Monobenzoate useful as a plasticizer in plastisol compositions

Abstract

A unique monobenzoate useful as a plasticizer in polymeric dispersions, such as plastisols and melt compounds. The monobenzoate comprises 3-phenyl propyl benzoate, a benzoate ester heretofore known as a flavoring and fragrance agent, but not previously utilized as a plasticizer in polymeric applications. Depending on the application, the advantages rendered by the use of the inventive monobenzoate include, among other things, excellent solvating properties, low viscosity, viscosity stability, and improved rheology, as well as health, safety and environmental advantages over traditional plasticizers. The monobenzoate may be used alone or in combination with a variety of plasticizers, including but not limited to phthalates, terephthalates, dibenzoates, other monobenzoates, or 1,2-cyclohexane dicarboxylate esters, and mixtures thereof.

Claims

1. A plastisol composition comprising: a. a polyvinyl chloride (PVC)-based or an acrylic-based polymer dispersion wherein the acrylic-based polymer is a homopolymer or copolymer of polymethacrylate, aromatic methacrylates, alkylacrylates, or acrylic acid; and b. a plasticizer consisting of 3-phenylpropyl benzoate, wherein the plasticizer provides improved solvation and rheology characteristics and improved gel/fusion temperatures over that achieved with other known high solvating plasticizers used in plastisols.

2. A plasticizer blend for use in plastisol compositions consisting of: 3-phenyl propyl benzoate, diisononyl-1,2-cyclohexane dicarboxylate, and a dibenzoate triblend comprising 20 wt. % of 1,2-propylene glycol dibenzoate and 80 wt % of a 4:1 diethylene glycol dibenzoate:dipropylene glycol dibenzoate.

3. The plasticizer blend of claim 2, wherein the plastisol composition comprises a polyvinyl chloride polymer dispersed in the plasticizer blend.

4. A plasticizer blend for use in plastisol compositions consisting of: 3-phenyl propyl benzoate, di-2-ethylhexyl terephthalate, and a dibenzoate triblend comprising 20 wt % of 1,2-propylene glycol dibenzoate and 80 wt. % of a 4:1 diethylene glycol dibenzoate:dipropylene glycol dibenzoate.

5. The plasticizer blend of claim 4, wherein the plastisol composition comprises a polyvinyl chloride polymer dispersed in the plasticizer blend.

6. A method of plasticizing a polyvinyl chloride (PVC) based-plastisol or an acrylic based-plastisol, comprising the step of: adding 3-phenylpropyl benzoate to a primary plasticizer selected from the group consisting of di-2-ethylhexyl terephthalate, diisononyl-1,2-cyclohexane dicarboxylate, a dibenzoate triblend comprising 20 wt. % of 1,2-propylene glycol dibenzoate and 80 wt. % of a 4:1 diethylene glycol dibenzoate:dipropylene glycol dibenzoate, and mixtures thereof, wherein the PVC-based plastisol comprises a homopolymer or copolymer of polyvinyl chloride, and wherein the acrylic-based plastisol comprises a homopolymer or copolymer of polymethacrylates, aromatic methacrylates, alkylacrylates, or acrylic acid.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows initial viscosity data obtained for the inventive monobenzoate as compared to a dibenzoate triblend and a general purpose phthalate plasticizer, DINP.

(2) FIG. 2 shows the gel/fusion curves for the inventive monobenzoate, a dibenzoate triblend and a general purpose phthalate plasticizer, DINP.

(3) FIG. 3 shows thermogravimetric data for neat plasticizers, including the inventive monobenzoate, DINP, IDB and Eastman's TXIB™.

(4) FIG. 4 reflects volatility data from the ASTM D-1203 Extended Test at 70° C. for the inventive monobenzoate, DINP, and IDB.

(5) FIG. 5 reflects initial, one-day and seven-day viscosities obtained using Brookfield RVT Viscosity, 20 RPM, 23° C. for the inventive monobenzoate, DINP and IDB.

(6) FIG. 6(a) shows rheology data: 1 day scan obtained for a basic plastisol composition comprising the inventive monobenzoate as compared to a dibenzoate triblend (X20, K-FLEX® 975P), BBP, DOTP, DINP and IDB.

(7) FIG. 6(b) shows gel fusion curves for a basic plastisol composition comprising the inventive monobenzoate as compared to a dibenzoate triblend (X20, K-FLEX® 975P), BBP, DOTP, DINP and IDB.

(8) FIGS. 7(a), (b) and (c) reflect tensile strength, modulus, and elongation values, respectively, for a plastisol comprising the inventive monobenzoate as compared to DINP and IDB.

(9) FIG. 8 shows Brookfield viscosities obtained for various plastisol formulations at initial, 1 day, 3 day and 7 day as compared to a control formulation comprising 50 phr DINP.

(10) FIG. 9 shows gel/fusion curves for various plastisol formulations as compared to a control formulation comprising 50 phr DINP.

(11) FIG. 10 shows initial shear data for various plastisol formulations as compared to a control formulation comprising 50 phr DINP.

