US3246963A

US3246963A - Compositions containing wax and either a wax-naphthalene condensation product or certain fumarate ester containing polymers

Info

Publication number: US3246963A
Application number: US255703A
Authority: US
Inventors: Richard E Merz; Edward P Cashman
Original assignee: Exxon Research and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 1963-02-01
Filing date: 1963-02-01
Publication date: 1966-04-19
Anticipated expiration: 1983-04-19

Description

United States Patent ce 3246963 Patented Apr. 19, 1966 3,246,963 utilization in the manufacture of candles and the coating COMPOSITIONS CONTAINING WAX AND EI- of Paper- THER A WAX-NAPHTHALENE CONDENSATION PRGDUCT 0R CERTAIN FUMARATE ESTER CONTAINllNG POLYMERS Richard E. Merz, Berkeley Heights, and Edward P. Cashman, Bayonne, N.J., assignors to Esso Research and Engineering Company, a corporation of Delaware N0 Drawing. Filed Feb. 1, 1963, Ser. No. 255,703 8 Claims. (Cl. 447.5)

This application is a continuation-in-part of copending application Serial Number 80,743, filed January 5, 1961, now abandoned.

The present invention relates to a new wax composition and particularly to a wax composition having improved properties for making candles and for coating paper.

It is well known in the art to prepare wax candles from petroleum waxes secured by various techniques. In general, these wax candles can be prepared from waxes having the following general range of properties.

ASTM melting point, F. 1 10 to 150.

Color 21 Tag Robinson to +30 Saybolt.

Oil Content, percent 0.5 to 3.0.

In the past, it has been the practice that the wax candle be prepared from a wide cut scale wax. Both narrow cut and wide cut scale waxes are secured from crude oils by various techniques, such as by propane dewaxing, ketone treating, and the like, followed, if desired, by some means of improving color, such as hydrofining or clay filtering. The width of cut is controlled by either the distillation range on the waxy distillate feed prior to deoiling or by distilling the finished wax to the desired range. A narrow cut wax is defined as a wax having less than 110 F. spread between 95-5% point in a 10 mm. distillation. The waxes produced in this way vary in melting point from about 120 to 150 F. The scale wax so produced is a parafiin type wax having about 1 to 3% oil content.

Heretofore, it was not possible to use narrow out waxes for the manufacture of seven-day religious candles even though narrow cut waxes possess many advantages. This was due to the fact that a large hole was formed in the seven-day candle below the surface and around the wick as the wax crystallized. Consequently, when the candle was lit it burned satisfactorily for only a few hours. When the roof over the hole melted, the liquid wax head flowed into the hole but did not fill it. The wick then burned down below the surface of the still unmelted wax on the walls of the container. With continued burning, the wax from the container walls melted and raised the liquid level. This had the eifect of reducing flame size and, in some cases, putting out the rfla-me. In cases where flame size was merely reduced, excessive bangup occurred on the walls giving the burned candle container an unsightly appearance.

In coating paper with wax, it is desirable to provide a wax composition having good properties with regard to laminating strength and with regard to imparting gloss to the coated paper.

It is, therefore, an object of this invention to provide a wax composition which [has improved properties for Other objects of the invention will be apparent from the following remarks.

The objects of this invention are obtained by employing a minor amount of a crystalline modifier in a petroleum wax The modifier should be employed within a range of from 0.01 to 5.0 wt. percent and preferably from 0.05 to 1.0%.

The petroleum wax can be a wide cut paraflin wax, a narrow cut parafiin wax having less than 110 F. spread between 5% point in a 10 mm. Hg distillation, a microwax, or mixtures of a parafiin wax and a rnicrocystalline wax. Certain waxes are preferred for particular uses as described hereinafter.

The crystalline modifiers of this invention include waxnaphthalene condensation products (Paraflow 149) having a molecular weight within the range of about 2,000 to 5,000 and having an intrinsic viscosity within the range of from about 0.06 to 0.17, polymethacrylates (Acryloid 150 and Acryloid 763) having a molecular weight within the range of about 20,000 to 65,000 and having an intrinsic viscosity within the range of about 0.6 to 2.0, an ester copolymer (Partone 430) having a molecular weight within the range of about 12,000 to 20,000 and having an intrinsic viscosity of about 0.4 to 0.6, and a fumarate polymer having an intrinsic viscosity within the range of about 0.05 to 0.10 and a molecular weight within the range of about 1725 to 3500.

