TECHNICAL FIELD

[0001] The present disclosure relates generally to the field of masterbatch compositions. More particularly, the present disclosure provides a masterbatch composition for improving paintability of polyolefins. Another aspect of the present disclosure provides a paintable polyolefin composition.

BACKGROUND

[0002] Background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.

[0003] Improving paintability of polyolefins has been a subject of rigorous research at least for a decade if not more. The current approaches to improve paintability of the polyolefins rely on introducing/incorporating polar group into the polyolefin (such as polypropylene) backbone to increase its hydrophilicity, common strategies being used there for includes: grafting of hydrophilic monomers such as acrylics, acrylates, alcohols and the likes onto the polyolefin backbone, blending of polar polymers with non-polar polyolefins, addition of fillers and surface irradiation. However, these strategies/techniques suffer from several-fold shortcomings, including, but not limited to, (i) presence of unreacted monomers in the final product requiring additional removal steps, (ii) presence of higher quantity of reactive monomers in the product resulting in corrosion of the processing equipments, (iii) requirement of usage of compatibilizer(s), which may make the polymer translucent or opaque affecting its aesthetics while increasing the density of the polymer (and hence, weight of the final product), (iv) difficulty in performing on the uneven surfaces, often requiring additional pre-treatment(s) of such surfaces, such as irradiation.

[0004] Consequently, there is a persistent need in the state of the art for a masterbatch composition for improving paintability of polyolefins that alleviates, at least in part, one or more shortcomings associated with the conventional strategies, precluding the necessity of reactive grafting, usage of acidic monomers, fillers or surface irradiation.

[0005] Each of the documents referred in the background section are incorporated herein, in its entirety, by way of reference. Further, none of the abovementioned documents are to be construed as relevant prior-art for the invention as embodied in the present disclosure. The sole intention of referring to and providing the abovementioned documents is to highlight some of the work already done in the technical field of paintable polyolefin.

OBJECTS OF THE INVENTION

[0006] An object of the present disclosure is to provide a masterbatch composition for improving paintability of polyolefins that alleviates one or more shortcomings of the state-of- art.

[0007] Another object of the present disclosure is to provide a masterbatch composition for improving paintability of polyolefins that does not necessitates reactive grafting, usage of acidic monomers, fillers or surface irradiation.

[0008] Another object of the present disclosure is to provide a masterbatch composition for improving paintability of polyolefins that is easy to manufacture and economical.

[0009] Further object of the present disclosure is to provide a masterbatch composition for improving paintability of polyolefins that is universal in nature and can be readily mixed in suitable proportion with wide varieties of polyolefins.

[0010] Other objects of the present invention will be apparent from the description of the invention herein below.

SUMMARY

[0011] The present disclosure relates generally to the field of masterbatch compositions. More particularly, the present disclosure provides a masterbatch composition for improving paintability of polyolefins. Another aspect of the present disclosure provides a paintable polyolefin composition.

[0012] An aspect of the present disclosure provides a masterbatch composition for improving paintability of polyolefin, said composition comprising: a poly(diacetone acrylamide) (PDAAM) in an amount ranging from 60% to 95% by weight of the composition; and a surfactant in an amount ranging from 5% to 40% by weight of the composition.

[0013] In an embodiment, the poly(diacetone acrylamide) has molecular weight ranging from 5000 to 10000 gm/mol and PDI ranging from 1.5 to 1.7. In an embodiment, the poly(diacetone acrylamide) has glass transition temperature (T _g ) ranging from 94°C to 97°C. In an embodiment, the surfactant is a non-ionic surfactant. In an embodiment, the surfactant is Tween-20. In an embodiment, the polyolefin is any or a combination of polypropylene and polyethylene.

[0014] In an embodiment, the composition comprises: (i) poly(diacetone acrylamide) in an amount ranging from 60% to 95% by weight of the composition; and (ii) Tween-20 in an amount ranging from 5% to 40% by weight of the composition.

