MXPA01002046A - Blends of poly(1,3-propylene 2,6-naphthalate) - Google Patents

Abstract

Disclosed are physical blends of poly(1,3-propylene 2,6-naphthalate) polymer compositions with other polymers in which the concentration of poly(1,3-propylene 2,6-naphthalate) is from 1 to 99 mole%.

Description

POLY (1, 3-PROPILEN 2, 6-NAFTALATE) MIXTURES FIELD OF THE INVENTION This invention concerns physical blends of polymeric compositions of poly (1,3-propylene 2,6-naphthalate) with other polymers, in which the concentration of poly (1,3-propylene 2,6-naphthalate) is 1 to 99% mol.

TECHNICAL BACKGROUND OF THE INVENTION This invention relates to polymer blends of poly (1,3-propylene-2,6-naphthalate) (referred to herein as 3GN or 3GN polymers) with other polymers.

The U.S. patent No. 3,937,754 discloses a polyethylene 2,6 naphthalate (PEN) film oriented in biaxial form, which comprises PEN containing not more than 10% mol of non-component forming PEN and 0.5 to 10% of a polyester containing the minus 90 mol% of a homopolyester unit instead of PEN, which has a softening point of at least 1 ° C higher than its equilibrium softening point. The (127378) patent concessionaires teach that improvements in resistance to thermal degradation and Young's modulus are acquired after the softening point of the PEN resin decreases, and before it decreases to a point of at least 1 ° C higher than its equilibrium softening point. In this way, patent licensors teach that a little reaction is necessary, but not complete among the polyesters to achieve their desired benefits.

It is an object of the invention to provide physical mixtures, in which essentially no reaction occurs between the polymeric components.

DESCRIPTION OF THE INVENTION The present invention relates to compositions comprising physical mixtures of polymer compositions of poly (1,3-propylene 2,6-naphthalate) with one or more second polymers, wherein the concentration of 3GN is from 1 to 99 mol%, and in which essentially no reaction takes place between the polymeric components.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a differential scanning calorimetry (DSC) data plane for various mixes of 3GN / 3GT, pure 3GN and pure 3GT.

DETAILED DESCRIPTION OF THE INVENTION The 3GN compositions of the present invention can be formed in immiscible mixtures with one or more polymers. For example, mixtures of 3GN with polyesters, such as, for example, poly (ethylene terephthalate), poly (ethylene 2,6-naphthalate), poly (1,3-propylene terephthalate) (3GT), or poly (1) can be used. , 3-propylene isophthalate) and / or copolymers thereof. Other polymers which are suitable for forming immiscible mixtures with 3GN, include alcohol and vinyl alcohol and copolymers thereof, aliphatic polyamides and copolyamides, partially aromatic polyamide copolymers, such as poly (1,3-xylylene adipamide), polyacetals, such as poly (oxymethylene), polycarbonate, acrylic polymers such as poly (methyl methacrylate), and polyolefins and copolymers thereof, such as polypropylene and polystyrene. More preferred compositions are the following mixtures: poly (1,3-propylene 2,6-naphthalate) with poly (ethylene terephthalate); poly (1,3-propylene 2,6-naphthalate) with poly (1,3-propylene terephthalate); poly (1,3-propylene 2,6-naphthalate) with poly (1,3-propylene isophthalate); and poly (1,3-propylene 2,6-naphthalate) with poly (ethylene 2,6-naphthalene), wherein the concentration of poly (1,3-propylene 2,6-naphthalate) is from 1 to 99% mol.

The mixtures can be prepared using methods known in the art to prepare immiscible mixtures, such as melts by continuous mixing in a twin or single screw extruder, or intermittently in Banbury mixers. The mixtures according to the invention contain at least about 1 mol% to about 99 mol% of 3GN. By immiscible it is understood that a differential scanning calorimetry (DSC) scan of the mixtures shows multiple vitreous transition temperatures (Tg), each Tg is characteristic of the individual polymeric components of the mixture, when compared to the miscible mixtures that show a simple composition dependent on Tg.

When mixing 3GN with polyesters or other polymers that can react with 3GN during melt mixing, such as polyamides, the mixture should be handled in the melt for no more than about 10 minutes in order to minimize the degree of transesterification and formation. of copolymer. The melt mixing temperature should not be higher than 30 ° C higher than the highest melting component of the mixture. Preferably, there is less than about 5 mol% of copolymer formed by transesterification means, as indicated by an absence of maximum values in the proton and 13C nuclear magnetic resonance spectrum (detection sensitivity = 1-2 mol%) instead of those corresponding to the individual polymeric components.

The utility of the compositions of the present invention is in fabrications or molded articles, especially films. Certain compositions are especially useful in the manufacture of films oriented in biaxial form.