(12) FIG. 11 shows data from the Brabender heat rise experiment for the inventive monobenzoate.

(13) FIG. 12 shows heat rise experiment data comparing the inventive monobenzoate to DINP.

(14) FIG. 13 shows Brookfield viscosities obtained initially and at 1 day, 3 day and 7 day for plastisol formulations having various concentrations of the inventive monobenzoate (shown as X-613) in combination with a dibenzoate triblend.

(15) FIGS. 14, 15, 16 and 17 show initial, 1 day, 3 day and 7 day shear results obtained for a dibenzoate triblend blend with no and various concentrations (wt. %) of the inventive monobenzoate.

(16) FIGS. 18(a) and (b) show inflection (start of gelation) and G′ Max (peak gelation), respectively, for various concentrations (wt. %) of the inventive monobenzoate in a plasticizer component.

(17) FIG. 19 shows viscosities obtained for DINP, DINCH®, and various 3:2 DINCH®:benzoate blends.

(18) FIGS. 20 and 21 show initial and 1 day shear results obtained for DINP, DINCH® and various 3:2 DINCH®:benzoate blends.

(19) FIG. 22 shows viscosities obtained for DINP, DINCH® and various 2:3 DINCH®:benzoate blends.

(20) FIGS. 23 and 24 show initial and 1 day shear results, respectively, obtained for DINP, DINCH®, and various 2:3 DINCH®:benzoate blends.

(21) FIG. 25 shows viscosities obtained for DINP, DINCH®, and various 1:4 DINCH®:benzoate blends.

DETAILED DESCRIPTION OF THE INVENTION

(22) The present invention is directed to a monobenzoate plasticizer useful for a variety of applications as a primary or secondary plasticizer, including but not limited to plastisols. The monobenzoate plasticizer comprises a unique monobenzoate, 3-phenyl propyl benzoate (3-PPB), not previously known or used as a plasticizer in polymeric applications. The present invention is also directed to a dibenzoate triblend that is useful in blends with other plasticizers, in particular 1,2-cyclohexane dicarboxylate esters, to improve performance properties.

(23) A preferred embodiment of the invention is 3-PPB, alone or in a blend with other plasticizers, in combination with a polymeric dispersion. Another preferred embodiment is 3-PPB blended with a dibenzoate triblend to improve the performance properties of 1,2-cyclohexane dicarboxylate ester plasticizers in a polymeric dispersion. The inventive monobenzoate plasticizer can generally be utilized as a primary plasticizer or a secondary plasticizer in blends with other plasticizers in numerous polymeric dispersions, often as a substitute or alternative for conventional diluent plasticizers having a higher VOC content or plasticizers that do not provide advantageous solvation and rheology.

(24) The present invention is not restricted to any particular polymer, although it may be described in terms of vinyl polymers. Any of the known polymers that can be formulated into a plastisol, melt compound, injection molding, extrusion, or calendaring polymer can be used in combination with novel monobenzoate to prepare a low VOC content composition in accordance with the present invention.

(25) In particular, the plasticizer(s) of the present invention can generally be utilized with numerous thermoplastic, thermoset, or elastomeric polymers often as an alternative for conventional plasticizers. By way of example, the inventive monobenzoate and/or blends thereof may be used to prepare a reduced viscosity PVC, PVC copolymer or acrylic-based plastisol in accordance with the present invention.

(26) Acrylic polymer compositions for various applications may also be used with the plasticizers of the invention and include various polyalkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, or allyl methacrylate; or various aromatic methacrylates, such as benzyl methacrylate; or various alkyl acrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate; or various acrylic acids, such as methacrylic acid and styrenated acrylics.

(27) In addition to PVC and acrylic plastisols, the inventive monobenzoate and/or blends thereof set forth herein may be useful in other polymeric compositions, including but not limited to various vinyl polymers comprising polyvinyl chloride and copolymers thereof, vinyl acetate, vinylidene chloride, diethyl fumarate, diethyl maleate, or polyvinyl butyral; various polyurethanes and copolymers thereof; various polysulfides; cellulose nitrate; polyvinyl acetate and copolymers thereof; and various polyacrylates and copolymers thereof.

(28) Other polymers for which the inventive monobenzoate and/or blends thereof may be useful as a plasticizer include epoxies, phenol-formaldehyde types; melamines; and the like. Still other polymers useful with the plasticizer(s) of the invention will be evident to one skilled in the art.

(29) For purposes of the invention, “plastisol” means a liquid polymer composition comprising a particulate form of at least one non-crosslinked organic polymer dispersed in a liquid phase comprising a plasticizer for the polymer. As used in the invention, “plastisol” also means and includes an “organosol” that is a plastisol in which solvents, such as liquid hydrocarbons, ketones, or other organic liquids, are used in amounts greater than about 5 wt. % to control viscosity and other properties of a plastisol.

(30) As used herein, “high solvator” or “high solvating” is a term that describes the plasticizer's efficiency in penetrating, thickening, and gelling dispersed polymer particles before full physical properties are developed. All of the plasticizer is absorbed into the PVC of a plastisol at lower temperatures than general purpose plasticizers, thus facilitating a faster formation of a homogenous phase.

