USOO9388293B2

(12) United States Patent (10) Patent No.: US 9,388,293 B2

Olsen et al. (45) Date of Patent: *Jul. 12, 2016
(54) POLYVINYL CHLORIDE COMPOSITIONS 4.414,267 A 11/1983 Coran et al.
4,515,909 A 5, 1985 Sawano et al.
(71) Applicant: Eastman Chemical Company, 4,562,173 A 12/1985 Terano et al.
Kingsport, TN (US) 4,599,376 A 7/1986 Takimoto et al.
4,605.465 A 8/1986 Morgan
4,654.390 A 3/1987 Siegel
(72) Inventors: David Justin Olsen, Kingsport, TN 4,666,765 A 5, 1987 Caldwell et al.
(US); Martin James Stimpson, 4,764449 A 8/1988 VanIseghem
Lockeridge (GB) 4,792.464 A 12/1988 Martenson
4,806,590 A 2/1989 Padget et al.
(73) Assignee: Eastman Chemical Company, 4,900,771 A 2f1990 Gerace et al.
Kingsport, TN (US) 4,975.480 A 12/1990 Bullen
5,071,690 A 12/1991 Fukuda et al.
5,179,138 A 1/1993 Uemura et al.
(*) Notice: Subject to any disclaimer, the term of this 5,236,883. A 8, 1993 Nakazawa et al.
patent is extended or adjusted under 35 5,288,797 A 2f1994 Khali1 et al.
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claimer. 5,366,550 A 11/1994 Schad
5,401,708 A 3, 1995 Shimizu et al.
5.432.222 A * 7/1995 Igarashi et al. ............... 524.399
(21) Appl. No.: 13/749,225 5,454,801 A 10, 1995 Lauritzen
5,476,889 A 12, 1995 Owen
(22) Filed: Jan. 24, 2013 5,489,618 A 2f1996 Gerkin
5.492,960 A 2f1996 Muehlbauer et al.
(65) Prior Publication Data 5,494,707 A 2/1996 Wang et al.
5,519,072 A 5/1996 Wieczorek, Jr. et al.
US 2013/O137789 A1 May 30, 2013 5,523,344 A 6/1996 Maksymkiv et al.
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Related U.S. Application Data 5.535,469 A 7/1996 Terry
5,539,011 A 7/1996 Hilker et al.
(63) Continuation of application No. 1 1/202,543, filed on 5,559,175 A 9/1996 Kroggel et al.
Aug. 12, 2005, now Pat. No. 8,372,912. 5,571,860 A 11/1996 Kukkala et al.
(Continued)
(51) Int. C.
CSK 3/092 (2006.01) FOREIGN PATENT DOCUMENTS
CSK 3/12 (2006.01)
CSK 5/55 (2006.01) CA 2 485 133 A1 11, 2003
CSK 3/52 (2006.01) CA 2624332 A1 4/2007
(52) U.S. C. (Continued)
CPC. C08K5/092 (2013.01); C08K5/12 (2013.01);
C08K 5/1515 (2013.01); C08K 5/52 (2013.01); OTHER PUBLICATIONS
C08K 2201/014 (2013.01)
(58) Field of Classification Search Hansen, C.M.; "Hansen Solubility Parameters—A User's Hand
CPC ....................................................... CO8K 5/092 book”: pp. 9-10, 167-185; CRC Press, Boca Raton, FL.
USPC .......................................................... 524/569 Herman, Stephen J.; Edited by David Rowe, "Chemistry and Tech
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 US 9,388.293 B2
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 US 9,388.293 B2
Page 3

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 US 9,388,293 B2
1. 2
POLYVINYL CHLORIDE COMPOSITIONS The PVC compositions of the present invention have a variety
ofuses such as in adhesives and Sealants, coated fabrics, wire
CROSS-REFERENCE TO RELATED and cable coatings, foams, footwear, gaskets, inks, cosmetics,
APPLICATION and medical devices. PVC-based applications include floor
coverings, wallpaper, roofing membranes, tubing, inks, and
This application is a continuation of U.S. patent applica calendared film.
tion Ser. No. 1 1/202,543 filed on Aug. 12, 2005, the disclo DETAILED DESCRIPTION
sure of which is incorporated herein by reference in its
entirety.
