WO2002076385A2 - Asymmetric benzaldehyde alditol derivatives, methods of making thereof, and compositions and articles containing same - Google Patents
Asymmetric benzaldehyde alditol derivatives, methods of making thereof, and compositions and articles containing same Download PDFInfo
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- WO2002076385A2 WO2002076385A2 PCT/US2002/007852 US0207852W WO02076385A2 WO 2002076385 A2 WO2002076385 A2 WO 2002076385A2 US 0207852 W US0207852 W US 0207852W WO 02076385 A2 WO02076385 A2 WO 02076385A2
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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 asymmetric substituted dibenzylidene sorbitol acetals having various types of pendant groups on the benzyl systems thereof, such as, without limitation, opposing electron withdrawing and electron donating groups (to form dipolar compounds), mixed alkyl-halogen or other types groups, multi-alkyl substitutions, cyclic pendant groups, and the like. Polymer compositions comprising such compounds are also contemplated which may be utilized within, as merely examples, food or cosmetic containers and packaging. These inventive asymmetric dibenzylidene 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 l5 R 2 , R , and R ⁇ are selected from hydrogen, lower alkyl, hydroxy, methoxy, mono- and di-alkylamino, amino, nitro, and halogen, with the proviso that at least one of R l5 R 2 , R , and R is chlorine or bromine.
- Effective concentrations of the disclosed substituted DBS derivatives range from 0.01 to about 2 percent by weight of the total composition 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:
- R ⁇ and R 2 are independently selected from lower alkyl groups containing 1-4 carbons which can also form a carbocyclic ring containing up to 5 carbon atoms. Also disclosed are polyolefin plastics containing the above group of dibenzylidene sorbitols.
- Nideau 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 polyolefms.
- alkyl group methyl, ethyl, or the like
- halogen fluorine, chlorine, or the like
- DBS Dibenzylidene sorbitol
- di(meta-fluorobenzylidene) sorbitol and di(meta-chlorobenzylidene) sorbitol are extremely useful as gelling agents in the preparation of antiperspirant gel sticks. These two respective DBS systems form effective hard gels and show improved gel stability in the acidic environment of antiperspirant formulations.
- a polyolefin plastic composition having improved transparency which comprises a polymer selected from aliphatic polyolefms and copolymers containing at least one aliphatic olefin and one or more ethylenically unsaturated comonomers and at least one di-acetal of an alditol (such as sorbitol, xylitol, and ribitol) conforming to at least one of the following structures (I), (II), (III), or (IN):
- R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each the same or different and are selected from electron donating groups, such as hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and electron withdrawing groups, such as halogens (meaning fluorine, chlorine, bromine, and iodine);
- R l5 R 2 , R 3 , and R are the same or different and are selected from electron donating groups, such as hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, or any two are combined to form a carbocyclic or methylenedioxy ring, and electron withdrawing groups, such as nitro and halogens; with the first proviso that if one of said R l5 R 2 , R 3 , or RJ, groups is nitro, then no other nitro groups are present anywhere on the compound; with a second proviso that at least at least two electron withdrawing groups (
- R is selected from hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and fluorine;
- Ri, and R 2 are selected from lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and halogens;
- R and are selected from lower alkyl groups containing 1-4 carbon atoms and which together may form a carbocyclic ring containing up to 6 carbon atoms, lower alkoxy groups, halogens, and hydrogen; with the proviso that only one of Ri and R is halogen; and p is 0 or 1 ;
- R ls R 2 , R 3 , R , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently selected from the group consisting of hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, nitro, halogen, or any two adjacent groups may be combined to form a cyclic group;
- Ri, R 2 , R , and R are independently selected from the group consisting of hydrogen, lower alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, fluorine, and trifluoroalkyl groups contaimng 1-4 carbon atoms; with the proviso that either one of Ri and R 2 or R 3 and R 4 is fluorine or trifluoroalkyl, as defined above, such that if one of said groups is a fluorine or trifluoroalkyl on a first ring system, then no other fluorines are present on the same first ring system, and, if said first
- R l5 R 2 , R 3 , R , R 5 , R 6) R ) R 8) R , and Rio are independently selected from the group consisting of hydrogen, alkyl groups containing 3- 6 carbon atoms, alkoxy groups containing 1-6 carbon atoms, phenyl, naphthyl, and substituted benzyl, or any two adjacent groups may be combined to form a cyclic group, wherein said cyclic group is selected from methylenedioxy, cyclohexyl, and cyclopentyl; with the provisos that at least two groups of Ri, R 2 , R 3 , R , R 5j R 6 , R , R 8 , R 9 , and Rio are a group other than hydrogen, that at least one pendant group other than hydrogen is present on each ring, and that the entire compound is asymmetric.