(31) The novel monobenzoate and other plasticizer blends of the invention may be used as low VOC substitutes for other diluent plasticizers, such as isodecyl benzoate, or as an alternative plasticizer for various traditional polymer dispersions, including without limitation vinyl applications.

(32) The total amount of the inventive monobenzoate and/or other plasticizer blends of the invention that are used in any particular polymeric dispersion would depend on the particular polymer, the characteristics of the polymer and other components, the process, the application or use and the results desired. The total amount of the inventive monobenzoate, 3-PPB, would range broadly depending on the application, generally from about 1 to about 300, desirably from about 10 to about 100, and preferably from about 20 to about 80 parts by weight for every 100 total parts by weight of the one or more thermoplastic, thermoset, or elastomeric polymers, including without limitation those identified above. For 3-PPB, a particularly preferred embodiment for a plastisol would range from about 5 to about 20 parts by weight of 3-PPB for every 100 total parts by weight of the plasticizer, resulting in a total plasticizer content ranging from 30 to 120 phr. Amounts of 3-PPB ranging from 5-10 phr of the total plasticizer content are particularly useful as a viscosity lowering, high solvator in plastisol formulations.

(33) Useful amounts of the plasticizers of the invention are set forth in the examples. It is expected that one skilled in the art would be able to arrive at additional acceptable amounts based on the intended use and desired performance in the particular polymeric application.

(34) The inventive monobenzoate may be, but is not required to be, blended with various other conventional plasticizers to enhance or augment properties of polymeric compositions, including but not limited to improving compatibility and processability in a plastisol and enhancing solvating power. Conventional plasticizers have been described herein and include, but are not limited to, various phthalate esters, phosphate esters, adipate, azelate, oleate, succinate and sebacate compounds, citrates, trimellitates, terephthalate esters such as DOTP, 1,2-cyclohexane dicarboxylate esters, epoxy plasticizers, fatty acid esters, glycol derivatives, sulfonamides, sulfonic acid esters, benzoates, bioplasticizers, such as PG disoyate and PG monosoyate, chloroparaffins, polyesters, and various other hydrocarbons and hydrocarbon derivatives that are often utilized as secondary plasticizers, such as epoxidized soybean oil, and the like. Particularly useful blends include 3-PPB in combination with DOTP, DINP or diisononyl-1,2-cyclohexane dicarboxylate. Another useful blend includes 3-PPB in combination with a unique dibenzoate triblend (comprising DEGDB, DPGDB and 1,2-propylene glycol dibenzoate, further blended with diisononyl-1,2-cyclohexane dicarboxylate. Still another useful blend includes the dibenzoate triblend alone with diisononyl-1,2-cyclohexane dicarboxylate.

(35) Monobenzoates, such as isononyl benzoate, isodecyl benzoate, and 2-ethylhexyl benzoate, as well as 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB™, an Eastman trademark) can also be blended with the inventive monobenzoate, or the 3-PPB can replace any of these with the advantage that less is needed to achieve solvation and maintain processable viscosity and rheology.

(36) The inventive monobenzoate may also be blended with solid plasticizers such as sucrose benzoate, dicyclohexyl phthalate, triphenyl phosphate, glycerol tribenzoate, 1,4-cyclohexane dimethanol (CHDM) dibenzoate, pentaerythritol tetrabenzoate, and alkyl glycol esters.

(37) Other suitable blending plasticizers will be known to one skilled in the art.

(38) The plasticizers of the invention may also be combined with or include various amounts of conventional additives such as oils, diluents, antioxidants, surfactants, heat stabilizers, flame retardants, surfactants, blending resins, fillers, waxes, solvents and the like, depending on the particular application or polymeric dispersion. Additives amounts can generally vary widely and often range from about 0.1 to about 100 parts by weight for every 100 parts by weight of the plastisol composition.

(39) For vinyl applications, there are two different methods of fusing: plastisols and melt compounding. A plastisol is a liquid dispersion of PVC (or other polymer) in plasticizer, which may be heated as a spread coating, fused in slush molding, dip molding or rotationally molded. The plastisols of the invention may be compounded by simple mixing or blending, followed by de-aerating in most instances. Melt compounding is a process that uses heat and pressure while mixing to fuse vinyl (or other polymer). Its overall purpose is to combine the polymer and plasticizer into a homogeneous material which can be formed through a calendar, extruder or injection mold.

(40) Exemplary formulations for simple basic starting plastisols and melt compounds are set forth in the examples; however, the invention is not limited to these formulations.

(41) The inventive monobenzoate and/or blends thereof provide a lower VOC content alternative over secondary and diluent type plasticizers and, depending on the application, provides comparable or better compatibility, viscosity stability, and rheology, among other advantages. In many instances, the inventive monobenzoate outperforms industry standard plasticizers, including traditional and newer dibenzoate blends. Many traditional plasticizers have either high solvating properties or low viscosity, but not both. Surprisingly, the inventive monobenzoate strikes a good balance between high solvating power, better rheology and lower viscosity, even when used alone. In blends, it lowers the viscosity and improves the rheology profile of newer high solvating dibenzoate blends.