10 The composition of the present invention comprises a PVC
FIELD OF THE INVENTION resin and a plasticizer selected from di-butyl terephthalate,
di-isobutyl terephthalate or a mixture thereof. As used herein,
This invention pertains to novel polyvinyl chloride com the term “PVC resin' means homopolymers of polyvinyl
positions. More particularly, this invention pertains to novel chloride resin(s), copolymers of polyvinyl chloride resin(s),
compositions containing an intimate admixture of polyvinyl 15 and mixtures thereof. Copolymers of vinyl chloride are
chloride and an ester plasticizer. More particularly, the formed by the copolymerization of vinyl chloride and other
present invention pertains to polyvinyl chloride compositions monomers or monomer blends. Suitable monomers include
including a plasticizer selected from di-butyl terephthalate, vinyl acetate, ethylene, propylene, maleate, methacrylate,
di-isobutyl terephthalate and mixtures thereof. acrylate, high alcohol vinyl ester, urethane, chlorinated ure
thane, methylmethacrylate, and mixtures thereof. Examples
BACKGROUND OF THE INVENTION of monomer blends include ethylene-vinyl acetate copoly
mer, acrylonitrile-butadiene-styrene terpolymer, acryloni
Polyvinyl chloride (commonly referred to as “PVC) has trile-butadiene copolymer, and mixtures thereof. The mono
been used for a number of years in the manufacture of soft, mers or monomer blends may be present in an amount of up
flexible films for food packaging, in molded rigid products 25 to 10 parts per hundred parts resin (the term “parts per hun
(such as pipes, fibers, upholstery and bristles), and in a variety dred parts resin' is used herein to define the quantity of the
of other products, including electric wire and cable-cover components based on the weight of the resin and is abbrevi
ings, film finishes for textiles, raincoats, belting, gaskets and ated “PHR).
shoe soles. A variety of plasticizers have been used to produce The PVC resin component of the present invention has a
flexible PVC articles. The plasticizer compounds differ in 30 degree of polymerization (DP) which is between 650 and
many respects but all of them must possess certain character 1600, preferably between 900 and 1100, and an inherent
istics. For example, the plasticizer compound must be com viscosity (IV) between 0.5 and 1.4 (based on ASTMD-1243).
patible with the PVC resin and render the PVC more flexible The PVC-based resin of the present invention may be formu
and/or softer. In PVC, the plasticizer also assists in the fusion lated from a single PVC resin or a mixture of two or more
of the PVC formulation to produce the final article. In the 35 different PVC resins. When two or more different PVC resins
typical fusion process, the PVC resin particles dissolve and/or are used, the PVC resins preferably have degrees of polymer
break apart, intermingle with all the other additives to pro ization which are relatively close invalue. The di-butyl and/or
duce the final homogenously mixed material. Plasticizers that di-isobutyl terephthalate plasticizer compounds may be used
have a high affinity for PVC resin resulting in very quick alone, together or they may be used in combination with
fusion are called high-Solvating plasticizers. Fusion in dry 40 additional plasticizers in the PVC composition. Examples of
blends is accomplished by a combination of stress and tem Such additional plasticizers include, but are not limited to,
perature. Fusion in plastisols occurs mainly by temperature. dioctyl phthalate, di-2-ethyl hexyl phthalate, diisooctyl
There are a number of chemical classes of high-solvating phthalate, diisononyl phthalate, di-linear nonyl phthalate, di
plasticizers such as benzoates, butyl benzyl phthalate, linear nonyl, undecyl phthalate, di-linear undecyl phthalate,
dihexyl phthalate, and others. High-solvating plasticizers 45 diundecyl phthalate, diisodecylpthalate, Co-Co straight
provide faster fusion allowing fusion to occur at lower tem chain phthalates, C, linear phthalate, Colinear phthalate, C
peratures or to occur faster at a given temperature. A disad linear phthalate, ditridecyl phthalate, undecyl dodecyl phtha
Vantage for plastisols is high Solvating plasticizers are typi late, di(2-propylheptyl phthalate), nonylundecyl phthalate,
cally not as stable to viscosity increases as general purpose texanolbenzylphthalate, polyester phthalate, diallylphtha
plasticizers. 50 late, n-butylphthalyl-n-butyl glycosate, dicaprylphthalate,
butylcyclohexyl phthalate, dicyclohexyl phthalate, butyl
BRIEF SUMMARY IF THE INVENTION octyl phthalate, dioctylterephthalate, di-2-ethylhexyltereph
thalate, dioctyl adipate, di-2-ethyl hexyl adipate, diisonyl
We have found that di-butyl terephthalate (DBTP) and adipate, diisooctyladipate, diisodecyl adipate, ditridecyladi
di-isobutyl terephthalate (DIBTP) are high-solvating plasti 55 pate, dibutoxyethyl adipate, dibutoxyethoxy adipate, di(noc
cizers for PVC resins and provide advantages compared to tyl, indecyl)adipate, polyester adipate, poly glycol adipates,
