US3284399A

US3284399A - Vinyl halide resins plasticized with an alkanol terminated oligoester

Info

Publication number: US3284399A
Application number: US262775A
Authority: US
Inventors: John O Van Hook
Original assignee: Rohm and Haas Co
Current assignee: Rohm and Haas Co
Priority date: 1963-02-11
Filing date: 1963-03-04
Publication date: 1966-11-08
Anticipated expiration: 1983-11-08
Also published as: DE1569322A1; BE641317A; CH465857A; NL297228A; GB1037625A; DE1468545A1

Description

1966 J. o. VAN HOOK 3,284,399

VINYL HALIDE RESINS PLASTICIZED WITH AN ALKANOL TERMINATED OLIGOESTER Filed March 4. 1965 Q I I o 20 40 so so 100 y MOLE PERCENT'OF AROMATIC ACID IN RESIDUE A United States Patent 3,284,399 VINYL HALIDE RESINS PLASTICIZED WITH AN ALKANOL TERMINATED OLIGOESTER John 0. Van Hook, Abington, Pa., assignor to Rohm &

Haas Company, Philadelphia, Pa., a corporation of Delaware Filed Mar. 4, 1963, Ser. No. 262,775 17 Claims. (Cl. 26031.8)

This is a continuation-in-part of application Serial No. 257,445, filed February 11, 1963, Oligoesters.

This invention deals with oligoesters and resinous compositions plasticized with such oligoesters. The oligoesters may be represented by the formula L (I) in which R is at least one alcohol residue, A is at least one dibasic acid residue, G is at least one glycol residue, x represents the number of recurring glycol-dibasic acid units in the oligoester and ranges from 1.2 to 4.6, n, the sum of the carbon atoms in one mole of R, A, and G, is a number in the range of 14 to 30.

The symbols R, A, and G may be further defined as follows: R is at least one saturated aliphatic alcohol residue which has an average content of 7 to 13 carbon atoms, A is a mixed dibasic acid residue comprising at least one aromatic acid and at least one saturated aliphatic acid, the mole percent of aromatic acid, y, being in the range of 30 to 85 and the mole percent of aliphatic acid being in the range of 70 to 15. The symbol A may be further defined as having an average content of 4 to 14 carbon atoms, G is at least one glycol residue which has an average content of 2 to 6 carbon atoms.

The oligoesters may be defined by reference to the annexed graph, FIGURE I. On the graph, x represents the number of recurring glycol-dibasic acid units in the oligoester; the symbol y is the mole percent aromatic acid in the mixed dibasic acid residue. The value of y and x are related so that, as may be seen from the graph, for any one value of y, a value for x may be found which falls within the area bounded by the lines A, B, 'C, D, and E. Preferred values of y and x fall within the areas limited to L, F, K, G and H, I, J. The overall range of y is 30 to 85 and that of x is 1.20 to 4.60. The lines numbered 14 and 30 represent the limits for n, the sum of carbon atoms in one mole of the components of the oligoester represented by R, A, and G. The symbol n may have any value, including fractional units, intermediate 14 and 30 and the graph illustrates units between 14 and 30. Any value for 11, including fractional values, is, therefore, represented by a line that belongs to a family of lines of which the line AB and the line DC are the extreme limits and the unit values of which are represented by additional lines labelled to 29 in FIGURE I, approximately parallel to lines AB and DC. Accordingly, any one oligoester of the invention has a value for y and x which may be represented by a point in the pentagram ABCED or within the more preferred areas LFKG or HII. In addition, the oligoester has a value for n which is not less than the value for n in FIGURE I, as represented by the line in the above described family of lines, and which bisects the point defined by x and y.

Accordingly, for any one fixed value of n-between 14 and 30x and y represent a point which falls within the area defined by the following lines: (1) the line, N1, represented by a line in the family of lines the value for nsaid line having two ends, a first end on a first point on line BC and a second end on a second point on line AD, (2) the line running from said first point to point C.

(3) the lines CED, and (4) the line running from point 3,284,399 Patented Nov. 8, 1966 D to said second point on line AD. For the one extreme value for n'where :2 equals 14the point represented by x and y falls in the area DCE. For the other extreme value for n-where n equals 30the point represented by x and y falls in the area BCEDA.

