Polyvinyl chloride, polycarbonate and copolyester compositions and articles manufactured using these compositions

Abstract

The present disclosure relates to novel polyvinyl chloride compositions comprising a polyvinyl chloride resin, a polycarbonate resin, and a copolyester resin. More specifically, the present disclosure relates to polyvinyl chloride compositions comprising a blend of a polycarbonate and a high glass transition temperature (Tg) copolyester to increase the Tg and heat distortion temperature under load (HDTUL) of the polyvinyl chloride composition.

Description

Technical Field

[0001] The present disclosure relates to novel polyvinyl chloride compositions. More specifically, the present disclosure relates to novel compositions comprising a polyvinyl chloride resin, a polycarbonate resin, and a copolyester resin. More specifically, the present disclosure relates to polyvinyl chloride compositions comprising a mixture of a polycarbonate resin and a high glass transition temperature (Tg) copolyester resin for increasing the Tg and heat distortion temperature under load (HDTUL) of the polyvinyl chloride composition.

Background Art

[0002] Rigid polyvinyl chloride (PVC) formulations have been used for many years to manufacture articles such as vinyl siding, window profiles, decking profiles, fences, and railing. These products are typically limited to light colors such as white, off-white, beige, or bright pastel greens, blues, yellows, etc., and dark, rich colors are not typically offered. The reason for the limitation to light colors is that these formulations can exceed the glass transition temperature (Tg) and heat distortion temperature under load (HDTUL) of the rigid PVC formulation due to absorption of infrared portions of the high temperature and solar spectrum.

[0003] Manufacturers of these products have had to limit the design and color offerings in order to reduce distortion of these products. Or, attempts have been made to increase the Tg and HDTUL of the PVC formulation using materials such as α-methylstyrene acrylonitrile copolymer (AMSAN). These options have drawbacks and often limit the geographical areas where these products can be used or cause processes and product defects that must be addressed. For example, AMSAN reduces thermal stability, increases yellowing, and loses impact properties. In the present disclosure, surprisingly, certain polycarbonate resins and high Tg copolyester compositions have been found to be melt processable at typical rigid PVC processing temperatures without adversely affecting processing properties and to increase Tg and HDTUL without losing impact properties.

SUMMARY OF THE INVENTION

[0004] The polyvinyl chloride composition of the present disclosure includes at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one copolyester resin.

[0005] One embodiment of the present disclosure is a polyvinyl chloride composition including at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one copolyester resin, wherein the copolyester resin (a)(i) about 90 to about 100 mol% of terephthalic acid residues, and (ii) about 0 to about 10 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, a dicarboxylic acid component containing, and (b)(i) about 20 to about 60 mol% of a modified glycol consisting of 2 to 20 carbon atoms, and (ii) about 40 to about 80 mol% of a second modified glycol consisting of 2 to 20 carbon atoms, a glycol component containing, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%.

[0006] One embodiment of the present disclosure is a polyvinyl chloride composition including at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one copolyester resin, wherein the copolyester resin (a)(i) about 50 to about 100 mol% of terephthalic acid residues, and (ii) about 0 to about 50 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, a dicarboxylic acid component containing, and (b)(i) about 60 to about 100 mol% of a modified glycol consisting of 2 to 20 carbon atoms, and (ii) about 0 to about 40 mol% of a second modified glycol consisting of 2 to 20 carbon atoms, A glycol component containing A composition comprising, wherein the total molar % of the dicarboxylic acid component is 100 mol% and the total molar % of the glycol component is 100 mol%.

[0007] In one embodiment, the Tg of the copolyester is at least about 90 °C or higher.

[0008] In one embodiment, the Tg of the copolyester is at least about 100 °C or higher.

[0009] In one embodiment, the copolyester is amorphous.

[0010] In one embodiment, the copolyester has a semi-crystallization time of about 5 minutes or more.

[0011] In one embodiment, the content of the copolyester resin in the PVC composition is about 1 to about 100 parts per 100 parts of resin (phr) based on the content of the PVC resin in the composition.

[0012] In one embodiment, the content of the polycarbonate resin in the PVC composition is about 1 to about 50 parts per 100 parts of resin (phr) based on the content of the PVC resin in the composition.

[0013] In one embodiment, the content of the polycarbonate resin in the PVC composition is about 1 to about 50 parts per 100 parts of resin (phr) based on the content of the PVC resin in the composition, and the content of the copolyester resin is about 1 to about 100 parts per 100 parts of resin (phr).

[0014] In one embodiment, the polyvinyl chloride composition is rigid.

[0015] In one embodiment, the polyvinyl chloride resin is a polyvinyl chloride resin, a chlorinated polyvinyl chloride resin or an alloy thereof.

[0016] In one embodiment, the polycarbonate resin is a bisphenol-based polycarbonate resin.

[0017] The composition according to claim 1 or 2, wherein the ratio of polyvinyl chloride resin to copolyester on a mass fraction basis is greater than about 1.

[0018] The composition according to claim 1 or 2, wherein the ratio of polyvinyl chloride resin to copolyester and polycarbonate on a mass fraction basis is greater than about 1.

[0019] One embodiment of the present disclosure is to extrude at least one polyvinyl chloride resin composition, at least one polycarbonate resin, and at least one copolyester to produce a viscous blend of thermoplastic materials, wherein the copolyester is (a)(i) about 90 to about 100 mol% of terephthalic acid residues, and (ii) about 0 to about 10 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, a dicarboxylic acid component containing, and (b)(i) about 20 to about 60 mol% of a modified glycol consisting of 2 to 20 carbon atoms, and (ii) about 40 to about 80 mol% of a second modified glycol consisting of 2 to 20 carbon atoms, a glycol component containing, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%, introducing the blend of the thermoplastic material into a calendering, extrusion molding, or injection molding process to produce a polyvinyl chloride article, A method for producing a polyvinyl chloride composition, comprising.

[0020] One embodiment of the present disclosure is to extrude at least one polyvinyl chloride resin composition, at least one polycarbonate resin, and at least one copolyester to produce a viscous blend of thermoplastic materials, wherein the copolyester is (a)(i) From about 50 to about 100 mol% of terephthalic acid residues, and (ii) From about 0 to about 50 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, A dicarboxylic acid component containing, and (b)(i) From about 60 to about 100 mol% of a modified glycol consisting of 2 to 20 carbon atoms, and (ii) From about 0 to about 40 mol% of a second modified glycol consisting of 2 to 20 carbon atoms, A glycol component containing, Containing, the total mol% of the dicarboxylic acid component being 100 mol% and the total mol% of the glycol component being 100 mol%, Introducing the blend of the thermoplastic material into a calendering, extrusion or injection molding process to produce a polyvinyl chloride article, A method for producing a polyvinyl chloride composition containing.

[0021] One embodiment of the present disclosure is to blend a miscible mixture of at least one polycarbonate resin and at least one copolyester resin to produce a viscous thermoplastic material, wherein the copolyester resin is (a)(i) From about 90 to about 100 mol% of terephthalic acid residues, and (ii) From about 0 to about 10 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, A dicarboxylic acid component containing, and (b)(i) From about 20 to about 60 mol% of a modified glycol consisting of 2 to 20 carbon atoms, and (ii) From about 40 to about 80 mol% of a second modified glycol consisting of 2 to 20 carbon atoms, A glycol component containing, Containing, the total mol% of the dicarboxylic acid component being 100 mol% and the total mol% of the glycol component being 100 mol%, Blending the formulation with at least one polyvinyl chloride resin composition, and Introducing the blend into a calendaring, extrusion molding or injection molding process to produce a polyvinyl chloride article. A method for producing a polyvinyl chloride composition, comprising.

[0022] One embodiment of the present disclosure is to blend at least one polycarbonate resin and at least one copolyester resin to produce a viscous thermoplastic material, wherein the copolyester resin is (a)(i) About 50 to about 100 mol% of terephthalic acid residues, and (ii) About 0 to about 50 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, A dicarboxylic acid component containing, and (b)(i) About 60 to about 100 mol% of a modified glycol consisting of 2 to 20 carbon atoms, and (ii) About 0 to about 40 mol% of a second modified glycol consisting of 2 to 20 carbon atoms, A glycol component containing, Containing, the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%, Blending the formulation with at least one polyvinyl chloride resin composition, and Introducing the blend into a calendaring, extrusion molding or injection molding process to produce a polyvinyl chloride article. A method for producing a polyvinyl chloride composition, comprising.

