Additives to lower melt PVC processing temperatures and PVC formulations with lower melt processing temperatures

Abstract

Disclosed is a polyvinyl chloride composition comprising a matrix comprising a polyvinyl chloride resin, and a polymer additive which is a reaction product of reactants comprising one or more monoethylenically unsaturated ester monomers, a chain transfer agent in an amount of 0.1 to 10 weight percent, and up to 10 weight percent of a crosslinker, wherein weight percent is based on total amount of reactants. A process for reducing the fusion temperature of a polyvinyl chloride composition is also disclosed.

Description

ADDITIVES TO LOWER MELT PVC PROCESSING TEMPERATURES AND PVC FORMULATIONS WITH LOWER MELT PROCESSING TEMPERATURES FIELD OF THE INVENTION

[0001] The invention relates to additives to lower melt PVC processing temperatures and PVC formulations with lower melt processing temperatures. BACKGROUND

[0002] Rigid polyvinyl chloride (PVC) is an energy intensive process as the PVC is currently processed at a general temperature range between 165 to 195 °C depending on the processing technique, such as, for example, extruding, calendaring, injection molding, etc.

[0003] There is an industry-wide focus on sustainability and identifying ways to reduce the carbon footprint of manufacturing processes. There are various ways to lower carbon footprints including recycling, reusing, reduction in materials, and developing more energy efficient processes. To meet sustainability targets, there have been attempts to develop additives that can help increase recycled content, as well as to develop additives that improve the carbon footprint in other ways, such as reducing energy requirements.

[0004] Because the energy required for processing PVC to produce a final product depends on the processing temperature, lowering the PVC processing temperature presents an opportunity to lower energy usage and the overall carbon footprint of the product.

[0005] Lowering the processing temperature of existing processes with currently used additives, however, results in various issues such as inferior quality, higher scrap or waste production, higher downtime, and lower production yield.

[0006] Therefore, a need exists for additives and processes that allow for PVC production at lower temperature. The present invention attempts to solve one or more of these problems. SUMMARY OF THE INVENTION

[0007] Disclosed herein is a composition comprising a matrix comprising a polyvinyl chloride resin, and a polymer additive which is a reaction product of reactants comprising one or more monoethylenically unsaturated ester monomers, a chain transfer agent in an amount of 0.1to 10 weight percent, and up to 10 weight percent of a crosslinker, wherein weight percent is based on total amount of reactants.

[0008] Also disclosed herein is a process for reducing the fusion temperature of a polyvinyl chloride resin comprising adding a polymer additive to the polyvinyl chloride resin, wherein the polymer is a reaction product of reactants comprising one or more monoethylenically unsaturated ester monomers, a chain transfer agent in an amount of 0.1 to 10 weight percent, and up to 10 weight percent of a crosslinker, wherein weight percent is based on total amount of reactants. DETAILED DESCRIPTION OF THE INVENTION

[0009] Disclosed herein is a composition comprising a matrix comprising a polyvinyl chloride resin and a polymer additive, wherein the polymer additive reduces the fusion temperature of the polyvinyl chloride resin.

[0010] The polyvinyl chloride resin may form all or a part of a continuous phase (i.e., the matrix) in the composition for preparing a polymer article and the article prepared therefrom. The selection of the polyvinyl chloride resin is typically a function of the desired end use application of the polymer composite article formed with the composition, as various polymers have different melting point temperatures (and / or glass transition temperatures) and physical / mechanical properties, as well as suitable or acceptable continuous use application temperatures. The polyvinyl chloride resin preferably has a softening point temperature that is less than a degradation temperature of other components in the composition. For example, the polyvinyl chloride resin may have a softening point temperature of less than 250 °C, alternatively less than 225 °C, alternatively less than 200°C. The softening point temperature may also be referred to as the processing temperature. In at least one embodiment, the polyvinyl chloride resin has a softening point temperature ranging from 150 to 250°C, such as from 160 to 220°C or from 170 to 210°C. The polyvinyl chloride resin may be in the form of pellets or a powder.

[0011] The polyvinyl chloride resin may be a rigid polyvinyl chloride resin. As used herein, the phrase “rigid polyvinyl chloride resin” means that a plasticizer is not added to the polyvinyl chloride resin, i.e., the polyvinyl chloride resin does not comprise an added plasticizeror the composition comprising the polyvinyl chloride resin does not comprise an added plasticizer. Preferably, the polyvinyl chloride resin is a rigid polyvinyl chloride resin.

[0012] Elastomers and / or rubbers can be added to or compounded with the polyvinyl chloride resin to modify or improve properties, such as impact strength. Preferably, the polyvinyl chloride resin comprises at least one acrylic processing additive. Additives may include those known in the art, such as the additives disclosed by Stevenson et al., Journal of Vinyl Technology, December 1993, Vol.15, No.4, pages 244-251, which is incorporated herein by reference.

[0013] In certain embodiments, the matrix in the polyvinyl chloride composition consists essentially of a polyvinyl chloride resin. By consist essentially of, it is meant that the matrix can include one or more additional polymers other than a polyvinyl chloride resin so long as such additional polymers can be processed along with the polyvinyl chloride resin to form the polymer article. When the matrix does not consist of a polyvinyl chloride resin, the matrix includes a polyvinyl chloride resin in an amount of at least 50, alternatively at least 60, alternatively at least 65, alternatively at least 70, alternatively at least 75, alternatively at least 80, alternatively at least 85, alternatively at least 90, alternatively at least 95, alternatively at least 96, alternatively at least 97, alternatively at least 98, alternatively at least 99, wt.% based on the total weight of the matrix utilized in the composition.

