Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/042—Gels
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/34—Alcohols
  • A61K8/345—Alcohols containing more than one hydroxy group
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
  • A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q15/00—Anti-perspirants or body deodorants
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
  • C07D493/04—Ortho-condensed systems
• • 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
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring

Definitions

• This invention relates to plastic additives which are useful as nucleating agents and which are especially useful for improving the optical properties of polymeric materials. More particularly, this invention relates to certain alkyl (or alkoxy) substituted halo-benzylidene sorbitol acetals, as well as symmetric DBS compounds comprising specific pendant groups, such as C 3 -C 6 alkyl, C ⁇ -C 6 alkoxy, nitro, as well as phenyl and methylenedioxy(as the combination of two available sites on the pertinent ring system), and furthermore the benzylidene rings may be indan or tetralin, and polymer compositions thereof any such compounds and mixtures thereof. Such compounds may be utilized within, as merely examples, food or cosmetic containers and packaging.
• inventive halogenated (that is, chlorinated, brominated, or iodinated) and alkylated benzylidene sorbitol acetals are also useful as gelling agents for water and organic solvents, particularly those used in the preparation of antiperspirant gel sticks.
• melt sensitive additives possess melting points below or near the normal processing temperatures of polyolefm-based resins and include dibenzylidene sorbitol (DBS) systems. Melt insensitive additives do not melt at normal processing temperatures and include sodium benzoate and salts of organic phosphates as examples.
• R, R ls R 2 , R , and R 4 are selected from hydrogen, lower alkyl, hydroxy, methoxy, mono- and di-alkylamino, amino, nitro, and halogen, with the proviso that at least one of Rj, R 2 , R 3 , and R 4 is chlorine or bromine.
• Effective concentrations of the disclosed substituted DBS derivatives range from 0.01 to about 2 percent of the total composition by weight. Further improvements in transparency characteristics are disclosed by Titus, et al. in U.S. Pat. No. 4,808,650. In this patent mono and disubstituted DBS derivatives having the formula:
• Ri and R 2 are independently selected from lower alkyl groups containing 1-4 carbons or which together form a carbocyclic ring containing up to 5 carbon atoms.
• polyolefin plastics containing the above group of dibenzylidene sorbitols.
• Videau, in U.S. Patent No. 5,696,186 discloses substituted DBS derivatives with an alkyl group (methyl, ethyl, or the like) or halogen (fluorine, chlorine, or the like) on the benzene rings for use as nucleation/clarification agents in polyolefins.
• DBS Dibenzylidene sorbitol
• a polyolefin plastic composition having improved transparency which comprises a polymer selected from aliphatic polyolefins and copolymers containing at least one aliphatic olefin and one or more ethylenically unsaturated comonomers and at least one one mono-, di-, or tri-acetal which is the reaction product of at least one mole of alditol (such as sorbitol, xylitol, ribitol, and the like) and at least one mole of a benzaldehyde selected from the compounds conforming with either of Formula (I) or Formula (II)
• R is independently selected from hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and halogen;
• R 3 , and R are selected from lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, chlorine, bromine, iodine, and fluorine; with the proviso that one and only one of R 3 and ⁇ is selected from the group consisting of chlorine, bromine and iodine;
• Ri, R 2 , R 3 , ⁇ , and R 5 are independently selected from the group consisting of hydrogen, alkyl groups containing 3-6 carbon atoms, alkoxy groups containing 1-6 carbon atoms, and phenyl, or any two adjacent groups may be combined to form a cyclic group, wherein said cyclic group is selected from the group consisting of methylenedioxy, cyclopentyl, and cyclohexyl; with the proviso that at least one group of R ls R 2 , R 3 , R , and R 5 is a group other than hydrogen.
• such a reaction product is a di-acetal (and thus the result of a 1 :2 molar ratio reaction between the alditol and benzaldehyde), and particularly where the alditol is sorbitol, said di-acetal of the alditol having the structure of either Formula (III) [in correlation with the benzaldehyde of Formula (I)]:
• R is independently selected from hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and halogen;
• R ls R 2 , R 3 , and J 4 are selected from lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, chlorine, bromine, iodine, and fluorine; with the proviso that one and only one of Ri and R 2 is selected from chlorine, bromine, and iodine, and one and only one of R 3 and R is the same chlorine, bromine or iodine as the Ri or R group, such that the entire compound is symmetrical; or
• R 1 ⁇ R 2 , R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen, alkyl groups containing 3-6 carbon atoms, alkoxy groups containing 1-6 carbon atoms, or any two adjacent groups may be combined to form methylenedioxy; with the proviso that at least one group of R ls R 2 , R 3 , T , and R 5 is a group other than hydrogen.