[0023] One embodiment of the present disclosure is a polyvinyl chloride article having a Tg and HDTUL (heat distortion temperature under load) increased by at least 3°C.

[0024] One embodiment of the present disclosure is a polyvinyl chloride article having a Tg of at most 110°C or an HDTUL of at most 130°C.

Brief Description of the Drawings

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Mode for Carrying Out the Invention

[0032] The polyvinyl alcohol composition of the present disclosure includes at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one copolyester.

[0033] One embodiment of the present disclosure is a polyvinyl chloride composition including at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one copolyester, wherein the copolyester (a)(i) about 90 to about 100 mol% of terephthalic acid residues, and (ii) about 0 to about 10 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, a dicarboxylic acid component containing, and (b)(i) about 20 to about 60 mol% of a modified glycol consisting of 2 to 20 carbon atoms, and (ii) about 40 to about 80 mol% of a second modified glycol consisting of 2 to 20 carbon atoms, a glycol component containing, wherein the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%.

[0034] One embodiment of the present disclosure is a polyvinyl chloride composition including at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one copolyester, wherein the copolyester (a)(i) about 50 to about 100 mol% of terephthalic acid residues, and (ii) from about 0 to about 50 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, a dicarboxylic acid component comprising, and (b) (i) from about 60 to about 100 mol% of a modified glycol consisting of 2 to 20 carbon atoms, and (ii) from about 0 to about 40 mol% of a second modified glycol consisting of 2 to 20 carbon atoms, a glycol component comprising, comprising, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%, a composition.

[0035] Copolyester Any amorphous or essentially amorphous copolyester is suitable for use in the present disclosure. For example, in one embodiment, any copolyester can be used in the present disclosure as long as they are essentially amorphous and have a minimum semi-crystallization time of at least about 5 minutes or at least about 7 minutes. In another embodiment, any copolyester can be used as long as its minimum semi-crystallization time is at least about 8 minutes. In another embodiment, any copolyester can be used as long as its semi-crystallization time is at least about 10 minutes. The amorphous copolyesters in the present disclosure can, in some embodiments, have a semi-crystallization time up to infinity. In one aspect of the present disclosure, blends of amorphous copolyesters with other polymers (including other polyesters and copolyesters) are suitable for use as long as the blend has a minimum semi-crystallization time of at least about 5 minutes.

[0036] The semi-crystallization time can be measured using a differential scanning calorimeter according to the following procedure. A sample of about 10.0 mg of the copolyester is sealed in an aluminum pan, heated to about 290 °C at a rate of about 20 °C / min in a helium atmosphere, and held for about 2 minutes. Next, the sample is immediately cooled to an isothermal crystallization temperature in the range of about 140 °C to about 200 °C at intervals of about 10 °C at a rate of about 20 °C / min. Next, the semi-crystallization time at each temperature is determined as the time required to reach the peak of the exothermic curve. The minimum semi-crystallization time is the temperature at which the crystallization rate is the fastest.

[0037] In one embodiment of the present disclosure, the copolyester (a)(i) about 50 to about 100 mol% of terephthalic acid residues, and (ii) about 0 to about 50 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, a dicarboxylic acid component containing, and (b)(i) about 20 to about 60 mol% of a modified glycol consisting of 2 to 20 carbon atoms, and (ii) about 40 to about 80 mol% of a second modified glycol consisting of 2 to 20 carbon atoms, a glycol component containing, wherein the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%.

[0038] In one embodiment of the present disclosure, the copolyester resin (a)(i) about 50 to about 100 mol% of terephthalic acid residues, and (ii) about 0 to about 50 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, a dicarboxylic acid component containing, and (b)(i) about 60 to about 100 mol% of a modified glycol consisting of 2 to 20 carbon atoms, and (ii) about 0 to about 40 mol% of a second modified glycol consisting of 2 to 20 carbon atoms, a glycol component containing, including, wherein the total molar % of the dicarboxylic acid component is 100 mol%, and the total molar % of the glycol component is 100 mol%.

[0039] Unless the context clearly indicates otherwise, the terms "polyester" and "copolyester" are used interchangeably herein. The term "polyester" is intended to include "copolyester" and is understood to mean a synthetic polymer prepared by polycondensation of one or more difunctional carboxylic acids (or diacids) and one or more difunctional hydroxyl compounds (or diols). In one embodiment, the difunctional carboxylic acid is a dicarboxylic acid and the difunctional hydroxyl compound is a dihydric alcohol such as, for example, a glycol and a diol.

[0040] The term "residue" means any organic structure incorporated into the polymer via a polycondensation reaction in which the corresponding monomer is involved. The term "repeat unit" means an organic structure having a dicarboxylic acid residue (or diacid component) and a diol residue (or diol component) linked via a carbonyloxy group. Thus, a dicarboxylic acid residue can be derived from a dicarboxylic acid monomer or an acid halide, ester, salt, anhydride or mixture thereof related thereto.

[0041] In one embodiment, the copolyesters of the present disclosure are amorphous. In one embodiment, the copolyesters of the present disclosure are essentially amorphous.

[0042] In one embodiment, the copolyester includes repeat units from a dicarboxylic acid and a diol, based on 100 mol% of the dicarboxylic acid residue and 100 mol% of the diol residue, respectively.

[0043] In one embodiment, the diacid component comprises at least about 50 mol% of residues of aromatic dicarboxylic acids having from about 8 to about 14 carbon atoms. The copolyester may optionally be modified with up to about 50 mol% of one or more different dicarboxylic acids other than aromatic dicarboxylic acids, based on 100 mol% of the dicarboxylic acid residues, for example, residues of saturated aliphatic dicarboxylic acids having from 4 to 12 carbon atoms and alicyclic dicarboxylic acids having from 8 to 12 carbon atoms. Specific examples of dicarboxylic acids include terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and the like. The polyester can be prepared from one or more of the above dicarboxylic acids.

[0044] It should be understood that the use of the corresponding acid anhydrides, esters, and acid chlorides of these acids is included in the term "dicarboxylic acid".

[0045] In one embodiment, the diol component comprises at least about 60 mol% of residues of diols containing from 2 to 20 carbon atoms. Further, the diol component can optionally be modified with up to about 40 mol% of residues of one or more other diols, based on 100 mol% of the diol residues. Specific examples of diols include ethylene glycol, diethylene glycol, triethylene glycol, isosorbide, propane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,3-diol (neopentyl glycol), 2,2,4,4-tetramethyl-1,3-cyclobutanediol, pentane-1,5-diol, hexane-1,6-diol, 1,4-cyclohexanedimethanol, 3-methyl-pentanediol-(2,4), 2-methylpentanediol-(1,4), 2,2,4-tri-methylpentane-diol-(1,3), 2-ethylhexanediol-(1,3), 2,2-diethylpropane-diol-(1,3), hexanediol-(1,3), 1,4-di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)-propane, 2,2-bis-(4-hydroxypropoxyphenyl)-propane, and the like. The polyester can be prepared from one or more of the above diols.

[0046] In one embodiment, the diacid component comprises at least about 90 mol% of residues of aromatic dicarboxylic acids having up to about 20 carbon atoms. The copolyester may optionally be modified with up to about 10 mol% of one or more different dicarboxylic acids other than aromatic dicarboxylic acids, based on 100 mol% of the dicarboxylic acid residues, for example, residues of saturated aliphatic dicarboxylic acids having 4 to 12 carbon atoms and alicyclic dicarboxylic acids having 8 to 12 carbon atoms. Specific examples of dicarboxylic acids include terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and the like. The polyester can be prepared from one or more of the above dicarboxylic acids.

[0047] It should be understood that the use of the corresponding acid anhydrides, esters and acid chlorides of these acids is included in the term "dicarboxylic acid".