[0015] Another aspect of the present disclosure provides a paintable polyolefin composition, said composition comprising: (i) a carrier polymer in an amount ranging from 85% to 99% by weight of the composition, said polymer being a polyolefin; and (ii) a masterbatch, said masterbatch comprising: a poly (diacetone acrylamide) (PDAAM) in an amount ranging from 60% to 95% by weight of the masterbatch; and a surfactant in an amount ranging from 5% to 40% by weight of the masterbatch. In an embodiment, the composition includes said masterbatch in an amount ranging from 1% to 15% by weight of the composition.

BRIEF DESCRIPTION OF DRAWINGS

[0016] The accompanying drawings are included to provide a further understanding of the present disclosure, and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments of the present disclosure and, together with the description, serve to explain the principles of the present disclosure.

[0017] FIG. 1 illustrates an exemplary FTIR spectra of diacetone acrylamide monomer and poly(diacetone acrylamide) prepared in accordance with an embodiments of the present disclosure.

[0018] FIG. 2 illustrates an exemplary thermogravimetric analysis (TGA) of diacetone acrylamide monomer and poly(diacetone acrylamide) prepared in accordance with an embodiments of the present disclosure.

[0019] FIG. 3 illustrates an exemplary differential scanning calorimetric (DSC) analysis of diacetone acrylamide monomer and poly (diacetone acrylamide) prepared in accordance with an embodiments of the present disclosure.

[0020] FIG. 4 illustrates exemplary snippets showing results of the paintability of different polypropylene samples prepared in accordance with embodiments of the present disclosure.

[0021] FIG. 5 illustrates exemplary snippets showing results of the paintability of different polypropylene samples prepared in accordance with embodiments of the present disclosure. DETAILED DESCRIPTION

[0022] The following is a detailed description of embodiments of the disclosure depicted in the accompanying drawings. The embodiments are in such detail as to clearly communicate the disclosure. However, the amount of detail offered is not intended to limit the anticipated variations of embodiments; on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure as defined by the appended claims.

[0023] Each of the appended claims defines a separate invention, which for infringement purposes is recognized as including equivalents to the various elements or limitations specified in the claims. Depending on the context, all references below to the “invention” may in some cases refer to certain specific embodiments only. In other cases it will be recognized that references to the “invention” will refer to subject matter recited in one or more, but not necessarily all, of the claims.

[0024] As used in the description herein and throughout the claims that follow, the meaning of “a,” “an,” and “the” includes plural reference unless the context clearly dictates otherwise. Also, as used in the description herein, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise.

[0025] All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g. “such as”) provided with respect to certain embodiments herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

[0026] Various terms as used herein are shown below. To the extent a term used in a claim is not defined below, it should be given the broadest definition persons in the pertinent art have given that term as reflected in printed publications and issued patents at the time of filing.

[0027] The term “Polyolefin” as used herein throughout the present disclosure denotes the group of polymers typically formed by the polymerization of olefin monomeric units (or monomers) having a general formula C _n H2 _n . Examples of the polyolefins include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very-low-density polyethylene (VLDPE), ultra-low-density polyethylene (ULDPE), medium-density polyethylene (MDPE), polypropylene (PP), polymethylpentene (PMP), polybutene- 1 (PB-1); ethylene-octene copolymers, stereo-block polypropylene, olefin block copolymers, propylene-butane copolymers, polyisobutylene (PIB), poly(a-olefin), ethylene propylene rubber (EPR) and EPDM rubber, but not limited thereto.

[0028] The term “poly(diacetone acrylamide)” as used herein throughout the present disclosure denotes the polymer formed by the polymerization of diacetone acrylamide monomeric units (or monomers).

[0029] The present disclosure relates generally to the field of masterbatch compositions. More particularly, the present disclosure provides a masterbatch composition for improving paintability of polyolefins. Another aspect of the present disclosure provides a paintable polyolefin composition.

[0030] An aspect of the present disclosure provides a masterbatch composition for improving paintability of polyolefin, said composition comprising: a poly(diacetone acrylamide) (PDAAM) in an amount ranging from 60% to 95% by weight of the composition; and a surfactant in an amount ranging from 5% to 40% by weight of the composition.