- one and only one of the benzylidene substituents is 3,4-dimethyl substituted for these above-listed structures.
- the important characteristic of such compounds is that they are asymmetric and meet the basic definitions set forth above.
- the 3,4-disubstitution has been found to provide the best overall performance within target polyolefms and gelling solvents.
- the electron donating group- containing ring (and electron withdrawing group-containing ring) must be 3,4-disubstituted with such groups, although such a limitation is not required.
- inventive compounds are also encompassed individually and in combination within the scope of this invention, particularly in its broadest sense an asymmetric alditol di-acetal comprising at least two arylidene components wherein one of said arylidene components possesses either a single nitro pendant group or at least two electron drawing pendant groups and the other arylidene component must comprise at least two electron donating pendant groups.
- Such compounds are novel in structure and in utilization as thermoplastic additives.
- the individual compounds as defined for Structure (II) are inventive compounds alone as well, broadly stated as asymmetric alditol di-acetal compounds comprising at least two arylidene components wherein one of said benzylidene components at least possesses one halogen pendant group in either the 3- or 4- position and one pendant group selected from lower alkyl and lower alkoxy in the 3- or 4- position.
- asymmetrical as it pertains to di-acetals of alditols is intended to mean wherein such alditol acetals possess 1,3- and 2,4- acetal linkages derived from different aldehydes.
- the compounds conforming with the structures of most of the formulae above may also be utilized individually within the target polyolefin formulations or combined in some manner and in any proportions as well. More particularly, it is contemplated that reaction product mixtures of isomeric compounds confirming to the structure of the formulae listed above as well as other most likely symmetrical dibenzylidene alditol compounds will be formed during production of the desired asymmetric compounds of this invention. It is important to note that the reaction necessary to produce the desired asymmetric diacetals requires the utilization of different benzaldehyde reactants. In such a reaction, invariably different diacetal compounds will be produced.
- Example 1 shows the production of a mixture of l,3-O-(3,4-dichlorobenzylidene):2,4-O- (3,4-dimethylbenzylidene) sorbitol, l,3-O-(3,4-dimethylbenzylidene):2,4-O-(3,4- dichlorobenzylidene) sorbitol, l,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol, and 1,3:2,4- bis(3,4-dichlorobenzylidene) sorbitol simultaneously.
- Example 9 shows the production of a mixture of l,3-O-(4-fluoro-3-methylbenzylidene):2,4-O-(3,4- dimethylbenzylidene) sorbitol and l,3-O-(3,4-dimethylbenzylidene):2,4-O-(4-fluoro-3- methylbenzylidene) sorbitol, l,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol, and l,3:2,4-bis(4- fluoro-3-methylbenzylidene) sorbitol simultaneously. Due to the similar solubilities of such DBS compounds (in each instance, not just in Examples 1 and 9), it has been found to be extremely difficult to separate these individual compounds from the reaction product mixture.
- Such a mixture thus not only includes the desired inventive asymmetric compound or compounds, but such a mixture is an inventive composition as well.
- the terms "diacetal compositions”, as well as “reaction product mixtures” are intended to encompass such an inventive mixture including the desired asymmetries.
- the starting materials hi order to produce such diacetal compositions (and thus the inventive asymmetric compounds themselves), the starting materials must include the desired alditol (such as D- sorbitol), and at least two different substituted benzaldehydes (or one could be unsubstituted), including arylaldehydes.
- the molar ratio of alditol to benzaldehyde reactant is at least 1 :2 for diacetal formation.
- the same general molar ratio is followed (with the ability to use more or less of either type of reactant if desired); however, the benzaldehyde component is measured as a total amount of the at least two different benzaldehyde reactant compounds necessary for asymmetric production.
- the benzaldehyde component is split into at least two different measurements of the individual reactants utilized. Such a split of amounts can be as disparate as a range of from 1:25 to 25:1 of molar ratios of benzaldehydes, if desired.