[0048] In one embodiment, the diol component comprises at least about 20 mol % of residues of diols containing from 2 to 20 carbon atoms. Further, the diol component may optionally be modified with up to about 80 mol % of residues of one or more other diols, based on 100 mol % of the diol residues. Specific examples of diols include ethylene glycol, diethylene glycol, triethylene glycol, isosorbide, propane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,3-diol (neopentyl glycol), 2,2,4,4-tetramethyl-1,3-cyclobutanediol, pentane-1,5-diol, hexane-1,6-diol, 1,4-cyclohexanedimethanol, 3-methyl-pentanediol-(2,4), 2-methylpentanediol-(1,4), 2,2,4-tri-methylpentane-diol-(1,3), 2-ethylhexanediol-(1,3), 2,2-diethylpropane-diol-(1,3), hexanediol-(1,3), 1,4-di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)-propane, 2,2-bis-(4-hydroxypropoxyphenyl)-propane, and the like. The polyester can be prepared from one or more of the above diols.

[0049] The polyester can also include minor amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyester-forming polyacids or polyols commonly known in the art.

[0050] In one embodiment, the copolyester comprises (i) a diacid component comprising residues of at least about 50 mol% of terephthalic acid, naphthalenedicarboxylic acid, 1,4 - cyclohexanedicarboxylic acid, isophthalic acid, or mixtures thereof, and (ii) a diol component comprising residues of at least about 80 mol% of a diol containing from 2 to 10 carbon atoms. In one embodiment, the diacid component of the copolyester comprises residues of at least about 80 mol% of terephthalic acid, naphthalenedicarboxylic acid, 1,4 - cyclohexanedicarboxylic acid, isophthalic acid, or mixtures thereof. And in one embodiment, the diol component of the copolyester comprises residues of ethylene glycol, 1,4 - cyclohexanedimethanol, diethylene glycol, neopentyl glycol, 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol, or mixtures thereof.

[0051] In another embodiment, the copolyester comprises (i) a diacid component comprising at least about 80 mol% terephthalic acid residues and (ii) a diol component comprising at least about 80 mol% residues of ethylene glycol and 1,4 - cyclohexanedimethanol. In yet another embodiment, the copolyester comprises (i) a diacid component comprising at least about 80 mol% terephthalic acid residues and (ii) a diol component comprising at least about 80 mol% residues of ethylene glycol, 1,4 - cyclohexanedimethanol, and diethylene glycol. In yet another embodiment, the copolyester comprises (i) a diacid component comprising at least about 80 mol% terephthalic acid residues and (ii) a diol component comprising at least about 80 mol% residues of ethylene glycol and neopentyl glycol. In yet another embodiment, the copolyester comprises (i) a diacid component comprising at least about 80 mol% terephthalic acid residues and (ii) a diol component comprising at least about 80 mol% residues of 1,4 - cyclohexanedimethanol and 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol.

[0052] In one embodiment, the copolyester composition comprises at least one polyester, and the polyester is (a)(i) 70 to 100 mol% of terephthalic acid residues, and (ii) 0 to 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, a dicarboxylic acid component containing, and (b)(i) 0 to 40 mol% of 2,2-dimethylpropane-1,3-diol (neopentyl glycol or NPG) residues, (ii) 0 to 100 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, (iii) 0 to 70 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, (iv) 0 to 40 mol% of diethylene glycol (DEG) residues, whether formed in situ or not, a glycol component containing, containing, wherein the remainder of the glycol component is (v) residues of ethylene glycol, and (vi) optionally, 0 to 10 mol% of residues of at least one other modifying glycol, containing, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%.

[0053] In one embodiment, the copolyester composition comprises at least one polyester, and the polyester is (a)(i) 70 to 100 mol% of terephthalic acid residues, and (ii) 0 to 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, a dicarboxylic acid component containing, and (b)(i) 10 to 70 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, (ii) 0 to 40 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, (iii) 0 to 10 mol% of diethylene glycol (DEG) residues, whether formed in situ or not, A glycol component containing including, wherein the remainder of the glycol component is (iv) residues of ethylene glycol, and (v) optionally, residues of at least one other modifying glycol in an amount of 0 to 10 mol%, including, wherein the total molar percentage of the dicarboxylic acid component is 100 mol% and the total molar percentage of the glycol component is 100 mol%.

[0054] In one embodiment, the copolyester composition includes at least one polyester, and the polyester (a)(i) 70 to 100 mol% of terephthalic acid residues, and (ii) 0 to 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, including a dicarboxylic acid component, and (b)(i) 10 to 70 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, (ii) 60 to 80 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, (iii) Whether formed in situ or not, 0 to 10 mol% of diethylene glycol (DEG) residues, including a glycol component, wherein the remainder of the glycol component is (iv) residues of ethylene glycol, and (v) optionally, residues of at least one other modifying glycol in an amount of 0 to 10 mol%, including, wherein the total molar percentage of the dicarboxylic acid component is 100 mol% and the total molar percentage of the glycol component is 100 mol%.

[0055] The copolyesters useful in the present disclosure can have an intrinsic viscosity of about 0.4 to about 1.2 dL / g. When used, the intrinsic viscosity (or IhV) herein is the viscosity of a dilute solution of the polymer. Specifically, IhV is the viscosity of a 60 / 40 (wt% / wt%) phenol / tetrachloroethane solution at about 25 °C or about 30 °C with a polyester concentration of about 0.25 g per 50 mL of solution, measured by ASTM 4603. This viscosity measurement represents the molecular weight of the polymer.

[0056] For example, in one embodiment, the copolyester has an intrinsic viscosity of about 0.45 to about 0.9 dL / g or about 0.60 to about 0.90, measured at about 25 °C using 0.50 grams of polymer per 100 mL of solvent consisting of 60 wt% phenol and 40 wt% tetrachloroethane.

[0057] In one embodiment, the copolyesters useful in the present disclosure have a glass transition temperature of about 30 °C to about 155 °C. For example, in one embodiment, the glass transition temperature of the copolyester is about 90 °C to about 120 °C. In one embodiment, the glass transition temperature of the copolyester is about 95 °C to about 140 °C. In another embodiment, the glass transition temperature of the copolyester is about 100 °C to about 150 °C. In one embodiment, the copolyesters useful in the present disclosure have a glass transition temperature of at least about 90 °C. In one embodiment, the copolyester has a glass transition temperature of at least about 100 °C or at least about 110 °C or at least about 120 °C.

[0058] The copolyesters can be prepared by conventional polycondensation procedures well known in the art. Such processes include direct condensation of a dicarboxylic acid and a diol, or transesterification using a dialkyldicarboxylate. For example, dialkyl terephthalates such as dimethyl terephthalate are transesterified with a diol at elevated temperature in the presence of a catalyst. The polyesters can also be subjected to solid-state polymerization. Suitable methods include reacting one or more dicarboxylic acids with one or more glycols at a temperature of about 100°C to about 315°C and a pressure of about 0.1 to about 760 mmHg for a time sufficient to form the polyester. Reference is made to U.S. Patent No. 3,772,405 for methods of making polyesters, and the disclosure of such methods is incorporated herein by reference.

[0059] Copolyesters suitable for use in the present disclosure are commercially available from Eastman Chemical Company.

[0060] Polycarbonate Any polycarbonate ("PC") polymer resin is suitable for use in the present disclosure. For example, in one embodiment, polycarbonate resins useful in the present disclosure include aromatic polycarbonates. Aromatic polycarbonates suitable for the compositions of the present disclosure include, for example, polymers derived from diphenols such as bisphenol A, 1,1(4-hydroxyphenol)ketone, bis-(4-hydroxyphenyl)methane, 1,1-bis-(hydroxyphenyl)ethane, phenolphthalein, and 1,1 bis(hydroxyphenol)sulfone, and aromatic polycarbonates having alkyl or halogen substituents on the phenyl ring.In another embodiment, examples of the aromatic polycarbonate suitable for the composition of the present disclosure include polymers derived from diphenols such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 1,1-bis(4-hydroxyphenyl)-1-phenyl-ethane (bisphenol AP), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (bisphenol AF), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), bis-(4-hydroxyphenyl)diphenylmethane (bisphenol BP), 2,2-bis(3-methyl-4-hydroxyphenyl)propane (bisphenol C), bis(4-hydroxyphenyl)-2,2-dichloroethylene (bisphenol C2), 1,1-bis(4-hydroxyphenyl)ethane (bisphenol E), bis(4-hydroxyphenyl)methane (bisphenol F), 2,2-bis(4-hydroxy-3-isopropyl-phenyl)propane (bisphenol G), 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene (bisphenol M), bis(4-hydroxyphenyl)sulfone (bisphenol S), 1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene (bisphenol P), 5,5'-(1-methylethylidene)-bis[1,1'-(biphenyl)-2-ol]propane (bisphenol PH), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (bisphenol TMC), 1,1-bis(4-hydroxyphenyl)-cyclohexane (bisphenol Z), 2,2-bis(4-hydroxy-3-nitrophenyl)propane (dinitrobisphenol A), and 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane (tetrabromobisphenol A).