[0031] In an embodiment, the poly(diacetone acrylamide) has molecular weight ranging from 500 to 100000 gm/mol, preferably, ranging from 2000 to 25000 gm/mol, and more preferably, ranging from 5000 to 10000 gm/mol.

[0032] In an embodiment, the poly(diacetone acrylamide) has polydispersity index (PDI) ranging from 1.2 to 1.9, preferably, ranging from 1.3 to 1.8, and more preferably, ranging from 1.5 to 1.7.

[0033] In an embodiment, the poly(diacetone acrylamide) has glass transition temperature (Tg) ranging from 94°C to 97 °C when measured using Differential Scanning Calorimetry (DSC).

[0034] In an embodiment, the surfactant is a non-ionic surfactant such as fatty alcohol ethoxylates like narrow-range ethoxylate, octaethylene glycol monododecyl ether and pentaethylene glycol monododecyl ether; alkylphenol ethoxylates like Nonoxynols and Triton X-100; fatty acid ethoxylates; ethoxylated amines and fatty acid amides like polyethoxylated tallow amine, cocamide monoethanolamine and cocamide diethanolamine; terminally blocked ethoxylates like poloxamers; fatty acid esters of polyhydroxy compounds; fatty acid esters of glycerol like glycerol monostearate and glycerol monolaurate; fatty acid esters of sorbitol like sorbitan monolaurate, sorbitan monostearate, sorbitan tristearate, Tween 20, Tween 40, Tween 60, Tween 80; fatty acid esters of sucrose; alkyl polyglucosides like decyl glucoside, lauryl glucoside and octyl glucoside and the likes. In an embodiment, the surfactant is Tween-20.

[0035] In an embodiment, the composition comprises: (i) poly(diacetone acrylamide) in an amount ranging from 60% to 95% by weight of the composition; and (ii) Tween-20 in an amount ranging from 5% to 40% by weight of the composition.

[0036] The masterbatch composition of the present disclosure can serve as a universal masterbatch composition for improving paintability of wide variety of polyolefins. During experimentation, it could be noted that addition of the masterbatch composition of the present disclosure affords improvement in paintability by 15% to as high as 90% without requirement of grafting of hydrophilic monomers on the PP backbone, without affecting aesthetic properties of the polymer and precluding the need of surface treatment such as surface irradiation.

[0037] Accordingly, another aspect of the present disclosure provides a paintable polyolefin composition, said composition comprising: (i) a carrier polymer in an amount ranging from 85% to 99% by weight of the composition, said polymer being a polyolefin; and (ii) a masterbatch, said masterbatch comprising: a poly(diacetone acrylamide) (PDAAM) in an amount ranging from 60% to 95% by weight of the masterbatch; and a surfactant in an amount ranging from 5% to 40% by weight of the masterbatch.

[0038] In an embodiment, the composition includes said masterbatch in an amount ranging from 1% to 15% by weight of the composition.

[0039] In an embodiment, the composition includes: said carrier polymer in an amount ranging from 85% to 99% by weight of the composition; and said masterbatch in an amount ranging from 1% to 15% by weight of the composition.

[0040] In an embodiment, the composition comprises: (i) a carrier polymer in an amount ranging from 85% to 99% by weight of the composition, said polymer being a polyolefin; and (ii) the rest being a masterbatch, said masterbatch comprising: a poly(diacetone acrylamide) (PDAAM) in an amount ranging from 60% to 95% by weight of the masterbatch; and a surfactant in an amount ranging from 5% to 40% by weight of the masterbatch.

[0041] In an embodiment, the paintable polyolefin composition comprises: (i) a carrier polymer in an amount ranging from 85% to 99% by weight of the composition, said polymer being a polyolefin; (ii) poly(diacetone acrylamide) in an amount ranging from 1% to 15% by weight of the composition; and (iii) a surfactant in an amount ranging from 0.1% to 5% by weight of the composition. [0042] In an embodiment, the carrier polymer is one or a combination of polyolefins. Polyolefins may include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very-low-density polyethylene (VLDPE), ultra-low-density polyethylene (ULDPE), medium-density polyethylene (MDPE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1); ethylene-octene copolymers, stereo-block polypropylene, olefin block copolymers, propylene-butane copolymers, polyisobutylene (PIB), poly(a-olefin), ethylene propylene rubber (EPR) and EPDM rubber, but not limited thereto. In an embodiment, the carrier polymer includes any or a combination of polyethylene (PE), polypropylene (PP) and co-polymers thereof.