(42) There are a large variety of uses for the plastisols and melt compounds of the invention, including but not limited to resilient flooring, wear layers, wall coverings, toys, gloves, and leather and textile applications. Other uses will be known to one skilled in the art.

(43) The invention is further described by the examples set forth herein.

EXAMPLES

(44) Experimental Methodology

(45) Plastisol and Vinyl Preparation:

(46) The plastisols were prepared in a Hobart Model N-50 mixer. A ten minute mix at speed one (1) was used. A high speed disperser was also used to prepare other plastisols evaluated employing a ten minute mix at 1000 RPM's. All of the plastisols were degassed at 1 mmHg until as air free as possible.

(47) The vinyl for the basic screen was fused in a closed mold at a thickness of 1.2 mm at 177° C. for 15 minutes in a Blue M oven.

(48) Tests/Evaluations

(49) The goal was to determine the basic performance parameters of the inventive plasticizer versus known or standard and currently available plasticizers. Tests demonstrating efficiency (Shore A and tensile properties), permanence (extraction and volatility) and processability (viscosity, viscosity stability, rheology, and gel/fusion) were utilized. Unless otherwise indicated in specific examples, the general tests and/or methodologies described below were used. The tests and methods are known to one skilled in the art.

(50) Viscosity and Rheology: Low shear—Viscosity measurements were made using a Brookfield RVT at 20 RPM's for 10 revolutions at 23±2° C. ASTM D1823. High shear—TA AR2000ex used. Parallel plates were set at appropriate gap (350 microns). Shear to 1000 sec.sup.−1. Viscosity Response: Both the initial and 24 hour viscosities were measured.

(51) Gel/Fusion: TA AR2000ex in oscillatory mode. Parallel plates were set at appropriate gap (600 microns). The test temperature was started at 40° C. and heated at a rate of 5° C./minute to 220° C.

(52) Efficiency: Shore A—ASTM D2240; Tensile—ASTM D638, type IV die, 50.8 cm/minute pull rate.

(53) Permanence: Volatility—EPA 24, ASTM D2369 volatility, 110° C. for one hour. A TGA isothermal for one hour under air at 110° C. was also employed. ASTM D1203 was also utilized as an extended test for volatile loss.

Example 1

Basic Plastisol Evaluations—Processability

(54) The following examples show the efficacy of the inventive monobenzoate with a basic starting plastisol formulation described below:

(55) TABLE-US-00001 Material PHR Dispersion Resin, K76, Geon 121 A 100 Plasticizer 70 Ca/Zn stabilizer, Mark 1221 3

(56) The inventive monobenzoate was compared to K-FLEX® 975P (a new dibenzoate triblend (comprising 20 wt. % 1,2-propylene glycol dibenzoate and 80 wt. % of an 80/20 DEG/DPG dibenzoate blend) and DINP. FIG. 1 shows initial viscosity data obtained for the inventive monobenzoate, which compares favorably to a general purpose phthalate and reflects better rheology than the new dibenzoate triblend.

(57) Table 1, below, reflects gel fusion values obtained for 3-PPB, 975 P (shown as X-20 in FIG. 1), and DINP (a general purpose phthalate plasticizer).

(58) TABLE-US-00002 TABLE 1 Initial G′ Maximum G′ × G″ Inflection Temp Modulus Temp Plasticizer Temp (° C.) (° C.) (Pa) (° C.) 3-PPB 57 81 1.6 × 10.sup.6 169 975P 58 87 1.2 × 10.sup.6 168 DINP 79 125 3.5 × 10.sup.5 177

(59) FIG. 2 shows the gel/fusion curves for 3-PPB, 975P (X-20), and DINP.

(60) The results above reflect that 3-PPB is a viable alternative for use in plastisol compositions and is an acceptable partial substitute for general purpose phthalates traditionally used in this type of application. Unexpectedly, 3-PPB has low viscosity, better rheology, and higher solvating properties when used in plastisol applications over both general purpose and other high solvating plasticizers. The 3-PPB also achieved a lower fusion temperature as shown in Table 1 and FIG. 2, which facilitates faster processing times and/or lower energy costs in plastisol applications. These results are consistent with heat rise experiments conducted with melt compounds comparing 3-PPB and DINP as reflected in FIG. 12.

Example 2

Basic Plastisol Evaluations—Processability, Permanence

(61) The basic plastisol formulation of Example 1 was utilized in this example.

(62) The inventive monobenzoate (X-613) was compared to DINP, IDB (isodecyl benzoate), and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB™, an Eastman trademark).

(63) The thermogravimetric data of the neat plasticizers is shown in FIG. 3. The results demonstrate that 3-PPB is significantly less volatile than TXIB™ and IDB, has more permanence and provides a lower VOC alternative over these two plasticizers. An extended test showing volatile loss over 3 days at 70° C. comparing DINP, IDB and 3-PPB is shown in FIG. 4. The results show that 3-PPB is somewhat better than IDB in terms of volatility (permanence) over the three day period.