[0061] In one embodiment, the polycarbonate is a high molecular weight thermoplastic aromatic polycarbonate, including homopolycarbonates, copolycarbonates, and mixtures thereof, having a number average molecular weight of greater than about 8,000 to greater than 200,000, or about 10,000 to 80,000, and an intrinsic viscosity of 0.30 to 1.0 deciliter / gram (dl / g) as measured in a methylene chloride solution at 25°C. The polycarbonate is derived from, for example, dihydric phenols such as 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-(3,5,3’5-tetrachloro-4,4'-dihydroxyphenyl)propane, 2,2-(3,5,3’5-tetrabromo-4,4'-dihydroxydiphenyl)propane, and (3,3'-dichloro-4,4'-dihydroxydiphenyl)propane, and (3,3'-dichloro-4,4'-dihydroxydiphenyl)methane. Other dihydric phenols for use in the preparation of the above polycarbonates are disclosed in U.S. Patent Nos. 2,999,835, 3,028,365, 3,334,154, and 4,134,575, which are hereby incorporated by reference.

[0062] In one embodiment, the polycarbonate resin in the present disclosure is a bisphenol-based polycarbonate. In one embodiment, the polycarbonate resin in the present disclosure is a bisphenol A-based polycarbonate. In one embodiment, the polycarbonate resin in the present disclosure is a bisphenol S-based polycarbonate. In one embodiment, the polycarbonate resin in the present disclosure is a bisphenol C-based polycarbonate. In one embodiment, the polycarbonate resin is a bisphenol A-based polycarbonate having a melt flow of about 3 to about 80 g / 10 min at 300°C and 3.8 kgwt (ASTM).

[0063] Polycarbonate can be manufactured by known methods. For example, in one embodiment, polycarbonate is prepared by reacting a dihydric phenol with a carbonate precursor such as phosgene according to the methods disclosed in the above-mentioned documents and U.S. Patent Nos. 3,989,672, 4,018,750, and 4,123,436, or by a transesterification process as disclosed in U.S. Patent No. 3,153,008, and other methods known to those skilled in the art, all of which are hereby incorporated by reference.

[0064] In one embodiment, the polycarbonate is an aromatic polycarbonate and includes polymer derivatives of dihydric phenols, dicarboxylic acids, and carbonic acid as disclosed in U.S. Patent No. 3,169,121.

[0065] In one embodiment, a copolymer or interpolymer of two or more different dihydric phenols or a dihydric phenol and a glycol or an acid-terminated polyester or a dibasic acid is used instead of a homopolymer in the preparation of the aromatic polycarbonate. Blends of any of the above materials can also be used.

[0066] In one embodiment, a branched polycarbonate as described in U.S. Patent No. 4,001,184 is utilized, and blends of linear polycarbonate and branched polycarbonate can also be utilized.

[0067] In one embodiment, the polymer is produced by reacting a dihydric phenol, such as 2,2-bis(4-hydroxyphenyl)propane, with a carbonate precursor, such as phosgene, in the presence of an acid binder. In one embodiment, the polycarbonate resin is derived from the reaction of bisphenol A and phosgene. In one embodiment, these polycarbonates have an intrinsic viscosity of 0.3 to 1.0 dl / g or 0.40 to 0.65 dl / g as measured at 25°C in methylene chloride or a similar solvent.

[0068] Polyvinyl chloride Any polyvinyl chloride ("PVC") polymer resin is suitable for use in the present disclosure. For example, in one embodiment, polyvinyl chloride polymers useful in the present disclosure include those described in the Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 24, 4th Edition, (1997) pp. 1017-1053, "Vinyl Chloride Polymers", which is hereby incorporated by reference herein.

[0069] In some embodiments, suitable PVC polymers in the present disclosure include homopolymers of polyvinyl chloride resins, copolymers of polyvinyl chloride resins, and mixtures thereof.

[0070] In some embodiments, the polyvinyl chloride resin is a polyvinyl chloride resin, a chlorinated polyvinyl chloride resin, or an alloy thereof.

[0071] In some embodiments, the copolymer of vinyl chloride is formed by copolymerization of vinyl chloride with other monomers or monomer blends. In some embodiments, suitable monomers include vinyl acetate, ethylene, propylene, maleate, methacrylate, acrylate, higher alcohol vinyl esters, urethane, chlorinated urethane, methyl methacrylate, and mixtures thereof. In some embodiments, examples of monomer blends include ethylene-vinyl acetate copolymers, acrylonitrile-butadiene-styrene terpolymers, acrylonitrile-butadiene copolymers, and mixtures thereof.

[0072] For example, in some embodiments, PVC polymers useful according to the present disclosure include homopolymers of vinyl chloride, and vinyl chloride polymer resins having at least about 70 wt% repeating units polymerized from vinyl chloride monomers, or vinyl chloride polymer resins having at least about 80 wt% or at least about 90 wt% or even about 95 wt% or more repeating units polymerized from vinyl chloride monomers.

[0073] In some embodiments, the polyvinyl chloride polymer composition of the present disclosure can include repeating units polymerized from vinyl chloride monomer, and can also include up to about 30 wt% of comonomers of the copolymer, and examples of the comonomers include, but are not limited to, esters of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, cyanoethyl acrylate, vinyl esters such as vinyl acetate and vinyl propionate, esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, butyl methacrylate, nitriles such as acrylonitrile and methacrylonitrile, acrylamides such as methylacrylamide, N-methylolacrylamide, N-butoxymethacrylamide, halogen-containing vinyl monomers such as vinylidene chloride, vinylidene fluoride, vinyl bromide, vinyl ethers such as ethyl vinyl ether, chloroethyl vinyl ether, vinyl ketone, styrene derivatives including α-methylstyrene, vinyl toluene, chlorostyrene, vinyl naphthalene, olefins such as ethylene, butene, isobutylene, propylene and hexene, and one or more of other copolymerizable monomers or mixtures of monomers having an appropriate reactivity ratio with vinyl chloride as known to those skilled in the art.

[0074] In one embodiment, examples of the copolymer include, but are not limited to, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl maleate and vinyl fumarate chloride copolymer, vinyl chloride-olefin copolymer, vinyl chloride-acrylonitrile copolymer, and combinations thereof.

[0075] Some embodiments of the present disclosure can use a PVC blend with crosslinked PVC or crosslinked PVC alone. Crosslinked PVC polymers can be produced by polymerizing vinyl chloride in the presence of crosslinkable monomers such as diallyl phthalate, trimethylolpropane triacrylate, allyl methacrylate, etc. as taught in U.S. Patent Nos. 4,755,699 and 5,248,546 (the relevant portions of which are incorporated herein by reference).

[0076] The described homopolymers and copolymers are commercially available and can be produced by any suitable polymerization method including suspension, dispersion or mixing. For example, in one embodiment, a polyvinyl chloride polymer prepared using a suspension process is suitable for use in the present disclosure.

[0077] In some embodiments, the PVC composition is rigid. Any rigid PVC composition is suitable for use in the present disclosure. For example, in some embodiments, the rigid composition is unmodified, or unplasticized, or contains a small amount or no plasticizer. In some embodiments, the rigid composition contains up to about 12 phr of plasticizer or plasticizing additive. On the other hand, flexible or plasticized PVC typically may contain levels of plasticizer in excess of about 12 phr. Thus, the rigid PVC according to the present disclosure is characterized by having a higher level of tensile strength than modified PVC compositions classified as flexible. As used herein, "parts per 100 parts of resin" defines the amount of a component based on the mass of the resin and is abbreviated as "phr".