other high solvating plasticizers when incorporated into PVC trioctyl trimellitate, tri-2-ethylhexyl trimellitate, triisooctyl
resins. DBTP-containing PVC compositions have better low trimellitate, tri isononyl trimellitate, triisodecyl trimellitate,
temperature properties and exhibits stain resistance equiva tri-n-hexyl trimelitate, dioctyl azelate, di-2-ethylhexyl glut
lent to PVC plasticized with benzoate esters (which are very 60 arate, di-2-ethylhexyl sebecate, dibutyl sebecate, dibutoxy
stain resistant plasticizers) and better than other high Solvat ethyl sebecate, triethyl citrate, acetyl triethyl citrate, tri-n-
ing plasticizers such as butylbenzyl phthalate At the same butyl citrate, acetylri-n-butyl citrate, acetyltri-n-hexylcitrate,
time, DBTP-containing plastisols also are lower in viscosity n-butyl tri-n-hexyl citrate, isononyl benzoate, isodecyl ben
and maintain this difference as the plastisolages. The present Zoate, 1.4 cyclohexane dimethanol dibenzoate, 2.2.4 trim
invention thus provides a novel PVC composition comprising 65 ethyl-1.3 pentane diol dibenzoate, 2.2.-dimethyl-1,3 pro
a PVC resin containing a plasticizing amount of di-butyl panediol dibenzoate, Co-C alkane phenol esters or alkyl
terephthalate, di-isobutyl terephthalate or a mixture thereof. Sulphonic phenol ester, acetic acid reaction products with
 US 9,388,293 B2
3 4
fully hardened castor oil, pentaerythritol tetrabenzoate, glyc tors, anti-oxidants, light stabilizers, fire retardants, pigments,
erol tribenzoate, polypropylene glycol dibenzoate, tri and mixtures thereof. These additives are generally known in
arylphosphates, diisononyl cyclohexane 1.2 dicarboxylate, the art and may be present in the compositions in an amount
polymers of adipic acid/phthalates/adipates/Sebecates/ with sufficient to impart the desired property (generally below 10
glycols and often acid terminated, butylbenzyl phthalate, PHR). Anti-static and anti-fogging agents include Sorbitan
alkylbenzyl phthalate, C7-Cobutyl phthalate, diethylene gly fatty ester, sorbitol fatty ester, glycerine fatty
col dibenzoate, dipropylene glycol dibenzoate, 2-ethylhexyl Di-butyl terephthalate (DBTP) and di-isobutyl terephtha
benzoate, texanolbenzoate, ethylene glycol dibenzoate, pro late (DIBTP) have been found to be high solvating plasticiz
pylene glycol dibenzoate, triethylene glycol dibenzoate, di ers for PVC and PVC-based polymeric materials. High sol
heptyl phthalate, dihexyl phthalate, dimethyl phthalate, 10 Vating plasticizers such as butylbenzyl phthalate fuse at a
diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, and faster rate/lower temperature than do general purpose plasti
mixtures thereof. The plasticizer or plasticizers are present in cizers such as di(2-ethylhexyl)phthalate (DOP) and
the compositions of the present invention in amounts ranging di(isononyl)phthalate (DINP). Plastisols are dispersions of
from about 20 to 800 PHR, more typically about 40 to 120 certain polyvinyl chloride resins of very small to medium
PHR, and most preferably from about 40 to 80 PHR. Di-butyl 15 particle size, e.g., average particle size of about 1 to 100
terephthalate and/or di-isobutyl terephthalate constitute from microns, in liquid plasticizers. Dry plasticized PVC compo
about 10 to 100 weight percent, preferably about 25 to 100 sitions typically are prepared for PVC resins having large
weight percent of the total plasticizer present in the compo particle size, e.g., average particle size of about 100 to 400
sitions. microns. Viscosity is an important property for the processing
The compositions of the present invention may contain one of plastisol PVC compositions. The application often dictates
or more stabilizers such as metal Soaps, organic phosphites, the absolute value. Excessively high Viscosity can cause prob
epoxy compounds, tin stabilizers, and mixtures thereof. The lems pumping and filling mold features. Too low viscosity
stabilizers provide protection against deficient PVC homopo may result in material run off and give parts or articles that are
lymerization and copolymerization, and functions to elimi too thin. Viscosity stability also is important because if the
nate or retard the process of polymer degradation. The total 25 Viscosity increases too fast, the time for using the plastisol
amount of stabilizer present in the compositions ranges from may be insufficient. Problems resulting from high viscosity in
0.1 to 10 PHR, preferably from 1 to 7 PHR, and most prefer plastisols include poor filling of molds, difficulty in coating to
ably 2 to 5 PHR. Preferably, the stabilizer is a mixture of given thicknesses, inability to pump the plastisol, and even
metal soaps and epoxy compounds, or a mixture of metal tually premature gelling of the composition. When parts are
Soaps, epoxy compounds and organic phosphites. 30 made on a Volume basis, lower density is advantageous since
Metal Soap stabilizers include Zinc Stearate, barium Stear more parts per weight of PVC may be produced.