[0043] In an embodiment, the poly(diacetone acrylamide) has molecular weight ranging from 500 to 100000 gm/mol, preferably, ranging from 2000 to 25000 gm/mol, and more preferably, ranging from 5000 to 10000 gm/mol. In an embodiment, the poly(diacetone acrylamide) has polydispersity index (PDI) ranging from 1.2 to 1.9, preferably, ranging from 1.3 to 1.8, and more preferably, ranging from 1.5 to 1.7. In an embodiment, the poly(diacetone acrylamide) has glass transition temperature (Tg) ranging from 94°C to 97°C when measured using Differential Scanning Calorimetry (DSC).

[0044] In an embodiment, the surfactant is a non-ionic surfactant such as fatty alcohol ethoxylates like narrow-range ethoxylate, octaethylene glycol monododecyl ether and pentaethylene glycol monododecyl ether; alkylphenol ethoxylates like Nonoxynols and Triton X-100; fatty acid ethoxylates; ethoxylated amines and fatty acid amides like polyethoxylated tallow amine, cocamide monoethanolamine and cocamide diethanolamine; terminally blocked ethoxylates like poloxamers; fatty acid esters of polyhydroxy compounds; fatty acid esters of glycerol like glycerol monostearate and glycerol monolaurate; fatty acid esters of sorbitol like sorbitan monolaurate, sorbitan monostearate, sorbitan tristearate, Tween 20, Tween 40, Tween 60, Tween 80; fatty acid esters of sucrose; alkyl polyglucosides like decyl glucoside, lauryl glucoside and octyl glucoside and the likes. In an embodiment, the surfactant is Tween-20.

[0045] While the foregoing describes various embodiments of the invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof. The scope of the invention is determined by the claims that follow. The invention is not limited to the described embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the invention when combined with information and knowledge available to the person having ordinary skill in the art. EXAMPLES

[0046] Preparation of poly(diacetone acrylamide) and characterization thereof

[0047] A sample of poly(diacetone acrylamide) was prepared by precipitation polymerization technique using thermal initiation using water as the continuous media. Diacetone acrylamide was dissolved in water to maintain solid content of about 30% and purged with nitrogen for 1 hr. Temperature was raised to 80°C and thereafter, mode of nitrogen addition was changed from purging to blanketing type. After reaching the desired temperature, initiator (potassium persulphate) was added (0.5% by wt. of monomer). Stirring speed throughout process was maintained at about 200 rpm. As the reaction progressed, poly(diacetone acrylamide) got precipitated; which was separated once no further precipitation could be observed. To be on a better conversion side, reaction was further progressed for 30 min and then the reaction was subjected to cooling and subsequent product separation. Separated product was washed with water (3 times) and dried in hot air oven at about 105°C for about 5 hours. The sample so prepared was labeled as “PDAAM-1”.

[0048] FIG. 1 illustrates an exemplary FTIR spectra of diacetone acrylamide monomer and poly(diacetone acrylamide) prepared above (PDAAM-1), wherein conversion of diacetone acrylamide (DAAM) monomers to poly(diacetone acrylamide) (PDAAM) was confirmed by observation of decrease in the intensity of C=C peak at 1620 cm’ ¹ . FIG. 2 illustrates an exemplary thermogravimetric analysis (TGA) of diacetone acrylamide monomer and poly(diacetone acrylamide) prepared above, wherein as can be seen from the graph, with polymerization, improvement in the thermal stability could be observed. FIG. 3 illustrates an exemplary differential scanning calorimetric analysis (DSC) of diacetone acrylamide monomer and poly(diacetone acrylamide) prepared above, wherein as can be seen from the graph, diacetone acrylamide (DAAM) exhibited Melting at the temperature of about 56°C, whereas poly(diacetone acrylamide) exhibited Tg of about 95.87°C confirming polymerization.