- compositions of from about 25 to 90% of (a) and from about 25 to 90% of another compound [or the same with (b)] are highly effective as well.
- the preferred diacetals of the present invention are thus generally considered condensation products of sorbitol and at least two substituted benzaldehydes (or arylaldehydes).
- Suitable substituted reactants include 3,4-dichlorobenzaldehyde, 3,4-dimethylbenzaldehyde, 3,4-difluorobenzaldehyde, 3,4-diethylbenzaldehyde, 2,4- dichlorobenzaldehyde, 2,4-difluorobenzaldehyde, 2,4-dimethylbenzaldehyde, 3,4- diethylbenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 3,4- dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 3,4-diethoxybenzaldehyde, 2,4- diethoxybenzaldehyde, 6-formyltetralin, 5-formylindan, 3,4-methylenedioxybenzaldehyde (piperonal), 4-fluoro-3 -methylbenzaldehyde, 3-fluoro-4-methylbenzaldehyde, 4-flu
- aldehydes to be used in conjunction (and thus as the opposing benzylidene group on the target diacetal) with these possible subsituted benzaldehydes include, again, without limitation, benzaldehyde, 4-methyl benzaldehyde, 4-ethylbenzaldehyde, 4-propylbenzaldehyde, 4-butylbenzaldehyde, 4- fluorobenzaldehyde, 4-chloro-benzaldehyde, 4-bromobenzaldehyde, 3-fluorobenzaldehyde, 3-trifluoromethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, 2,4- dimethylbenzaldehyde, 2,3-dimethylbenz-aldehyde, 2,5-dimethylbenzaldehyde, 3,4- difluorobenzaldehyde, 3,4-dichloro-benzal
- Non-limitiiig preferred diacetals of the present invention thus include l,3-O-(3,4- dichlorobenzylidene) :2,4-O-(3 ,4-dimethylbenzylidene) sorbitol, 1 ,3 -O-(3 ,4- dimethylbenzylidene):2,4-O-(3,4-dichlorobenzylidene) sorbitol, l,3-O-(3,4- difluorobenzylidene):2,4-O-(3 ,4-dimethylbenzylidene) sorbitol, , l,3-O-(3,4- dimethylbenzylidene):2,4-O-(3,4-difluorobenzylidene) sorbitol, l,3-O-(3,4- dichlorobenzylidene):2,4-O-(3,4-dimethoxybenzylidene) sorbito
- compositions of the present invention also include solvent gels containing 0.2%> to 10%) of the above diacetals 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 diacetals of the present invention may be prepared by the reaction of one mole of sorbitol with about 1 mole each of two different benzaldehydes in the presence of an acid catalyst.
- the temperature employed in the reaction will vary widely depending upon the characteristics, such as melting points or boiling points, of the benzaldehydes 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 diacetals of the invention is similar to that 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 resultant product mixture has an appreciable majority (about 63%> by weight) of the dipolar asymmetric diacetals.
- the remaining products are present, but in much lower proportions as compared to their theoretical yields.
- Formula (I) dipolar asymmetric compounds provide excellent clarifying properties to polyolefin compositions (such as, preferably polypropylene).
- polyolefin compositions such as, preferably polypropylene
- inventive sorbitol diacetals prepared by the above techniques may contain a minor or even a major portion of by-product monoacetal and triacetal as impurities (in addition to the aforementioned expected reaction product mixture of diacetals). Although it may not always be necessary to remove these impurities prior to incorporation of the diacetal into the polyolefin, it may be desirable to do so and such purification may serve to enhance the transparency of the resin produced thereby. Purification of the diacetal may be accomplished, for instance, by removal of the triacetal impurities by the extraction thereof with a relatively non-polar solvent.
- the product may be purified so that the amount of diacetal in the additive composition contains, preferably, though not necessarily, at least about 90 percent and even up to 95 percent of the diacetal composition or more.
- the proportion of diacetal 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 diacetal composition 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 diacetal composition 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 10 percent or less or even about 5 percent or less, of the entire polyolefin, based upon the total weight of the polyolefin.
- Such comonomers may serve to assist in clarity improvement of the polyolefin, or they may function to improve other properties of the polymer. Examples include acrylic acid and vinyl acetate, etc.