[0014] The matrix may further comprise an elastomer. Non-limiting examples of elastomers include styrene-butadiene rubber, polyether urethane rubber, polyester urethane rubber, butyl rubber, nitrile rubber, chloroprene rubber (neoprene), polyacrylate rubber, ethylene acrylate rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene propylene diene monomer (EPDM), ethylene propylene rubber (EPR), fluorosilicone rubber, fluorocarbon rubber, perfluorinated elastomer, styrene butadiene rubber, chlorosulfonated polyethylene, polyisoprene rubber, polysulfide rubber, ethylene acrylate rubber, epichlorohydrine rubber, perfluoroelastomer (e.g. Kalrez™), polysulfide rubber, chlorinated polyethylene (e.g. chlorinated polyethylene comprising up to 40 weight percent chlorine), and combinations thereof.

[0015] When the matrix comprises a polymer in addition to a polyvinyl chloride resin, the matrix may further comprise at least one polymer that is fully or partially thermodynamically miscible with the polyvinyl chloride resin. Such polymers include, but are not limited to, poly(methyl methacrylate) (PMMA), polyethylene oxide (PEO), thermoplastic polyurethane(TPU), polycaprolactone (CPL), and styrene-acrylonitrile resin (SAN). Other thermodynamically miscible polymers are known in the art and are disclosed, for example, Robeson, L. M. (1990), Miscible polymer blends containing poly(vinyl chloride). J. Vinyl Addit. Technol., 12: 89-94, which is incorporated herein by reference.

[0016] The polyvinyl chloride resin can comprise virgin polymer and / or recycled polymer. The recycled polymer, if utilized, may be sourced from industrial production streams, as well as from post-industrial and / or post-consumer sources. The selection of the polyvinyl chloride resin, as well as any ratio of virgin polymer to recycled polymer, if utilized in concert, is typically a function of cost and desired properties of the polymer composite article formed therewith.

[0017] It is noted that recycled polyvinyl chloride may contain some level of plasticizer. As defined above, a rigid polyvinyl chloride resin does not comprise an added plasticizer. Therefore, a rigid polyvinyl chloride resin according to the present invention may comprise recycled polyvinyl chloride containing a plasticizer so long as no additional plasticizer is added.

[0018] The polymer additive in the polyvinyl chloride composition is a reaction product of reactants comprising one or more monoethylenically unsaturated ester monomers, a chain transfer agent in an amount of 0.1 to 10 weight percent, and up to 10 weight percent of a crosslinker, wherein weight percent is based on total amount of reactants.

[0019] The polymer additive may be linear or branched. Preferably, the polymer additive is branched. More preferably, the polymer additive is branched without being cross-linked. To avoid cross-linking, the amount of cross-linker may not greater than the amount of chain transfer agent. Thus, according to certain embodiment the moles of cross-linker is no greater than or is less than the moles of chain transfer agent. According to certain embodiments the weight percent of crosslinker is less than the weight percent of chain transfer agent.

[0020] Suitable monoethylenically unsaturated ester monomers useful in making the branched polymer according to certain embodiments can have the structure R’-C(O)O-R where R is a hydrocarbyl group (e.g. alkyl group or aryl group). and R’ is a monoethylenically unsaturated aliphatic group having at least 2 or 3 carbon atoms. According to certain embodiments R is an alkyl group of at least 1 or 2 or 3 carbon atoms. According to certain embodiments R is an alkyl group having no more than 12 or 10 or 8 or 6 or 5 carbon atoms. According to certain embodiments R is an aryl group of 6 to 12 carbon atoms. According tocertain embodiments R’ has no more than 6 carbon atoms. Examples of suitable monomers include butyl acrylate, ethyl hexyl acrylate, ethyl acrylate, methyl methacrylate, butyl methacrylate, cyclohexyl (meth)acrylate, cyclopentyl methacrylate, tetrahydrofurfyl methacrylate, and benzyl (meth)acrylate. Combinations of two or more such monoethylenically unsaturated ester monomer may be used. For example, a combination of methyl methacrylate and butyl methacrylate can be used. For example, the amount of methyl methacrylate can be at least 20, 30, 40, 50, 60, 70 or 80 weight percent of the reactants and can be for example less than 99.8, 99, 98, 97, 96, 95, 90, 85 weight percent of the reactants. A second monoethylenically unsaturated ester monomer (e.g. butyl acrylate) can be 0 or greater than 0, 1, 2, 3, 4, 5 weight percent of the reactants and less than 60, 50, 40, 30, 20, or 10 of the reactants. In certain embodiments, additional monoethylenically unsaturated ester monomers may be used. The combination of the second and additional monoethylenically unsaturated monomer(s) taken together in such embodiments is greater than 0, 1, 2, 3, 4, 5 weight percent of the reactants and less than 60, 50, 40, 30, 20, or 10 of the reactants.

[0021] According to certain embodiments one or more additional monounsaturated addition-polymerizable (e.g. monoethylenically unsaturated) monomers may be included. For example, styrene or acrylonitrile could be added. The amount of such additional is preferable less than 10 or 5 weight percent based on weight of the reactants.

[0022] Preferably, the monoethylenically unsaturated ester monomers are selected from methyl methacrylate or a combination of methyl methacrylate and butyl acrylate.

