US3284399A - Vinyl halide resins plasticized with an alkanol terminated oligoester - Google Patents

Vinyl halide resins plasticized with an alkanol terminated oligoester Download PDF

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US3284399A
US3284399A US262775A US26277563A US3284399A US 3284399 A US3284399 A US 3284399A US 262775 A US262775 A US 262775A US 26277563 A US26277563 A US 26277563A US 3284399 A US3284399 A US 3284399A
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oligoester
terminated
carbon atoms
value
glycol
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John O Van Hook
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Rohm and Haas Co
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Rohm and Haas Co
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Priority to NL297228D priority Critical patent/NL297228A/xx
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Priority to US262775A priority patent/US3284399A/en
Priority to DE19631468545 priority patent/DE1468545A1/de
Priority to DE19631569322 priority patent/DE1569322A1/de
Priority to GB26965/63A priority patent/GB1037625A/en
Priority to ES290568A priority patent/ES290568A1/es
Priority to AT696563A priority patent/AT264844B/de
Priority to DK410063A priority patent/DK109473C/da
Priority to FR957324A priority patent/FR1469454A/fr
Priority to BE641317A priority patent/BE641317A/xx
Priority to CH1549463A priority patent/CH465857A/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • R has an average of 9 carbon atoms
  • A has an average of 7 carbon atoms
  • G has an average of 2 carbon atoms
  • 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.
  • 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.
  • 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.
  • the points F, K, and G correspond to points C, E, and D, respectively; and point L to points A, B.
  • 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.
  • point I corresponds to ponts F and K, point I to point G, and point H to point L.
  • 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.
  • 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:
  • 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,
  • 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.
  • 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.
  • 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.
  • It ranges from 16 to 25.7; the mole percent, y, of aromatic acid in mixture A ranges from 60 to 80.
  • x ranges from 2.25 to 3.85.
  • oligoesters are those in which the alcohol residue contains an average of carbon atoms ranging from 8.5 to 10.5
  • 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,
  • 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.
  • the temperature of the esterification is maintained in the range of 160 to 220 C.
  • 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.
  • 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.
  • n-octyl terminated [hexamethylene adipate/phthalate(1/1) ]2.0
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • an ester of an nip-unsaturated dicarboxylic acid such as diethyl maleate or other esters of maleic, fumaric, aconitic, itaconic acid, etc.
  • 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.
  • 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.
  • esters of this 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.
  • conventional plasticizers such as alkyl ph-thalates, alkyl phosphates, monomeric or poly- 'rneric epoxides, and other plasticizers known in the art.
  • polyvinyl halide resin there may be incorporated various stabilizers, fillers, dyes, pigments, and the like.
  • esters of the invention is further demonstrated by the following illustrations.
  • a standard resinous composition is made up from the following ingredients.
  • 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.
  • 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.
  • 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.
  • High or medium molecular weight conventional polyesters average about 15 to about 60 days in the high humidity conditions of Test 5.
  • 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 resulting resinous compositions are supple and flexible exhibiting the same general properties as shown in Table III.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • A comprises 65 to mole percent of aromatic acid
  • x is a number ranging from 2.2 to 2.4.
  • A comprises 65 to 80 mole percent of aromatic acid
  • x is a number ranging from 2.5 to 2.8.
  • composition of claim 13 in which the oligoester is octyl/decyl(l/1)terminated [ethylene adipate/phthalate(1/2)]2.2.
  • composition of claim 1 in which the oligoester is decyl terminated [ethylene isosebacate/ 4-methy1 phthalate(1/ 1 2.0.
  • composition of claim 1 in which the oligoester is isodecyl terminated [ethylene adipate/ phthalate(1/ 2)] 2.7.
  • A comprises 50 to 80 mole percent of aromatic acid
  • x is a number ranging from 2.2 to 2.8.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US262775A 1963-02-11 1963-03-04 Vinyl halide resins plasticized with an alkanol terminated oligoester Expired - Lifetime US3284399A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
NL297228D NL297228A (enrdf_load_stackoverflow) 1963-02-11
US262775A US3284399A (en) 1963-02-11 1963-03-04 Vinyl halide resins plasticized with an alkanol terminated oligoester
DE19631468545 DE1468545A1 (de) 1963-02-11 1963-06-25 Oligoester und Verfahren zu ihrer Herstellung
DE19631569322 DE1569322A1 (de) 1963-02-11 1963-06-25 Weichmacher fuer Polyvinylchlorid- oder Acrylatharze
GB26965/63A GB1037625A (en) 1963-02-11 1963-07-08 Complex esters
ES290568A ES290568A1 (es) 1963-03-04 1963-08-03 Metodo para preparar una composición resinosa plastificada
AT696563A AT264844B (de) 1963-03-04 1963-08-29 Weichgemachte Harzzusammensetzung
DK410063A DK109473C (da) 1963-03-04 1963-08-29 Blødgjort polyacrylatharpiks eller vinylchloridpolymerharpiks, der som blødgøringsmiddel indeholder mindst én dicarboxylsyreoligoester med endestillede alkanolrester.
FR957324A FR1469454A (fr) 1963-02-11 1963-12-16 Compositions résineuses contenant des oligoesters
BE641317A BE641317A (enrdf_load_stackoverflow) 1963-02-11 1963-12-16
CH1549463A CH465857A (fr) 1963-02-11 1963-12-17 Composition résineuses plastifiées