[0078] Also, according to the present disclosure, rigid PVC refers to the properties of a given compound that exceed a specific tensile modulus. For example, PVC is characterized as rigid when the tensile modulus exceeds about 105 psi (or about 689 MPa), semi-rigid when the tensile modulus is from about 105 psi to about 3000 psi (about 20.7 MPa), and flexible when the tensile modulus is less than about 3000 psi (or about 20.7 MPa) (the values of the tensile modulus are based on standard ASTM conditions of 23°C and 50% relative humidity). Thus, the rigid PVC according to the present disclosure can have tensile modulus values that vary over a wide range. For example, the tensile modulus value can be from about 800 MPa to about 1000 MPa or from about 1000 MPa to about 2000 MPa or even 3000 MPa or more.

[0079] In some embodiments, the PVC compositions of the present disclosure are suitable for use in a variety of applications, including, for example, buildings and structures, corner profiles, decking, fencing, railing, soffits, vinyl siding, cladding, window profiles, door frames, sheathing, fences, gutters, pipes, conduits, electrical and electronic enclosures, electrical junction boxes, automotive interiors and exteriors, appliances, office equipment, sign enclosures, medical devices, aircraft interiors, and other high-temperature applications.

[0080] In some embodiments, the polyvinyl chloride resin composition includes additives such as processing aids, plasticizers, stabilizers, impact modifiers, biocides, flame retardants, blowing agents, foaming agents, UV stabilizers, UV absorbers, heat stabilizers, minerals, pigments, dyes, colorants, fillers, fibers, waxes, fusion promoters, antioxidants, antistatic agents, mold release agents, lubricants, additional resins, heat distortion temperature modifiers, and optionally other additives. In some embodiments, the amount of polyvinyl chloride in the commercially available rigid polyvinyl chloride resin compositions used is typically less than about 100%.

[0081] Any type of PVC resin known in the art can be useful as a component of the disclosed compositions. In some embodiments, the PVC resin can be in the form of a plastisol or a dry blend. Further, in some embodiments, the disclosed compositions can include virgin PVC, recycled PVC such as PVC recycled from various roofing products, and combinations of virgin and recycled PVC.

[0082] In one embodiment, the PVC resin of the present disclosure has an intrinsic viscosity in the range of about 0.50 to about 1.60 dl / g or more, such as about 0.65 to about 1.40 dl / g, such as about 0.83 to about 1.00 dl / g, as determined by ASTM D1243.

[0083] In one embodiment, the polyvinyl chloride resin has a Tg of about 75°C to about 80°C. In one embodiment, the polyvinyl chloride resin has a heat distortion temperature (HDT) of about 60°C to about 75°C.

[0084] In one aspect of the present disclosure, when the Tg of the copolyester exceeds about 90°C, the Tg of the PVC resin composition increases and the HDT of the composition improves.

[0085] For example, in some embodiments, polyvinyl chloride articles manufactured using the disclosed compositions have a Tg of up to 110°C or an HDT of up to 130°C while maintaining impact strength. In some embodiments, the articles have an increase in Tg and HDT of at least 3°C while maintaining impact strength.

[0086] In some embodiments, the ratio of PVC resin to copolyester on a mass fraction basis is greater than about 1.

[0087] In some embodiments, the ratio of PVC resin to copolyester and polycarbonate on a mass fraction basis is greater than about 1.

[0088] In some embodiments, when adding polyvinyl chloride resin and copolyester at appropriate concentrations to produce a PVC composition, the resulting composition has increased tensile strength and modulus as determined by ASTM D638, and increased flexural strength and modulus as determined by ASTM D790.

[0089] The copolyester in the present disclosure is miscible with PVC. The term "miscible" refers to a blend or mixture of two or more polymers that is homogeneous at the molecular level, behaves as a single-phase mixture, and exhibits only one glass transition temperature (Tg).

[0090] The resulting PVC compositions disclosed herein can be processed using any standard PVC processing apparatus at any standard PVC processing temperature (from about 170 °C to about 230 °C) and any standard PVC processing method such as extrusion molding, injection molding, profile extrusion, and sheet extrusion.

[0091] In some embodiments, the copolyester of the present disclosure has a Tg of from about 75 °C to about 120 °C. In some embodiments, the copolyester of the present disclosure has a Tg of at least about 90 °C or higher. In some embodiments, the copolyester of the present disclosure has a Tg of at least about 100 °C or higher. In some embodiments, the copolyester of the present disclosure has a Tg of at least about 110 °C or higher.

[0092] The copolyester used in certain embodiments of the present disclosure does not have a distinct melting point. Instead, the viscosity decreases as the processing temperature rises above its glass transition temperature. By using a lower molecular weight copolyester, a lower viscosity copolyester can be obtained.

[0093] In one embodiment of the present disclosure, the copolyester has a viscosity range of about 1,000 to about 1,000,000 poise, or about 10,000 to about 500,000 poise, or about 20,000 to about 300,000 poise, as measured at about 170 °C to about 200 °C and a shear rate of 10 1 / s. The viscosity measurement in this aspect of the present disclosure is performed by conducting a small amplitude oscillatory shear (SAOS) experiment using a Rheometrics RDA II rheometer and determining, in accordance with ASTM D4440, a frequency sweep over a range of 1 to 400 s at a plurality of temperatures above Tg. -1 This is done by performing a frequency sweep over a range of 1 to 400 s at a plurality of temperatures above Tg. In some embodiments, the viscosity is measured at a PVC processing temperature of about 170 °C to about 230 °C.

[0094] In one embodiment of the present disclosure, the copolyester has a semi-crystallization time of more than about 5 minutes, a glass transition temperature of at least about 90 °C, and a viscosity range of about 1,000 to about 1,000,000 poise, as measured at about 170 to about 230 °C and a shear rate of 10 1 / s.

[0095] In another embodiment of the present disclosure, the copolyester composition has a semi-crystallization time of more than about 5 minutes, a glass transition temperature of at least 100 °C, and a viscosity range of about 1,000 to about 1,000,000 poise, as measured at about 170 °C to about 230 °C and a shear rate of 10 1 / s.

[0096] In some embodiments, the PVC resin is combined with other additives such as processing aids, plasticizers, stabilizers, impact modifiers, biocides, flame retardants, blowing agents, foaming agents, heat stabilizers, UV stabilizers, UV absorbers, minerals, pigments, dyes, colorants, fillers, fibers, waxes, melt accelerators, antioxidants, antistatic agents, release agents, lubricants, additional resins, heat distortion temperature modifiers, and optionally other additives.

[0097] One embodiment of the present disclosure is to compound a miscible mixture of at least one polycarbonate resin and at least one copolyester to produce a viscous thermoplastic material, wherein the copolyester comprises (a)(i) about 90 to about 100 mol% of terephthalic acid residues, (ii) about 0 to about 10 mol% of a dicarboxylic acid component containing aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b)(i) about 20 to about 60 mol% of a modified glycol consisting of 2 to 20 carbon atoms, and (ii) about 40 to about 80 mol% of a second modified glycol consisting of 2 to 20 carbon atoms, blending the formulation with at least one polyvinyl chloride resin composition, and introducing the blend into a calendering, extrusion or injection molding process to produce a polyvinyl chloride article, which is a method for producing a polyvinyl chloride composition.

[0098] Another embodiment of the present disclosure is to compound at least one polyvinyl chloride resin with at least one copolyester to produce a viscous thermoplastic material, wherein the copolyester comprises (a)(i) about 90 to about 100 mol% of terephthalic acid residues, (ii) about 0 to about 10 mol% of a dicarboxylic acid component containing aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and (b)(i) about 20 to about 60 mol% of a modified glycol consisting of 2 to 20 carbon atoms, and (ii) about 40 to about 80 mol% of a second modified glycol consisting of 2 to 20 carbon atoms, mixing the compounded composition with a polyvinyl chloride resin to produce a polyvinyl chloride composition, extruding the polyvinyl chloride composition through a die to produce pellets, and introducing the pellets into a calendering, extrusion or injection molding process to produce a polyvinyl chloride article, which is a method for producing a polyvinyl chloride composition.

[0099] In some embodiments, the PVC compositions of the present disclosure are used to produce articles such as films, sheets, profiles or injection molded articles and parts.