[0023] The reactants further comprise a chain transfer agent (CTA). The chain transfer agent may be any compound known or found to be useful as a chain transfer agent in polymerization of acrylate or methacrylate monomers. For example, thiol chain transfer agents can be used. Examples of such thiol CTAs include monofunctional and polyfunctional thiols. Monofunctional thiols include, but are not limited to, propyl mercaptan, butyl mercaptan, hexyl mercaptan, octyl mercaptan, dodecyl mercaptan, thioglycollic acid, mercaptopropionic acid, alkyl thioglycollates e.g.2-ethyl hexyl thioglycollate or octylthioglycollate, mercaptoethanol, mercaptoundecanoic acid, thiolactic acid, thiobutyric acid. Polyfunctional thiols include trifunctional compounds such as trimethylol propane tris(3-mercaptopropionate), tetrafunctional compounds such as pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetrathioglycollate, pentaerythritol tetrathiolactate, pentaerythritol tetrathiobutyrate;hexafunctional compounds such as dipentaerythritol hexa(3-mercaptopropionate), dipentaerythritol hexathioglycollate; octafunctional thiols such as tripentaerythritol octa(3- mercaptopropionate), tripentaerythritol octathioglycollate. The use of polyfunctional thiols is a useful way to increase the degree of branching in the polymer. Optionally, the chain transfer agent may comprise a mixture of more than one type of compound. According to one embodiment, the CTA is selected from butyl 3-mercaptopropionate (BMP) and pentaerythritol tetrakis(3-mercaptopropionate)(PETMP) . When the CTA is PETMP, about one fourth the

[0024] Alternative chain transfer agents may be any species known to reduce molecular weight in the conventional free-radical polymerization of vinyl monomers. Examples include sulphides, disulphides, halogen-containing species. Also, catalytic chain transfer agents such as cobalt complexes, e.g. cobalt (II) chelates such as cobalt porphyrin compounds are useful chain transfer agents for the invention. Suitable cobalt chelates are known in the art and are described in WO 98 / 04603. A particularly suitable compound is bis(borondifluorodimethylglyoximate) cobaltate (II) also known as CoBF. Catalytic chain transfer agents may be used in relatively low concentrations compared to conventional thiol chain transfer agents, e.g. <0.5% preferably< 0.1% by weight (on monofunctional monomer), since they are generally highly effective at low concentrations. Catalytic chain transfer compounds based on cobalt complexes may be very effectively used at concentrations of less than 0.05% (500 ppm) w, e.g. 0.0001-0.01% w (1-100 ppmw) based on monofunctional monomer in the polymerization process of the present invention to give soluble branched polymers.

[0025] Preferably the chain transfer agent is present in an amount of at least 0.5 weight percent, more preferably at least 1 weight percent, and even more preferably at least 2 weightpercent based on the total amount of reactants. According to some embodiments the amount of chain transfer agent is no more than 10 or 8 or 6 or 5 weight percent based on total weight of the reactants.

[0026] The reactants may further comprise a crosslinker. Inclusion of a crosslinker provides branching in the polymer additive. Preferably, the amount of crosslinker is controlled so that the polymer additive does not crosslink. Preferably, the weight percent of crosslinker is less than or equal to the weight percent of chain transfer agent. Preferably, the weight ratio of chain transfer agent to cross linker is in the range of 1:1 or 1.5:1 to 10:1 based on the weight of chain transfer agent to weight of cross linker. Alternatively, the mole percent of crosslinker is less than the effective mole percent of chain transfer agent. Preferably, the mole ratio of chain transfer agent to cross linker is at least 1.2:1 or 1.4:1 or 1.5:1 or 1.7:1 or 2:1 or 4:1 based on the effective amount of chain transfer agent in moles to the amount of cross linker in moles. As used herein, “the effective amount of chain transfer agent in moles” is based on the number of functional groups on the chain transfer agent. For example, PETMP has four times the number of functional groups as BMP. Therefore, a molar amount of PETMP would have four times the effective amount of a similar molar amount of BMP, i.e., the effective amount of PETMP is four times the actual amount. Similarly, the term “effective mole percent” is also based on the number of functional groups in the chain transfer agent. According to an embodiment the mole ratio of chain transfer agent to cross linker is less than 20:1 or 15:1 or 10:1 based on the effective amount of chain transfer agent in moles to the amount of cross linker in moles.

[0027] The cross linker may be any polyfunctional unsaturated monomer – i.e. any monomer having two or more unsaturated groups available for addition polymerization. Examples of suitable bifunctional monomers include: ethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, allyl (meth)acrylate, divinyl benzene and derivatives thereof. Trifunctional examples include: tripropylene glycol tri(meth)acrylate, trimethylol propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate. Tetrafunctional monomers such as pentaerythritol tetra(meth)acrylate and hexafunctional monomers, e.g. dipentaerythritol hexa(meth)acrylate may also be used. Optionally, the polyfunctional monomermay comprise a mixture of more than one polyfunctional compound. According to one embodiment the crosslinker is

[0028] Preferably the crosslinker is present in an amount of at least 0.1 weight percent, more preferably at least 0.5 weight percent, and even more preferably at least 1 weight percent, based on the total amount of reactants. According to some embodiments the amount of cross linker is no more than 10 weight percent, preferably no more than 8 weight percent, even more preferably not more than 6 weight percent, and still more preferably no more than 5 weight percent based on total weight of the reactants.

[0029] When no crosslinker is present, the amount of chain transfer agent is preferably no more than 5 weight percent based on the total amount of reactants. Larger amounts of chain transfer agents in linear polymers leads to agglomeration of the polymer. Preferably the reactants comprise a crosslinker, which minimizes agglomeration.

[0030] According to certain embodiments the cross linker is BGDMA and the chain train agent is BMP. According to an embodiment the acrylate monomer (e.g. methyl methacrylate or a combination of methyl methacrylate and butyl acrylate) is present in amounts of from 90 to 99 weight percent, the amount of BGDMA is in the range of 1 or 2 to 4 or 3 weight percent and the amount of BMP is in the range of 1 or 2 or 3 to 7 or 6 weight percent based on total weight of acrylate monomer, BGDMA and BMP.