The wax-naphthalene condensation product (Paraflow 149) is a Friedel-Craf-ts alkylation product of chlorinated parafiin wax with naphthalene. A parafiin wax, for ex ample, having an average of about 22 carbon atoms, is chlorinated. The chlorinated wax then undergoes a Friedel-Crafts reaction with naphthalene in the presence of anhydrous aluminum chloride as a catalyst. Parafiow 149 is a dark viscous liquid having the following typical inspect-ions: viscosity at 210 ER, SSU 308; flash point, -F. 450; pour point, F. +55; Conradson carbon, wt. percent 1.9; density, lbs/gal. at 60 F. 7.5.

The fumarate polymer of this invention is prepared by polymerizing Lorol B fumarate ester using benzoyl peroxide as a catalyst. The fumarate ester is prepared by reacting fumaric acid with Lorol B alcohol using concentrated sulfuric acid as a catalyst.

P'araflow 449 is prepared by copolymerizing the above described Lorol B fumarate ester with vinyl acetate. It is preferred that 20 parts by weight of the vinyl acetate be employed with 80 parts by weight of the Lorol B fumarate.

The ester copolymer (Pa-ratone 430) is prepared by combining a C furnara-te and a C fumarate and polymerizing the combination with vinyl acct-ate and maleic anhydride using tertiary butyl perbenzoate as a catalyst.

Making a candle with the wax of this invention obviates the problem of the void or hole often formed below the surface and around the wick of candles made of other waxes. As a result, the candles burn more evenly and with reduced hangup on the glass container walls as compared to candles made of conventional waxes. The above-described crystalline modifiers are added to a petroleum wax in a concentration of from 0.01 to 5.0% and preferably from 0.05 to 1.0%. It is preferred to employ a narrow cut paraflin wax having less than 3 F. spread between 95-5% point in a 10 mm. distillation. However, the composition can consist of a blend Off the crystalline modifier in a. paraffin or a paraffin-microcrystalline wax blend.

The candle of the present invention may be more fully understood by reference to the following examples illustrating the same.

Example 1 Blends of additive and wax were prepared as listed in Table I. Seven-day candles were molded and tested by the following procedure:

(1) Center the wick in glass container.

(2) Pour about 50 gm. wax in container. Permit to stand for two hours at room temperature to solidify. This anchors the wick.

(3) Pour 500 gm. Wax in jar. Fix wick at top center of jar. This keeps wick taut and centered while wax cools.

(4) Permit to stand overnight.

(5) Remove candle from jar. presence or absence of center hole.

The data in Table I show that the additives claimed were eflective in eliminating the center hole.

TABLE I.EFFECT OF ADDITIVES ON CENTER HOLE OF SEVENDAY RELIGIOUS CANDLES Additive in 116 F. ASTM melting point Center hole Cut open and observe wax: in candle None Yes. 1.0% polymethacrylate A (Acryloid 150) No. 0.1% polymethacrylate (Acryloid l50) No. 1.0% polymethacrylate B (Acryloid 763) No. 0.1% polymethacrylate (Acryloid 763) No. 1.0% ester co-polymer (Paratone 430) No. 0.1% ester copolymer (Paratone 430) No. 1.0% Wax-naphthalene (Parafiow 149) No. 0.1% wax-naphthalene (Parafiow 149) Very slight 1.0% polybutene (Paratone N) Yes. 1.0% stearic acid Yes. 1.0% microcrystalline wax Yes.

Example 2 Table II compares the properties of a commercial candle wax which is composed of 99% of a 116 F. ASTM melting point, narrow-cut wax and 1% microwax (165 F. congealing point) with the product of the invention. The only difierence between these two waxes is the addition of 0.1% ester copolymer of approximately 0.5 intrinsic viscosity in the wax of the invention. The data show that the additive eliminates the center hole in the seven-day candles which consequently burn more steadily and leave no wax hangup. The candle made of commercial wax, however, burned with a varying rate and heavy hangup because of the center hole in the candle.