- 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) vinyl cyclohexane
- polystyrene 1-hexene, 1-octene, and 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 microcrystals contained in it is considered to be responsible for the deterioration of the transparency of the polymer. It is thought that the diacetal composition functions in the target polyolefin 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 diacetal composition directly to the olefin polymer or copolymer, and mixing them by any suitable means.
- a concentrate containing as much as about 20 percent by weight of the diacetal composition 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 diacetal composition.
- plasticizers such as those exemplified above may in fact aid in the improvement of the transparency by the diacetal composition.
- diacetal compositions 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 diacetal compositions of the present invention in the polyolefin composition in combination with the previously described dibenzylidene sorbitol additive disclosed in U.S. Pat. Nos.
- compositions of the present invention may be obtained by adding the desired inventive asymmetric compounds or reaction product compositions to the polymer or copolymer and merely mixing the resultant formulation 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).
- 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 excellent transparency and physical properties.
- reaction then proceeded with increased temperature to reflux. Water was removed continuously from the Dean-Stark trap, and additional solvent was added as needed. After 6 hours, the reaction mixture was cooled and neutralized with 3.3 g of KOH in methanol (40 mL). 500 mL of water was then added, and the cyclohexane layer was then removed azeotropically, producing a residual white solid which was then filtered. The white solid was then washed with water, hot methanol, and oven dried. The product was produced in 91%o yield, comprising about 63%o of l,3-O-(3,4-dichlorobenzylidene):2,4-O-(3,4-dimethylbenzylidene) sorbitol and 1,3-
- 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 42.00g of sorbitol (0.2306 moles), 700 mL of cyclohexane, 40.3g of 3,4- dichlorobenzaldehyde (0.2306 moles), 36.9 of 6-formyltetralin (0.2306 moles), 3.00g of p- toluenesulfonic acid, and 100 mL of methanol.
- the reaction was stirred and heated under reflux with removal of water through the Dean Stark trap. The reaction became very thick and additional solvent was added as needed.
- DSC analysis of the solid @ 20°C/min showed melting transitions at 255.8-256J°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 25.4 g of D-sorbitol (0.139 moles), 15.4 g of water, and 34.8 g of concentrated HC1 with stirring. Subsequently, 20.8 g (0.138 moles) of 4-nitrobenzaldehyde and 18.5 g (0.138 moles) of 3,4- dimethylbenzaldehyde were charged as a mixture and added to the homogenous mixture. A solid block of material formed within one hour of reaction and stirring was impossible. 200 mL of cold water and 56.2 g of KOH were then added permitting filtering of the resultant solids.
- the yellow filtrate measured a pH of about 14.
- the remaining solids were then washed with 300 mL of hot water and then 200 mL of hot methanol yielding a tan solid of 4- nitro/3, 4-dimethyl asymmetric DBS (46.5 g) mixture.
- the components of this mixture were determined to be (through standard analyses) 15.1% 3,4-dimethyldibenzylidene sorbitol, 18.9%) 4-nitrodibenzylidene sorbitol, and 62.4%> mixed asymmetries [l,3-O-(4- nitrobenzylidene):2,4-O-(3,4-dimethylbenzylidene) sorbitol and l,3-O-(3,4- dimethylbenzylidene:2,4-O-(4-nitrobenzylidene) sorbitol].
- the melting transition was found to be 224-227 °C by DSC analysis.
- the components of this mixture were determined to be (through standard analyses) 9.06%> bis(3,4-methylenedioxybenzylidene) sorbitol, 16.63% bis(4-nitrobenzylidene) sorbitol, and 74.31%> mixed asymmetries [l,3-O-(4- nitrobenzylidene):2,4-O-(3,4-methylenedioxybenzylidene) sorbitol and l,3-O-(3,4- methylenedioxybenzylidene):2,4-O-(4-nitrobenzylidene) sorbitol].
- the melting transition was found to be 194-204°C by DSC analysis.
- the reaction was stirred and heated under reflux with removal of water through the Dean Stark trap. The reaction became very thick and additional solvent was added as needed. After about six hours, the reaction was cooled, neutralized with potassium hydroxide, and filtered. The wet cake was washed thoroughly with water and cyclohexane and dried in a vacuum oven at 110°C to give 108.9g (98%>) of asymmetric 3,4- dichloro / 3,4-dimethyl DBX. The purity was determined to be 98%> through gas chromatography analysis.