Conversely, for any one value of x and y, as it is represented by a point in pentagram ABCED, n has a series of values each of which may be represented by a line in the family of lines which intercepts N2, which is parallel to line AD, having two ends: a first end on the point represented by the point representing the values for x and y and a second end which is the meeting point of said line N2 and line BC or BA, whichever said line N2 meets first. Thus, N2 is a line which is parallel to line AD and, therefore, perpendicular to DE, which, if extended beyond point xy, intersects (l) the family of lines extending from n equals 14 to n equals 30thus from DC to AB, and (2) the point representing the value for x and y. Accordingly, for one extreme value of xy, which is point D, n is from 14 to 30; where xy is point B, likewise, n is from 14 to 30. On the other hand, where xy is A or B, n is 30.

For example, in the compound octyl/decyl (1/ 1) terminated poly[ethylene adipate/phthalate (l/2)]2.2, R has an average of 9 carbon atoms, A has an average of 7 carbon atoms, and G has an average of 2 carbon atoms, and one mole of R, A, and G(n) has a value of 18 so that in the above compound, x is 2.2, y is 67 and n is 18. Based on this oligoester prototype, there is prepared a class of oligoesters in which, keeping x and y constant at 2.2 and 67, respectively, the values for It may vary along a line, N2, parallel to AD that has its first end on point xy and its second end on line BC. This allows, therefore, for variations in the nature of the alcohols of R, dibasic acids in A, and the glycols in G and/or in the proportions of the alcohols in R, and in the glycols in G, and in that of the aromatic acids or of the aliphatic acids in A, if each one of these is used in mixture while keeping the respective ratio, y, of aliphatic and aromatic acids constant.

For the compositions which are preferred and which are defined by the areas LFKG and HI], similar definitions apply, suitably redefined to reflect the more limited areas defined. Thus, the points F, K, and G correspond to points C, E, and D, respectively; and point L to points A, B. Thus, for a fixed value for xy within tetragram LFKG, n may be represented by a line, N2, which is parallel to LG having one end on point xy and the other end at its intersection with LF. Likewise, for the composition in triangle HJI, point I corresponds to ponts F and K, point I to point G, and point H to point L. Accordingly, a composition in triangle HII, for any fixed value of xy has a value for n which may be represented by a line, N2, parallel to JH, which has one of its ends on point xy and the other at its intersection with HI. Where n is kept constant within the range of 16 to 25.7its limits for this preferred group-x and y represent a point which falls within the area defined by the following lines:

(1) the line, N1, representing the value for n-said line having two ends, a first end on a first point on line HI and a second end on a second point on line H] or .II, i.e., on the bisegmented line HJI,

(2) the line running from said first point to point I,

(3) the line running from point I to said second point on the bisegmented line HJI.

The olifioesters of the invention have a calculated average molecular weight of at least 575. Wet analysis may give equal or slightly lower values. A preferred class of oligoesters are those which are liquid at 25 C. An other preferred class are those in which the average aliphatic carbon atoms to oxygen atoms ratio in the oligoesters does not exceed 3 to 1, an aliphatic carbon atom being defined as not to include aromatic carbon atoms and carbonyl carbon atoms.

Pentagram G, K, F, L represents a preferred class of oligoesters. This preferred class of oligoesters has a value of n which ranges from 15.5 to 27.5. Moreover, in this class, in the mixture of dibasic acids A, the mole percent of aromatic acids y ranges from 50 to 80; the aliphatic acids thereof contain an average of at least 5 carbon atoms; the aliphatic alcohol residue, R, averges from 8 to 12 crbon atoms. For this class of oligoesters, x ranges from 1.75 to 4.1. The oligoesters so defined in this preferred class have a calculated average molecular weight of at least 720 and their average aliphatic carbon atom to oxygen atom ratio does not exceed 2.4 to 1.

Triangle H, I, J represents a further favored class of oligoesters. In this preferred class, It ranges from 16 to 25.7; the mole percent, y, of aromatic acid in mixture A ranges from 60 to 80. In this class, x ranges from 2.25 to 3.85. Within the preferred class of oligoesters are those in which the alcohol residue contains an average of carbon atoms ranging from 8.5 to 10.5

Within the oligoesters of the invention, those in which the aliphatic dibasic acid is adipic acid and the aromatic acid is phthalic acid form a specially favored group.