ate, calcium stearate, cadmium stearate, barium ricinolate, Plastisol formulations of our novel compositions may be
calcium oleate, calcium laurelate, Zinc octoate, and mixtures prepared by mixing the liquid ingredients together using a
thereof. Preferably, the metal soap stabilizers are mixtures of high intensity mixer, e.g., a Cowles mixer, or a low intensity
barium Stearate, Zinc Stearate and cadmium Stearate. A pre 35 mixer, e.g., a Hobart mixer. The PVC resin and other solid
ferred barium stearate/zinc stearate mixture is sold by Bear ingredients are added over a short time period with mixing in
locher (Chemgrade UBZ-791), and preferred calcium stear either a high or low intensity mixers and the resultant disper
ate/zinc Stearate and barium Stearate/cadmium Stearate sion often is deaerated under vacuum or other conditions. The
mixtures are sold by Azko Interstab. (CZ-19A and BC-103L, plastisol then may be fused under a number of different heat
respectively). Epoxy compound stabilizers include epoxy 40 conditions such as knife coated to a certain thickness and
Soybean oil, e.g., Srapex 6.8, ESO, epoxy linseed oil, epoxy fused in an oven at varying temperature, in heated molds, in
polybutadiene, epoxy methylstearate, epoxy Stearate, epoxy cold molds that are Subsequently heated, and similar meth
ethylhexyl Stearate, epoxy Stearyl Stearate, epoxy propyl iso ods. Once fused, physical properties of the plastisol may be
cyanalate 3-(2-case INO)-1,2-epoxy propane, bis-phenol A determined.
diglycidyl ether, vinyl dicyclohexanediepoxide, 2.2-bis-(4- 45 Dry formulations of the PVC compositions may be pre
hydroxyphenol) propane and epichlorohydrine condensation pared by combining the Solid ingredients and mixing them in
copolymeration, and mixtures thereof. Organic phosphite sta a Henschel mixer. The liquid ingredients then are slowly
bilizers include diphenyldecyl phosphite, triphenyl phos added. The mixture is blended until a temperature of about
phite, tris-nonylphenyl phosphite, tri-steareal phosphite, 88° C. is reached, at which temperature PVC is below its
octyldiphenylphosphite, and mixtures thereof. Tinstabilizers 50 fusion temperature. This procedure produced a free-flowing
include tin dilaurate, dibutyl tin maleate, organic tin mercap powder of PVC particles having the other ingredients
tide and organic tin Sulfonic amide, and mixtures thereof. absorbed therein. The free-flowing powder then may be fused
The above stabilizers may be used individually or in any on a 2 roll mill at a temperature of about 140 to 150° C. to
combination. Preferably, the stabilizers are mixtures of Zinc produce a fused PVC sheet.
Stearate, barium Stearate, calcium Stearate, and epoxy com 55
pounds. A preferred epoxy stabilizer is epoxy soybean oil. In EXAMPLES
addition, organic phosphites may be used in conjunction with
the Zinc Stearate, barium Stearate, cadmium Stearate, and The preparation and properties of the compositions pro
epoxy compound mixtures. Particularly preferred stabilizer vided by the present invention are further illustrated by the
mixtures are barium Stearate/zinc Stearate and epoxy soybean 60 following examples 1-3. The compositions of the following
oil, calcium Stearate/zinc stearate and epoxy soybean oil, and examples were prepared by mixing the liquid ingredients
barium Stearate/cadmium Stearate and epoxy soybean oil. In together using a high intensity mixer, e.g., a Cowles mixer, or
addition to PVC or a PVC-based resin, the di-butyl and/or a low intensity mixer, e.g., a Hobart mixer and mixed suffi
di-isobutyl terephthalate plasticizer compounds primary ciently to produce a substantially homogeneous mixture. The
plasticizer(s) and optional stabilizer(s), the compositions of 65 PVC resin and other solid ingredients are added over a short
the present invention may include additional additives, such time period with mixing in either a high or low intensity
as anti-static agents, anti-fogging agents, ultra-violet inhibi mixers and the resultant dispersion often is deaerated under