• the term "symmetrical" as it pertains to di- or tri-acetals of alditols is intended to mean wherein such alditol acetals that possess all acetal linkages (such as 1,3- and 2,4- for di-acetals) derived from the same benzaldehyde.
• the diacetals, triacetals, and monoacetals of the present invention are condensation products of alditol, such as sorbitol or xylitol, and a chloro-, bromo-, or iodo-alkyl substituted benzaldehyde.
• suitable substituted benzaldehydes include 4-ch ⁇ oro-3- methylbenzaldehyde, 3-chloro-4-methylbenzaldehyde, 4-chloro-2,3-dimethylbenzaldehyde,
• Preferred di-acetals of the present invention include l,3:2,4-bis(4-chloro- 3-methylbenzylidene) sorbitol, l,3:2,4-bis(3-chloro-4-methylbenzylidene) sorbitol, 1,3:2,4- bis(3-bromo-4-isopropylbenzylidene) sorbitol, l,3:2,4-bis(3-bromo-4-methylbenzylidene) sorbitol, and l,3:2,4-bis(3-bromo-4-ethylbenzylidene) sorbitol.
• Suitable substituted benzaldehydes include 4-t-butylbenzaldehyde, 4-isopropylbenzaldehyde, 3,4-methylene-dioxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,4-diethoxybenzaldehyde, and the like, to provide the required symmetrical compounds in reaction with an alditol (such as sorbitol, xylitol, ribitol, and the like).
• an alditol such as sorbitol, xylitol, ribitol, and the like.
• Suitable substituted benzaldehydes for this inventive compounds include, without limitation, 2,4-diisopropylbenzaldehyde, 2,4-di-t- butylbenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,4- diethoxybenzaldehyde, 4-? ⁇ -pentylbenzaldehyde, 3-methyl-4-methoxybenzaldehyde, 4- methoxy-2,3-dimethylbenzaldehyde, 3-methoxy-2,4-dimethylbenzaldehyde, 2,4-dimethoxy- 3-methylbenzaldehyde, 4-ethoxy-3,5-dimethylbenzaldehyde, and 3-isopropyl-4- methoxybenzaldehyde, and the like.
• Preferred di-acetals of the present invention include l,3:2,4-bis(4-t-butylbenzylidene) sorbitol and l,3:2,4-bis(3,4-methylenedioxybenzylidene) sorbitol.
• compositions of the present invention also include solvent gels containing 0.2% to 10% of the above di-acetals as a gelling agent.
• Solvents useful herein include, as merely examples, lower monohydric alcohols, polyhydric alcohols, and mixtures thereof. Water may also be included as a portion of the solvent. However, the solvent will generally comprise water at levels no greater than 5% by weight of the final composition.
• polyethylene glycols, polypropylene glycols, and polypropylene polyethylene glycol copolymers include alkyl ether derivatives of these compounds (e.g., ethyl, propyl, and butyl ether derivatives).
• alkyl ether derivatives of these compounds e.g., ethyl, propyl, and butyl ether derivatives.
• examples of such compounds are butyl ether derivatives of polypropylene polyethylene glycol copolymers, such as PPG-5-buteth-7.
• the preferred solvents for use herein include liquid polyethylene glycols, liquid polypropylene glycols, liquid polypropylene polyethylene glycol copolymers, propylene glycol, 1,3-butylene glycol, and 2,4-dihydroxy-2-methylpentane (sometimes referred to as hexylene glycol), and mixtures thereof.
• Particularly preferred solvents include propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, hexylene glycol, and mixtures thereof.
• organic solvents useful herein include aromatics, halogenated aromatics, nitrated aromatics, ketones, amines, nitriles, esters, aldehydes, and mixtures thereof.