TABLE IL-EFFECT OF CRYSTALLINE MODIFIER ON PROPERTIES OF CANDLE WAX gup Small Candles:

Sag Test at 105 F Staining at 105 F Does Not Sag Satisfactory Sag Test: Cylindrical wax specimen 1%) diameter, 2 5 high placed in air over at 105 F. After 16 hours specimen is observed for sagging or deformation.

Stain Test: Sag test specimen stored on brown kratt paper at 93 F. After 16 hours paper is observed for stain.

In addition to improving candle wax compositions, the crystalline modifiers of this invention improve wax laminating and coating compositions with regards to laminating strength and gloss.

The crystalline modifier is added to a pertoleum wax in a minor amount sufficient to increase laminating strength of the composition. This amount is usually within the range of from 0.01 to 5.0 Wt. percent and preferably within the range of from 0.05 to 0.1 wt. percent. A paraffin wax, microcrystalline wax, or paraffin/microcrystalline blend are suitable for the laminating composition. However, a microcrystalline wax having a congealing point within the range of from F. to 165 F. is the preferred laminating composition.

A major use of microcrystalline wax is in the paper coating industry in which the wax is used to laminate paper together. In particular, it is used to laminate a glassine type of paper or to laminate paper to foil. A criteria by which its laminating power is measured is the Laminating Strength Test as describe-d in the proposed TAPPI-ASTM Sealing Strength Method T642 sm 54. We have found that minor amounts of the heretofore mentioned pour depressants are very effective in improving the laminating strength of microcrystalline waxes.

Example 3 A microcrystalline wax of 142 F. congealing point with no additive was compared in strength to the same wax plus small amounts of the various pour depressants. The data in Table III show that the strength of the microwax containing pour depressant was considerably higher than the strength of the untreated microwax.

TABLE 3 TAPPIASTM,

Composition: laminating strength, gm./in. Microwax 142 F. congealing point 110 Microwax 142 F. congealing point+0.l%

Acryloid 150 Microwax 142 F. congealing point+0.5%

Acryloid 150 175 Microwax 142 F. congealing point+0.l%

Fumarate Polymer Microwax 142 F. congealing point+0.5%

Furmarate Polymer Microwax 142 F. congealing point+0.l%

Parafiow 149 130 Microwax 142 F. congealing point+0.5%

Parafiow 149 135 Microwax 142 F. congealing point+0.l%

Paratone 430 125 Microwax 142 F. congealing point+0.5%

Paratone 430 140 Microwax 142 F. congealing point+0.l%

Parafiow 449 130 Microwax 142 F. congealing point+0.5%

Parafiow 449 140 The crystalline modifiers improve wax coating compositions in general, but have particular utility in broad cut waxes with regard to improved gloss. Heretofore, it has usually been necessary to use narrow cut waxes where high gloss and good gloss stability were desired. This has caused manufacturing problems since it has been necessary to minimize contamination of the N-C wax with other waxes. It has now been found that a broad cut wax can be employed if a crystalline modifier is added to it.

Example 4 Blends of additive and wax were prepared as listed in Table IV. Wax coated strips (six for each blend) were prepared as follows:

(1) Adjust temperature of Wax to F.

(2) Dip Strip of paper (1%" 6") in wax for 5 seconds.

(3) Drain wax from paper for 2-3 seconds.

(4) Dip waxed paper in water at 50 F. for 30 seconds.

The data in Table IV show that the additives were effective in improving the gloss of the broad cut wax (Wax A) to the point where it was equal to that of the N-C wax (Wax B).

TABLE IV.EFFECT OF ADDITIVES ON GLOSS AND GLOSS STABILITY OF WAXED PAPER Wax A Plus 1% Ester Copolymer Wax A Plus 0.5% Ester Copolyrner Wax A Plus 0.5% Polymethaerylate Wax B 1 Waxed paper stored at 7212 F. and 50% EH. 2 Wax inspections.

Wax A Wax B ASTM Melting Point, F 136% 136% mm. Dist.:

5% O 470 482 95% Oil 562 546 In summary, this invention provides a novel wax composition having utility in manufacturing candles, laminating paper, and coating paper.