- the wet cake is washed thoroughly with water and cyclohexane, dried in a vacuum oven at 110°C to give 73.19g of Asymmetric 4-Fluoro-3-methyl / 3,4-Dimethyl [50/50] DBS.
- the purity was about 95% as judged by gas chromatography.
- the reaction was stirred and heated under reflux with removal of water through the Dean Stark trap. The 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 is washed thoroughly with water and cyclohexane, dried in a vacuum oven at 110°C to give 86.39g of Asymmetric 4- Fluoro-3-methyl / 4-Chloro [50/50] DBS. The purity was about 95% as judged by GC.
- the reaction was stirred and heated under reflux with 'removal of water through the Dean Stark trap. The 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 is washed thoroughly with water and cyclohexane, dried in a vacuum oven at 110°C to give 72.45g of asymmetric 4-Fluoro-3 -methyl / 3-Fluoro-4-methyl [50/50] DBS. The purity was about 95%o as judged by GC.
- 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 42.00g of sorbitol (0.2306 mole), 700 mL of cyclohexane, 31.85g of 4-fluoro-3- methylbenzaldehyde (0.2306 moles), 24.47g of benzaldehyde (0.2306 moles), 3.00g of p- toluenesulfonic acid, and 210 mL of methanol.
- the reaction was stirred and heated under reflux with removal of water through the Dean Stark trap. The reaction becomes very thick and additional solvent is added as needed.
- DSC analysis of the solid @ 20°C/min showed multiple melting transitions at 200.9 and 211.2°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 42.00g of sorbitol (0.2306 mole), 700 mL of cyclohexane, 31.85g of 4-fluoro-3- methylbenzaldehyde (0.2306 moles), 36.56g of 3-chloro-4-fluorobenzaldehyde (0.2306 moles), 3.00g of p-toluenesulfonic acid, and 210 mL of methanol.
- the reaction was stirred and heated under reflux with removal of water through the Dean Stark trap. The reaction becomes very thick and additional solvent is added as needed.
- reaction was stirred and heated under reflux with removal of water through the Dean Stark trap. The 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 is washed thoroughly with water and cyclohexane, dried in a vacuum oven at 110°C to give
- the reaction was stirred and heated under reflux with removal of water through the Dean Stark trap. The 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 is washed thoroughly with water and cyclohexane, dried in a vacuum oven at 110°C to give 72.96g of Asymmetric 4- fluoro / 3, 4-dimethyl DBS. The purity was about 95 %> as judged by GC.
- the reaction was stirred and heated under reflux with removal of water through the Dean Stark trap. The 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 is washed thoroughly with water and cyclohexane, dried in a vacuum oven at 110°C to give 71.21g of Asymmetric 3-trifluoromethyl / 3,4-dimethyl DBS. The purity was about 95%> as judged by GC.
- the wet cake is washed thoroughly with water and cyclohexane, dried in a vacuum oven at 110°C to give 78.29g of Asymmetric 4-Fluoro / benzyl DBS. After washing with methanol, the purity was about 95% as judged by GC.
- DSC analysis of the solid @ 2°C/min showed multiple melting transitions at 211.3 and 212.4°C.
- the system was flushed with argon and heated in an oil bath to reflux for 5 h.
- the methanol/water layer was continuously drained from the reaction system. Methanol was added as needed.
- the reaction mixture was cooled to room temperature and neutralized with KOH. Water was then added and the cyclohexane layer was then stripped azeotropically, leaving a white solid collected by filtration.
- EXAMPLE 26 Preparation of 4-isopropyl/ 3,4-dimethyl DBS D-Sorbitol (27 g, 0.15 mol), cyclohexane (500 mL), 4-isopropylbenzaldehyde (22 g, 0.15 mol), 3,4-dimethylbenzaldehyde (20 g, 0.15 mol), methanol (80 mL) and water (2.5 g) were added to a 2 L reaction kettle fitted with a mechanical stirrer, Dean-Stark trap with condenser and a thermometer. The system was flushed with argon and heated in an oil bath to reflux for 7 h. The methanol/water layer was continuously drained from the reaction system.