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US25744563A 1963-02-11 1963-02-11
US262775A US3284399A (en) 1963-02-11 1963-03-04 Vinyl halide resins plasticized with an alkanol terminated oligoester

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DE (2) DE1468545A1 (enrdf_load_stackoverflow)
GB (1) GB1037625A (enrdf_load_stackoverflow)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3376242A (en) * 1963-09-23 1968-04-02 Rohm & Haas Polyesters derived from adipic acid-isophthalic acid mixtures as plasticizers for vinyl halide polymers
WO2004011523A3 (en) * 2002-07-31 2004-05-27 Procter & Gamble Novel phase change solvents

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2647098A (en) * 1951-11-08 1953-07-28 Firestone Tire & Rubber Co Linear polyester plasticizers
US3057908A (en) * 1955-06-24 1962-10-09 Hoechst Ag Process for preparing high molecular linear polyesters from polymethylene glycols and esters of benzene dicarboxylic acids
US3057824A (en) * 1959-03-31 1962-10-09 Pittsburgh Plate Glass Co Tin salts as catalysts in forming polyesters
US3086044A (en) * 1960-05-27 1963-04-16 Cities Service Res & Dev Co Method of preparing complex diesters of a dibasic acid with a diol and an excess of a monohydric alcohol
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US3057908A (en) * 1955-06-24 1962-10-09 Hoechst Ag Process for preparing high molecular linear polyesters from polymethylene glycols and esters of benzene dicarboxylic acids
US3057824A (en) * 1959-03-31 1962-10-09 Pittsburgh Plate Glass Co Tin salts as catalysts in forming polyesters
US3088928A (en) * 1959-10-01 1963-05-07 Johnson & Son Inc S C Novel emulsifiable waxy linear polyesters
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* Cited by examiner, † Cited by third party
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US3376242A (en) * 1963-09-23 1968-04-02 Rohm & Haas Polyesters derived from adipic acid-isophthalic acid mixtures as plasticizers for vinyl halide polymers
WO2004011523A3 (en) * 2002-07-31 2004-05-27 Procter & Gamble Novel phase change solvents

Also Published As

Publication number Publication date
CH465857A (fr) 1968-11-30
NL297228A (enrdf_load_stackoverflow)
BE641317A (enrdf_load_stackoverflow) 1964-04-16
DE1468545A1 (de) 1969-03-13
DE1569322A1 (de) 1969-12-11
GB1037625A (en) 1966-07-27

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