(64) Initial, one-day and seven-day viscosities obtained for 3-PPB, DINP and IDB are shown in FIG. 5. This data demonstrates a higher viscosity for 3-PPB than that obtained for IDB, but much lower than the phthalate DINP. The data demonstrates that 3-PPB has good solvation properties and lower viscosity as compared to the traditional phthalate and is a viable alternative for plastisol applications. IDB has a lower viscosity, but is a poorer solvator than 3-PPB.

Example 3

Basic Plastisol Evaluation—Rheology and Gel/Fusion

(65) The basic plastisol formulation of Example 1 was utilized in this example.

(66) In this example, 3-PPB (X-613) was compared to DINP, Eastman's TXIB™, DOTP, 975 P (X-20), IDB and BBP (butyl benzyl phthalate). Rheology data (1 day scan) and gel/fusion curves were obtained for the group as reflected in FIGS. 6(a) and 6(b), respectively.

(67) Viscosity for DINP, IDB and 3-PPB remained level, while DOTP and BBP increased slightly and leveled off. The dibenzoate triblend (975 P or X-20) increased rapidly, before leading to “spitting”. The results show that 3-PPB is comparable to IDB and DINP and has superior rheology over X-20, BBP, and DOTP.

(68) Gel fusion data illustrates the relative solvation characteristics of various plasticizers. FIG. 6(b) shows the results of the gel/fusion evaluation, which reflected better results for 3-PPB as compared to X-20 and unexpectedly better than the BBP control that is considered an industry standard. DOTP, DINP, and IDB demonstrated much poorer solvation properties than 3-PPB. 3-PPB is far more efficient than IDB as a solvator, yet viscosity and rheology are not sacrificed.

(69) Overall, the results demonstrated that 3-PPB imparts a combination of excellent rheology and much better solvation properties than many currently available plasticizers.

Example 4

Basic Plastisol Evaluation—Efficiency

(70) Tensile Strength (psi), 100% Modulus (psi) and Elongation (%) values were obtained for DINP, IDB and 3-PPB (X-613). The results obtained are shown in FIGS. 7(a), (b) and (c), respectively, and reflect that 3-PPB is slightly more efficient than IDB overall.

Example 5

Plastisol Wear Layer Evaluations

(71) The basic formulations evaluated are set forth below in Table 2, including blends of DINP and IDB, DINP and 3-PPB, and DINP, IDB and 3-PPB (X-613).

(72) TABLE-US-00003 TABLE 2 Amount (PHR) 10 PHR 10 PHR 5 PHR 5 PHR IDB/ Raw Material Control IDB X613 IDB X613 X613 PVC (Geon 179) 100 100 100 100 100 100 DINP 50 40 40 45 45 40 Isodecyl Benzoate 0 10 0 5 0 5 X613 0 0 10 0 5 5 ESO 5 5 5 5 5 5 Mineral Spirits 5 5 5 5 5 5 Ca/Zn Stabilizer 3.5 3.5 3.5 3.5 3.5 3.5 (Mark 1221)

(73) FIG. 8 shows Brookfield viscosities obtained for the various formulations: initial 1 day, 3 day and 7 day as compared to the control formulation comprising 50 phr DINP. The results show that 3-PPB had higher viscosity initially than IDB, but lower than DINP.

(74) Over time, the viscosity of 3-PPB remained fairly stable, while the formulation having 5 phr IDB increased viscosity as compared to 5 phr 3-PPB.

(75) Gel/Fusion data obtained for the various formulations is shown below in Table 3 and gel/fusion curves are shown in FIG. 9. The results demonstrate that at equal levels, 3-PPB is better than DINP control in terms of relative solvation characteristics and is better than IDB in terms of its relative solvation characteristics.

(76) TABLE-US-00004 TABLE 3 G′ at 500 Pa G′Max G′ × G″ Plastisol (° C.) Temp (° C.) Modulus (Pa) (° C.) DINP (50 PHR) 91 141 4.8 × 10.sup.5 191 10 PHR IDB 87 139 2.8 × 10.sup.5 190  5 PHR IDB 89 140 4.0 × 10.sup.5 191 10 PHR X613 80 134 3.2 × 10.sup.5 188  5 PHR X613 86 137 3.8 × 10.sup.5 190  5 PHR IDB/ 84 136 4.1 × 10.sup.5 190  5 PHR X613

(77) Initial shear results are depicted in FIG. 10. The results show that all of the formulations performed better than the DINP control. The results for 3-PPB reflect that it has a good rheology profile making it a suitable plasticizer for use in plastisol formulations.

(78) The results above establish that 3-PPB is a high solvator having good solvation and lower viscosity than some traditional plasticizers, which make it suitable alone or in combination for use in plastisol applications. Traditionally used diluent plasticizers are also highly volatile, making them poor choices for use in plastisols, in view of increasing regulatory scrutiny. Traditional plasticizers often have excellent solvation or excellent rheology characteristics, but not both. Using blends of DINP (and other plasticizers) with IDB, in particular, is an attempt to achieve good solvation and rheology characteristics through blending. The present invention provides good solvation and rheology characteristics alone. It is also demonstrated to be very useful in blends.

