US3048551A - Polyethylene-wax compositions - Google Patents

Polyethylene-wax compositions Download PDF

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Publication number
US3048551A
US3048551A US854013A US85401359A US3048551A US 3048551 A US3048551 A US 3048551A US 854013 A US854013 A US 854013A US 85401359 A US85401359 A US 85401359A US 3048551 A US3048551 A US 3048551A
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US
United States
Prior art keywords
wax
density
waxes
weight
compositions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US854013A
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English (en)
Inventor
Robert G Lutz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell USA Inc
Original Assignee
Shell Oil Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to NL258061D priority Critical patent/NL258061A/xx
Priority to BE597186D priority patent/BE597186A/nl
Application filed by Shell Oil Co filed Critical Shell Oil Co
Priority to US854013A priority patent/US3048551A/en
Priority to CH1289760A priority patent/CH391295A/de
Priority to GB39500/60A priority patent/GB887987A/en
Priority to DEP1270A priority patent/DE1270209B/de
Priority to FR844186A priority patent/FR1284548A/fr
Application granted granted Critical
Publication of US3048551A publication Critical patent/US3048551A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/18Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising waxes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06Waxes
    • C08L91/08Mineral waxes

Definitions

  • This invention relates to improved wax compositions. More particularly, the invention relates to wax compositions containing a combination of particular polyethylenes or polypropylenes and having special utility as dairy carton wax coatings.
  • Waxes are broadly divided into several well established groups. These include parafiin waxes (normally obtained from petroleum oil lubricating distillates), microcrystalline wax (usually obtained from residual lubricating oil fractions), soft waxes which include isoparaffinic and napthenic waxes usually obtained during the deoiling of parafiin waxes, and the so-called high melting point waxes normally obtained by fractionating microcrystalline wax. Each of these wax types has been found to have specific physical properties making them especially attractive for particular utilities. For example, many of these waxes are used either alone or in combination for the waterproofing of food cartons and particularly for the preparation of dairy food cartons.
  • waxes must have critically limited properties due to the handling which such cartons are subjected to during their manufacture, storage and transportaion as well as the temperatures which they encounter during these stage of use.
  • the problem is complicated also by the specific size of the container since many smaller containers are not as critically demanding in the properties of the wax used to waterproof them as are the larger containers such as half-gallon size milk cartons.
  • It is normally the practice to combine several waxes having different properties in order to attain an optimum combination of properties including melting point, shock resistance, blocking point, resistace to flaking, and other properties which will be more fully discussed hereinafter.
  • Certain non-wax components are often added to wax compositions and particularly to food wax coating compositions. These include especially hydrocarbon polymers such as polyethylene.
  • wax compositions containing a variety of polyethylenes has been treated in numerous patents as well as in the technical literature.
  • polyethylenes employed have had average molecular weights in the range of about 1500 to about 20,000.
  • Certain combinations of polyethylenes have been shown to have certain advantages. The combinations have included a mixture of low and high average molecular weight polyethylenes in order to obtain an optimum combination of physical properties in the wax compositions. While these various additives and their combinations have been found to have beneficial results, they by no means have completely cured the objectionable features encountered in food carton coatings.
  • wax consumption by which is meant the amount of wax composition found to be necessary for satisfactory coating of the wax carton. Since these cartons are utilized on a large scale for low priced products, it is essential to provide satisfactory coatings using a minimum amount of the composition for this purpose. Consumption is a function of wax actually absorbed into the carton board, wax viscosity and its solidification characteristics.
  • improved wax compositions comprising a major amount of a petroleum wax having a melting point within the range from about to about F., the wax containing a combination of two types of polyalkene, one type being a low density polyalkene while the other is a relatively high density polyalkene.
  • dairy food wax compositions having improved properties relative to their shock resistance at cold temperatures combined with relatively lower wax consumption and reduced wax adsorption, said compositions comprising 40-60% by weight of a distillate parafiin wax having a melting point between about 122 and 142 F.; 5-20% by weight of a heavy distillate paraffin having a melting point between about 145 and 175 F.; 10-20% by weight of a residual microcrystalline wax; 25-40% by weight of an isoparafiinionapthenic plastic distillate wax having a melting point between about 102 and 115 F.; and a polyalkene, preferably polyethylene in an amount between about 0.255% (preferably 0.35-l.5%) having a density between about 0.870 and 0.900 at 20 C.