[0031] The polymer additive can be made using any free-radical polymerization method, e.g. solution, suspension, emulsion and bulk polymerization methods may all be used. For example, conventional emulsion polymerization may be used.

[0032] A surfactant or emulsifier may be used. Examples of emulsifiers include non- ionic, anionic and cationic emulsifiers.

[0033] Suitable nonionic emulsifiers are araliphatic or aliphatic nonionic emulsifiers, examples being ethoxylated mono-, di-, and trialkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C4-C10), ethoxylates of long-chain alcohols (degree of ethoxylation: 3 to 100, alkyl radical: C8-C36), and also polyethylene oxide / polypropylene oxide homopolymers andcopolymers. These may comprise the alkylene oxide units copolymerized in random distribution or in the form of blocks. Highly suitable are, for example, ethylene oxide / propylene oxide block copolymers. Preference is given to using ethoxylates of long-chain alkanols (alkyl radical C1-C30, average degree of ethoxylation 5 to 100) and, among these, particular preference to those having a linear C12-C20 alkyl radical and an average degree of ethoxylation of 10 to 50, and also ethoxylated monoalkylphenols.

[0034] Suitable anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C8-C22), of sulfuric monoesters with ethoxylated alkanols (degree of ethoxylation: 2 to 50, alkyl radical: C12-C18) and with ethoxylated alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C4-C9), of alkylsulfonic acids (alkyl radical: C12-C18) and of alkylarylsulfonic acids (alkyl radical: C9-C18). Further suitable emulsifiers are found in Houben- Weyl, Methoden der organischen Chemie, volume XIV / 1, Makromolekulare Stoffe, Georg- Thieme-Verlag, Stuttgart, 1961, pp.192-208. Also suitable as anionic emulsifiers are bis(phenylsulfonic acid) ethers and their alkali metal or ammonium salts which carry a C4-C24alkyl group on one or both aromatic rings. These compounds are common knowledge, from U.S. Pat. No.4,269,749, for example, and are available commercially, in the form for example of Dowfax™ 2A1 (Dow Chemical Company).

[0035] Suitable cationic emulsifiers are preferably quaternary ammonium halides, e.g., trimethylcetylammonium chloride, methyltrioctylammonium chloride, benzyltriethylammonium chloride or quaternary compounds of N-C6-C20-alkylpyridines, -morpholines or -imidazoles, e.g., N-laurylpyridinium chloride.

[0036] Other suitable surfactants or emulsifiers include phosphate surfactants and emulsifiers, such as the SOPROPHOR® phosphate surfactants available from Solvay and the RHODAFAC phosphate emulsifiers (e.g., RHODAFAC RS 610) available from Solvay.

[0037] The amount of emulsifier (or surfactant) can be at least 0.01 or 0.1weight percent to 10 or 5 weight percent, based on the amount of monomers to be polymerized.

[0038] Initiators may be used. Examples of initiators include may be initiated by any suitable method of generating free-radicals such as by thermally induced decomposition of a thermal initiator such as an azo compound, peroxide or peroxyester. Therefore the polymerisation mixture also preferably contains a polymerisation initiator which may be any of those known and conventionally used in free-radical polymerisation reactions. Examples of azoinitiators include azobis(isobutyronitrile) (AIBN), azobis(2-methylbutyronitrile), azobis(2,4- dimethylvaleronitrile), azobis(4-cyanovaleric acid). Examples of peroxide and peroxy initiators include hydrogen peroxide, sodium peroxide, potassium peroxide, t-butyl hydroperoxide, cumene hydroperoxide, dilauroyl peroxide, tert-butyl peroxyneodecanoate, dibenzoyl peroxide, cumyl peroxide, tert-butyl peroxy-2-ethyl hexanoate, tert-butyl peroxy diethyl acetate and tert- butyl peroxy benzoate. Examples of additional initiators include ammonium and / or alkali metal persulfates, sodium perborate, perphosphoric acid and salts thereof, potassium permanganate, and ammonium or alkali metal salts of peroxydisulfuric acid, examples being alkali metal or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert- butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tort-butyl peroxy-2- ethylhexanoate, tert-butyl permaleinate, cumene hydroperoxide, diisopropyl peroxydicarbamate, bis(o-toluoyl)peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile, 2,2'-azobis(2-amidino-propane)dihydrochloride or 2,2'-azobis(2- methylbutyronitrile). Also suitable are mixtures of these initiators. As initiators it is also possible to use reduction / oxidation (i.e., redox) initiator systems. The redox initiator systems are composed of at least one, usually inorganic, reducing agent and one organic or inorganic oxidizing agent. The oxidizing component comprises, for example, the emulsion polymerization initiators already specified above. The reducing component comprises, for example, alkali metal salts of sulfurous acid, such as sodium sulfite, sodium hydrogen sulfite, alkali metal salts of disulfurous acid such as sodium disulfite, bisulfite addition compounds of aliphatic aldehydes and ketones, such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic acid and salts thereof, or ascorbic acid. The redox initiator systems can be used along with soluble metal compounds whose metallic component is able to occur in a plurality of valence states. Typical redox initiator systems are, for example, ascorbic acid / iron(II)sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / Na hydroxymethanesulfinate. The individual components, the reducing component for example, may also be mixtures, an example being a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.

[0039] The amount of initiator is generally at least 0.01 or 0.05 or 0.01 weight percent to0 or 5 or 3 weight percent based on all of the monomers to be polymerized.