Example 6

Melt Compounding Evaluations

(79) Torque rheometry is a method for measuring real processing conditions of a compound. Heat rise experiments illustrate the differences between the temperatures at which fusion occurs with different plasticizers. The measured torque and temperature curves, along with the physical changes of the compound taking place can be studied. Another point of interest is the relative fusion temperature, which occurs when the stock temperature initially rapidly increases. This temperature indicates the point at which the surface solvation begins to take place, resulting in a considerable increase in torque leading to the generation of fusion in the melt compound. The relative fusion temperature is helpful in determining the solvating characteristics of the plasticizers used in plasticized PVC. From there, an analysis of how different plasticizers affect the processing ability of a PVC melt compound or plastisol can be conducted, to demonstrate how the processing factors of one plasticizer may be more favorable than the other.

(80) Brabender Heat Rise.

(81) The general heat rise formula shown in Table 4 below was weighed out and mixed using a metal spatula, forming a white cake-like powder. A C.W. Brabender Intellitorque® mixer was used for the study. The Brabender was equilibrated at a starting temperature of 40° C. and after being charged with 50 cc of sample, the temperature was ramped at a rate of 3° C./minute up to 200° C. Number 6 roller heads mixed the compound at a speed of 63 rpm with 1 second damping. After loading the chute was closed using a press and a 5 kg weight. Each sample was run until degradation began to occur. The plasticizers evaluated included K-FLEX® PG (referred to as PGDB, 1,2-polyethylene glycol dibenzoate), K-FLEX® 975P (referred to as 975 P or X-20, the new dibenzoate triblend comprising 20 wt. % 1,2-propylene glycol dibenzoate and 80 wt. % of an 80/20 (4:1) blend of DEG/DPG dibenzoate), K-FLEX® 850P (a dibenzoate diblend), X-613 (3-PPB), BBP, DINP, DIDC and DOTP.

(82) The results of the heat rise experiments are shown in Tables 5 and 6.

(83) TABLE-US-00005 TABLE 4 General Brabender heat rise formula Material PHR PVC 100 Plasticizer 50 Stearic Acid 0.5 Ca/Zn Stabilizer 3 Total: 153.5

(84) TABLE-US-00006 TABLE 5 Brabender heat rise data First Torque Peak Fusion Time Torque Temp, Time Torque Temp, Plasticizer (min) (Nm) ° C. (min) (Nm) ° C. X-613 5.6 50 88 42 3 164 PGDB 8.4 45 87 44 4 168 850P 7.9 50 87 44 4 168 975 P 7.9 48 87 45 3 169 BBP 8.5 41 92 42 4 165 DINP 14 36 98 48 3 177 DOTP 16 34 105 48 3 178 DIDC 17 26 105 49 3 182

(85) TABLE-US-00007 TABLE 6 Brabender heat rise data -- Degradation Time Torque Temp Initial Temp (min) (Nm) (° C.) (° C.) X-613 48 2 178 64 PGDB 51 2 183 66 850P 48 3 176 67 975P 48 3 176 67 BBP 46 3 175 69 DINP 48 3 178 83 DOTP 48 3 179 85 DIDC 50 3 182 89

(86) Table 5, above, illustrates the torque, time and temperature for each sample and indicated when the melt flow of the compound was reached. Overall, the benzoates showed faster fusion times than the general purpose plasticizers. Shorter fusion times indicate superior solvating properties of the plasticizer.

(87) Heat rise results of Table 6 indicate the time, torque, and temperature where degradation began to occur for each sample. The time, torque and temperature at which relative fusion occurs are also represented. DINP, DOTP and DIDC had the highest temperatures for relative fusion, indicating lower solvating ability.

(88) FIG. 11 shows Brabender heat rise data for 3-PPB, and FIG. 12 shows Brabender data for 3-PPB compared to DINP. FIG. 12 represents a good demonstration of the high solvating properties of 3-PPB versus general purpose plasticizers. Both compounds were run using the same starting temperatures and the same temperature ramp rate. The difference in their torque values was due to the differences in fusion characteristics that each sample produced. FIG. 12 shows unequivocally that 3-PPB fused quicker than the DINP melt compound. The 3-PPB compound began fusing within the first 5 minutes of starting the run. The DINP compound required a higher temperature and more energy in order to start fusing.

(89) Brabender Isothermal Evaluations—

(90) The same plasticizers tested in the heat rise experiments were tested for the isothermal tests. The formula utilized was modified slightly to include epoxidized soybean oil (ESO) as well as higher levels of stearic acid and plasticizer. The formula is set forth below in Table 7.

(91) Using the formula in Table 7, the raw materials were weighed out and mixed with a metal spatula. In this test, the Brabender Intellitorque® was programmed to remain at a constant temperature of 150° C. The sample volume of 50 cc was loaded in the same manner as in the heat rise tests. The experiments were terminated at the onset of rapid torque increase.