The oligoesters of this invention may be prepared from any suitable alcohols, dibasic acids, and glycols. Typical of the alcohols are alkanols, branched or straight chain alkanols, such as the following: butanol, hexanol, isohexanol, amyl alcohol, decanol, octanol, isooctanol, dodecanol, isodecanol, 3-ethyl-2-pentanol, isotridecanol, 3- methyl-l-butanol, tetradecanol, hexadecanol, 2-ethy1- hexanol, 2-ethylbu-tanol, 4-ethyl 4 methyl-3 hexanol, pentadecanol, and similar other alcohols. The alcohols may be used singly or in mixture.

Typical glycols suitable for the preparation of the oligoesters include the following: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butylene glycol, 1,5-pentanediol, trimethylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,4-pentanediol 1,6-hexamethylenediol, and 2-ethyl-1,3-butanediol. Many of the glycols are obtainable from olefin through the oxidation reactions. Mixtures of glycols are useful, as well as simple glycols.

Typical dicarboxylic acids which are suitable for making the oligoesters include the following: sebacic, azelic, suberic, pimelic, adipic, glutaric, succinic, isosebacic, dimethyl adipic, malonic, phthalic, isophthalic terephthalic, 3-methyl phthalic, 4-methyl phthalic, 3,4-dimethyl phthalic, and the like. These may be used individually or in mixtures. Instead of the glycols, alcohols and acids,

.there may be used any other suitable compounds that will yield the glycol, alcohol, and acid residue in the oligoester. For instance, there may be used esters of low boiling acids, anhydrides, or their equivalents in preparing the oligoesters of the invention.

The oligoesters of this invention are prepared by reacting appropriate amounts of the alcohol, the glycol, and the acid components under polyesterification conditions until the major proportion of acid is reacted, such as when the acid number is below 10, especially below 3. Generally, the temperature of the esterification is maintained in the range of 160 to 220 C. Preferably, a vacuum system and an esterification or transesterfication catalyst is used. Typical catalyst are: zinc acetate, zinc oxide, litharge, stannous oxaleate, dibutyl tin oxide, zinc dust, and stannous oxide. The reaction mixture is then further reacted 'by heating in the range of 185 to 200 C., thereby causing transesterification and removing excess glycol and alcohol. The reaction is generally completed when the hydroxyl number is below 15, preferably below 8. Ideally, the acid number does not exceed 1. Depending on the reactants employed, water or glycol will be evolved during the reaction and measurement of the quantity of the by-product evolved permits determination of the degree of completion of the reaction. The resulting oligoesters are, desirably, completely alcohol terminated. There may, however, remain some free residual hydroxyl groups in the oligoesters. Generally, these will not exceed 20 mole percent, and preferably, not more than 10 mole percent. Ideally, the oligoesters are almost completely alcohol-terminated as when they have a hydroxyl number of not more than 5. The oligoesters are light-colored, light to medium viscosity, sparkling, mobile fluids.

Typical of the oligoesters of the invention, there may be named the following; in the nomenclature used, the mole ratio of alcohol and acids used in the mixture is indicated in parenthesis with x being the number following the bracket.

