US3326835A - Intermediate and microcrystalline wax polybutene-1 resin blends - Google Patents

Intermediate and microcrystalline wax polybutene-1 resin blends Download PDF

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Publication number
US3326835A
US3326835A US395205A US39520564A US3326835A US 3326835 A US3326835 A US 3326835A US 395205 A US395205 A US 395205A US 39520564 A US39520564 A US 39520564A US 3326835 A US3326835 A US 3326835A
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United States
Prior art keywords
wax
polybutene
creased
microcrystalline
waxes
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Expired - Lifetime
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US395205A
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English (en)
Inventor
Richard A Signorelli
Joseph I Wrozina
John J Kaufman
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Allied Corp
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Allied Chemical Corp
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Publication date
Priority to BE669414D priority Critical patent/BE669414A/xx
Application filed by Allied Chemical Corp filed Critical Allied Chemical Corp
Priority to US395205A priority patent/US3326835A/en
Priority to NL6511669A priority patent/NL6511669A/xx
Priority to FR30775A priority patent/FR1458421A/fr
Priority to DE19651570066 priority patent/DE1570066A1/de
Application granted granted Critical
Publication of US3326835A publication Critical patent/US3326835A/en
Anticipated expiration legal-status Critical
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/18—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising waxes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • C09D191/06—Waxes
    • C09D191/08—Mineral waxes