- a one liter reaction flask equipped with a mechanical stirrer was charged with 21.8 g of sorbitol (0.12 mol), 24 g of water, 46 mL of concentrated HC1, and 0.5 g of dodecylbenzene sulfonate. This mixture was stirred for about ten minutes, at which point a solution of 2-naphthaldehyde (15.6g, 0.1 mole) in 20 mL of water, and 3,4- dimethylbenzaldehyde (13.4g, 0.1 mole) was added. The mixture was stirred for 4 h. Cold water and KOH were then added to the reaction mixture.
- Irganox® 1010 Primary Antioxidant (from Ciba) 500 ppm Irgafos® 168, Secondary Antioxidant (from Ciba) 1000 ppm
- 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 Killion 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 barrel molder was set at a temperature anywhere between 190 and 260°C, with a range of 210 to 240°C more preferred, and most preferably from about 220 to 230°C.
- 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.
- haze values were measured by ASTM Standard Test Method D 1003-61 "Standard Test Method for Haze and Luminous Transmittance of Transparent Plastics" using a BYK Gardner XL-211 Hazemeter. Nucleation capabilities were measured as polymer recrystallization temperatures (which indicate the rate of polymer formation provided by the presence of the nucleating additive) by melting the target plaques and recording the temperature at which polymer re-formation occurs. An asterisk (*) denotes no measurements were taken.
- the inventive asymmetric halogenated and alkylated alditol derivatives provided much improved optical and nucleation characteristics within the target thermoplastics as compared with the control.
- inventive single fluoro or fluorinated pendant group-containing asymmetric alditol derivatives provided much better 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 for between 5 and 120 minutes at an elevated temperature between about 100°F (77°C) and 300°F (149°C), preferably about 110°C, or at a temperature approaching, but not exceeding, the boiling point of the selected solvent (or solvents) to be gelled.
- the resultant solution was then poured into a mold and allowed to cool to room temperature 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 asymmetric fluorine or fluorinated alditol derivatives provide excellent gelling capabilities for solvents, depending on their concentration within the target solvents.
- inventive asymmetric halogenated and alkylated alditol derivatives provide excellent gelling capabilities for solvents, depending on their concentration within the target solvents.
- inventive asymmetric fluorine or fluorinated alditol derivatives provide excellent gelling capabilities for solvents, depending on their concentration within the target solvents.
- inventive asymmetric alditol derivatives provide acceptable gelling capabilities for certain solvents as well.
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2003-7012314A KR20030083006A (en) | 2001-03-23 | 2002-03-14 | Asymmetric benzaldehyde alditol derivatives, methods of making thereof, and compositions and articles containing same |
BR0208212-8A BR0208212A (en) | 2001-03-23 | 2002-03-14 | Asymmetric benzaldehyde derivatives alditol, production methods thereof and compositions and articles containing such derivatives |
AU2002257048A AU2002257048A1 (en) | 2001-03-23 | 2002-03-14 | Asymmetric benzaldehyde alditol derivatives, methods of making thereof, and compositions and articles containing same |
EP02726628A EP1370213A4 (en) | 2001-03-23 | 2002-03-14 | Asymmetric benzaldehyde alditol derivatives, methods of making thereof, and compositions and articles containing same |
JP2002574901A JP2004534005A (en) | 2001-03-23 | 2002-03-14 | Asymmetric benzaldehyde alditol derivative, method for producing the same, and composition and article containing the same |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/815,485 US6555696B2 (en) | 2001-03-23 | 2001-03-23 | Asymmetric dipolar multi-substituted alditol derivatives, methods of making thereof, and compositions and articles containing same |
US09/815,631 US6512030B2 (en) | 2001-03-23 | 2001-03-23 | Asymmetric monofluorinated benzaldehyde alditol derivatives and compositions and articles containing same |
US09/815,732 | 2001-03-23 | ||