(92) TABLE-US-00008 TABLE 7 General Brabender isothermal formula Material PHR PVC 100 Plasticizer 70 Stearic Acid 0.5 ESO 2 Ca/Zn Stabilizer 1.5 Total: 174

(93) The isothermal test is important because different plasticizers can be analyzed for effect of solvator class too. This experiment simulates actual processing conditions better and can be used to rank the ability of the plasticizers to facilitate the processing of vinyl. The data below in Table 8 show very little distinction between the various high solvating and general purpose plasticizers that were tested, as the melt compounds fused very rapidly, because they were subjected to such a high temperature for the entire test. None of the samples underwent degradation during their test times.

(94) The results of the melt compounding evaluations show that 3-PPB is compatible in PVC melt compounding applications and has excellent solvating properties compared to the dibenzoate blends and general purpose plasticizers.

(95) TABLE-US-00009 TABLE 8 Isothermal Brabender data MaxTorque Plasticizer (Nm) X-613 9 PGDB 11 850P 11 975P 12 BBP 10 DINP 8 DOTP 7 DIDC 6

Example 7

Monobenzoate/Dibenzoate Blends

(96) Evaluations of blends of the inventive monobenzoate, 3-PPB (X-613), with a unique dibenzoate triblend (K-FLEX® 975 P) were conducted.

(97) A control plastisol comprising 70 phr K-FLEX® 975P was compared to plastisols comprising 3.5 (5 wt. %), 7 (10 wt. %) and 10.5 phr (15 wt. %) X-613 in combination with 66.5, 63, and 59.5 phr of K-FLEX® 975P, respectively. The formulations evaluated are set forth below in Table 9.

(98) TABLE-US-00010 TABLE 9 5 wt. % 10 wt. % 15 wt. % Raw materials Control (phr) X-613 (phr) X-613 (phr) X-613 (phr) Geon 121 A 100 100 100 100 K-Flex ® 975P 70 66.5 63 59.5 X-613 — 3.5 7 10.5 Mark 1221 3 3 3 3 Totals 173 173 173 173

(99) FIG. 13 shows Brookfield viscosities obtained for the various formulations initially, and at days 1, 3 and 7. Overall, the addition of X-613 to the dibenzoate triblend, K-FLEX® 975 P, resulted in fairly stable viscosities over time regardless of the amount of monobenzoate included in the formulation. Viscosities obtained for the formulation having no monobenzoate are slightly higher than for formulations having various concentrations of X-613.

(100) FIGS. 14-17 reflect the initial, one-day, three-day, and seven-day shear results obtained for the various formulations. The formulations containing the inventive monobenzoate, X-613, showed lower viscosity increase with increasing shear as compared to the control with no X-613, thus confirming good rheology and improved processability of the plastisol with the added inventive monobenzoate. Formulations containing 15 wt. % monobenzoate showed exceptionally good rheology as compared to the control.

(101) FIGS. 18(a) and (b) show the gel/fusion results for the various formulations. All formulations containing the inventive monobenzoate, 3-PPB (X-613), had lower inflection (start of gelation) and lower G′ Max (peak gelation) as compared to the control. These results show that adding the inventive monobenzoate improved the solvating characteristics of the dibenzoate triblend.

Example 8

Monobenzoate/Dibenzoate/DINCH® Blends

(102) Additional evaluations were conducted with a variety of basic plastisol formulations containing one or more of DINP (diisononyl phthalate), K-FLEX® 975 P, Hexamoll® DINCH® (diisononyl-1,2-cyclohexane dicarboxylate; a registered trademark of BASF SE, FED. REP. Germany), and the inventive monobenzoate, X-613. The formulations evaluated are set forth in Table 10, below.

(103) TABLE-US-00011 TABLE 10 Formulation Raw Materials PHR Wt. % 100% DINP Geon 121 A 100 57.8 DINP 70 40.5 Mark 1221 3 1.7 Totals 173 100 100% DINCH Geon 121 A 100 57.8 DINCH 70 40.5 Mark 1221 3 1.7 Totals 173 100 100% X-613 Gaon 121 A 100 57.8 X613 70 40.5 Mark 1221 3 1.7 Totals 173 100 60:40 DINCH/975P Geon 121A 100 57.8 DINCH 42 24.3 975P 28 16.2 Mark 1221 3 1.7 Totals 173 100 60:40 DINCH/(15:85 X- Geon 121 A 100 57.8 613/975P) DINCH 42 24.3 X613 4.2 2.4 975 P 23.8 13.8 Mark 1221 3 1.7 Totals 173 100 60:40 DINCH/(5:95 X- Geon 121 A 57.8 57.8 613/975P) DINCH 42 24.3 X613 1.4 0.8 975 P 26.6 15.4 Mark 1221 3 1.7 Totals 173 100 40:60 DINCH/975P Geon 121 A 100 57.8 DINCH 28 16.2 975 P 42 24.3 Mark 1221 3 1.7 Totals 173 100 40:60 DINCH/X-613 Geon 121 A 100 57.8 DINCH 28 16.2 X613 42 24.3 Mark 1221 3 1.7 Totals 173 100 40:60 DINCH/(15:85 X- Geon 121 A 100 57.8 613/975P) DINCH 28 16.2 X613 6.3 3.6 975 P 35.7 20.6 Mark 1221 3 1.7 Totals 173 100 40:60 DINCH/(5:95 X- Geon 121 A 100 57.8 613/975P) DINCH 28 16.2 X613 2.1 1.2 975 P 39.9 23.1 Mark 1221 3 1.7 Totals 173 100 20:80 DINCH/975 P Geon 121 A 100 57.8 DINCH 14 8.1 975 P 56 32.4 Mark 1221 3 1.7 Totals 173 100 20:80 DINCH/X-613 Geon 121 A 100 57.8 DINCH 14 8.1 X613 56 32.4 Mark 1221 3 1.7 Totals 173 100 20:80 DINCH/(15:85 X- Geon 121 A 100 57.8 613/975P) DINCH 14 8.1 X613 8.4 4.9 975 P 47.6 27.5 Mark 1221 3 1.7 Totals 173 100