 US 9,388,293 B2
5
vacuum or other conditions. The plastisol was placed in a TABLE II-continued
1778 micron (70 mil) mold and fused in an oven at 175 to 190° Example C-1 1
C. and test bars were cut from the fused sheets.
Modulus of elasticity and the tensile strength are measured Brittlenesss Temp, C. -41 -46
according to ASTM D142. Fusion was done using ASTM D Cottonseed Oil Extractionl, 9% loss 21.3(0.6) 17.9(0.9)
2538 (fusion properties and gel properties are determined Hexane Extraction, % loss 34.6(3.2) 27.4(1-4)
1% Soap Water Extraction, % loss 2.9(0.5) -0.2(0.2)*
with this test). The elongation, modulus of elasticity and the Carbon Extraction, % loss 2.5 (0.1) 5.5(1.3)
tensile strength are measured according to ASTM D412. The
tear resistance was measured according to ASTM D624, and 10
the brittleness temperature was measured according to ASTM Example 2 and Comparative Examples C-2 and C-3
D746. Brookfield viscosity (centipoises) was determined
according to ASTM D1824, typically at ambient temperature
or 25°C. Unless specified otherwise, spindle #5 was used in Using the above-described procedure, three compositions
the Brookfield viscosity measurements. Tear resistance was were prepared from a 70:30 by weight mixture of 2 different
measured according to ASTM D624, brittleness temperature 15 PVC resins: 70 parts Oxy. 6547 resin and 30 parts Oxy 625
was measured according to ASTM D746, chemical extrac resin, 70 PHR plasticizer, 3 PHR epoxidized soybean oil
tions were D1239, carbon extraction D1203, specific gravity (Drapex 6.8) and 2 PHR of a mixed metal stabilizer
D792, and shore A hardness D2240. (Akcrostab 4398 supplied by Akcros Chemical). The Oxy230
PVC powder has an internal viscosity IV of 0.95 and a
Example 1 and Comparative Example C-1 molecular weight factor K of 68. In the first composition, the
plasticizer was DBTP (Example 2); in the second composi
Using the above-described procedure, two compositions tion, the plasticizer was diethylene glycol dibenzoate (Ex
were prepared from PVC (Oxy 75HC resin supplied by Oxy ample C-2); and in the third composition, the plasticizer was
chem), 70 PHR plasticizer, 2 PHR epoxidized soybean oil butylbenzyl phthalate (Example C-3).
(Drapex 6.8 supplied by Crompton-Witco) and 2 PHR of a 25
The Brookfield viscosity, fusion and gel properties of the
mixed metal stabilizer (Akcrostab LT 4798 supplied by Akros two compositions were determined and are set forth in Table
Chemicals). In the first composition, the plasticizer was a III. The Brookfield viscosity was determined for 1 hour and
75:25 by weight blend of dioctal terephthalate (DOTP) and 24 hours at 2.5 RPM and 20 RPM. The viscosity values are
DBTP (Example 1). In the second composition, the plasti centapoise, the fusion and gel time is given in minutes:sec
cizer was a 75:25 by weight blend of DOTP and diethylene 30
onds, fusion and gel temperature is given in F./C., fusion
glycol dibenzoate (Example C-1). and gel torque is given in metersgram
The Brookfield viscosity, fusion and gel properties of the
two compositions were determined and are set forth in Table TABLE III
I. The Brookfield viscosity was determined for 1 hour and 24
35
hours at 2.5 revolutions perminute (RPM) and 20 RPM. The Example 2 C-2 C-3
Viscosity values are centipoise, the fusion and gel time is Brookfield Viscosity
given in minutes:seconds, fusion and gel temperature is given
in F./C., fusion and gel torque is given in metersgram 1 hour (a) 2.5 RPM 16SO 2550 1950
1 hour (a) 20 RPM 1368 2531 1837
TABLE I 40 24 hours (a) 2.5 RPM 3300 S400 3OOO
24 hours (a) 20 RPM 2493 4800 262S
Fusion Time 10:09 10:02 10:12
Example C-1 1
Fusion Temp 178.81 1768O 179,82
Brookfield Viscosity Fusion Torque 821 956 857
Gel Time 5:42 5:17 6:20
1 hour (a) 2.5 RPM 368O 2240 45 Gel Temp 126,52 120.49 133,56
1 hour (a) 20 RPM 2400 1700 Gel Torque 5 5 5
24 hours (a) 2.5 RPM 7450 66SO
Fusion Time 18:00 18:23
Fusion Temp 266,130 269,131 Various physical properties for the three compositions
Fusion Torque 815 761 were determined using the procedures described above.