[0040] The polymer additive is preferably not cross-linked. For example, this can be demonstrated by evaluating the solubility of the polymers in a solvent such as tetrahydrofuran. A cross-linked polymer will not be soluble.

[0041] Branched polymers according to certain embodiments can be characterized by a polymer branching ratio, g’, of less than 1, 0.95, 0.9, 0.8. According to some embodiments g’ is at least 0.5 or 0.6 or 0.7. The polymer branching ratio (g’) is calculated by comparing measured the intrinsic viscosity of the branched polymer ([η]branched) at each elution volume increment to the intrinsic viscosity of the linear polymer ([η]linear) with the same molecular weight (M) (Eq. 1) in gel permeation chromatography (GPC) analysis. For a linear polymer, g’ value equals to 1 and, for a branched polymer, g’ is smaller than 1. ^^ = ^^^^^^^^^^^^^^^^^^^^^ ^(Eq.1) ^

[0042] Molecular Weight Analysis: The polymer absolute molecular weights (Mw, Mn), PMMA-relative molecular weights (Mw_PMMA, Mn_PMMA), intrinsic viscosity ([η]w, [η]n), and branching ratio (g’) can be measured by gel permeation chromatography with online multi-angle light scattering (MALS) detector, viscometer (VS), and differential refractive index (dRI) detector. For example, the GPC instrument setup can include an Agilent 1200 series HPLC system (degasser, pump, autosampler and column oven), a Wyatt HELEOS II MALS detector, a Wyatt ViscoStar II viscometer, and a Wyatt T-rEX dRI detector. The polymer separation can be carried out on a column set e.g. having two PLgel mixed B LS columns (10 µm particle size, 7.5 x 300 mm length) using tetrahydrofuran (THF) as the mobile phase at a flow rate of 1 mL / min. Column oven temperature is set at 30oC. A set of 10 points PMMA standards (Agilent EasiCal PM-1) is used to calibrate the GPC columns and provide the PMMA-relative molecular weight. The absolute molecular weights are obtained from the MALS detection using Zimm formalism and the intrinsic viscosity data are obtained from the viscometer. High molecular weight fractions data (PMMA-relative molecular weight larger than 6500 Da) are used to calculate average g’ values. For consistency of g’ calculation, a linear PMMA model from Mark-Houwink equation (Eq. 2, where K = 0.0383 mL / g and α = 0.581 for non-BA containing samples in Table 2 and K = 0.03044mL / g and α = 0.615 for BA containing polymers in Table 2) is used to obtain the ([η]linear) in Eq. 1 using the M data from MALS detection. ^^^ = ^^^(Eq.2)

[0043] The weight average molecular weight, Mw, as measured by GPC of the branched polymer is preferably in the range of at least 8000 or 10,000 or 15,000 or 20,000 g / mol. Preferably, the weight average molecular weight is no more than 100,000 or 80,000 g / mol. The number average molecular weight, Mn, of the branched polymer as measured by GPC is preferably at least 3000 or 4000 or 5000 g / mol. Preferably, the number average molecular weight is no more than 50,000 or 40,000 or 30,000, or 20,000 g / mol.

[0044] Preferably, the amount of polymer additive in the composition is at least 1 or 3 or 5 or 10 wt% relative to the total weight of the polyvinyl chloride composition. The composition may be in a concentrated form and then mixed with a polyvinyl chloride resin to get to the desired amount of polymer additive in the composition that is being processed (e.g. extruded, injection molded). In concentrated form, the amount of polymer additive may comprise a significant portion of the composition, for example up to 60 or 50 or 40 weight percent. For use in processing, to get the benefits of higher melt flow index (lower viscosity), the composition may according to certain embodiments comprise the polymer additive in amounts up to 30 or 25 or 20 weight percent.

[0045] The composition may further comprise a filler. The filler may be a single filler or a combination of two or more fillers that differ in at least one property such as type of filler, method of preparation, treatment or surface chemistry, filler composition, filler shape, filler surface area, average particle size, and / or particle size distribution.

[0046] The shape and dimensions of the filler is also not specifically restricted. For example, the filler may be spherical, rectangular, ovoid, irregular, and may be in the form of, for example, a powder, a flour, a fiber, a flake, a chip, a shaving, a strand, a scrim, a wafer, a wool, a straw, a particle, and combinations thereof. Dimensions and shape are typically selected based on the type of the filler utilized, the selection of other components included within the composition, and the end use application of the polymer composite article formed therewith.

[0047] Non-limiting examples of fillers include quartz and / or crushed quartz, aluminum oxide, magnesium oxide, silica (e.g. fumed, ground, precipitated), hydrated magnesium silicate, magnesium carbonate, dolomite, silicone resin, wollastonite, soapstone, kaolinite, kaolin, mica muscovite, phlogopite, halloysite (hydrated alumina silicate), aluminum silicate, sodium aluminosilicate, glass (fiber, beads or particles, including recycled glass, e.g. from wind turbines or other sources), clay, magnetite, hematite, calcium carbonate such as precipitated, fumed, and / or ground calcium carbonate, calcium sulfate, barium sulfate, calcium metasilicate, zinc oxide, talc, diatomaceous earth, iron oxide, clays, mica, chalk, titanium dioxide (titania), zirconia, sand, carbon black, graphite, anthracite, coal, lignite, charcoal, activated carbon, non- functional silicone resin, alumina, silver, metal powders, , magnesium oxide, magnesium hydroxide, magnesium oxysulfate fiber, aluminum trihydrate, aluminum oxyhydrate, coated fillers, carbon fibers (including recycled carbon fibers, e.g. from the aircraft and / or automotive industries), poly-aramids such as chopped KEVLAR™ or Twaron™, nylon fibers, mineral fillers or pigments (e.g. titanium dioxide, non-hydrated, partially hydrated, or hydrated fluorides, chlorides, bromides, iodides, chromates, carbonates, hydroxides, phosphates, hydrogen phosphates, nitrates, oxides, and sulfates of sodium, potassium, magnesium, calcium, and barium); zinc oxide, antimony pentoxide, antimony trioxide, beryllium oxide, chromium oxide, lithopone, boric acid or a borate salt such as zinc borate, barium metaborate or aluminum borate, mixed metal oxides such as vermiculite, bentonite, pumice, perlite, fly ash, clay, and silica gel; rice hull ash, ceramic and, zeolites, metals such as aluminum flakes or powder, bronze powder, copper, gold, molybdenum, nickel, silver powder or flakes, stainless steel powder, tungsten, barium titanate, silica-carbon black composite, functionalized carbon nanotubes, cement, slate flour, pyrophyllite, sepiolite, zinc stannate, zinc sulphide), and combinations thereof. Preferably, the filler is selected from the group consisting of calcium carbonate, glass fibers, carbon fibers, mica, graphite, talc, kaolin, aluminum trihydrate, and combinations thereof. More preferably, the filler comprises talc.