  • a higher density poly alkene preferably polyethylene, having a density between about 0.915 and about 0.960, the average molecular weights of each of the polyalkenes being between about 1000 and about 12.000. Best results are obtained if the high density polyethylene has a cloud point above F.
  • compositions exhibit a substantial (4-15 F.) difference between the congealing point (ASTM Test D 938) and the melting point (ASTM Test D 87).
  • the polyalkenes comprise one or more lower density materials and one or more higher density materials.
  • the densities at 20 C. of the materials as described herein are obtained by a hydrostatic method in air and kerosene.
  • these polyalkenes have molecular weights within the range from 1,000 to about 12,000 and more particularly from about 1,500 to about 6,000.
  • the effects of the combination of polyalkenes as described appear to be largely independent of the average molecular weight of each of the two polyalkenes.
  • the polyalkenes may be either polyethylene or polypropylenes and may be prepared by any of the well known methods, such as those described in the book Polyethylene, by Ralf and Allison, Interscience Publishers Incorporated (1956). Table I below gives typical examples of polyethylenes regarded as having low densities according to the range of densities recited herein.
  • the invention applies broadly to the modification of .any petroleum Wax with the high and low density polyalkenes.
  • dairy food carton compositions which meet a stringent and interlocking series of requirements relative to their physical properties.
  • Ordinary paraflin waxes have been found to be entirely too brittle when utilized alone at dairy storage temperatures.
  • Their use, in unmodified form, as coating compositions is entirely unsatisfactory due to their brittle nature at low temperatures, which results in very excessive flaking and disintegration of the coating.
  • One of the earlier modifications of such compositions was to combine a substantial amount of microcrystalline wax with paraffin wax.
  • Microcrystalline waxes are obtained from residual lubricating oil fractions and comprise only minor amounts of normal paraflin waxes but over about of highly branched and napthenic waxes of relatively high molecular weight. These are characterized by their malcrystalline or microcrystalline structure as contrasted with the highly crystalline character of ordinary distillate normal parafiin waxes.
  • the resulting blend while an improvement over distillate paraffin waxes for use as carton coatings, still lacks many of the properties suitable for use as dairy carton coating compositions such as excessive absorption. Also, the melt viscosity was relatively high if more than a modest amount of microcrystalline wax was present. Also, low temperature flexibility of the composition was not improved to the most desirable extent.
  • the soft waxes so obtained comprise a mixture of isoparaflin and napthenic waxes of relatively low molecular weight which are normally contaminated by the presence of substantial amounts of oil. Consequently, the soft waxes obtained in the deoiling of distillate paraffin waxes must be deoiled for use in the present invention. They provide wax compositions with greatly increased flexibility at low temperatures and reduce the viscosity in the melted state, thus facilitating their use in the standard carton-making machinery.
  • the distillate paraflin waxes which form a major component in the present compositions preferably have melting points between about 122 and 142 F., preferably between and F. They are obtained normally by the well known operation of dewaxing the waxy distillate lubricating oil fractions obtained in petroleum refining. They comprise major amounts of normal parafiin waxes with minor amounts of non-normal paraffins, principally isoparaflins and naphthenes.
  • the heavy distillate :waxes are obtained from the highest boiling lubricating oil distillate fraction and normally have melting points between about and 175 F.
  • Residual microcrystalline waxes have only very minor amounts of normal paraffins present therein and largely predominate in highly branched and naphthenic waxes and have melting points in the order of 130-160 F., usually between about 140 and F.
  • the plastic waxes referred to hereinbefore are obtained as briefly described above, namely, by the deoiling and crude distillate waxes to obtain a so-called soft wax which contains up to about 30% by weight of oil. This oil is removed by ordinary deoiling operation at a reasonably low temperature so that the resulting wax obtained is highly isoparaffinic and naphthenic in nature and has a melting point in the order of 102-1 15 F. Consequently, the waxes which in total constitute greater than about 90% by weight of the present wax-polyalkene compositions, have the following preferred compositions:
  • Waxpolyalkene compositions are so compatible as to entail little if any problems in their assembly.
  • the waxes (assuming that more than one type of petroleum wax is utilized) are combined simply by melting the two waxes and stirring.
  • the polyalkenes are preferably incorporated by suspending them in a basket or other perforated piece of apparatus and circulating the wax melt therethrough until the polyalkene is thoroughly dispersed throughout the wax. This is preferably done at a tem perature between about 135 and 250 @F. There does not appear to be any noticeable advantage to dispersing either the low or the high density polyethylene in wax prior to incorporation of the second polyalkene.