[0100] The compositions of the present disclosure are useful as molded plastic parts or solid plastic objects. In some embodiments, films, sheets, profiles, injection molded articles and parts can be manufactured using any extrusion process including an extrusion molding process where the pellets are blended together (when using concentrated components) or added directly to an extruder (when using a fully formulated composition). In some embodiments, films, profiles and sheets can be manufactured using any calendering process.

[0101] In some embodiments, the melt processing of the compositions of the present disclosure includes, but is not limited to, extrusion using any device known in the art including twin screw extruders, single screw extruders, high intensity batch mixers, Banbury mixers, Brabender mixers, roll mills, co-kneaders or planetary gear extruders. The shear energy during mixing depends on the combination of equipment, blade design, rotational speed (rpm) and mixing time. The shear energy should be sufficient to disperse the copolyester throughout the polyvinyl chloride resin.

[0102] In some embodiments, the copolyester, polyvinyl chloride resin and additives can be combined in any order during the process. In one embodiment, the copolyester is premixed with the polyvinyl chloride resin. In another embodiment, the polyvinyl chloride resin is premixed with the additives and then mixed with the copolyester.

[0103] The present disclosure further relates to products comprising films and / or sheets comprising the polyvinyl chloride compositions described herein. In embodiments, the films and / or sheets of the present disclosure can be of any thickness apparent to one of ordinary skill in the art.

[0104] The present disclosure further relates to the molded articles described herein. The method of molding the polyvinyl chloride composition into a molded article can include any method known in the art. Examples of the molded articles of the present disclosure include, but are not limited to, injection molded articles and extrusion molded articles. Examples of the manufacturing methods of the molded articles include, but are not limited to, injection molding and extrusion molding.

[0105] The compositions of the polycarbonate, copolyester, and polyvinyl chloride resin of the present disclosure can be made into pellets using any standard procedure.

[0106] For example, the pellets of the present disclosure can be manufactured by the following method. In one embodiment, the polycarbonate / copolyester mixture and the polyvinyl chloride resin can be incorporated using a twin-screw compounding line. The polycarbonate, copolyester, and polyvinyl chloride resin are separately fed into the throat of an extruder, melted, and a viscous thermoplastic material is produced.

[0107] In one embodiment, the polycarbonate / copolyester mixture and the polyvinyl chloride resin can be added using a loss-in-weight feeder. When two screws are rotated, the polycarbonate / copolyester mixture and the PVC melt together. Next, the mixture is extruded through a die to produce a plurality of strands. The strands can be fed through a water bath to cool the pellets. After exiting the water bath, the strands are dried and fed to a pelletizer to cut the strands into pellets. Alternatively, the mixture can be extruded through a circular flat die having a plurality of openings into water. The flat die has a rotating cutter that slices the strands as they are extruded from the die to produce pellets. A continuous flow of water cools the pellets, transports them to a drying section, and then the pellets are typically separated from the water using a centrifuge.

[0108] In one embodiment, the polycarbonate / copolyester mixture and PVC can be incorporated using a two-rotor continuous compounding mixer (such as a Farrell continuous mixer). The polycarbonate / copolyester mixture can be fed into the throat of the mixer together with the PVC and melted to produce a viscous thermoplastic material. The copolyester can be pre-blended with the polycarbonate and then added to the PVC, and this mixture can be added to an extruder using a loss-in-weight feeder. The output speed of the mixer is controlled by varying the area of the discharge orifice. The melt is sliced into "ropes" and fed into the throat of a two-roll mill or a single-screw extruder. When the melt is fed into a two-roll mill, the melt can cover one of the rolls and the strip can be fed into the throat of a single-screw extruder. Next, the mixture is extruded through a die to produce a plurality of strands. The strands can be fed through a water bath to cool the pellets. After exiting the water bath, the strands are dried and fed to a pelletizer to cut the strands into pellets. Alternatively, the mixture can be extruded through a circular flat die having a plurality of openings into water. The flat die has a rotating cutter that slices the strands as they are extruded from the die to produce pellets. A continuous flow of water cools the pellets and transports them to a drying section, typically to a centrifuge that separates the pellets from the water. When the "ropes" are fed into a single-screw extruder, the mixture is extruded through a die to produce a plurality of strands. The strands can be fed through a water bath to cool the pellets. After exiting the water bath, the strands are dried and fed to a pelletizer to cut the strands into pellets. Alternatively, the mixture can be extruded through a circular flat die having a plurality of openings into water. The flat die has a rotating cutter that slices the strands as they are extruded from the die to produce pellets. A continuous flow of water cools the pellets and transports them to a drying section, typically to a centrifuge that separates the pellets from the water.

[0109] In some embodiments, the polycarbonate / copolyester mixture and the PVC resin can be incorporated into a plastics compounding line, such as a Banbury batch type mixer. In these embodiments, the polycarbonate / copolyester mixture is pre-mixed, and this mixture is mixed with the PVC and then fed into a Banbury type high-intensity mixer, lowering the ram to compress the mixture into the mixing chamber. Two rotating mixer blades melt the pellets and melt the mixture of the copolyester and the polycarbonate together with the PVC. When the desired temperature is reached, the door at the bottom of the mixer opens and the mixture drops into a two-roll mill. Next, the ribbon from the two-roll mill can be fed into a single-screw extruder. The mixture is then extruded through a die to produce a plurality of strands. The strands can be fed through a water bath to cool the strands. After exiting the water bath, the strands are dried and fed to a dicing machine to cut the strands into pellets. Alternatively, the mixture can be extruded through a circular flat die having a plurality of openings into water. The flat die has a rotating cutter that slices the strands as they are extruded from the die to produce pellets. A continuous flow of water cools the pellets, transports them to a drying section, and typically transports the pellets to a centrifuge to separate the pellets from the water.

[0110] The present disclosure contemplates several different ways to manufacture plastic articles: extrusion to produce continuous flat sheets or profiles, injection molding to produce individual articles, or extrusion to produce continuous films or sheets.

[0111] Another embodiment of the present disclosure consists of combining a copolyester / polycarbonate mixture with a PVC resin composition and using an extrusion process to produce a flat sheet or profile. In some embodiments, this can be achieved in several ways. For example, the copolyester / polycarbonate mixture and the PVC resin composition are separately added to the throat of a single-screw or twin-screw extruder. In another embodiment, a mixture of copolyester and polycarbonate is compounded with the PVC resin composition and then added to the throat of a single-screw or twin-screw extruder. In some embodiments, the compounded mixture is conveyed by the screw into the extruder barrel, compressed to melt the mixture, and the melt is discharged from the end of the extruder. Next, the melt can be fed to a die to create a continuous flat sheet or to a profile die to create a continuous shape. In embodiments using a flat sheet die, the melt is extruded onto a series of metal rolls (typically three) to cool the melt and finish the sheet. Next, the flat sheet is conveyed as a continuous sheet and the sheet is cooled. Next, it can be trimmed to the desired width and then wound into a roll, sheared, or cut into sheets. The flat sheet can also be processed into a desired shape by mechanical means to form the desired shape and then cooled by spraying water, passing through a water bath, or blowing air onto the profile. Next, it can be cut or sheared to the desired length.

[0112] In embodiments using a profile die, the die is designed to produce an article of the desired shape. After exiting the die, it can be cooled by spraying water, passing through a water bath, or blowing air onto the profile. Next, it can be cut or sheared to the desired length.

[0113] Another embodiment of the present disclosure consists of manufacturing an injection molded article by combining a copolyester / polycarbonate mixture with a PVC resin composition. This can be achieved in several ways by separately adding the copolyester / polycarbonate blend and the PVC resin to the throat of a single-screw or twin-screw extruder as described above. In another embodiment, a mixture of copolyester and polycarbonate is mixed with the PVC composition and then added to the throat of a single-screw or twin-screw extruder. The blended mixture is, in some embodiments, conveyed by the screw to the extruder barrel, compressed to melt the mixture, and the melt is discharged from the end of the extruder. When the pellets reach the desired temperature, the gate at the end of the extruder is opened and the molten plastic is pumped by the screw into a heated mold to form an article of the desired shape. After the mold is filled, a coolant is pumped through the mold to cool the mold and the molten plastic. After the plastic has solidified, the mold is opened and the article is removed from the mold.