[0048] The filler is present in an amount of at least 1 wt% relative to the total weight of the polyvinyl chloride composition. Preferably, the filler is present in an amount of at least 10 wt%, more preferably of at least 20 wt%, still more preferably at least 30 wt%, even more preferably at least 40 wt%, yet more preferably at least 50 wt%, and still even more preferably at least 60 wt%, relative to the total weight of the polyvinyl chloride composition. The filler ispresent in an amount of 80 wt% or less, preferably 75 wt% or less, relative to the total weight of the polyvinyl chloride composition.

[0049] The composition may further comprise additional additives as are desired for the final product. Examples of such additives include heat stabilizer and / or UV light stabilizers, antioxidants, pigments, and processing aids. According to certain embodiments that additives are selected such that the composition remains transparent. Examples of UV light stabilizers include benzophenones, benzotriazoles, trianzines, benzoxazinones, hindered amine light stabilizer (HALS) and hindered benzoates. Commercially available UV and light stabilizers are exemplified by Cyasorb Light Absorbers, and Light Stabilizers, and Cyasorb Cynergy Solutions from Solvay, TINUVIN FROM BASF, LowLite from Chemtura, OnCap from PolyOne, and Light Stabilizer 210 from E. I. du Pont de Nemours and Company of Delaware, U.S.A. Examples of antioxidants include phenolic antioxidants, and combinations of phenolic antioxidants with phosphites, thioethers or organic sulfides. Phenolic antioxidants include fully sterically hindered phenols and partially hindered phenols; and sterically hindered amines such as tetramethyl-piperidine derivatives. Suitable phenolic antioxidants include vitamin E and IRGANOX™ 1010 from BASF. IRGANOX™ 1010 comprises pentaerythritol tetrakis(3-(3,5-di- t-butyl-4-hydroxyphenyl)propionate).

[0050] The composition may be made by conventional melt compounding process the components.

[0051] The composition is useful in extruding, and injection molding applications due to the favorable melt flow index.

[0052] It has been found that adding the polymer to a polyvinyl chloride resin can reduce the fusion temperature and fusion energy, which directly reduces the amount of energy consumed when producing articles from the polyvinyl chloride compositions according to the present invention. EXAMPLES

[0053] Polymer additives were prepared by emulsion polymerization. The emulsion polymerization is carried out in a 5 liter 4-necked round bottom flask equipped with a mechanical stirrer, heating mantel, thermometer, temperature controller and N2 inlet. To the reactor is charged 1063 parts of deionized water, 6.01 parts of A18 alkyl sulfate surfactant (42%in water) and 0.091 parts of Fe-EDTA complex (as Sequestrene). The contents of the reactor were heated to 75 °C with an N2 sweep. A monomer emulsion is prepared in a separate container with 238.5 parts of deionized water, 24.04 parts of A18 alkyl sulfate surfactant (42% in water), 50 parts of butyl acrylate (BA), 875 parts of methyl methacrylate (MMA), 50 parts of butyl 3- mercaptopropioante (BMP) and 25 parts of 1,4 butanediol dimethacrylate (BGDMA). Mechanical agitation is applied to effect emulsification. The redox initiator system consists of 2 separate solutions. The first is a 2% (by weight) solution of t-butyl hydroperoxide (t-BHP) in water (oxidant) and the second is a 2% (by weight) solution of sodium formaldehyde sulfoxyate (SFS) in water (reductant), both 80 parts total.94.69 parts of the monomer emulsion were added to the reactor vessel and after 1 minute (time zero) simultaneous feeds of the t-BHP and SFS solutions were started at 0.89 parts / minute (both 90 minute feed times). The reactor temperature is maintained at 75 °C for the entire polymerization process. After 15 minutes the rest of the monomer emulsion is fed at 19.46 parts / minute (60 minute feed time). At the end of the monomer feed (total reaction time 75 minutes from time zero) the t-BHP and SFS continued for another 15 minutes (total reaction time 90 minutes from time zero). The reaction is then cooled to 40 °C and filtered through cheesecloth. The emulsion particle size of a polymer made by this method was measured to be 124 nm (by light scattering), the solids content was 39.9% (by gravimetry) and the residual BA and MMA monomers were 27 and 98 ppm respectively (by headspace gas chromatography). Some of the latex is then freeze dried to a powder using dry ice and then a vacuum oven.