Gel Time
Gel Temp
8:45
161.72
9:11
165,74
50 These physical properties are set forth in Table IV.
Gel Torque 11 11
TABLE IV

Various physical properties for the two compositions were Example 2 C-2 C-3
determined using the procedures described above. These 55 Tensile Strength, MPa. 11.7(0.4) 14.6(0.4) 15.7(1.1)
physical properties are set forth in Table II. The values in Modulus at 100% Elong, MPa. 4.5 (0.5) 5.3 (0.1) 5.4(0.2)
parentheses are standard deviations. Elongation at Break, %
Shore A Hardness
361 (36)
53(3)
401(10)
67(1)
383(18)
56(4)
Tear Resis, kN/M 32.9(2.6) 43.1 (1.6) 41.0(4.4)
TABLE II Specific Gravity, g/cm 1.228 (0.009) 1.292 (0.001) 1.278(0.006)
60 Tear Force, N 45 (10) 31 (6) 53(9)
Example C-1 1 Brittleness Temp, C. -45 -24 -28
Tensile Strength, MPa. 8.6(2.1) 12.4(1-4)
Modulus at 100% Elong, MPa. 5.1 (0.2) 5.0 (0.1)
Elongation at Brk,% 198(64) 345 (53) Example 3 and Comparative Example C-4
Shore A Hardness 64(2) 65(1)
Tear Resistance, kN/M 40.7(3.9) 43.8(2.3) 65
Specific Gravity, g/cm 1.205 (0.003) 1.1856(0.001) Using the above-described procedure, two compositions
were prepared from a 80:20 by weight mixture of 2 different
 US 9,388,293 B2
7
PVC resins: 80 parts Oxy 75HC resin and 20 parts Oxy 625 TABLE VII
resin, 60 PHR plasticizer, 3 PHR epoxidized soybean oil
(Drapex 6.8) and 2PHR of a mixed metal stabilizer (Akrostab Example Example C-5 Example 4 Example 5
4398). In the first composition, the plasticizer was DBTP Fusion Time 6:46 6:25 6:13
(Example 3) and in the second composition, the plasticizer Fusion Temp 277.136 277.136 276/135
was butylbenzyl phthalate (Example C-4). Fusion Torque 899 839 845
Gel Time 2:35 3:07 2:58
The Brookfield viscosity, fusion and gel properties of the Gel Temp
Gel Torque
263,128
4.08
264,129
467
265,129
479
two compositions were determined and are set forth in Table
V. The Brookfield viscosity was determined for 1 hour at 2.5 10
RPM and 20 RPM. The viscosity values are centipoise, the Various physical properties for the two compositions were
fusion and gel time is given in minutes:seconds, fusion and determined using the procedures described above. These
gel temperature is given in F./C., fusion and gel torque is physical properties are set forth in Table VIII.
given in metersgram
15 TABLE VIII
TABLEV Example Example C-5 Example 4 Example 5
Example 3 C-4 Tensile Strength, 19.79(0.826) 19.16(0.661) 18.31 (0.857)
MPa.
Brookfield Viscosity Modulus at 100% 11.02(0.133) 10.20(0.217) 13.08 (0.848)
Elong, MPa.
1 hour (a) 2.5 RPM 392O 472O Elongation at 307.7(30.58) 327.0(20.70) 197.0(12.15)
1 hour (a) 20 RPM 1880 2990 Brk,9%
Fusion Time 7:56 8:04 Shore A Hardness 77(2) 77(3) 78(2)
Fusion Temp 163,73 161.72 Tear Force, N 123.0(4.29) 127.3(9.85) 128.5(13.69)
Fusion Torque 2O33.4 1821.O Tear Resistance, 76.7(2.97) 79.1 (4.73) 78.2(6.80)
25 kNAM
Gel Time 4:43 5:23 Specific Gravity, 1.2516(0.00510) 1.2376(0.00398) 1.2358(0.00237)
Gel Temp 11948 126,52 g/cm
Gel Torque 16 15 Brittleness -28 -33 -28
Temp, C.
% Soapy water Loss 0.42 Gain 0.02 Gain 0.04
Various physical properties for the two compositions were 30 extraction, %
Cottonseed oil Loss 1.35 Loss 1.58 Loss 1.55
determined using the procedures described above. These extraction, %
physical properties are set forth in Table VI. Hexane Loss 5.69 Loss 21.96 Loss 21.50
extraction, %
Carbon Loss 0.56 Loss 1.52 Loss 2.12
TABLE VI 35 extraction, %
Example Example 3 Example C-4
Tensile Strength, MPa. 14.51 (1.067) 16.62(1.512) Example 6 and Comparative Examples C-6 and C-7
Modulus at 100% Elong, MPa. 4.48(0.068) 5.65 (0.150)
Elongation at Brk,% 401.5(24.28) 351.1(32.69)
Shore A Hardness 61(2) 60(2) 40 Using the above-described procedure, three compositions
Tear Resistance, kN/M
Specific Gravity, g/cm
39.7(1.90) 49.7(3.38)
1.2302(0.00251) 1.2719(0.00322)
were prepared from a blend of PVC resins consisting of 91.4
Tear Force, N 45.1(3.33) 39.3(4.55)
parts by weight Oxy. 80HCPVC and 8.6 parts by weight PVC
Cottonseed Oil Extraction, % loss 3.5(0.3) 1.6(0.4) blending resin Oxy 567 (both supplied by Oxychem),30PHR
Hexane Extraction, % loss 15(3) 6(2) plasticizer, 17 PHR TXIB (2,2,4-trimethyl-1,3-pentanediol
1% Soap Water Extraction, % loss 0.70(0.02) 0.64(0.30) 45 disobutyrate), 8 PHR mineral spirits, 3 PHR poly(ethylene
Carbon Extraction, % loss 8.2(0.7) 2.6(0.1) glycol) 400 and 5 PHR of a mixed metal stabilizer (Akrostab
4798). In the first composition, the plasticizer was a mixed
benzoate plasticizer blend (BenZoflex 6000 from Velsicol)
Example 4 and 5 and Comparative Example C-5 (Example C-6); in the second composition, the plasticizer
50 was butylbenzyl phthalate (Santicizer 160 supplied by Ferro
(Example C-7); and in the third composition, the plasticizer
Using the above-described procedure, three compositions was DBTP (Example 6). The plastisol were placed in a 508
were prepared from a PVC resin (Oxy 240F), 50 PHR plas micron (20 mil) mold and fused in oven at 20.4°C. (400°F.)
ticizer, 2 PHR epoxidized soybean oil (Drapex 6.8) and 2 for 2 minutes.