  • wax compositions were modified with a combination of high and low density polyethylenes having substantially the same average molecular weight namely, about 4,000.
  • the wax composition utilized for this purpose was as follows:
  • Percent Distillate parafiin waX 138-140 -F. melting point 45 Heavy distillate wax, 158160 F. melting point Isoparafiinic-naphthenic plastic distillate wax, 110 F.
  • melting point 30 Residual microcrystalline wax, 145 F. melting point- This composition was modified by the high and low density polyethylenes of the same average molecular weights and by a combination of these two polyethylenes, all as shown in Table III which follows:
  • the density of the low density polyethylene employed above was 0.880, while the density of the high density polyethylene was 0.920 or 0.927 at 20 C., as indicated.
  • Half-gallon cartons were prepared utilizing the following: the same mixture of waxes employed in the tests described in Table III, modified with 1% low density polyethylene and 0.25% high density polyethylene (Sample 7, Table III).
  • the wax composition including the polyethylenes had a melting point in the order of 138 F. and a blocking temperature of 106 F.
  • Table TV which follows lists a number of important properties of this composition as applied to a standard milk carton board containing about 5% moisture when formed into half-gallon cartons.
  • the cartons formed from a composition of this invention exhibit excellent properties such as those widely demanded by dairy carton manufacturers and consumers.
  • the most significant data insofar as this invention is concerned are the remarks relative to loose strings, loose flakes" and wax consumption, the other properties such as amount of cracking, serpentining rating, etc. being highly desirable but not necessarily essential.
  • a composition of matter comprising at least by weight of petroleum wax having a melting point between and 145 F., 0.25-5% by weight of a lower density polyalkene having a density between about 0.870 and about 0.910 at 20 C. and 0.050.75% by weight of a higher density polyalkene having a density between about 0.915 and about 0.960, at 20 C., the monomeric alkenes from which the polyalkenes are prepared having 2-3 carbon atoms per molecule, each of the polyalkenes having average molecular weights between about 1,000 and about 12,000.
  • a composition of matter comprising at least 90% by Weight of a petroleum wax having a melting point between about 125 and 145 F., said wax being a mixture of 40-60% by weight of a distillate paraflin wax having a melting point of -140 F., 520% by weight of heavy distillate wax having a melting point of l45175 F., l0-20% by weight of a residual microcrystalline Wax having a melting point of l40150 F., and 2540% by weight of an isoparaffinic naphthenic plastic distillate wax having a melting point of 102-115" R, 0.351.5% by weight of a lower density polyethylene having a density between about 0.870 and about 0.900 at 20 C. and 0.05-
  • a higher density polyethylene having a density between about 0.915 and about 0.960, the average molecular Weights of each of the polyethylenes being between about 1,000 and about 12,000.
  • a composition of matter comprising 40-60% by weight of a distillate parafiin wax having a melting point between about 122 and about 142 F., 20% by weight of a heavy distillate paraffin wax having a melting point between about 142 and about 175 F., l020% by weight of a residual microcrystalline Wax, 25-40% by weight of an isoparatfinic-naphthenic plastic distillate wax having a melting point between about 102 F. and about 115 F., 0.35-1.5 by weight of a lower density polyethylene having a density between about 0.870 and about 0.900 at 20 C. and 0.05-0.75% by weight of a higher density polyethylene having a density between about 0.915 and about 0.960, the average molecular weights of each of the polyethylenes being between about 1,000 and about 12,000.
  • a wax composition comprising greater than 97% by weight of a mixture of waxes, said mixture including about 45% by Weight based on the mixture of a distillate paraffin wax having a melting point of 138140 F., about 10% by weight of the mixture of heavy distillate paraffin wax having a melting point of 158-160 F., about by Weight of the mixture of isoparaflinic-naphthenic distillate wax having a melting point of 102115 F., about 15% by Weight of the mixture of microcrystalline wax having a melting point of about -150 F., said mixture being modified with 0.35-1.5% by weight based on the mixture of a lower density polyethylene having a density between about 0.870 and about 0.9000 at 20 C. and 0.05-0.75 by weight based on the mixture of a higher density polyethylene having a density between about 0.915 and about 0.960, the average molecular weights of each of the polyethylenes being between about 1,000 and about 12,000.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paper (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
US854013A 1959-11-19 1959-11-19 Polyethylene-wax compositions Expired - Lifetime US3048551A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL258061D NL258061A (en, 2012) 1959-11-19
BE597186D BE597186A (en, 2012) 1959-11-19
US854013A US3048551A (en) 1959-11-19 1959-11-19 Polyethylene-wax compositions
CH1289760A CH391295A (de) 1959-11-19 1960-11-17 Wachsmasse
GB39500/60A GB887987A (en) 1959-11-19 1960-11-17 A wax composition
DEP1270A DE1270209B (de) 1959-11-19 1960-11-17 Wachshaltige UEberzugsmasse
FR844186A FR1284548A (fr) 1959-11-19 1960-11-17 Composition de paraffine destinée aux emballages de produits alimentaires