What is claimed is:

1. A wax composition consisting essentially of a pctroleum wax and about 0.01 to 5.0 wt. percent of a crystalline modifier selected from the group consisting of (a) a wax-naphthalene condensation product having a molecular weight of from about 2,000 to 5,000 and having an intrinsic viscosity within the range of from about 0.06 to 0.17 (b) a copolymer consisting of an ester copolymerization product of a C and C alkyl fumarate mixture, vinyl acetate and maleic anhydride, said copolymeriza' tion product having a molecular weight within the range of about 12,000 to 20,000 and having an intrinsic viscosity of about 0.4 to 0.6 and (c) a polymer consisting of the polymerization product of Lorol B fumarate ester, said polymer having a molecular weight within the range of about 1725 to 3500 and having an intrinsic viscosity within the range of about 0.05 to 0.10.

2. A Wax composition according to claim 1 wherein the said petroleum wax is a broad cut paraflin wax.

3. A wax composition according to claim 1 wherein said petroleum wax is a narrow cut wax having less than 6 F. between the 95-5 distillation point at 10 mm. Hg.

4. A wax composition according to claim 1 wherein said petroleum wax is a microcrystalline wax having a congealing point between the range of F to F.

5. An improved wax candle comprising a narrow petroleum scale wax containing from about 0.01 to 5.0 wt. percent of a crystalline modifier selected from the group consisting of (a) a wax-naphthalene condensation product having a molecular weight of from about 2,000 to 5,000 and having an intrinsic viscosity in the range of from about 0.06 to 0.17 (b) a copolymer consisting of an ester copolymerization product of a C C alkyl fumarate, vinyl acetate and maleic anhydride, said copolymerization product having a molecular weight within the range of about 12,000 to 20,000 and having an intrinsic viscosity of about 0.4 to 0.6 and (c) a polymer consisting of the polymerization product of Lorol B fumarate ester having a molecular weight within the range of about 1725 to 3500 and having an intrinsic viscosity within the range of about 0.05 to 0.10.

6. The candle according to claim 5 wherein the amount of crystalline modifiers present in the range of from about 0.05 to 1.0% by weight.

7. The candle according to claim 5 wherein said crystalline modifier is a wax-naphthalene condensation product having a molecular weight of from about 2,000 to 5,000.

8. The candle according to claim 5 wherein the crystalline modifier is a copolymer consisting of an ester copolymerization product of a C -C alkyl fumarate, vinyl acetate and maleic anhydride, said copolymerization product having a molecular weight Within the range of about 12,000 to 20,000 and having an intrinsic viscosity of about 0.4 to 0.6.

References Cited by the Examiner UNITED STATES PATENTS 2,877,196 3/1959 Reding 260-285 2,967,817 1/1961 Marple et a1. 260-285 FOREIGN PATENTS 529,399 11/ 1940 Great Britain.

OTHER REFERENCES Strain et al., Methacrylate Resins, E. I. du Pont de Nemours and Co., Inc., Wilmington, Delaware, April 1939.

MORRIS LIEBMAN, Primary Examiner.

Claims

1. A WAX COMPOSITION CONSISTING ESSENTIALLY OF A PETROLEUM WAX AND ABOUT 0.01 TO 5.0 WT. PERCENT OF A CRYSTALLINE MODIFIER SELECTED FROM THE GROUP CONSISTING OF (A) A WAX-NAPHTHALENE CONDENSATION PRODUCT HAVING A MOLECULAR WEIGHT OF FROM ABOUT 2,000 TO 5,000 AND HAVING AN INTRINSIC VISCOSITY WITHIN THE RANGE OF FROM ABOUT 0.06 TO 0.17 (B) A COPOLYMER CONSISTING OF AN ESTER COPOLYMERIZATION PRODUCT OF A C8 AND C13 ALKYL FURMARATE MIXTURE, VINYL ACETATE AND MALEIC ANHYDRIDE, SAID COPOLYMERIZATION PRODUCT HAVING A MOLECULAR WEIGHT WITHIN THE RANGE OF ABOUT 12,000 TO 20,000 AND HAVING AN INTRINSIC VISCOSITY OF ABOUT 0.4 TO 0.6 AND (C) A POLYMER CONSISTING OF THE POLYMERIZATION PRODUCT OF LOROL B FURMARATE ESTER, SAID POLYMER HAVING A MOLECULAR WEIGHT WITHIN THE RANGE OF ABOUT 1725 TO 3500 AND HAVING AN INTRINSIC VISCOSITY WITHIN THE RANGE OF ABOUT 0.05 TO 0.10.