PHR of a mixed metal stabilizer (Across LT 4798. In the first 55 The compositions were evaluated for stain resistance by
composition, the plasticizer was a 75:25 by weight blend of applying to (staining) the fused sheets prepared from the
DOTP and diethylene glycol dibenzoate (BenZoflex 2-45 compositions brown color paste shoe polish, a 2 percent by
from Velsicol) (Example C-5); in the second composition, the weight solution of iodine in ethanol, and blue Magic Marker.
plasticizer was a 75:25 blend of DOTP and DBTP (Example The staining materials were allowed to remain on the fused
4); and in the third composition, the plasticizer was a 75:25 60 sheets for periods of time of 1 hour and 24 hours and then
blend of DOTP and DIBTP (Example 5). were removed by rubbing with a cotton cloth and a cleaning
solution. For both the shoe polish and marker, mineral spirits
The fusion and gel properties of the three compositions were used. For the Iodine, isopropanol followed by mineral
were determined and are set forth in Table VII. The fusion and spirits were used. The stains remaining on the fused sheets
gel times are given in minutes:seconds, fusion and gel tem 65 then were evaluated and rated according to the following
perature is given in F./C., fusion and gel torque is given in rating system: 5-severe staining, 4-considerable staining,
metersgram 3 moderate staining, 2-slight staining and 1 no staining.
 US 9,388,293 B2
10
The results of the staining evaluations values for the 1-hour 6. The free-flowing powder composition of claim 1,
and 24-hour tests are set forth in Tables IX and X, respec wherein the composition further comprises one or more addi
tively. tional components selected from stabilizers, anti-static
agents, anti-fogging agents, ultra-violet inhibitors, anti-oxi
TABLE IX dants, light stabilizers, fire retardants, pigments, or combina
Staining tions of two or more of the foregoing.
Materials Example C-6 Example C-7 Example 6 7. The free-flowing powder composition of claim 1
Shoe Polish 3 4 4
wherein the at least one additional plasticizer selected from
Iodine 3 4 3 10
di-2-ethylhexyl terephthalate, disononyl phthalate,
Blue Marker 3 4 3 disononyl cyclohexane 1,2-dicarboxylate, di-2-propylheptyl
phthalate, and di-2-ethylhexyl adipate.
8. The free-flowing powder composition of claim 7
TABLE X wherein at least 25 weight percent of said plasticizer is di
15 butyl terephthalate, di-isobutyl terephthalate or a mixture
Staining thereof.
Materials Example C-6 Example C-7 Example 6 9. The free-flowing powder composition of claim 1
Shoe Polish 3 4 4 wherein the at least one additional plasticizer is selected from
Iodine 3 4 3 the group consisting of di-2-ethylhexyl terephthalate,
Blue Marker 3 4 3
disononyl phthalate, and diisononyl cyclohexane 1,2-dicar
boxylate.
Having described the invention in detail, those skilled in 10. The free-flowing powder composition of claim 9
the art will appreciate that modifications may be made to the wherein at least 25 weight percent of said plasticizer is di
various aspects of the invention without departing from the butyl terephthalate, di-isobutyl terephthalate or a mixture
scope and spirit of the invention disclosed and described 25 thereof.
herein. It is, therefore, not intended that the scope of the 11. A method comprising applying heat to the free-flowing
invention be limited to the specific embodiments illustrated powder composition of claim 1 under conditions effective to
and described but rather it is intended that the scope of the fuse the free-flowing powder composition.
present invention be determined by the appended claims and 12. A fused polyvinyl chloride composition made by the
their equivalents. Moreover, all patents, patent applications, 30 method of claim 11.
publications, and literature references presented herein are 13. An article comprising the fused polyvinyl chloride
incorporated by reference in their entirety for any disclosure composition of claim 12.
pertinent to the practice of this invention. 14. The article of claim 13, wherein the article is an adhe
sive, a sealant, a coated fabric, a wire coating, a cable coating,
We claim: 35 a foam, a footwear, a gasket, an ink, a cosmetic, a medical
1. A free-flowing powder composition comprising PVC device, a floor covering, a wallpaper, a roofing membrane,
resin particles, a plasticizer selected from the group consist tubing or a calendared film.