• solvents which may be utilized in the present invention include xylenes (o, m, and p- substituted), 2-chlorotoluene, fluorobenzene, nitrobenzene, benzonitrile, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), and l-methyl-2-pyrrolidinone (NMP).
• the di-acetals and monoacetals of the present invention may be prepared by a variety of techniques, some of which are known in the art. Generally, such procedures employ the reaction of one mole of D-sorbitol with about 2 moles of aldehyde (for diacetals), with 1 mole of aldehyde for monoacetals, in the presence of an acid catalyst (of course, to produce triacetals a 1 : 3 molar ratio should be followed; for monoacetals, 1 : 1 ratios are necessary) .
• the temperature employed in the reaction will vary widely depending upon the characteristics, such as melting point, of the aldehyde or aldehydes employed as a starting material in the reaction.
• the reaction medium may be an aqueous medium or a non-aqueous medium.
• One very advantageous method that can be employed to prepare di-acetals of the invention is described in U.S. Pat. No. 3,721,682, to Murai et al. (New Japan Chemical Company Limited), the disclosure of which is hereby incorporated herein by reference.
• the di-acetal may be accomplished, for instance, by removal of any tri-acetals by the extraction thereof with a relatively non-polar solvent.
• the product may be purified so that the amount of di-acetal in the additive composition contains at least about 90 percent and even up to 95 percent di-acetal or more.
• the proportion of di-acetal, triacetal, or monoacetal in the composition of this invention is an amount sufficient to improve the transparency of the composition, generally from about 0.01 to about 2 percent by weight, preferably about 0.1 to about 1 percent by weight, based upon the total weight of the composition may be provided.
• the content of the di-acetal is less than about 0.01 percent by weight, the resulting composition may not be sufficiently improved in respect to transparency characteristics.
• the content of di-acetal, triacetal, or monoacetal is increased beyond about 2 percent by weight, no additional advantage can be observed.
• the polyolefin polymers of the present invention may include aliphatic polyolefins and copolymers made from at least one aliphatic olefin and one or more ethylenically unsaturated comonomers.
• the comonomers if present, constitute a minor amount, e.g., about
• olefin polymers whose transparency can be improved conveniently according to the present invention are polymers and copolymers of aliphatic monoolefins containing 2 to about 6 carbon atoms which have an average molecular weight of from about 10,000 to about 2,000,000, preferably from about
• polyethylene linear low density polyethylene
• polypropylene crystalline ethylenepropylene copolymer
• poly(l-butene) 1-hexene
• 1-octene vinyl cyclohexane
• polymethylpentene polymethylpentene.
• the polyolefins of the present invention may be described as basically linear, regular polymers that may optionally contain side chains such as are found, for instance, in conventional, low density polyethylene.
• the olefin polymer or copolymer used in the composition of the present invention is crystalline, and the diffraction of light caused by micro crystals contained in it is considered to be responsible for the deterioration of the transparency of the polymer. It is thought that the di-acetal functions in the composition to reduce the size of the microcrystals thereby improving the transparency of the polymer.
• composition of the present invention can be obtained by adding a specific amount of the di-acetal or monoacetal directly to the olefin polymer or copolymer, and merely mixing them by an suitable means.
• a concentrate containing as much as about 20 percent by weight of the di-acetal in a polyolefin masterbatch may be prepared and be subsequently mixed with the resin.
• inventive alditol derivatives may be present in any type of standard polyolefin additive form, including, without limitation, powder, prill, agglomerate, liquid suspension, and the like, particularly comprising dispersion aids such as polyolefin (e.g., polyethylene) waxes, stearate esters of glycerin, montan waxes, mineral oil, and the like.
• dispersion aids such as polyolefin (e.g., polyethylene) waxes, stearate esters of glycerin, montan waxes, mineral oil, and the like.
• any form may be exhibited by such a combination or composition including such combination made from blending, agglomeration, compaction, and/or extrusion.
• additives such as a transparent coloring agent or plasticizers (e.g., dioctyl phthalate, dibutyl phthalate, dioctyl sebacate, mineral oil, or dioctyl adipate), can be added to the composition of the present invention so long as they do not adversely affect the improvement of transparency of the product. It has been found that plasticizers such as those exemplified above may in fact aid in the improvement of the transparency by the di-acetal.