The poly (1,3-propyl 2, 6-naphthalate) component of the compositions of the present invention can be prepared by transesterification of a dialkyl ester of 2,6-naphthalene dicarboxylic acid and 1,3-propanediol or esterification of 2,6-naphthalenedicarboxylic acid and 1,3-propanediol followed by polycondensation.

For example, in a batch process, a dialkyl ester C? .- C of 2,6-naphthalenedicarboxylic acid and 1,3-propanediol react in an inert atmosphere, such as nitrogen in a molar ratio of about 1: 1.2. at about 1: 3.0 in the presence of a transesterification catalyst at a temperature between about 170 ° C and 245 ° C at atmospheric pressure to form a monomer and a C? -C alkanol corresponding to the C? -C4 alkanol components of the dialkyl ester of 2,6-naphthalenedicarboxylic acid. The C? -C 4 alkanol is removed when it is formed during the reaction. Examples of transesterification catalysts include manganese, zinc, calcium, cobalt, titanium, and antimony compounds such as Mn (ace tat o) 2, Zn (acetate) 2, Co (acetate) 2, tetrabutyl titanate, t titanate and Raisopropyl, and antimony trioxide. The resulting reaction product, comprising the monomer bis (3-hydroxypropyl 1) 2,6-naphthalate and oligomers thereof, is subsequently polymerized at temperatures between about 240 ° C and 280 ° C under a reduced pressure of below about 30 mm Hg in the presence of a polycondensation catalyst, with removal of excess 1,3-propanediol, to form 3GN, which has an inherent viscosity in the range of 0.2-0.8 deciliter / gram (dl / g).

Examples of suitable polycondensation catalysts include antimony, titanium, and germanium compounds such as antimony trioxide, tetrabutyl titanate, tet rai sopropiol titanate. A titanium catalyst can be added before the transesterification, both for the polycondensation catalyst and for the transesterification.

The polycondensation and transesterification reactions can be carried out in continuous processes.

Other comonomers may be included during the preparation of 3GN. For example, one or more diols (instead of 1,3-propanediol), preferably in an amount above about 10 mol% based on the total diol (including 1,3-propanediol and the diol), and / or one or more carboxylic acids or C? -C dialkyl ester of a carboxylic acid (instead of 2,6-naphthalenedicarboxylic acid and C? -C diesters thereof), preferably in an amount above about 10% mol based in the dialkyl ester or total diacid (which includes the 2,6-naphthalenedicarboxylic acid or dialkyl ester C? -C thereof and the other dicarboxylic acid or C1-C4 dialkyl ester thereof) may be added before or during the esterification or transesterification reaction. Examples of comonomers that may be used include terephthalic acid or isophthalic acid and C? ~ C4 diesters thereof, and C1-C10 glycols such as ethylene glycol, 1,4-butanediol, and 1,4-cyclohexane dimethanol. . The inherent viscosity of 3GN can be further increased using solid phase polymerization methods. 3GN particles having an inherent viscosity of about 0.2-0.7 dl / g may be in solid phase in a general form at an inherent viscosity of 0.7-2.0 dl / g by means of a first crystallization at a temperature between about 165 ° C C and 190 ° C for at least 6 hours, preferably 12-18 hours, followed by solid phase polymerization under an inert atmosphere, such as a nitrogen purge, at a temperature between about 190 ° C to 220 ° C, preferably between about 195 ° C to 205 ° C, at least about 12 hours, however, the period of time may be in the range of 16-48 hours. The solid phase polymerization of the 3GN particles can also be conducted under a vacuum of about 0.5-2.0 mm Hg. 3GN preferably has an inherent viscosity in the film-forming range, generally between about 0.2-1.0 dl / g, more preferably 0.5-0.9 dl / g, more preferably 0.55-0.85 dl / g.

EXAMPLES TEST METHODS The inherent viscosity was measured at 60% by weight of phenol / 40% by weight of 1, 1, 2, 3-tetra-chloroethane at 30 ° C at a polymer concentration of 0.50% by weight, according to the ASTM D method -4603-91.

The melting point, crystallization temperature and glass transition temperature were determined using the method of ASTM D-3418 (1988) using a DuPont DSC Model 2100 Instrument. The heating and cooling rates were 10 ° C / min.

The density was measured in grams per cubic centimeter (g / cc) using the density-gradient method, according to ASTM D-1505-85.

The number average molecular weight and weight average molecular weight (Mn and Mw) are measured by size exclusion chromatography using hexafluoroisopropanol as a solvent.

The nuclear magnetic resonance spectrum (NMR) of the 3GN mixtures is measured by dissolving the mixtures in hexafluoroisopropanol deuterated. The proton and 13C NMR were measured on a Bruker high resolution NMR spectrometer. The 13C to 400 Hz spectra are collected with a 30 second relaxation delay and reverse gate decoupling.

