °C ( ⁇ 0.4 ) and this gradually increases to 46.6 °C ( ⁇ 0.3 ) with the addition of 25%> of nylon 66 component.
  • the DT for nylon 66 is 30.8 °C ( ⁇ 0.3 ) which increases to 39.8 °C ( ⁇ 0.5 ) with the addition of 21% of nylon 6.
  • Such copolymers due to their lower crystallization rate ( i.e., larger DT ), develop lower crystallinity than their homopolymer counterparts during fast cooling rate melt processing, and therefore, are better materials for orientation / drawing applications.
  • Example 1 is repeated except the compositions are physical mixtures of commercially available nylon 6 homopolymer and commercially available random N6/N66 copolymers (84/16). Table 3 gives the proportion of each polymer component as well as the proportion of N66 in the overall composition.
  • Example 19 of this invention have a single melting point which is not depressed.
  • Example 3 and Figure 3 show that up to 50% of N6(84) / N66(16) copolymer can be melt blended into N6 homopolymer while retaining a single T m , indicative of a totally homogenous blend. When the amount of copolymer exceeds about 65%, the composition tends to become non- homogeneous. Note that a maximum DT @ 47 °C is observed for this blend system which is much higher than that for either of the two blend constituents, i.e., a case of synergistic interaction between the N6 homopolymer and the N6(84) / N66(16) copolymer (Example 3).
  • the melting temperature of conventional copolymers of nylon 6/nylon 66 are compared to the blends of this invention.
  • N6(21) / N66(79) copolymer when blended into N6, does not offer any advantages in terms of larger DT.
  • Figure 7 shows that N66 homopolymer can similarly be modified by melt blending with a N6(84) / N66(16) copolymer.
  • a blend of 75% N66 homopolymer and 25% N6(84) / N66(16) copolymer appears identical to the N66 homopolymer in terms of melting pattern.
  • Such a miscible blend, containing 21% N6, has a 47 °C higher T m than a conventional random copolymer containing 21% N6 ( Figures 4 & 7 ) and much different from a blend of 79 % N66 and 21% N6 which would be expected to exhibit two Tm's ( Figure 1 ).
  • the copolymer rich in N66 i.e., N6(21) / N66(79) is more effective in enhancing the DT of N66, as opposed to the N6(84) / N66(16) copolymer ( Figure 5 ).
  • N12 can be incorporated in N6 by melt blending N6 homopolymer and a random copolymer of N6(83)/N12(17). The resulting blend is totally homogeneous, characterized by just one T m .
  • Nylon 6 Compositions of Reduced Crystallizability.
  • Example 7 shows that by blending 17% of an amorphous nylon into N6, the super-cooling is increased, ( i.e., crystallization rate reduced ) from 38.4 °C ( ⁇ 0.4 ) to 43.8 °C ( ⁇ 1.2 ) and the developable crystallinity decreases from 28.8 %( ⁇ 0.5 ) to 23.2 % ( ⁇ 0.8 ).
  • N66 by replacing part of the amorphous nylon by N66 through this invention, i.e., by blending-in a N6 / N66 random copolymer rich in N6, e.g., N6(84) / N66(16), these effects are more enhanced ( Example 7 ).
  • the overall composition is still a homogenous, single, miscible phase.
  • Example 7 shows that N66 could be replaced with N12 by using a random copolymer of N6 / N12.
  • Examples 7-8 demonstrate the versatility of this invention in terms of 5 incorporating multi-component polyamides into a single, homogenous, and miscible phase while improving properties such as higher melting temperature, reduced crystallization rate, and lower developable crystallinity.
  • compositions of the present invention for nylon blends which are homogenous have only a single significant

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  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

L'invention concerne un procédé relatif à l'élaboration de mélanges très uniformes obtenus par voie fondue, d'homopolymères de nylon semi-cristallins et de copolymères de nylon semi-cristallins. Lesdits mélanges ont un point de fusion significatif unique qui remplace les points de fusion individuels propres aux différents constituants de nylon. Selon une variante, l'écart entre la température de fusion du mélange et sa température de cristallisation est supérieur à l'écart entre ces deux températures pour chacun des homopolymères et copolymères constitutifs susmentionnés. Selon une autre variante, le mélange a une température de fusion à peu près équivalente à celle de l'homopolymère de nylon semi-cristallin.
EP99911086A 1998-03-10 1999-03-04 Melanges miscibles multiconstituants de nylons a proprietes ameliorees Withdrawn EP1062277A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US3766498A 1998-03-10 1998-03-10
US37664 1998-03-10
PCT/US1999/004693 WO1999046334A1 (fr) 1998-03-10 1999-03-04 Melanges miscibles multiconstituants de nylons a proprietes ameliorees

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EP1062277A1 true EP1062277A1 (fr) 2000-12-27

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EP99911086A Withdrawn EP1062277A1 (fr) 1998-03-10 1999-03-04 Melanges miscibles multiconstituants de nylons a proprietes ameliorees

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EP (1) EP1062277A1 (fr)
JP (1) JP2002506109A (fr)
KR (1) KR20010041775A (fr)
AU (1) AU2981399A (fr)
BR (1) BR9908698A (fr)
CA (1) CA2323204A1 (fr)
WO (1) WO1999046334A1 (fr)

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JP6979847B2 (ja) * 2017-10-16 2021-12-15 昭和電工パッケージング株式会社 蓄電デバイス用外装材及び蓄電デバイス

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Publication number Publication date
CA2323204A1 (fr) 1999-09-16
KR20010041775A (ko) 2001-05-25
BR9908698A (pt) 2001-10-30
AU2981399A (en) 1999-09-27
WO1999046334A1 (fr) 1999-09-16
JP2002506109A (ja) 2002-02-26

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