Definitions

  • This invention relates to petroleum fwax compositions and more particularly to petroleum wax coating compositions widely used in forming protective coatings for wrapping paper and paperboard in the production of low-cost cartons for liquids.
  • Petroleum wax is deficient in several properties such as creased barrier properties, hardness, grease resistance, and heat sealing properties. Many additives have been proposed -for blending with petroleum Wax to improve the properties thereof.
  • the petroleum industry generally classifies petroleum waxes in three main categories, namely, (1) paraflins; (2) intermediate; and (3) microcrystalline waxes.
  • Other classes of waxes are known such as the scale waxes and slack waxes; these are low-cost crude waxes.
  • This invention is concerned with the upgrading of the intermediate and microcrystalline waxes, which, as noted, are distinct, well-known grades of refined waxes distinguishable from the parains and also the crude or low-cost waxes such as the scale and :slack waxes.
  • the paraffins are predominantly the normal paraflins, i.e., straight chain saturated hydrocarbons lwith minor amounts of isoparaflins.
  • microcrystalline waxes are predominantly cyclic saturated hydrocarbons (naphthenes) and iso parati-ins.
  • the intermediate waxes are blends or mixtures of paraffin and microcrystalline waxes. In Table I below is given the ranges of certain physical and .chemical properties of these three classes of waxes.
  • sealing strength values are determined by the standard Socony-Vacuum Seal Tester. Samples are pulled at 3 in./min. with a 100 g. load. The values given are the weight in grams required to pull apart two coated specimens which are sealed together under the predetermined temperature, pressure and dwell time specified in the test procedure. In the case-of the test results given in the specification the test specimens were each rectangular, l2 inches along, 2 inches wide, arranged in superimposed relation with a l inch seal at a temperature of 20G-250 F., pressure of 6-10 p.s.i.g. for a dwell ltime of i-LS minutes.
  • Grease resistance is a measure of the time required for a drop of the specified grease to penetrate through the coated uncreased test specimen.
  • the grease used in the test results given herein was Wesson Oil applied at ambient temperatures and maintained at F. until failure of the coating.
  • intermediate and microcrystalline waxes are ugraded by blending therewith from 10% to 40%, preferably 15% to 25%, based on the weight of the coating material (wax plus polybutene-l resin) of a polybutene-l resin having a molecular weight of from 100,000 to 300,000, preferably 100,000 to 200,000, and an isotactic content of from 50% to 75%, preferably 60% to 70%.
  • this invention involves wax coating compositions consisting essentially of intermediate or microcrystalline waxes blended with from 10% to 40%, preferably 10% to 25% of the aforesaid polybutene-l resins.
  • the wax coating compositions of this invention have outstandingly good creased WVTR values.
  • creased WVTR values For example, in the case of an intermediate wax of F. melting point having a creased WV IR of 6.0, the blending with such wax of 25% polybutene-l having an isotacticity of from 65-70% and a molecular weight of 150,000 to 190,- 000 reduced the creased WV IR value to 0.5.
  • the irnprovement in creased WVTR values is significantly better than with commercial additives for waxesincluding the ethylene vinyl acetate copolymers (Elvax 250 and Elvax 420).
  • wax blends of this invention have good heat seal strength, good grease resistance and generally better overall properties than the base wax and the base wax with other additives such as polyethylene, polypropylene and even with polybutene-l resins not having the molecular weight and isotacticity hereinabove given for the polybutene-l resins blended with the intermediate and ⁇ microcrystalline waxes.
  • isotactic is used in its conventional sense to mean the material in the polymer remaining after extraction with diethyl ether; the isotactic material is substantially insoluble in hexane Iand naphtha.
  • the diethyl ether extraction removes the amorphous or atactic material (which is the material soluble in hexane and naphtha) and leaves a polymer containing the isotac-tic material.
  • the polybutene-l resin employed in forming the wax blends of the present invention can be prepared by polymerizing butene-l using a Ziegler type catalyst and conducting the polymerization under conditions to produce a polymer having the desired isotactic content of from 50%l to 75% and desired molecular weight of from 100,000'to 300,000.
  • any of the known Ziegler catalysts can be used; Vfor example, catalysts obtained by reaction between compounds of metals of Group IV-A (titanium, zirconium, hafnium or thorium), V-A (vanadium, columbiu'm or tantalurn), VI-A (chromium, molybdenum, tungsten or uranium) with alkyl compounds of aluminum a or a metal of Group II (beryllium, magnesium, calcium,
  • Polybutene produced by polymerization using stereospecic catalysts such as CrO3 or SiOz-AlgOa support or a catalystkconsisting of a promoted M003 may also be used. In all cases the polymerization must be timed and moderated Ato produce ;a polybutene-l having the desired molecular weight and isotactic content. Hydrogen can be introduced into the polymerization reaction mixture to control the molecular weight and percent isotacticity. Polybutene-l polymers having an isotactic content of from 50% to 75 and a molecular weight of from 100,000 to 300,000 produced by any known procedure can be used.
  • Polybutene-l resins having the above noted isotactic contents and molecular weights blend readily with the intermediate and microcrystalline waxes.
  • a three-necked ask equipped with an electric drive stirrer, a thermometer, and a nitrogen inlet tube is charged with a measured amount of the wax.
  • the Wax is heated under nitrogen with moderate stirring until a clear liquid results.
  • a charge of the polybutene-l resin having the molecular weight and is-otacticity and in amount all as herein disclosed.
  • the mixture is heated to a temperature above the melting point of the wax and stirred to assist solution.
  • the mixture can be maintained under a continuous blanket of nitrogen ⁇ during the heating and stirring, if desired, and particularly when the heating is carried out under higher temperatures than C.
  • the polybutene-l charge is completely dissolved in the wax -in approximately onehalf hour; this is evident upon visual inspection. Desirably, however, heating of the blend is continued for an additional one-quarter hour to insure complete dissolution of the resin in the wax.
  • the blend is thereupon allowed to cool to( ambient temperature.
  • FIGURE 1 is a graph showing the creased WVTR plotted against the precent concentration of two polybutene resins, one having a molecular weight of 150,000 and an isotactic content of 64% (hereinafter referred to as PB-l) and the other a molecular weight of 190,000 and an isotactic content of 68% (hereinafter referred to as PB-Z).
  • PB-l molecular weight of 150,000 and an isotactic content of 64%
  • PB-Z isotactic content of 68%
  • Curve B is the ygraph for blends of this intermediate wax with both polybutene-l resins; the creased WVTR values for 4blends with both resins are substantially the same.
  • Line C is the graph for blends of the intermediae wax with an ethylene vinyl acetate copolymer (Elvax 250). It will be noted that at concentrations of 15%, the creased WVTR value for the Elvax wax blend is appreciably greater than that for the base wax whereas the blends with polybutene resin have creased WVTR values of about 3 as compared with 5 for the base wax. At 20% concentration the creased WVTR value for the Elv ⁇ ax wax blend is about 6 and for the polybutene resin wax blends is about 1.
  • FIGURE 2 is a graph showing the creased WVTR values plotted against percent concentration for (l) the base wax, an intermediate Wax; (2) a polybutene-l intermediate wax blend of this invention in which the polybutene-l resin is PB-2; (3) lan ethylene vinyl acetate copolymer having a vinyl acetate content of 28% (Elvax 250); and (4) a second ethylene vinyl acetate co-polymer having a vinyl acetate content of about 18% (Elvax 420).
  • the marked and surprising improvement in creased WV IR effected in the base intermediate wax by blending therewith the polybutene-l resins herein disclosed as compared with Elvax is evident from FIGURE 2.
  • Table IV which follows is given the comparative creased WVTR values for a microcrystalline wax, substantially the same as the typical microcrystalline wax the properties of which are given in Table II above, blended with polybutene resins PB-1 and PB-Z and for comparative purposes the creased WVTR values of blends of the same microcrystalline wax with an ethylene vinyl acetate copolymer (Elvax 250).
  • the creased WVTR Value of the base microcrystalline wax was 9.8.
  • Table V which follows gives the Sealing Strength values for blends of intermediate ⁇ and mirocrystalline waxes with PB-l and PB-2 resins at 20% and 25 concentrations.
  • the sealing strength of the base intermediate wax was 27 and that of the base microcrystalline wax was 150.
  • Table VI which follows gives the grease resistance of blends of intermediate Wax with PB-l and PB-2 in concentration of and 20%. This test was carried out on uncreased paper with Wesson Oil applied at ambient temperatures and maintained at 105 F,
  • Examples of this invention have been give in the above including the tables which include comparative data demonstrating the improvements in creased WVTR values and sealing strength values embodied in the blends of intermediate and microcrystalline wax with polybutene-l resins having a molecular weight of from 100,- 000 to 300,000 and an isotactic content of from 50% to 75% as compared with Iblends of the same base wax with known commercial additives, namely the ethylene polyvinyl acetate copolymers.
  • the wax blends embodying the present invention are eminently satisfactory for use in existing coating equipment. They can be employed in all lields Where wax coatings of superior creased barrier properties, heat seal strength, or good grease resistance nd application.
  • the blends of this invention, in the molten state, can be applied by known coating techniques to foil, parchment, kraft, glassine, chipboard and other paper stocks to produce packaging materials having an attractive gloss and exceptionally good creased vapor barrier.
  • a petroleum wax blend consisting essentially of a petroleum wax from the group consisting of intermediate Wax distilling within the temperature range of about S-900 F. and microcrystalline wax distilling within the 2O temperature range of about 950-1050" F. and from 10% to 40% by weight of a polybutene-l resin having a molecular weight of from 100,000 to 3000,000 and an isotactic content of from 50% to 75 by weight, said blend having creased Water vapor transmission rate less than that of 25 the petroleum Wax.
  • a petroleum wax blend of improved creased resistance to transmission of water vapor therethrough and improved heat sealability which consists essentially of an intermediate wax blended with from 15% to 25 by weight of a polybutene-l resin having a molecular weight of from 100,000 to 200,000 and an isotactic content of from 60% to 70% by Weight.
  • a petroleum wax blend of improved creased :resistance to transmission of water vapor therethrough and improved heat scalability which consists essentially of a 40 microcrystalline wax blended with from 15 to 25 by weight of a polybutene-l resin having a molecular Weight of from 100,000 to 200,000 land an isotactic content of from 60% to 70% by weight.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US395205A 1964-09-09 1964-09-09 Intermediate and microcrystalline wax polybutene-1 resin blends Expired - Lifetime US3326835A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE669414D BE669414A (pt) 1964-09-09
US395205A US3326835A (en) 1964-09-09 1964-09-09 Intermediate and microcrystalline wax polybutene-1 resin blends
NL6511669A NL6511669A (pt) 1964-09-09 1965-09-07
FR30775A FR1458421A (fr) 1964-09-09 1965-09-08 Mélanges de cires de pétrole avec une polyoléfine, avantageux pour enduire du papier et des matières similaires
DE19651570066 DE1570066A1 (de) 1964-09-09 1965-09-09 Erdoelwachs und Polybuten-1 enthaltende Massen