US09/815,732 US6548581B2 (en) | 2001-03-23 | 2001-03-23 | Asymmetric halogen-alkyl alditol derivatives as nucleators and clarifiers for polyolefins, and polyolefin plastic compositions containing same |
US09/815,486 | 2001-03-23 | ||
US09/815,486 US6495620B1 (en) | 2001-03-23 | 2001-03-23 | Asymmetric substituted benzaldehyde alditol derivatives and compositions and articles containing same |
US09/815,485 | 2001-03-23 | ||
US09/815,631 | 2001-03-23 |
Publications (2)
Publication Number | Publication Date |
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WO2002076385A2 true WO2002076385A2 (en) | 2002-10-03 |
WO2002076385A3 WO2002076385A3 (en) | 2003-03-13 |
Family
ID=27505849
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US2002/007852 WO2002076385A2 (en) | 2001-03-23 | 2002-03-14 | Asymmetric benzaldehyde alditol derivatives, methods of making thereof, and compositions and articles containing same |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1370213A4 (en) |
JP (1) | JP2004534005A (en) |
KR (1) | KR20030083006A (en) |
CN (1) | CN1303076C (en) |
AU (1) | AU2002257048A1 (en) |
BR (1) | BR0208212A (en) |
WO (1) | WO2002076385A2 (en) |
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TWI633143B (en) * | 2014-12-31 | 2018-08-21 | 美力肯及公司 | Polyolefin composition and process for preparing the same |
CN105622627A (en) * | 2016-02-03 | 2016-06-01 | 苏州亚培克生物科技有限公司 | DBS polyolefin nucleating agent and preparation method and application thereof |
US11905366B2 (en) | 2018-03-27 | 2024-02-20 | Nof Corporation | Method for producing multi-arm type polyethylene glycol derivative |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4016118A (en) * | 1974-08-16 | 1977-04-05 | E. C. Chemical Industries & Co., Ltd. | Polyolefin plastic compositions |
US4154816A (en) * | 1975-10-17 | 1979-05-15 | Naarden International N.V. | Solid antiperspirant composition and process for its preparation |
US4371645A (en) * | 1980-04-24 | 1983-02-01 | Milliken Research Corporation | Polyolefin plastic compositions comprising meta- or papa-derivatives (choro- or bromo-) of di-benzyuidene sorbitol |
US5049605A (en) * | 1989-09-20 | 1991-09-17 | Milliken Research Corporation | Bis(3,4-dialkylbenzylidene) sorbitol acetals and compositions containing same |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0523168B1 (en) * | 1990-04-06 | 1996-02-07 | The Procter & Gamble Company | Gel stick antiperspirant compositions |
US6049605A (en) * | 1997-05-30 | 2000-04-11 | Zenith Electronics Corporation | Telephone line access arrangement |
-
2002
- 2002-03-14 AU AU2002257048A patent/AU2002257048A1/en not_active Abandoned
- 2002-03-14 CN CNB028071204A patent/CN1303076C/en not_active Expired - Fee Related
- 2002-03-14 BR BR0208212-8A patent/BR0208212A/en not_active IP Right Cessation
- 2002-03-14 WO PCT/US2002/007852 patent/WO2002076385A2/en active Application Filing
- 2002-03-14 EP EP02726628A patent/EP1370213A4/en not_active Withdrawn
- 2002-03-14 JP JP2002574901A patent/JP2004534005A/en active Pending
- 2002-03-14 KR KR10-2003-7012314A patent/KR20030083006A/en not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4016118A (en) * | 1974-08-16 | 1977-04-05 | E. C. Chemical Industries & Co., Ltd. | Polyolefin plastic compositions |
US4016118B1 (en) * | 1974-08-16 | 1988-07-05 | ||
US4154816A (en) * | 1975-10-17 | 1979-05-15 | Naarden International N.V. | Solid antiperspirant composition and process for its preparation |
US4371645A (en) * | 1980-04-24 | 1983-02-01 | Milliken Research Corporation | Polyolefin plastic compositions comprising meta- or papa-derivatives (choro- or bromo-) of di-benzyuidene sorbitol |
US5049605A (en) * | 1989-09-20 | 1991-09-17 | Milliken Research Corporation | Bis(3,4-dialkylbenzylidene) sorbitol acetals and compositions containing same |
Non-Patent Citations (1)
Title |
---|
See also references of EP1370213A2 * |
Also Published As
Publication number | Publication date |
---|---|
AU2002257048A1 (en) | 2002-10-08 |
BR0208212A (en) | 2004-04-20 |
CN1303076C (en) | 2007-03-07 |
CN1514717A (en) | 2004-07-21 |
EP1370213A4 (en) | 2005-01-26 |
JP2004534005A (en) | 2004-11-11 |
KR20030083006A (en) | 2003-10-23 |
EP1370213A2 (en) | 2003-12-17 |
WO2002076385A3 (en) | 2003-03-13 |
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