[0114] For example, one embodiment of the present disclosure is a method of manufacturing a polyvinyl chloride composition, which includes extruding at least one polyvinyl chloride resin composition and at least one copolyester / polycarbonate mixture as described above to produce a viscous blend of thermoplastic materials, and introducing the blend of thermoplastic materials into a calendering, extrusion molding, or injection molding process to produce a polyvinyl chloride article.

[0115] Another embodiment of the present disclosure is a method of manufacturing a polyvinyl chloride composition, which includes blending a compatible blended mixture of at least one polyvinyl chloride resin composition and at least one copolyester / polycarbonate mixture as described above to produce a viscous thermoplastic material, extruding the compound through a die to produce pellets, and introducing the pellets into a calendering, extrusion molding, or injection molding process to produce a polyvinyl chloride article. In some embodiments, the polyvinyl chloride composition is rigid.

[0116] Useful applications of these PVC compositions include many architectural and construction applications such as corner profiles, decking, fencing, railing, window profiles, and other interior and exterior applications.

[0117] Other applications of these PVC compositions include use in electrical appliances, electrical and electronic enclosures, sign enclosures, automotive applications, aircraft interiors, and other applications where rigid PVC formulations are limited due to low tensile strength and modulus of elasticity as well as low flexural strength and modulus of elasticity.

[0118] For example, in some embodiments, the PVC articles of the present disclosure are used in the following applications: architectural and construction, corner profiles, decking, fencing, railing, soffit, vinyl siding, cladding, window profiles, door frames, siding, fences, gutters, pipes, tubing, electrical and electronic enclosures, electrical junction boxes, automotive interiors and exteriors, electrical appliances, office equipment, sign enclosures, medical devices, aircraft interiors, and other applications. In some embodiments, the polyvinyl chloride articles are rigid.

[0119] This disclosure can be further illustrated by the following examples, which are included for illustrative purposes only and are not intended to limit the scope of the disclosure unless otherwise specifically stated.

Examples

[0120] The following tables and figures summarize the experimental results and comparative examples of the disclosure.

Table 1

[0121] Table 1 is the control formulation used in all examples. All data generated used the control formulation and the additives were included in various parts per 100 parts of resin based on 100 parts of PVC resin. All samples were melted and prepared by mixing 280 grams of compound in a Brabender Intelli-Torque mixer set at 190 °C and a blade speed of 30 rpm. Samples were removed from the Brabender at 190 °C and transferred to a Dr. Collin Two Roll Mill. The front roll temperature was set at 180 °C and the back roll temperature was set at 175 °C. The molten material was placed on the mill and the roll speed was set at 20 rpm. The temperature of the material reached 175 °C and was then removed from the mill. Films were removed from the mill at 0.010 inches (250 microns) and allowed to cool.

Table 2

[0122] Table 2 summarizes the sample compositions. The sample compositions were produced by blending the control formulation of Table 1 with various amounts of HDT1, HDT2, and HDT3 as described to create mixtures containing various amounts of polycarbonate from 0 wt% to about 31 wt%.

[0123] The amorphous copolyester is commercially available from Eastman Chemical Company and has a glass transition temperature of about 116 °C. Makrolon 2608 of polycarbonate is a medium-viscosity amorphous bisphenol A polycarbonate resin made by Covestro and has a glass transition temperature of about 148 °C.

[0124] The Makrolon 2658 resin of polycarbonate, which is a medium-viscosity amorphous bisphenol A polycarbonate resin made by Covestro and has a glass transition temperature of about 148 °C, was also used in some examples.

[0125] Example 1: DSC and HDT Samples were prepared by adding HDT1, HDT2, and HDT3 at 30, 40, 50, 60, and 80 phr. Additional samples were prepared by adding mixtures of HDT2 and HDT3 at ratios of 50 / 10, 30 / 30, 10 / 50 (total 60 phr) and 65 / 15, 40 / 40, and 15 / 65 (total 80 phr). Table 3 includes the results of differential scanning calorimetry (DSC) (ASTM D3418) and heat deflection temperature under load (HDTUL) at 1% and 2% strain (ASTM D1637). The data shows that the Tg determined by DSC for all compositions including HDT1, HDT2, HDT3, and mixtures of HDT2 and HDT3 was higher than that of the control sample. The Tg values determined by DSC were obtained at the midpoint of the glass transition region. The data also shows that the HDTUL determined by tensile DMA at 1% and 2% strain was higher than that of the control formulation.

Table 3

[0126] Example 2: Impact properties Samples were prepared by adding HDT1, HDT2, and HDT3 at 30, 40, 50, 60, and 80 phr. Additional samples were prepared by adding mixtures of HDT2 and HDT3 at ratios of 50 / 10, 30 / 30, 10 / 50 (total 60 phr) and adding mixtures of HDT2 and HDT3 at 65 / 15, 40 / 40, and 15 / 65 (total 80 phr). Table 4 is a summary of the results of instrumented impact (ASTM D3763). The data, determined by visual inspection of the impacted samples, show that all compositions containing only HDT1 are ductile. The data show that compositions containing the polycarbonate Makrolon 2608 exhibit nearly ductile impact properties up to a loading of about 15 wt%, as determined by visual inspection of the impacted samples. The data also show that, although brittle, there was no significant decrease in impact strength as measured by average maximum load (kN), average energy at maximum load (J), average puncture energy (J), and average total energy (J) until the polycarbonate Makrolon 2608 content reached about 25%.

Table 4

[0127] Example 3: Tensile Properties Samples were prepared by adding HDT1, HDT2, and HDT3 at 30, 40, 50, 60, and 80 phr. Additional samples were prepared by adding mixtures of HDT2 and HDT3 at ratios of 50 / 10, 30 / 30, 10 / 50 (total 60 phr) and adding mixtures of HDT2 and HDT3 at 65 / 15, 40 / 40, and 15 / 65 (total 80 phr). Table 5 summarizes the tensile property data (ASTM D-638). Measurements were made in the direction in which the film was pulled from the two-roll mill (machine direction) and perpendicular to the direction in which the film was pulled from the mill (transverse direction). Using % elongation at break as a surrogate for impact strength, the data in the machine direction and transverse direction generally reflect the instrumented impact data and no complete embrittlement was seen until the polycarbonate Makrolon 2608 content reached about 25%.

Table 5

[0128] Example 4: Processing Characteristics Samples were prepared by adding HDT1, HDT2, and HDT3 at 80 phr. Additional samples were prepared by adding mixtures of HDT2 and HDT3 at 65 / 15, 40 / 40, and 15 / 65 (total 80 phr). Additional samples were prepared by adding amorphous copolyester at 20, 40, 60, 80, and 100 phr. Figures 1 and 2 include the relationship of viscosity data vs. shear rate at 190 °C as determined by parallel plate rheometry. The data indicate that formulations containing polycarbonate tend to have lower melt viscosities than formulations containing PVC and amorphous copolyester.

[0129] Example 5. Glass Transition Temperature and Miscibility Samples were prepared by adding HDT2 and HDT3 to the control formulation at 30, 40, and 50 phr. Figures 3 and 4 show the storage modulus and tan δ charts of HDT2 added at 30, 40, and 50 phr. Figures 5 and 6 show the storage modulus and tan δ charts of HDT3 added at 30, 40, and 50 phr. All charts show a single integrated glass transition temperature for all mixtures. The storage modulus charts show a single sharp descending gradient starting at about 90 - 95 °C and ending at about 100 °C. The tan δ charts show a single peak in the range of about 95 - 100 °C. These data indicate that the polymer is a single miscible mixture since immiscible polymer mixtures are expected to have two or more distinct glass transition temperatures.

[0130] Comparative Example 1: Tensile Properties, Impact Properties, and Compatibility of Polycarbonate at 20, 40, and 60 phr Samples were prepared by adding Makrolon 2658, which is a polycarbonate, to the PVC control formulation at 20, 40, and 60 phr. Table 6 summarizes the tensile property data and the instrumented impact data. Figure 7 includes the dynamic mechanical analysis (DMA) data. Makrolon 2658, which is a polycarbonate, has a Tg of about 145 °C, and polycarbonates are generally known as tough polymers. The data in Table 6 show that all levels of Makrolon 2658 polycarbonate tested have low impact properties due to low percent elongation at break and brittle instrumented impact properties. Figure 7 shows that the blend of Makrolon 2658 polycarbonate and the PVC control formulation is immiscible, as indicated by two distinct glass transition temperatures (Tg) determined by the tan δ peak. This data shows that simply incorporating a high-Tg thermoplastic into rigid PVC is not sufficient to increase the Tg and HDTUL and maintain the impact properties of the blend. The high-Tg thermoplastic must also be miscible and compatible.