(104) FIG. 19 shows the viscosities obtained for formulations comprising 100% DINP and DINCH® and for three 3:2 (60:40) DINCH® blends, one comprising 975 P alone, another comprising a 3:17 (15:85) blend of X-6131975P, and the third comprising a 1:19 (5:95) blend of X-6131975P. Results for the blends containing the inventive monobenzoate, X-613, and the dibenzoate triblend were only slightly higher than with DINCH® alone, particularly at the 15 wt. % concentration of X-613 in the dibenzoate triblend blended with DINCH®, and were lower than that obtained for the general purpose plasticizer, DINP.

(105) FIGS. 20 and 21 show initial and one-day shear results obtained for the three, 3:2 DINCH® blends above as compared to DINP and DINCH® alone. Results show comparable rheology profiles, initially and at one-day, for the 3:2 DINCH®:benzoate blends as compared to DINP and DINCH® alone. X-613 in the blend with 975P (triblend) had a better rheology profile than DINP, which is the industry benchmark for plasticizer performance. DINCH® achieved slightly lower viscosities alone, but its gel fusion properties without the inclusion of high solvators was really poor. X-613 contributed both solvating properties and good rheology to the blends.

(106) FIG. 22 shows viscosity results obtained for formulations containing 100% DINP and DINCH® as compared to four 2:3 (40:60) DINCH®/Benzoate blends. Viscosity results for the 2:3 DINCH®:benzoate blends containing the dibenzoate triblend alone and in combination with X-613 were very comparable to that obtained for the general purpose plasticizer DINP. Viscosity results obtained for a 2:3 DINCH®:X-613 (100%) blend were lower than that obtained for DINCH.

(107) FIGS. 23 and 24 show initial and one-day shear results obtained for DINP, DINCH®, and 2:3 DINCH®:benzoate blends, one of which comprised the dibenzoate triblend (975 P) alone and two of which comprised the dibenzoate triblend in combination with 5 wt. % and 15 wt. % X-613. Overall, the DINCH®:benzoate blends had similar rheology to DINCH® and DINP alone, albeit at higher viscosities. The 2:3 DINCH:benzoate blend comprising 15 wt. % X-613 in the dibenzoate triblend performed as well as DINP or DINCH®. All of the blends performed comparably and no worse than DINP alone. All of the blends exhibited reasonable viscosity and were processable. Moreover, when the inventive monobenzoate, X-613, was used alone with the DINCH® very good stability resulted.

(108) FIG. 25 shows viscosity results obtained for formulations comprising 100% DINP and DINCH®, and for three 1:4 DINCH®:benzoate blends, one comprising the dibenzoate triblend alone, another comprising the inventive monobenzoate (X-613) alone, and the other comprising a blend of the dibenzoate triblend and the monobenzoate. Viscosities rose over time for the 1:4 DINCH®:benzoate blends as compared to the lower rise in viscosity for DINP and DINCH®. The 1:4 DINCH®:X-613 blend showed very comparable viscosity to DINCH® alone.

(109) The results above demonstrated that the inventive monobenzoate alone, or in combination with the dibenzoate triblend, or the dibenzoate triblend alone, are better solvators that can improve the compatibility in plastisols of poorer solvators, such as DINP and DINCH®. In plastisols, the inventive monobenzoate alone tended to exhibit lower viscosities than the general purpose type plasticizers. The dibenzoate triblend (975P) demonstrated higher viscosities than the monobenzoate and general purpose plasticizer controls, but showed much better gel/fusion characteristics than the general purpose plasticizers. When the inventive monobenzoate is blended with the triblend, the viscosity was lowered and rheology was improved. All of the plastisols using the plasticizers of the invention achieved processable viscosities.

(110) In accordance with the patent statutes, the best mode and preferred embodiments have been set forth; the scope of the invention is not limited thereto, but rather by the scope of the attached claims.