• plasticizers such as those exemplified above may in fact aid in the improvement of the transparency by the di-acetal.
• di-acetals or monoacetals disclosed above in combination with other conventional additives having known transparency improving effects such as, for instance, para-t-butylbenzoic acid, its salts, low molecular weight waxy polypropylene and the like. It may even be desirable to provide the particular di-acetals or monoacetals of the present invention in the polyolefin composition in combination with the previously described dibenzylidene sorbitol additive disclosed in U.S. Pat. Nos. 4,016,118 to Hamada et al., 5,049,605 to Rekers, and the like. In such applications, generally at least about 10 percent, preferably about 25 percent, or even about 50 percent or more of the clarity improving component will be the diacetals of the present invention, with the remainder being comprised of other known clarifying agents, plasticizers, etc.
• compositions of the present invention may be obtained by adding the inventive symmetrical benzylidene sorbitol acetal to the polymer or copolymer and merely mixing the resultant composition by any suitable means.
• the composition may then be processed and fabricated by any number of different techniques, including, without limitation, injection molding, injection blow molding, injection stretch blow molding, injection rotational molding, extrusion, extrusion blow molding, sheet extrusion, film extrusion, cast film extrusion, foam extrusion, thermoforming (such as into films, blown-films, biaxially oriented films), thin wall injection molding, and the like into a fabricated article.
• additives may also be used in the composition of the present invention, provided they do not interfere with the primary benefits of the invention. It may even be advantageous to premix these additives or similar structures with the nucleating agent in order to reduce its melting point and thereby enhance dispersion and distribution during melt processing.
• additives are well known to those skilled in the art, and include plasticizers, lubricants, catalyst neutralizers, antioxidants, light stabilizers, colorants, other nucleating agents, and the like. Some of these additives may provide further beneficial property enhancements, including improved aesthetics, easier processing, and improved stability to processing or end use conditions.
• organoleptic improvement additives be added for the purpose of reducing the migration of degraded benzaldehydes from reaching the surface of the desired article.
• organoleptic improvement additive is intended to encompass such compounds and formulations as antioxidants (to prevent degradation of both the polyolefin and possibly the target alditol derivatives present within such polyolefin), acid neutralizers (to prevent the ability of appreciable amounts of residual acids from attacking the alditol derivatives), and benzaldehyde scavengers (such as hydrazides, hydrazines, and the like, to prevent the migration of foul tasting and smelling benzaldehydes to the target polyolefin surface).
• Such compounds and formulations can be added in any amounts in order to provide such organoleptic improvements as needed. However, the amounts should not appreciably affect the haze results for the target polyolefin itself. Thus, lower amounts on the order of from about 20 ppm to about 2,000 ppm of the total polyolefin component are desired.
• compositions of the present invention are suitable as additives to improve the clarity of packaging materials and container materials for cosmetics, food-stuffs, and the like, because they give film, sheet, and other fabricated articles having excellent transparency and physical properties.
• reaction becomes very thick and additional solvent is added as needed. After about six hours, the reaction is cooled, neutralized with potassium hydroxide, and filtered. The wet cake was washed thoroughly with water and cyclohexane, dried in a vacuum oven at 110°C to give 85.18g of bis(3-chloro-4-methylbenzylidene)sorbitol (as determined by standard analyses). The purity was about 95% as determined by GC. The peak melting transition was determined to be (DSC @ 20°C/min) about 239.8°C.
• a one liter four-necked cylindrical shaped reaction flask equipped with a Dean-Stark trap, condenser, thermometer, nitrogen inlet, and a mechanical stirrer was charged with 42g of D-sorbitol (0.23 mole), 500 mL of cyclohexane, 98g of 3-bromo-4 ⁇ ethylbenzaldehyde (0.46 moles), 80 mL of methanol, and 2.5 g of water.
• the system was then flushed with argon and heated in an oil bath with stirring.
• the mixture was then heated to a vapor temperature of 40°C, at which time 3.0 g of p-toluenesulfonic acid in 40 mL of methanol was slowly added.