Experiment 1 This example describes the synthesis of poly (1,3-propylene 2,6-naphthalate) (3GN). Dimethyl 2, 6-naphthalenedicarboxylate (36.36 kg, 149 moles) (purchased from Amoco Chemical Company, with offices in Chicago, IL) and 1,3-propanediol (purchased from Degussa, with offices in Ridgefield Park, NJ) (24.91 kg) , 327.8 moles) react under atmospheric pressure in nitrogen in the presence of 6.1 g of Tyzor® titanium tetraisopropoxide catalyst (100 ppm of catalyst based on the total weight of the ingredients and catalyst) (commercially available from EI du Pont de Nemours and Company, Wilmington, DE) in 300 ml of 1,3-propanediol in a stirred tank that was heated with a hot oil system. The tank was heated to 242 ° C for a period of approximately 330 minutes. When the temperature of the reaction mixture reaches 188 ° C, the methanol that is formed begins to be discharged and is removed as a condensate by means of distillation. The development of methanol lasts until about 180 minutes after the start of the reaction, when the temperature reached around 213 ° C. The excess of 1,3-propanediol started to be fired, and is collected as a condensate by means of distillation , when the temperature reached around 217 ° C and it is prolonged to say goodbye for another 150 minutes when the mixture heats up to 242 ° C.

The pressure in the reaction tank is subsequently reduced from about atmospheric pressure to about 10 mm Hg, while the temperature is increased to about 275 ° C over a period of about 90 minutes. The pressure is subsequently reduced further to 0.5 mm Hg, while the temperature is raised to 208 ° C. Polymerization is allowed to proceed 30 minutes more to obtain a polymer which has an inherent viscosity of 0.56 deciliter / gram (dl / g) .

The polymer obtained is translucent white in color, and is identified as poly (1,3-propylene 2,6-naphthalate) by analyzing the maximum values in the C-13 NMR used as solvent hexaf luoroisopropanol. The polymer had a melting point of 201-203 ° C, a crystallization temperature of 166 ° C, and a vitreous transition temperature of 79 ° C. The inherent viscosity of the polymer was 0.56 dl / g, with a molecular weight number average (Mn) of 22,000 and a weight average molecular weight (Mw) of 36,000.

EXAMPLE 1 This example describes the preparation of a mixture of 60 mol% of 3GN with poly (1,3-propylene terephthalate). 27. 1 g (0.106 mol) of 3GN prepared in Experiment 1 and 12.9 g (0.063 mol) of poly (1, 3-propylene terephthalate) (3GT) having an inherent viscosity of 0.9 dl / g synthesized, using the conditions described in J. Polym. Science Al, (4), 1851-1859 (1996) were melt-mixed at 250 ° C for 8 minutes under a nitrogen atmosphere in a Plastic-corder mixer (type REE 230 V8 5 amp, made by Brabender Instruments Inc., South Hackensack, NJ) at a rotation speed of 100 rpm. The resulting mixture is sprayed at approximately 20 mesh in a laboratory mill and compression molded at 250 ° C for 2 minutes, and then cooled with room temperature air to form an opaque pressed film of 6-7 mils. inch (0.15-0.18 mm) thick.

Nuclear magnetic resonance (NMR) analysis of the 3GN / 3GT film showed that all the maximum NMR values were attributed to the individual polymeric components, without indicating extra maximum values that were not substantially present in the co-polymerization as an exchange result of ester. Differential scanning calorimetry (DSC) showed two vitreous transition temperatures (Tg), 73 ° C and 45 ° C, and two melting points Tm, 203 ° C and 228 ° C, corresponding respectively to the Tg and Tm of the 3GN and 3GT original.

EXAMPLES 2, 3, 4 Using the materials that were used in Example 1, and the melt mixing methods of Example 1, the 3GN and 3GT mixtures are prepared respectively in the ratios 80:20, 40:60, and 20:80. In all cases, nuclear magnetic resonance analyzes (NMR) of the 3GN / 3GT film showed that all the observed maximum values of the NMR are attributed to the individual polymeric components, without indicating extra maximum values that there was not substantially in the co-polymerization as a result of ester exchange. Differential scanning calorimetry (DSC) showed two glass transition temperatures (Tg) (see Table 1), and two melting points Tm (see Table 1), corresponding respectively to the Tg and Tm of the 3GN and 3GT origixiales.