[0054] Polymer additives of varying composition were prepared using the process described above. Polymer Additives #2 to 7 varied the amount of butyl acrylate, the amount of chain transfer agent, and amount of crosslinker in the composition, as shown below in Table 1. Table 1 Polymer Compositions Additive MMA (wt%) BA (wt%) BMP (wt%) BGDMA (wt%) PA1 87.5 5 5 2.5 PA2 93.5 0 5 1.5 PA3 92.5 5 2.5 0 PA4 90 5 5 0PA5 85 5 10 0 PA6 91.25 5 2.5 1.25 PA7 80 5 10 5 MMA is methyl methacrylate, BA is butyl acrylate, BMP is butyl 3-mercaptopropionate, and BGDMA is 1,4-butanediol dimethacrylate Polyvinyl Chloride Masterbatch

[0055] A PVC masterbatch was prepared having a composition as shown in Table 2, where the amounts are based on weight in parts per hundred resin. The exemplary polyvinyl chloride master batch powder formulations were prepared by adding the materials in Table 2 sequentially. The dry blends were prepared by adding the PVC at room temperature to a Gunther Papenmeier / Welex blender, ramping the power to 15A, adding the heat stabilizer at 125°F, adding the lubricant package at 150°F, adding the acrylic processing aids and impact modifiers at 170°F, adding CaCO3 at 195°F. After the powder blended was cold to room temperature. Table 2 PVC Masterbatch Amount FORMOSA F662 PVC 100 IMERYS MW100 – CaCO3 300 Heat Stabilizer 10 Ge Chalin DP-6 1.34 Emery Loxiol G-60 1.6 PARALOID™ K125 6.67 PARALOID™ KMX100 6 Total 425.61 PVC Compositions with Polymer Additive

[0056] Polymer compositions comprising the PVC masterbatch and the plastic additives PA1 and PA2 at the weight ratio listed in Table 3 were mixed manually with a spatula in a paper cup, was then fed to a torque rheometer, where the fusion data of plastic additives PA1 and PA2 and PVC masterbatch was collected.

[0057] A control was also prepared with no additive. The formulations are shown in Table 3, where the values are weight percentages based on the total weight of the formulation. Sample Control Ex.1 Ex.2 Ex.3 Ex.4 PVC MB 100 95 95 90 90 PA1- 5 - 10 -PA2- - 5 - 10100 100 100 100 100

[0058] Fusion data was measured by a torque rheometer.80g of Pre-mix of the plastic additive and PVC masterbatch was fed to a torque rheometer at 180°C. Speed of the torque rheometer was 45rpm. The time at which powder started compacting to start fusion process (bottom of the fusion peak) was recorded as compaction time and the torque at that point was recorded at compaction torque. The time at which fusion process was completed (top of the fusion peak) was recorded as fusion time. The consequent torque was recorded as fusion torque. The temperature and energy at the fusion time is also recorded. The equilibrium torque is the value of torque at the end of the fusion test, i.e. at 7 min. The consequent temperature is recorded as equilibrium temperature. All above data is captured by Brabender software on the torque rheometer. As shown in Table 4, the fusion temperature dropped from 182 °C (Control) to as low as 162 °C. Energy also decreased from 12 kmg to 6.5 kmg. Table 4 Compaction Fusion Equilibrium Time Torque Time Torque Temp Energy Torque Temp (min:sec) (sec) (min:sec) (mg) C (kmg) ( mg) C Control 0:54 1300 1:38 5220 182 12.0 3285 203 Ex.1 0:16 5040 0:26 5647 165 7.4 2983 200 Ex.2 0:14 5332 0:22 6020 162 6.5 3043 201 Ex.3 0:26 5066 0:32 5090 171 8.8 2675 197 Ex.4 0:34 5364 174 10.4 2770 199

[0059] In addition to fusion data, capillary viscosity was also measured. The addition of plastic additives PA1 and PA2 lowered the melt viscosity at constant pressure. Melt viscosity was maintained at lower temperatures indicating reduced melt processing tempeartures.

[0060] To determine the effect of the amount of chain transfer agent and crosslinker, plastic additives PA1 and PA3 to PA7 were incorporated into PVC formulations according to Table 5 below, where the values are weights in terms of parts per hundred resin. Table 5 CE1 Ex.5 Ex.6 Ex.7 Ex.8 Ex.9 Ex.10 Oxy 225P 100 100 100 100 100 100 100 PLS 5032 10 10 10 10 10 10 10 F1020 (Int lube) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 AC629A PE Wax (Ext Lube) 1 1 1 1 1 1 1 XL-165F Paraffin Wax (Ext) 0.75 0.75 0.75 0.75 0.75 0.75 0.75 PARALOID™ K-125 4.0 4.0 4.0 4.0 4.0 4.0 4.0 PARALOID™ KM- X100 6.0 6.0 6.0 6.0 6.0 6.0 6.0 CaCO3 (Imerys MW100) 300 300 300 300 300 300 300 PA1 - 50 - - - - - PA3 - - 50 - - - - PA4 - - - 50 - - - PA5 - - - - 50 - - PA6 - - - - - 50 - PA7 - - - - - - 50 Total 423.25 473.25 473.25 473.25 473.25 473.25 473.25