[0049] Four different samples of poly(diacetone acrylamide) were prepared and each of them were subjected to Gel Permeation Chromatography (GPC) for characterizing molecular weights. Results are shown in the Table 1 below, wherein it can be observed that the samples had molecular weight in the range of 5600 Mn to 9500 Mw with PDI ranging from about 1.52 to 1.66. Table 1: Gel Permeation Chromatography (GPC) of PDAAM samples

[0050] Preparation of masterbatch compositions

[0051] Masterbatch compositions were prepared by uniformly mixing Tween-20 (surfactant) with poly(diacetone acrylamide) prepared above (PDAAM- 1), compositions whereof are provided in Table 2 below:

Table 2: Masterbatch compositions

[0052] Preparation of paintable polyolefin compositions [0053] Paintable polyolefin compositions were prepared by uniformly mixing the masterbatch compositions prepared above with polypropylene (as a carrier polymer, MANGPOL PP HM012T, obtainer commercially from Mangalore Refinery and Petrochemicals Limited), compositions whereof are provided in Table 3 below, wherein PTPP-1 was prepared by addition of PDTN-1 to Carrier PP, PTPP-2 was prepared by addition of PDTN-2 to Carrier PP and PTPP-3 was prepared by addition of PDTN-3 to Carrier PP:

Table 3: Paintable Polypropylene Compositions

[0054] Each of the paintable polyolefin compositions prepared above were then subjected to extrusion and paintability thereof were assessed and contact angle, surface and volume resistance, tensile strength (MPa), Elongation at yield (%), Impact resistance (J/m), MFI (gm/10 minutes), Tg (°C), Tc (°C) and Tm (°C) were measured, results whereof are provided in Table 4 and Table 5 below:

Table 4: Characteristics of the Paintable Polypropylene Compositions

Table 5: Characteristics of the Paintable Polypropylene Compositions [0055] Paintability of each of the samples prepared above versus carrier PP is illustrated in FIG. 4.

[0056] OPTIMIZATION OF PAINTABLE POLYPROPYLENE COMPOSITIONS

[0057] Samples of paintable polypropylene compositions were prepared by mixing different amounts of masterbatch composition PDTN-1, prepared above with carrier polypropylene (as a carrier polymer, MANGPOL PP HM012T), compositions whereof are provided in Table 6 below:

Table 6: Paintable Polypropylene Compositions [0058] Each of the paintable polyolefin compositions prepared above were then subjected to extrusion and paintability thereof were assessed and contact angle, surface and volume resistance, tensile strength (MPa), Elongation at yield (%), Impact resistance (J/m), MFI (gm/10 minutes), Tg (°C), Tc (°C) and Tm (°C) were measured, results whereof are provided in Table 7 and Table 8 below: Table 7: Characteristics of the Paintable Polypropylene Compositions

Table 8: Characteristics of the Paintable Polypropylene Compositions

[0059] Paintability of each of the samples prepared above versus carrier PP is illustrated in FIG. 5.

[0060] Although the subject matter has been described herein with reference to certain preferred embodiments thereof, other embodiments are possible. As such, the spirit and scope of the appended claims should not be limited to the description of the preferred embodiment contained therein. Furthermore, precise and systematic details on all above aspects are currently being made. Work is still underway on this invention. It will be obvious to those skilled in the art to make various changes, modifications and alterations to the invention described herein. To the extent that these various changes, modifications and alterations do not depart from the scope of the present invention, they are intended to be encompassed therein.

ADVANTAGES

[0061] The present disclosure provides a masterbatch composition for improving paintability of polyolefins that alleviates one or more shortcomings of the state-of-art.

[0062] The present disclosure provides a masterbatch composition for improving paintability of polyolefins that does not necessitate reactive grafting, usage of acidic monomers, fillers or surface treatment such as surface irradiation.

[0063] The present disclosure provides a masterbatch composition for improving paintability of polyolefins that is easy to manufacture and economical.

[0064] The present disclosure provides a masterbatch composition that is universal in nature and can be readily mixed in suitable proportion with wide varieties of polyolefins.