ing of di-butyl terephthalate, di-isobutyl terephthalate and 15. A free-flowing powder composition comprising PVC
mixtures thereof, and at least one additional plasticizer resin particles, di-butyl terephthalate, and at least one addi
selected from the group consisting of di-2-ethylhexyltereph 40 tional plasticizer selected from the group consisting of di-2-
thalate, triethyl citrate, acetyl triethyl citrate, tri-n-butyl cit ethylhexyl terephthalate, triethyl citrate, acetyl triethyl cit
rate, acetytri-n-butyl citrate, acetyltri-n-hexylcitrate, n-butyl rate, tri-n-butyl citrate, acetytri-n-butyl citrate, acetyltri-n-
tri-n-hexylcitrate, diisononyl phthalate, diisononyl cyclohex hexylcitrate, n-butyl tri-n-hexylcitrate, diisononyl phthalate,
ane 1,2-dicarboxylate, dioctyl terephthalate, tri-2-ethylhexyl disononyl cyclohexane 1,2-dicarboxylate, dioctyl terephtha
trimellitate, di-2-propylheptyl phthalate, diisodecyl phtha 45 late, tri-2-ethylhexyl trimellitate, di-2-propylheptyl phtha
late, diisoundecyl phthalate, ditridecyl phthalate, trisononyl late, diisodecyl phthalate, diisoundecyl phthalate, ditridecyl
trimellitate, and di-2-ethylhexyl adipate: phthalate, trisononyl trimellitate, and di-2-ethylhexyl adi
wherein the plasticizers are present in the composition in pate,
an amount from about 20 to 120 parts plasticizer per 100 wherein the plasticizers are present in the composition in
parts PVC resin, and wherein at least 10 weight percent 50 an amount from about 20 to 120 parts plasticizer per 100
of the total plasticizer is di-butyl terephthalate, di-isobu parts PVC resin, and wherein at least 10 weight percent
tyl terephthalate or a mixture thereof. of the total plasticizer is di-butyl terephthalate.
2. The free-flowing powder composition of claim 1 16. The free-flowing powder composition of claim 15
wherein the plasticizer is present in the composition in an wherein the plasticizer is present in the composition in an
amount from about 40 to 120 parts plasticizer per 100 parts 55 amount from about 40 to 120 parts plasticizer per 100 parts
PVC resin. PVC resin.
3. The free-flowing powder composition of claim 1 17. The free-flowing powder composition of claim 15
wherein the plasticizer is present in the composition in an wherein the plasticizer is present in the composition in an
amount from about 40 to 80 parts plasticizer per 100 parts amount from about 40 to 80 parts plasticizer per 100 parts
PVC resin. 60 PVC resin.
4. The free-flowing powder composition of claim 1 18. The free-flowing powder composition of claim 15
wherein at least 25 weight percent of the plasticizer is di-butyl wherein at least 25 weight percent of said plasticizer is di
terephthalate, di-isobutyl terephthalate or a mixture thereof. butyl terephthalate, di-isobutyl terephthalate or a mixture
5. The free-flowing powder composition of claim 1, thereof.
wherein the PVC resin has a degree of polymerization 65 19. The free-flowing powder composition of claim 15
between 650 and 1600 and an inherent viscosity between 0.5 wherein the at least one additional plasticizer is selected from
and 1.4 based on ASTM D-1243. the group consisting of di-2-ethylhexyl terephthalate,
 US 9,388,293 B2
11
disononyl phthalate, disononyl cyclohexane 1,2-dicarboxy
late, di-2-propylheptyl phthalate, and di-2-ethylhexyl adi
pate.
20. The free-flowing powder composition of claim 19
wherein at least 25 weight percent of said plasticizer is di- 5
butyl terephthalate, di-isobutyl terephthalate or a mixture
thereof.
21. The free-flowing powder composition of claim 15
wherein the at least one additional plasticizer is selected from
the group consisting of di-2-ethylhexyl terephthalate, 10
disononyl phthalate, and diisononyl cyclohexane 1,2-dicar
boxylate.
22. The free-flowing powder composition of claim 21
wherein at least 25 weight percent of said plasticizer is di
butyl terephthalate, di-isobutyl terephthalate or a mixture 15
thereof.
23. A method comprising applying heat to the free-flowing
powder composition of claim 15 under conditions effective to
fuse the free-flowing powder composition.
24. A fused polyvinyl chloride composition made by the 20
method of claim 23.
25. An article comprising the fused polyvinyl chloride
composition of claim 24.
26. The article of claim 25, wherein the article is an adhe
sive, a sealant, a coated fabric, a wire coating, a cable coating, 25
a foam, a footwear, a gasket, an ink, a cosmetic, a medical
device, a floor covering, a wallpaper, a roofing membrane,
tubing or a calendared film.
k k k k k