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3389107A (en) * 1965-06-21 1968-06-18 Chevron Res Wax-(propene/butene copolymer) films
US3619272A (en) * 1967-09-01 1971-11-09 Princeton Chemical Res Inc Method for coating polyolefin or paper supports with chlorinated butene-1 polymer coatings
US4954373A (en) * 1988-11-30 1990-09-04 Conoco Inc. Fibrous substrates containing hot melt coatings made from a novel petroleum wax
US4965305A (en) * 1988-11-30 1990-10-23 Conoco Inc. Hot melt coatings made from a novel petroleum wax
US5010126A (en) * 1988-11-30 1991-04-23 Conoco Inc. Process for producing a petroleum wax composition
US20120045587A1 (en) * 2010-08-23 2012-02-23 Sharoyan Davit E Papermaking Additives for Roll Release Improvement
WO2014138659A2 (en) 2013-03-08 2014-09-12 Ultradent Products, Inc. Wax-based compositions, articles made therefrom, and methods of manufacture and use
US20150176213A1 (en) * 2010-06-07 2015-06-25 Solenis Technologies, L.P. Creping release agents
US10913853B2 (en) 2013-10-11 2021-02-09 Ultradent Products, Inc. Wax-based compositions, articles made therefrom, and methods of manufacture and use