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US854013A US3048551A (en) 1959-11-19 1959-11-19 Polyethylene-wax compositions

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US3048551A true US3048551A (en) 1962-08-07

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US854013A Expired - Lifetime US3048551A (en) 1959-11-19 1959-11-19 Polyethylene-wax compositions

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US (1) US3048551A (en, 2012)
BE (1) BE597186A (en, 2012)
CH (1) CH391295A (en, 2012)
DE (1) DE1270209B (en, 2012)
FR (1) FR1284548A (en, 2012)
GB (1) GB887987A (en, 2012)
NL (1) NL258061A (en, 2012)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3224984A (en) * 1962-01-02 1965-12-21 Shell Oil Co Process of preparing expanded polystyrene containing a polyolefin
US3243396A (en) * 1962-03-12 1966-03-29 Socony Mobil Oil Co Inc Coating compositions containing waxes, polyethylene, polypropylene, and a polyterpene resin
US3297610A (en) * 1963-06-24 1967-01-10 Sinclair Research Inc Coating and laminating compositions consisting of a blend of paraffin, isoparaffin and microcrystalline waxes with ethylene-vinyl acetate copolymer
US3312648A (en) * 1962-08-09 1967-04-04 Sinclair Research Inc Composition containing waxes and polyethylene
US3322708A (en) * 1965-05-17 1967-05-30 Exxon Research Engineering Co Polypropylene compositions
US3385720A (en) * 1964-07-17 1968-05-28 Shell Oil Co Wax laminating composition
US4224601A (en) * 1978-03-27 1980-09-23 Davidson Sam A Electrodynamic printing system
US4239546A (en) * 1978-07-21 1980-12-16 Petrolite Corporation Hydrocarbon polymers to improve the hardness of waxes
US4342602A (en) * 1979-10-20 1982-08-03 Hoechst Aktiengesellschaft Dulling agent on the basis of wax for varnishes, and process for the manufacture thereof
US4343863A (en) * 1980-05-27 1982-08-10 Petrolite Corporation Drag reducing ski wax
US4487856A (en) * 1983-03-14 1984-12-11 E. I. Du Pont De Nemours And Company Ethylene polymer composite heat storage material
US6599334B1 (en) 2000-04-25 2003-07-29 Jill M. Anderson Soybean wax candles

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100189674A1 (en) * 2007-05-11 2010-07-29 Sonneborn Inc. Petrolatum Having Silicone-Like Properties

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2638459A (en) * 1950-12-04 1953-05-12 Gulf Research Development Co Method of preparing petroleum wax compositions containing a small amount of a polyethylene
US2761851A (en) * 1949-10-26 1956-09-04 Sinclair Refining Co Processing of wax
US2882246A (en) * 1954-06-01 1959-04-14 Phillips Petroleum Co Polyethylene-wax composition and process of blending same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2842508A (en) * 1957-08-23 1958-07-08 Socony Mobil Oil Co Inc Polyethylene-wax compositions and method for preparing same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2761851A (en) * 1949-10-26 1956-09-04 Sinclair Refining Co Processing of wax
US2638459A (en) * 1950-12-04 1953-05-12 Gulf Research Development Co Method of preparing petroleum wax compositions containing a small amount of a polyethylene
US2882246A (en) * 1954-06-01 1959-04-14 Phillips Petroleum Co Polyethylene-wax composition and process of blending same

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3224984A (en) * 1962-01-02 1965-12-21 Shell Oil Co Process of preparing expanded polystyrene containing a polyolefin
US3243396A (en) * 1962-03-12 1966-03-29 Socony Mobil Oil Co Inc Coating compositions containing waxes, polyethylene, polypropylene, and a polyterpene resin
US3312648A (en) * 1962-08-09 1967-04-04 Sinclair Research Inc Composition containing waxes and polyethylene
US3297610A (en) * 1963-06-24 1967-01-10 Sinclair Research Inc Coating and laminating compositions consisting of a blend of paraffin, isoparaffin and microcrystalline waxes with ethylene-vinyl acetate copolymer
US3385720A (en) * 1964-07-17 1968-05-28 Shell Oil Co Wax laminating composition
US3322708A (en) * 1965-05-17 1967-05-30 Exxon Research Engineering Co Polypropylene compositions
US4224601A (en) * 1978-03-27 1980-09-23 Davidson Sam A Electrodynamic printing system
US4239546A (en) * 1978-07-21 1980-12-16 Petrolite Corporation Hydrocarbon polymers to improve the hardness of waxes
US4342602A (en) * 1979-10-20 1982-08-03 Hoechst Aktiengesellschaft Dulling agent on the basis of wax for varnishes, and process for the manufacture thereof
US4343863A (en) * 1980-05-27 1982-08-10 Petrolite Corporation Drag reducing ski wax
US4487856A (en) * 1983-03-14 1984-12-11 E. I. Du Pont De Nemours And Company Ethylene polymer composite heat storage material
US6599334B1 (en) 2000-04-25 2003-07-29 Jill M. Anderson Soybean wax candles

Also Published As

Publication number Publication date
CH391295A (de) 1965-04-30
BE597186A (en, 2012)
GB887987A (en) 1962-01-24
FR1284548A (fr) 1962-02-16
DE1270209B (de) 1968-06-12
NL258061A (en, 2012)

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