[0061] Fusion data was acquired for the formulations shown in Table 5. As shown below in Table 6, the addition of the plastic additive reduced the fusion temperature and energy in all ofthe samples. Melt viscosity testing further demonstrated a significant drop in melt viscosity, indicating a need to drop processing temperature to main melt viscosity during melt processing. Table 6 Compaction Fusion Equilibrium Time Torque Time Torque Temp Energy Torque Temp (min:sec) (sec) (min:sec) (mg) C (kmg) ( mg) C CE 0:34 1224 1:56 2727 193 16.4 2006 206 Ex.5 0:20 3202 0:48 3345 182 13.8 1817 209 Ex.6 0:22 3370 0:46 3571 184 14.3 1905 211 Ex.7 0:24 3261 0:40 3332 181 11.1 1736 209 Ex.8 0:12 3517 0:28 3393 170 8.0 1551 207 Ex.9 0:24 3491 0:48 3666 185 15.0 1946 212 Ex.10 0:20 3396 0:36 3343 177 10.1 1685 208

[0062] Various loading levels were tested using plastic additive PA7. Formulations were prepared as shown in Table 7. Table 7 CE2 Ex.11 Ex.12 Ex.13 Ex.14 Oxy 225P 100 100 100 100 100 PLS 5032 10 10 10 10 10 F1020 (Int lube) 1.5 1.5 1.5 1.5 1.5 AC629A PE Wax (Ext Lube) 1 1 1 1 1 XL-165F Paraffin Wax (Ext) 0.75 0.75 0.75 0.75 0.75 PARALOID™ K-125 4.0 4.0 4.0 4.0 4.0 PARALOID™ KM-X100 6.0 6.0 6.0 6.0 6.0 CaCO3(Imerys MW100) 300 300 300 300 300PA7 50 30 20 15 Total 423.25 473.25 453.25 443.25 438.25

[0063] As shown below in Table 8, fusion temperature dropped from 193 °C to 181 °C while energy dropped from 19.7 to 11.9 kmg. As loading levels of plastic additive PA7 lowered, the drop in fusion temperature and energy also decreased. Similarly, lower levels of plastic additive PA7 resulted in lower reductions in melt temperature. Table 8 Compaction Fusion Equilibrium Time Torque Time Torque Temp Energy Torque Temp Sample (min:sec) (sec) (min:sec) (mg) C (kmg) ( mg) C CE2 0:24 3382 1:06 3904 193 19.7 2683 215 Ex.11 0:10 3519 0:44 3171 181 11.9 1676 208 Ex.12 0:24 3052 0:56 3591 184 14.5 1945 210 Ex.13 0:24 2714 1:08 3286 188 15.8 2078 211 Ex.14 0:10 2095 1:18 2931 190 14.6 1955 209

Claims

What is claimed is:

1. A polyvinyl chloride composition comprising: a matrix comprising a polyvinyl chloride resin, and a polymer additive which is a reaction product of reactants comprising one or more monoethylenically unsaturated ester monomers, a chain transfer agent in an amount of 0.1 to 10 weight percent, and up to 10 weight percent of a crosslinker, wherein weight percent is based on total amount of reactants.

2. The composition of claim 1 wherein the amount of crosslinker in moles is less than the effective amount of chain transfer agent in moles.

3. The composition of claim 1 or 2 wherein the crosslinker is present in an amount of 0.1 to 8 weight percent based on the total amount of reactants.

4. The composition of any of the preceding claims wherein the polymer additive is not cross-linked.

5. The composition of any of the preceding claims wherein the one or more monoethylenically unsaturated ester monomers has the structure R’-C(O)O-R where R is a hydrocarbyl group of 1 to 12 carbon atoms and R’ is a monoethylenically unsaturated aliphatic group having at least 2 or 3 carbon atoms.

6. The composition of any of the preceding claims wherein the chain transfer agent is selected from the group consisting of propyl mercaptan, butyl mercaptan, hexyl mercaptan, octyl mercaptan, dodecyl mercaptan, thioglycollic acid, mercaptopropionic acid, alkyl thioglycollates, mercaptoethanol, mercaptoundecanoic acid, thiolactic acid, thiobutyric acid, trimethylol propane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetrathioglycollate, pentaerythritol tetrathiolactate, pentaerythritol tetrathiobutyrate; dipentaerythritol hexa(3-mercaptopropionate), dipentaerythritol hexathioglycollate; tripentaerythritol octa(3-mercaptopropionate), tripentaerythritol octathioglycollate, butyl 3- mercaptopropioante, pentaerythritol tetrakis(3-mercaptopropionate) and combinations of two or more thereof.

7. The composition of any of the preceding claims wherein the crosslinker is selected from the group consisting of ethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate,tripropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, allyl (meth)acrylate, divinyl benzene and derivatives thereof, tripropylene glycol tri(meth)acrylate, trimethylol propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate dipentaerythritol hexa(meth)acrylate, 1,4 butanediol dimethacrylate, and combinations of two or more thereof.

8. The composition of any of the preceding claims wherein the amount of crosslinker is from 0.5 to 5 weight percent.

9. The composition of any of the preceding claims wherein the amount of chain transfer agent is from 1 to 5 weight percent.

10. The composition of any of the preceding claims wherein the polymer additive is present in an amount of 1 to 50 weight percent relative to the total weight of the composition.

11. The composition of claim 10 wherein the polymer is present in an amount of 2 to 35 weight percent relative to the total weight of the composition.

12. The composition of any of the preceding claims wherein the polymer is branched.

13. The composition of any of the preceding claims further comprising a filler, wherein the filler is present in an amount ranging from 1 to 80 wt% relative to the total weight of the composition.

14. An article comprising the composition of any one of the preceding claims.

15. A process for reducing the fusion temperature of a polyvinyl chloride resin comprising adding a polymer additive to the polyvinyl chloride resin, wherein the polymer additive is a reaction product of reactants comprising one or more monoethylenically unsaturated ester monomers, a chain transfer agent in an amount of 0.1 to 10 weight percent, and up to 10 weight percent of a crosslinker, wherein weight percent is based on total amount of reactants.

Images