octyl/decyl 1/ 1 )terminated [ethylene adipate/phthalate(2/1) ]2.0,

octyl/ decyl( 1/ 1 terminated [ethylene adipate/phthalate( 1/ 1) ]2.0,

octyl/decyl(l/1)terminated [ethylene adipate/phthalate(1/2)]1.3,

n-octyl terminated [butylene succinate/phthalate(1/ 1) ]2.0,

isooctyl terminated [ethylene adipate/ phthalate 1/ 2) 1.86,

2-ethylhexyl terminated [propylene glutarate/phthalate(1/ 1 ]2.0,

octyl/decyl( 1/ 1)terminated [ethylene adipate/ phthalate 1/ 2) ]2.2,

octyl terminated [ethylene azelate/phthalate(1/ 1 2.0,

octyl/decyl( 1/ 1 terminated [ethylene adipate/ phthalate( 1/ 5) 1.6,

n-octyl terminated [hexamethylene adipate/phthalate(1/1) ]2.0,

octyl/decyl( 1 1 )terminated [1,2-propylene adipate/ phthalate 1 2) 1.8,

n-octyl terminated [ethylene adipate/terephthalate(1/1)]2.0,

octyl/decyl( 1/ 1 )terminated [1,3-butylene adipate/phthalate(1/2)]2.0,

dodecyl terminated [ethylene adipate/isophthalate(1/1)]2.0,

octyl/decyl( 1/ 1 (terminated [1,3-butylene adipate/phthalate l /2) ]2.3,

dodecyl terminated [ethylene pimelate/phthalate(1/ 1 2.0,

octyl/decyl( 1/ 1 )terminated [1,4-butylene adipate/ phthalate( 1/ 2) 2.3,

do decyl terminated [ethylene malonate/phthalate(1/5) ]2.0,

octyl/decyl 1/ 1 )terminated [1,4-pentylene adipate/ phthalate( 1/ 2) 2.0,

octyl terminated [ethylene sebacate/phthalate(1/1)]2.0,

octyl/decyl (l/ 1 terminated [ethylene adipate/ isophthalate( 1/ 2) ]2.0,

dodecyl terminated [ethylene tetradecandioate/ phthalate 1/ 5 ]2.0,

isodecyl terminated [ethylene adipate/ phthalate 1 2) 2.0,

decyl terminated [ethylene suberate/phthalate(1/1)]2.2,

isodecyl terminated [ethylene adipate/ phthalate( l/ 2) 2.7,

decyl terminated [ethylene isosebacate/4-methyl phthalate(1/1)]2.0,

isodecyl terminated [ethylene adipate/phthalate(1/2)]2.8,

decyl terminated [ethylene dimethyladipate/phthalate(1/ 1 ]2.0, and

isotridecyl terrminated [ethylene adipate/ phthalate( 1/ 2 3 .4.

The following non-limitative examples are illustrative of the preparation of the oligoesters of the invention.

By the same procedure, by suitable substitution of the reactants, other oligoesters of the invention are similarly obtained.

EXAMPLE 1 A l-liter 3-necked flask equipped with a stirrer, a gas inlet tube, a thermometer, and a Dean-Stark Trap topped with a reflux condenser, is charged with 210 parts (1.44 mole) of a mixture of n-octyl and n-decyl alcohol, 94 parts (1.52 mole) of ethylene glycol, 170 parts (1.15 mole) of phthalic anhydride, 84 parts (0.575 mole) of adipic acid, and 1.15 parts of zinc acetate. The mixture is then stirred and heated under a blanket of nitrogen gas until the pot temperature reaches 220 C. and then at 220 C. until the acid number drops to 1.5 or less. During this time, water of reaction is removed from the Dean-Stark Trap. The condenser is then set for downward distillation and the mixture is distilled at a pot temperature of 185 to 200 C. at less than 1 mm. pressure until the hydroxyl number of the residue falls below 5. The distillate weighs 65 parts. The residue is treated with Celite and filtered to give the product as a sparkling liquid with Gardner color 1" and a Gardner- Holdt viscosity V. The yield is quantitative, giving oc-tyl/ decyl terminated [ethylene adipate/phthalate]2.0.

EXAMPLE 2 Following the same procedure, there is prepared decyl terminated [ethylene 1'sosebacate/4-methyl phthalate] from n-decyl alcohol, ethylene glycol, isosebacic acid, and 4-rnethyl phthalic acid.

EXAMPLE 3 Following the same procedure, there is prepared octyl terminated [ethylene azelate/phthalate] from equivalent amounts of octyl alcohol, ethylene glycol, azelaic acid, and phthalic anhydride.

EXAMPLE 4 Following the same procedure, there is prepared 2- ethylhexyl terminated [propylene glutarate/phthala'te] from equivalent amounts of Z-ethylhexanol, propylene glycol, glutaric acid, and phthalic anhydride.

EXAMPLE 5 Following the same procedure, there is prepared dodecyl terminated [ethylene adipate/isophthalate] from equivalent amounts of dodecyl alcohol, ethylene glycol, adipic acid, and isophthalic acid.

The oligoesters of the invention are particularly useful as plasticizers for polyvinyl halide type resins and for acrylate type resins. For polyvinyl halide resins, they are characterized by a unique combination of properties: they show exceptionally good compatibility retention in high humidity and exceptionally good electrical properties; they also show 'high resistance to extraction by hydrocarbon liquids. They combine the high plasticizing efliciency, the low viscosity and easy processing of monomeric plasticizers while having the good compatibility retention of polymeric plasticizers. With acrylate resins, the oligoesters of the invention have good compatibility and permanence. They give acrylate resins that are highly plasticized, supple, and flexible for extended periods of use. The plasticized acrylates are ideally suited for many applications like in coatings, textile treatment, and the like. The acrylate resins that are plasticized with the oligoesters of the invention include the homopolymers of esters of acrylic and methacrylic acid and the copolymers of acrylic and methacrylic esters with at least one monomer copolymerizable therewith. Typical acrylate resins, suitable for plasticization, are known in the art, such as shown in United States Patents Nos. 3,050,412, columns 6, 7, 8 and 14, 2,940,950 and 3,037,955