TABLE 1 Thermal properties of 3GT / 3GN mixtures All temperatures are in ° C Sample Molar ratio gi g2 Tmi of 3GN / 3GN Control 1 100/0 72 - 203 - Example 2 80/20 47 71 203 227 Example 1 60/40 45 73 203 228 Example 3 40/60 56 74 203 229 Example 4 20/80 56 75 202 229 Control 2 0/100 53 _ '230 _ EXAMPLE 5 This example describes the preparation of pressed films of a mixture of 60 mol% of 3GN with poly (ethylene terephthalate). 28. 1 g (0.110 mol) of 3GN as prepared in Experiment 1 and 11.9 g (0.062 mol) of PET (MYLAR® X299, 0.8 dl / g) (available from EI du Pont de Nemours and Company, Wilmington, DE) melt blended at 280 ° C and pulverized using the procedure described in Example 1. The mixture was subsequently compression molded at 280 ° C for 2 minutes and then cooled with air to form an opaque film of 6-7. thousandths of an inch (0.15-0.18 mm) thick.

NMR analyzes of the 3GN / PET films showed that all the observed maximum values of the NMR were attributed to the individual polymeric components, without indicating extra maximum values that there was substantially no in the co-polymerization as a result of ester exchange. The DSC showed that the Tg of the 3GN and PET components were very close and overlap at approximately 76.5 ° C. There were two maximum melting values at 201 ° C and 243 ° C, corresponding respectively to the melting points of the original 3GN and PET.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following claims is claimed as property:

Claims (13)

1. A composition characterized in that it comprises a physical mixture of a polymeric composition of poly (1,3-propylene-2,6-naphthalate) with one or more second polymers, wherein the concentration of poly (1,3-propylene 2, 6 naphthalate) is from 1 mol% to 99 mol%, and in which it has been melt blended under conditions in which essentially no reaction takes place.

2. A composition characterized in that it comprises a physical mixture of from 20 mol% to 80 mol% of a polymer composition of poly (1,3-propylene 2,6-naphthalate) with 80 mol% to 20 mol% of one or more second polymers, in it, essentially no reaction takes place.

3. The composition of any of the preceding claims, characterized in that a differential scanning calorimetry (DSC) scan of the mixture shows multiple vitreous transition temperatures (Tg), each Tg is characteristic of the individual polymer components of the mixture, when compared to miscible mixtures that exhibit a simple Tg-dependent composition.

4. The composition of any of the preceding claims, characterized in that there is less than about 5 mol% of copolymer formed by means of transesterification of the polymer composition of poly (1,3-propylen-2,6-naphthalate) with one or more second polymers , as indicated by an absence of maximum values in the proton and 13C nuclear magnetic resonance spectrum (detection sensitivity = 1-2% mol) instead of those corresponding to the individual polymeric components.

5. The composition of any of the preceding claims, characterized in that it has been melt-blended at a temperature not higher than 30 ° C higher than the highest melting component of the mixture.

6. The composition of claim 5, characterized in that it has been handled in the melt no more than about 10 minutes.

7. The composition according to any of the preceding claims, characterized in that it is in the form of a film.

8. The composition of claim 7, characterized in that the film is a film oriented in biaxial form.

9. The composition of any one of the preceding claims, characterized in that the second polymer is selected from the group consisting of poly (ethylene terephthalate), poly (ethylene 2, naphthalene to), poly (1,3-propylene-terephthalate), and pol i (1,3-propylene isophthalate) or copolymers thereof.

10. The composition of any of claims 1-8, characterized in that the second polymer__ is selected from the group consisting of alcohol and vinyl alcohol and copolymers thereof, aliphatic polyamides and copolyamides, partially aromatic polyamide copolymers, polyacetals such as pol i ( oximet i leño), polycarbonate, acrylic polymers such as pol i (methymethacrylate), and polyolefins and copolymers thereof such as polypropylene and polystyrene.

11. The composition of any of the preceding claims, characterized in that the polymer of poly (1,3-propylene 2,6-naphthalate) is prepared with (a) above about 10% mol, based on total diol, of one or more diols (instead of 1,3-propanediol) and / or (b) above 10 mol%, based on total diacid or dialkyl ester (which includes 2,6-naphthalenedicarboxylic acid or dialkyl ester C1- C4 thereof), of one or more carboxylic acids or C1-C4 dialkyl ester of a dicarboxylic acid (instead of 2,6-naphthalenedicarboxylic acid and Ci-C4 diesters thereof).

12. A process for preparing the composition of any of the preceding claims, characterized in that it comprises the proportion of the polymer composition of poly (1,3-propylene-2,6-naphthalate) and one or two polymers, and the melt mixing of both at a temperature not higher than 30 ° C higher than the highest melting component of the mixture, so that essentially no reaction takes place between the composition of poly (1,3-propylene 2,6-naphthalate) and one or more seconds polymers.

13. The process of claim 12, characterized in that the composition is handled in the melt no more than about 10 minutes.