Table 6

Claims

1. A polyvinyl chloride composition comprising at least one polyvinyl chloride resin, at least one polycarbonate resin, and at least one amorphous copolyester, wherein the amorphous copolyester comprises (a) (i) 90 to 100 mol% of terephthalic acid residues, and (ii) 0 to 10 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, a dicarboxylic acid component, and (b) (i) 20 to 60 mol% of a first glycol having 2 to 20 carbon atoms, and (ii) 40 to 80 mol% of a second glycol having 2 to 20 carbon atoms, a glycol component, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%, or (a) (i) 50 to 100 mol% of terephthalic acid residues, and (ii) 0 to 50 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, a dicarboxylic acid component, and (b) (i) 60 to 100 mol% of a first glycol having 2 to 20 carbon atoms, and (ii) 0 to 40 mol% of a second glycol having 2 to 20 carbon atoms, a glycol component, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%, the first glycol is 1,4-cyclohexanedimethanol and the second glycol is ethylene glycol, or the first glycol is 2,2,4,4-tetramethyl-1,3-cyclobutanediol and the second glycol is 1,4-cyclohexanedimethanol, the Tg of the amorphous copolyester is at least 90 °C or higher, and further based on the content of the polyvinyl chloride resin in the composition, the polycarbonate resin is 1 to 50 parts (phr) per 100 parts of resin, and the amorphous copolyester is 1 to 100 parts (phr) per 100 parts of resin. Composition.

2. The polyvinyl chloride composition according to claim 1, wherein the intrinsic viscosity of the amorphous copolyester is 0.50 to 0.80 dL / g as determined at 25 °C at a concentration of 0.25 g / 50 ml in phenol / tetrachloroethane at 60 / 40 (wt / wt).

3. The polyvinyl chloride composition according to claim 1, wherein the Tg of the amorphous copolyester is at least 100 °C or higher.

4. The amorphous copolyester is 1 to 100 parts (phr) per 100 parts of the resin based on the content of the polyvinyl chloride resin in the composition, or the amorphous copolyester is 1 to 50 parts (phr) per 100 parts of the resin based on the content of the polyvinyl chloride resin in the composition. The polyvinyl chloride composition according to claim 1.

5. The amorphous copolyester is amorphous or has a semi-crystallization time of 5 minutes or more. The polyvinyl chloride composition according to claim 1.

6. The polyvinyl chloride resin is a polyvinyl chloride resin, a chlorinated polyvinyl chloride resin, or an alloy thereof. The polyvinyl chloride composition according to claim 1.

7. The polycarbonate resin is a bisphenol-based polycarbonate resin or a bisphenol A-based polycarbonate resin. The polyvinyl chloride composition according to claim 1.

8. The amorphous copolyester has a viscosity range of 1,000 to 1,000,000 poises as measured at 170 to 230 °C and a shear rate of 10 1 / sec. The polyvinyl chloride composition according to claim 1.

9. The ratio of polyvinyl chloride resin:amorphous copolyester based on mass fraction is greater than 1, or the ratio of polyvinyl chloride resin:amorphous copolyester and polycarbonate resin based on mass fraction is greater than 1. The composition according to claim 1.

10. Manufacturing a viscous thermoplastic material by blending at least one polycarbonate resin and at least one miscible mixture of an amorphous copolyester, where the amorphous copolyester is (a)(i)90 to 100 mol% of terephthalic acid residues, and (ii)0 to 10 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, comprising a dicarboxylic acid component, and (b)(i)20 to 60 mol% of a first glycol consisting of 2 to 20 carbon atoms, and (ii)40 to 80 mol% of a second glycol consisting of 2 to 20 carbon atoms, comprising a glycol component, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%. The first glycol is 1,4 - cyclohexanedimethanol, and the second glycol is ethylene glycol, or the first glycol is 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol, and the second glycol is 1,4 - cyclohexanedimethanol, The Tg of the amorphous copolyester is at least 90 °C or higher, and further Based on the content of the polyvinyl chloride resin in the composition, the polycarbonate resin is 1 to 50 parts per hundred parts of resin (phr), and the amorphous copolyester is 1 to 100 parts per hundred parts of resin (phr). Blending the viscous thermoplastic material with at least one polyvinyl chloride resin composition, and Introducing the blend into a calendering, extrusion molding or injection molding process to produce a polyvinyl chloride article, A method for producing a polyvinyl chloride composition, comprising.

11. Blending at least one polycarbonate resin and at least one amorphous copolyester to produce a viscous thermoplastic material, wherein the amorphous copolyester comprises (a)(i) 50 to 100 mol% of terephthalic acid residues, and (ii) 0 to 50 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, A dicarboxylic acid component comprising, and (b)(i) 60 to 100 mol% of a first glycol consisting of 2 to 20 carbon atoms, and (ii) 0 to 40 mol% of a second glycol consisting of 2 to 20 carbon atoms, A glycol component comprising, Wherein the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%, The first glycol is 1,4 - cyclohexanedimethanol, and the second glycol is ethylene glycol, or the first glycol is 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol, and the second glycol is 1,4 - cyclohexanedimethanol, The Tg of the amorphous copolyester is at least 90 °C or higher, and further Based on the content of the polyvinyl chloride resin in the composition, the polycarbonate resin is 1 to 50 parts per hundred parts of resin (phr), and the amorphous copolyester is 1 to 100 parts per hundred parts of resin (phr). Blending the tacky thermoplastic material into at least one polyvinyl chloride resin composition, and Introducing the blend into a calendering, extrusion or injection molding process to produce a polyvinyl chloride article, A method for producing a polyvinyl chloride composition, comprising:

12. A polyvinyl chloride article produced using the method according to claim 10 or 11, having a Tg of up to 110 ° C or an HDTUL of up to 130 ° C.

13. The polyvinyl chloride article has the following uses: construction and building, corner profiles, decking, fencing, railing, soffit, vinyl siding, cladding, window profiles, door frames, siding, fences, gutters, pipes, plumbing fixtures, electrical and electronic enclosures, electrical junction boxes, automotive interior and exterior, household appliances, office equipment or medical devices, sign enclosures, aircraft interiors and other high-temperature applications. The polyvinyl chloride article according to claim 12, which is used in any of the above.

14. The polyvinyl chloride resin composition further comprises at least one additive selected from the group consisting of processing aids, plasticizers, stabilizers, impact modifiers, biocides, flame retardants, blowing agents, foaming agents, heat stabilizers, UV stabilizers, UV absorbers, minerals, pigments, dyes, colorants, fillers, fibers, waxes, fusion promoters, antioxidants, antistatic agents, mold release agents, lubricants, additional resins and heat distortion temperature regulators. The method according to claim 10 or 11.

15. The polyvinyl chloride composition is a polyvinyl chloride resin, a chlorinated polyvinyl chloride resin or an alloy thereof. The method according to claim 10 or 11.

16. The polyvinyl chloride resin composition is rigid. The method according to claim 10 or 11.

17. The polycarbonate resin is a bisphenol-based polycarbonate resin or a bisphenol A-based polycarbonate resin. The method according to claim 10 or 11.

18. The Tg of the amorphous copolyester is at least 90 ° C or higher, or the Tg of the amorphous copolyester is at least 100 ° C or higher. The method according to claim 10 or 11.

19. Based on the content of the polyvinyl chloride resin in the polyvinyl chloride resin composition, the polycarbonate resin is 1 to 50 parts (phr) per 100 parts of resin, and the amorphous copolyester is 1 to 100 parts (phr) per 100 parts of resin. The method according to claim 10 or 11.

20. The method according to claim 10 or 11, wherein the amorphous copolyester is amorphous or the amorphous copolyester has a semi-crystallization time of 5 minutes or more.

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