The esters of the invention are valuable plasticizers for polyvinyl halide resins. The term polyvinyl halide resin refers to polymers containing a predominant quantity, that is, a quantity greater than 50%, generally over 60%, by weight of the monomer as vinyl halide units. This includes the homopolymers of the vinyl halides as Well as the copolymers and interpolymers of a vinyl halide and an unsaturated monomer copolymerizable therewith. Other monomers that may be copolymerized with the vinyl halide include the vinyl type monomers such as, for example, those having a single CH =C= group, such as vinylidene chloride, vinyl chloroacetate, chlorostyrene, chlorobut-adienes, etc., and those copolymers of such vinyl compounds and other unsaturated materials copolymerizable therewith, for example, copolymers of a vinyl halide, such as vinyl chloride with such materials as vinylidene chloride, vinyl esters of carboxylic acids, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; esters of unsaturated acids, for example, alkyl acrylates, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, allyl acrylate and the corresponding esters of methacrylic acid; vinyl aromatic compounds, for example, styrene; esters of a,;8-unsaturated carboxylic acids, for example, the methyl, ethyl, butyl, amyl, hexyl, octyl esters of maleic, crotonic, itaconic, fumaric acids and the like. Further useful copolymers are those obtained by copolymerization of vinyl chloride with an ester of an nip-unsaturated dicarboxylic acid, such as diethyl maleate or other esters of maleic, fumaric, aconitic, itaconic acid, etc., in which 5 to 20 parts by weight of diethyl maleate or other analogous esters are used for every to 80 parts by weight of vinyl chloride.

When the esters of the invention are employed as plasticizers for polyvinyl halide resins, they are ordinarily incorporated into the vinyl halide polymers by mixing the powdered resin with the liquid plasticizer followed by mixing and/ or kneading and then by curing the mix at an elevated temperature, for example, within the range from 150 to 200 C., on hot rolls or in a heated mixer, such as a Werner-Pileiderer or Banbury mixer. The proportion of esters that may be employed may vary over a great range since it is dependent on the particular esters of this invention which is selected, the specific polyvinyl halide resin to be plasticized, and the final degree of plasticizetion desired in the resin, this factor in itself being dependent on the ultimate application intended for the resin. With these facts in mind, one skilled in the art may use the esters in a plasticizing amount for most purposes this being from about 5 to parts, and more commonly from 20 to 60 parts, of esters per 100 parts of resin. In amounts exceeding 100 parts of ester per 100 parts of polyvinyl chloride resin, the esters of the invention are more commonly suitable for use in organosols and plastisols. One or more esters may be used in the polyvinyl halide resin.

In accordance with the invention, there may be employed one or more esters of this invention in polyvinyl halide compositions; also, the esters of the invention may be employed as the sole plasticizer; or they may be employed in conjunction with conventional plasticizers, such as alkyl ph-thalates, alkyl phosphates, monomeric or poly- 'rneric epoxides, and other plasticizers known in the art.

With the polyvinyl halide resin, there may be incorporated various stabilizers, fillers, dyes, pigments, and the like.

The value of the esters of the invention is further demonstrated by the following illustrations.

A standard resinous composition is made up from the following ingredients.

TABLE I.STAYNDARD FORMULATION Parts Polyvinyl chloride 60 Plasticizer 40 Barium cadmium laurate 1.0

The ester to be tested is incorporated into the vinyl halide polymer by the procedure described above and the resulting supple films are subjected to the following stand- 7 ard evaluation tests, further described below. Table II reports the composition of typical ester evaluated. Sample 16 is di-(2-ethylhexyl)phthalate. Table III reports the results of this evaluation.