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2691647A (en) * 1952-12-06 1954-10-12 Standard Oil Co Conversion of ethylene and/or propylene to solid polymers in the presence of group 6a metal oxides and alkali metals
US2824089A (en) * 1955-03-08 1958-02-18 Standard Oil Co Hydrocarbon conversion
US2932633A (en) * 1956-03-28 1960-04-12 Standard Oil Co Catalytic conversion and catalysts
GB849389A (en) * 1957-10-09 1960-09-28 Phillips Petroleum Co Blend of microcrystalline wax and olefin polymer and method for production thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2691647A (en) * 1952-12-06 1954-10-12 Standard Oil Co Conversion of ethylene and/or propylene to solid polymers in the presence of group 6a metal oxides and alkali metals
US2824089A (en) * 1955-03-08 1958-02-18 Standard Oil Co Hydrocarbon conversion
US2932633A (en) * 1956-03-28 1960-04-12 Standard Oil Co Catalytic conversion and catalysts
GB849389A (en) * 1957-10-09 1960-09-28 Phillips Petroleum Co Blend of microcrystalline wax and olefin polymer and method for production thereof

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3389107A (en) * 1965-06-21 1968-06-18 Chevron Res Wax-(propene/butene copolymer) films
US3619272A (en) * 1967-09-01 1971-11-09 Princeton Chemical Res Inc Method for coating polyolefin or paper supports with chlorinated butene-1 polymer coatings
US4954373A (en) * 1988-11-30 1990-09-04 Conoco Inc. Fibrous substrates containing hot melt coatings made from a novel petroleum wax
US4965305A (en) * 1988-11-30 1990-10-23 Conoco Inc. Hot melt coatings made from a novel petroleum wax
US5010126A (en) * 1988-11-30 1991-04-23 Conoco Inc. Process for producing a petroleum wax composition
US9267239B2 (en) * 2010-06-07 2016-02-23 Solenis Technologies, L.P. Creping release agents
US20150176213A1 (en) * 2010-06-07 2015-06-25 Solenis Technologies, L.P. Creping release agents
US8865263B2 (en) * 2010-08-23 2014-10-21 Solenis Technologies, L.P. Papermaking additives for roll release improvement
US20120045587A1 (en) * 2010-08-23 2012-02-23 Sharoyan Davit E Papermaking Additives for Roll Release Improvement
WO2014138659A2 (en) 2013-03-08 2014-09-12 Ultradent Products, Inc. Wax-based compositions, articles made therefrom, and methods of manufacture and use
EP2964142A4 (en) * 2013-03-08 2016-08-24 Ultradent Products Inc WAX BASE COMPOSITIONS, ITEMS PRODUCED THEREFROM, METHOD OF MANUFACTURE AND USE THEREOF
US10646318B2 (en) 2013-03-08 2020-05-12 Ultradent Products, Inc. Wax-based compositions, articles made therefrom, and methods of manufacture and use
US11931220B2 (en) 2013-03-08 2024-03-19 Ultradent Products, Inc. Wax-based compositions, articles made therefrom, and methods of manufacture and use
US10913853B2 (en) 2013-10-11 2021-02-09 Ultradent Products, Inc. Wax-based compositions, articles made therefrom, and methods of manufacture and use
US11597841B2 (en) 2013-10-11 2023-03-07 Ultradent Products, Inc. Wax-based compositions, articles made therefrom, and methods of manufacture and use

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DE1570066A1 (de) 1969-07-24
NL6511669A (pt) 1966-03-10
BE669414A (pt)

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