• the reaction was stirred and heated under reflux with removal of water through the Dean Stark trap as cyclohexane was returned to the system. Heating was then recommenced until the vapor temperature reached 70°C, at which time 40 mL of methanol were added slowly. The reaction mixture was allowed to heat up to the same vapor temperature and methanol was added slowly again, and repeated another 4 times. The reaction product was then cooled, neutralized with potassium hydroxide (4 g in 40 mL of methanol), and stripped of the resultant cyclohexane layer (by azeotrope with water).
• the mixture was then heated to a vapor temperature of 41.8°C, at which time 3.0 g of p-toluenesulfonic acid in 40 mL of methanol was slowly added.
• the reaction was seeded with 1.0 g of 3,4-dimethylbenzylidene sorbitol in 20 mL of methanol.
• the reaction was then stirred and heated (to about 120°C) under reflux with removal of water through the Dean Stark trap as cyclohexane was returned to the system. Heating was then recommenced until the vapor temperature reached 70°C, at which time 40 mL of methanol were added slowly.
• the reaction mixture was allowed to heat up to the same vapor temperature and methanol was added slowly again, and repeated another 5 times.
• reaction product (a white gel) was then cooled, neutralized with potassium hydroxide (7 g in 40 mL of methanol), and stripped of the resultant cyclohexane layer (by azeotrope with water). The gel remaining was then filtered and purified in boiling water and boiling methanol, giving 3-bromo-4-isopropylbenzaldehyde as a white solid (108.5 g, 78% yield)(as determined through standard analyses) exhibiting a peak melting transition of
• the white solid was collected by vacuum filtration and dried in a vacuum oven to give bis(3,4-methylene-dioxybenzylidene) sorbitol as a white solid (60 g, 90%) having a purity of 95% as determined by standard analyses, and exhibiting a melting transition of from 222.0 to 227.8°C.
• the base resin random copolymer, hereinafter "RCP"
• All additives were weighed and then blended in a Welex mixer for 1 minute at about 1600 rpm. All samples were then melt compounded on a KilHon single screw extruder at a ramped temperature from about 204° to 232°C through four heating zones. The melt temperature upon exit of the extruder die was about 246°C. The screw had a diameter of 2.54 cm and a length/diameter ratio of 24: 1. Upon melting the molten polymer was filtered through a 60 mesh (250 micron) screen. Plaques of the target polypropylene were then made through extrusion into an Arburg 25 ton injection molder. The molder barrel was set at a temperature anywhere between 190 and
• the plaques had dimensions of about 51 mm X 76 mm X 1.27 mm, and were made in a mold having a mirror finish.
• the mold cooling circulating water was controlled at a temperature of about 25 °C.
• inventive symmetrical benzaldehyde alditol derivatives provided much better haze and, at times, recrystallization temperature characteristics within the target thermoplastics as compared with the control.
• Solid gels were also produced comprising the inventive alditol derivatives through recognized, simple methods.
• specific organic solvents were combined with the additives in certain concentrations and mixed thoroughly.
• the resultant mixture was then heated to a temperature between about 170°F (77°C) and 300°F (149°C), as indicated below, under agitation for between 5 and 120 minutes.
• the resultant solution was then poured into a mold to produce a gel stick.
• the solvents listed below are not intended to be exhaustive as to the potential types which may be utilized to form gels with the inventive alditol derivatives, and thus are merely listed as preferred solvents for such purposes.
• the examples below were analyzed empirically and by touch to determine if a gel actually formed and the hardness properties as well as any formed gels.
• inventive halogenated and alkylated alditol derivatives provide excellent gelling capabilities for solvents, depending on their concentration within the target solvents.
• compositions with Other Clarifiers Formulations of certain inventive compounds from above were then produced incorporating DMDBS in various proportions.
• RCP polypropylene was compounded as noted above but with mixtures of DMDBS and the Example 2 compound into 50 mil plaques. Haze measurements were taken as noted above as well. The results are tabulated as follows:
• inventive compounds also exhibited excellent haze measurements in polypropylene in the presence of another clarifying agent.
• Fo ⁇ nulations of the inventive compound of Example 7 were then produced incorporating DMDBS in various proportions.
• RCP polypropylene was compounded as noted above but with mixtures of DMDBS and the Example 7 compound into 50 mil plaques. Haze measurements were taken as noted above as well. The results are tabulated as follows:
• inventive compound also exhibited excellent haze measurements in polypropylene in the presence of another clarifying agent.

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• 2002
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