The plasticized resins plasticized with the present oligoesters are especially useful for use in various electrical applications. For instance, the resins can be applied on electrical conductors by extrusion over the wire conduc- The symbols :2, x, R, A and G are defined in column 1. 5 tors. The plasticized resins provide excellent volume re- TABLE II.COMPOSITION OF THE OLIGOESTER Mole Per- Oligoester n cent of n R A G Aromatic Acid in A 18 33 2 9 7 Ethylene glycol. 18 50 2 9 7 D0. 17 07 1.86 8 7 Do. 18 67 1.3 9 7 Do. 18 67 2.0 9 7 Do. 1s 83 1.6 9 7 Do. 20 67 2. 0 9 7 1,3-butylenc glycol. 22 67 3. 4 13 7 Ethylene glycol. 19 07 2.7 10 7 Do. 67 2. 3 9 7 1,4butyle11c glycol. 20 67 2. 3 9 7 1,3-butylene glycol. 18 67 2. 0 9 7 Ethylene glycol. 19 67 1. 8 9 7 1,2-propylenc glycol. 21 07 2. 0 9 7 IA-pentanediol. 19 67 2. 8 10 7 Ethylene glycol.

TABLE Ill-PE RFORMANCE OF ESTER sistivity, a quality which has been shown to have excellent 25 correlation with insulation resistance. The electrical 2 3 4 5 properties in terms of insulation resistance are tested by subjecting the specimens to a significant number of volume resistivity tests which comprises subjecting the samples 1.7 5.4 10.5 o 1, 6,6 to (a) a temperature of 90 C. and 50% relative humid- 2-3 ity, and (b) a temperature of 60 C. after immersion for 115 3:0 513 Do: 20 hours in water heated to 60 C. The electrical prop- 3-2 2-; 33' erties of the plasticizing esters of this invention are com- 05 210 2.0 Do. pared with those of specimens plasticized with conveni-% 3% 3g: tional polyester plasticizers. The resins of the invention 0.7 3.5 3.3 Do. 35 are found to have typical values of volume resistivity of jg -3;-g ggabout 0.5 ohm-cm. 10 at 60 C., wet, and 0.1 ohm- 1.2 6.7 7.8 Do. cn1. l0 at 90 C., dry. The oligoesters of the inveng g1? 2' 38: tion, therefore, make excellent plasticizers for resins for extrusion over cables, wires, and various other conductors;

High or medium molecular weight conventional polyesters average about 15 to about 60 days in the high humidity conditions of Test 5.

It is apparent that the oligoester-plasticized polyvinyl chlorides of the invention have excellent resistance to extraction by solvents and soapy water combined with good resistance to high humidity conditions.

Oligoesters 1 and 2, 3 and 4 (20 parts of each), 4, 5, and 6 (10 parts of each), and 1, 2, 3, and 4 (10 parts of each) are blended into the polyvinyl chloride resin to make a standard formulation. The resulting resinous compositions are supple, pliable and evidence the general combination of properties as described in Table III.

The above standard formulations are modified by replacing polyvinyl chloride by copolymers of Parts Vinyl chloride 87 Vinyl acetate 13 Vinyl chloride 80 Vinylidene chloride 20 Vinyl chloride 80 Methyl acrylate 20 Vinyl chloride 95 Vinyl isobutyl ether 5 and integrating therewith oligoesters 1 to 15 of Table II.

The resulting resinous compositions are supple and flexible exhibiting the same general properties as shown in Table III.

for coatings, such as in dispersion coatings, for metal plates and the like. Also, the plasticized resins of the invention are useful in plastisol and organosol compositions.

Tests Test 1t0rsi0nal modulus at low temperatures.A 2% x A1. sample is cut and mounted in a Tinius-Olsen stiffness tester, which measures the torsional modulus of plastic at various temperatures. The temperature at which a specimen has a torsional modulus of 135,000 lbs./ sq. in., known as T of T135410) is determined. This roughly corresponds to the brittle point obtained by cantilever apparatus.

Test 2activated carbon volatility.2" squares of weighed specimens are placed between 2-inch layers of activated carbon in sealed glass jars, which are maintained at C. for 24 hours. The specimens are removed, dusted free of carbon and reweighed.

Test 3s0apy water extraction .-3" squares of Weighed specimens are immersed in a 1% aqueous solution of Ivory soap at 90 C. for 24 hours, after which they are thoroughly washed, dried, and reweighed.

Test 4hexane cxtracti0n.Weighed samples are immersed in white, lead-free hexane at 25 C. for two hours, after which they are thoroughly dried and reweighed.

Test 5high humidizy.Molded 1" x 2" specimens are suspended in a closed 2 ounce jar containing 10 ml. of water. The closed jar is placed in an oven at 60 C. for a definite exposure time. Upon removal from the jar, the samples are allowed to equilibrate and the amount of spew on the specimens is evaluated visually and manually. After a definite spew has developed, the number of days is recorded.

Test 6-v0lume resistivity.The procedure followed is described in Rubber Age, April 1956, on pages 9 108, by C. E. Balmer and R. F. Conyne, and in Resin Review, Rohm & Haas Company, Resinous Products, vol. VI, No. 1, pages 39.

METHOD FOR CALCULATING THE VALUE FOR w The value for x is calculated from the amount of alcohol and glycol consumed in the preparation of the oligoester: for example, in the preparation of octyl/decyl(l/ 1) terminated poly[ethylene adipate/phthalate(1/l)2.24, 189 parts of octyl/decyl alcohol (equivalent weight 147) and 81.2 parts of ethylene glycol are charged to the reaction along with 148 parts of phthalic anhydride and 73 parts of adipic acid. 49 parts of alcohol and 14.6 parts of glycol are recovered along with the product. The amount of alcohol consumed is, therefore, 140 parts or 0.952 mole. The amount of glycol consumed is 66.6 parts or 1.07 moles. The moles of glycol consumed per two moles of alcohol is, therefore, 2.24, which is the value of x.

I claim:

1. A plasticized vinyl chloride resinous composition comprising a vinyl chloride resin selected from the group consisting of homopolymers of vinyl chloride and copolymers of vinyl chloride with an ethylenically unsaturated monomer, said copolymer containing at least about 60% by weight of combined vinyl chloride, and incorporated therein a plasticizing amount of an alkanol terminated oligoester having the general formula L .L wherein R is a saturated aliphatic alcohol residue consisting of a hydrocarbon nucleus and an oxygen atom linked thereto having an average carbon content of 7 to 13 carbon atoms,

A is an organic dibasic acid residue consisting of a hydrocarbon nucleus and two carbonyl groups linked thereto, said organic dibasic acid residue further having an average of 4 to 14 carbon atoms derived from a mixture of an aliphatic dibasic acid and an aromatic dibasic acid,

G is a glycol residue consisting of a hydrocarbon nucleus and two oxygen atoms linked thereto having an average of 2 to 6 carbon atoms,

x represents the number of recurring glycol dibasic acid units in the oligoester and ranges from 1.2 to 4.6,

the oligoester being further characterized by the fact that the value for y, the molar percent of the aromatic residue in the organic acid residue of the oligoester and the value for x is a common point falling within the pentagram ABCED of FIGURE I of the annexed drawing, and that the value for n, the sum of the carbon atoms in one mole of the components R, A, and G of the oligoester is not less than the value represented by a line belonging to a family of lines, the limits of which are AB and DC.

2. The plasticized resinous composition of claim 1 in which said oligoester is present in the amount of from about to 100 parts per 100 parts of resin, all parts being on a weight basis.

3. The plasticized resinous composition of claim 1 in which said oligoester is present in the amount of from about 20 to 60 parts per 100 parts of resin, all parts being on a weight basis.

4. The composition of claim 1 in which the resin is a homopolymer of vinyl chloride.

5. The composition of claim 1 in which the resin is a copolymer of vinyl chloride and an unsaturated monomer copolymerizable therewith, said copolymer containing at least about 60% by weight of the combined vinyl chloride.

6. The plasticized resinous composition of claim 1 in which for the oligoester the value for x is a common point falling within the pentagram GLFK and n ranges between a value of 15.5 and 27.5.

7. The composition of claim 1 in which in the oligoester the number of recurring dibasic acid-glycol units in the oligoester is a number ranging from 2.2 to 4.6.

8. The plasticized resinous composition of claim 1 in which in the oligoester the saturated, aliphatic dibasic acid residue has a content of 5 to 10 carbon atoms.

9. The plasticized resinous composition of claim 8 in which in the oligoester the glycol residue is that of a glycol of the general formula HO (C H OH in which z is an integer of 2 to 5 and n is 1.

10. The plasticized resinous composition of claim 8 in which in the oligoester R is a residue of a straight chain alkanol having 8 to 12 carbon atoms.

11. The plasticized resinous composition of claim 8 in which in the oligoester R is a mixed octyl/decyl residue averaging 8 carbon atoms,

A comprises 65 to mole percent of aromatic acid,

and

x is a number ranging from 2.2 to 2.4.

12. The plasticized resinous composition of claim 8 in which in the oligoester R averages 12 carbon atoms,

A comprises 65 to 80 mole percent of aromatic acid,

and

x is a number ranging from 2.5 to 2.8.

13. The composition of claim 1 in which the oligoester is octyl/decyl(l/1)terminated [ethylene adipate/phthalate(1/2)]2.2.

14. The composition of claim 1 in which the oligoester is decyl terminated [ethylene isosebacate/ 4-methy1 phthalate(1/ 1 2.0.

15. The composition of claim 1 in which the oligoester is isodecyl terminated [ethylene adipate/phthalate(1/1)] 2.8.

16. The composition of claim 1 in which the oligoester is isodecyl terminated [ethylene adipate/ phthalate(1/ 2)] 2.7.

17. The composition of claim 1 in which in the oligoester R averages at least 9.2 carbon atoms,

A comprises 50 to 80 mole percent of aromatic acid,

and

x is a number ranging from 2.2 to 2.8.

References Cited by the Examiner UNITED STATES PATENTS 2,647,098 7/1953 Smith et al. 26031.8 3,057,824 10/ 1962 Le Bras et al. 3,057,908 10/1962 Gruschke et a1 260475 3,086,044 4/ 1963 Kerschner et al. 260-475 3,088,928 5/1963 Berres et al.

MORRIS LIEBMAN, Primary Examiner.

ALAN LIEBERMAN, Examiner.

L. T. JACOBS, Assistant Examiner.

Claims

1. A PLASTICIZED VINYL CHLORIDE RESINOUS COMPOSITION COMPRISING A VINYL CHLORIDE RESIN SELECTED FROM THE GROUP CONSISTINF OF HOMOPOLYMERS OF VINYL CHLORIDE AND COPOLYMERS OF VINYL CHLRIDE WITH AN ETHYLENICALLY UNSATURATED MONOMER, SAID COPOLYMER CONTAINING AT LEAST ABOUT 60% BY WEIGHT OF COMBINED VINYL CHLORIDE, AND INCORPORATED THEREIN A PLASTICIZING AMOUNT OF AN ALKANOL TERMINATED OLIGOESTER HAVING THE GENERAL FORMULA R-(A-G)X-A-R WHEREIN R IS A SATURATED ALIPHATIC ALCOHOL RESIDUE CONSISTING OF A HYDROCARBON NUCLEUS AND AN OXYGEN ATOM LINKED THERETO HAVING AN AVERAGE CARBON CONTENT OF 7 TO 13 CARBON ATOMS, A IS AN ORGANIC DIBASIC ACID RESIDUE CONSISTING OF A HYDROCARBON NUCLEUS AND TWO CARBONYL GROUPS LINKED THERETO, SAID ORGANIC DIBASIC ACID RESIDUE FURTHER HAVING AN AVERAGE OF 4 TO 14 CARBON ATOMS DERIVED FROM A MIXTURE OF AN ALIPHATIC DIBASIC ACID AND AN AROMATIC DIBASIC ACID, G IS A GLYCOL RESIDUE CONSISTING OF A HYDROCARBON NUCLEUS AND TWO OXYGEN ATOMS LINKED THERETO HAVING AN AVERAGE OF 2 TO 66 CARBON ATOMS, X REPRESENTS THE NUMBER OF RECURRING GLYCOL DIBASIC ACID UNITS IN THE OLIGOESTER AND RANGES FROM 1.2 TO 4.6, THE OLIGOESTER BEING FURTHER CHARACTERIZED BY THE FACT THAT THE VALUE FOR Y, THE MOLAR PERCENT OF THE AROMATIC RESIDUE IN THE ORGAIC ACID RESIDUE OF THE OLIGOESTER AND THE VALUE FOR X IS A COMMON POINT FALLING WITHIN THE PENTAGRAM ABCED OF FIGURE I OF THE ANNEXED DRAWING, AND THAT THE VALUE FOR N, THE SUM OF THE CARBON ATOMS IN ONE MOLE OF THE COMPONENTS R, A, AND G OF THE OLIGOESTER IS NOT LESS THAN THE VALUE REPRESENTED BY A LINE BELONGING TO A FAMILY OF LINES, THE LIMITS OF WHICH ARE AB AND DC.