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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C31/18—Polyhydroxylic acyclic alcohols
  • C07C31/26—Hexahydroxylic alcohols
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
  • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
• • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
• • 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
• • 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
  • C08K5/1575—Six-membered rings

Definitions

• acetals of sorbitol and xylitol which have been employed as clarifying agents, are described in several patents, including for example: Hamada, et al., United States Patent No. 4,016,118, dibenzylidene sorbitols; Kawai, et al., United States Patent No. 4,314,039, di(alkylbenzylidene) sorbitols; Mahaffey, Jr., United States Patent No. 4,371 ,645, di-acetals of sorbitol having at least one chlorine or bromine substituent; Kobayashi, et al., United States Patent No.
• a polyolefin additive composition is disclosed herein.
• the polyolefin additive composition provides improved transparency to plastic polymer compositions when added to such compositions.
• the additive composition will be advantageous when used in connection with polypropylene, although various applications in connection with other polymers are within the scope of the invention.
• Olefin polymers which can be nucleated by such compositions (and whose transparency may be improved according to the practice of the invention) include polymers and copolymers of aliphatic mono-olefins containing from 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 30,000 to about 300,000, such as polyethylene, including linear low density polyethylene, low density polyethylene and high density polyethylene, polypropylene, crystalline ethylene/propylene copolymer (random or block), poly(l-butene) and polymethylpentene.
• polyethylene including linear low density polyethylene, low density polyethylene and high density polyethylene, polypropylene, crystalline ethylene/propylene copolymer (random or block), poly(l-butene) and polymethylpentene.
• thermoplastic polymer resins which may be nucleated with the disclosed acetal compounds include polyester, poly(ethylene terephthalate) (PET) and po!y(butylene terephthalate) and polyamide, including nylon 6 and nylon 6,6, poly(phenylene sulfide), syndiotactic polystyrene and polyketones having carbonyl groups in their backbone.
• PET poly(ethylene terephthalate)
• polyamide including nylon 6 and nylon 6,6, poly(phenylene sulfide), syndiotactic polystyrene and polyketones having carbonyl groups in their backbone.
• the composition may comprise 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 mono-, di-, or tri-acetal of substituted alditol (such as allyl-sorbitol, propyl-sorbitol, allyl- xylitol, propyl-xylitol and the like).
• the mono-, di-, or tri-acetal of substituted alditol may include a composition as described below.
• a substituted alditol as in Formula (I) which is combined with at least one mole of benzaldehyde selected from the compounds with Formula (II), as shown below.
• Ri, R 2 , R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen, fluorocarbons, alkenyl, alkyl groups, alkynyl groups, alkoxy groups, carboxy groups, halides, and phenyl, or in some embodiments of the invention, any two adjacent groups may be combined to form a cyclic group, wherein said cyclic group may be comprised of methylenedioxy, cyclopentyl, cyclohexyl, or other similar cyclic groups.
• An acetal compound may be formed in one particular embodiment of the invention by the process of: (a) reacting a polyhydric alcohol with an alkenyl molecule to form a first compound; and (b) reacting in a condensation reaction said first compound with an aromatic aldehyde to form an acetal compound.
• the acetal compound thus formed may be a mono-, di-, or tri- acetal, but in many cases it has been found that a di-acetal is particularly useful.
• the acetal compound may comprise an allyl in one particular embodiment of the invention, as herein further described.
• such a reaction product or resulting composition is a di-acetal (and thus the result of a 1 :2 molar ratio reaction between the alditol and benzaldehyde).
• a composition may be provided having the structure of Formula (III), below.
• a single acetal, or a triacetal, could also be provided in the practice of the invention, but one particular di-acetal composition is shown below: (HI)
• n may be 0, 1 , or 2; and A ⁇ and Ar 2 are independently selected from substituted or unsubstituted aryl-containing groups.
• R may be selected from the group consisting of: alkenyls, alkyls, alkoxy, hydroxyl alkyls, and alkyl-halides.
• R may comprise an alkenyl, and in some particular embodiments of the invention, an allyl has been found to work quite well for the R group. It should be appreciated that the R group stereochemistry is not defined, and the invention is not limited to any particular R group stereochemistry, such that all chemical structures provided herein shall cover any isomers that occur due to stereoisomers of the carbon atom to which R is attached.
• the diacetals, triacetals, and monoacetals of the invention may be condensation products of substituted alditols, such as (but not limited to) allyl-sorbitol, propyl-sorbitol, 1-methyl-2-propenyl sorbitol, allyl-xylitol, propyl-xylitol, and a (substituted) benzaldehyde.
• substituteditols such as (but not limited to) allyl-sorbitol, propyl-sorbitol, 1-methyl-2-propenyl sorbitol, allyl-xylitol, propyl-xylitol, and a (substituted) benzaldehyde.
• Suitable (substituted) benzaldehydes include benzaldehyde, 4-ethylbenzaldehyde, 4-isobutylbenzaldehyde, 4-fluoro-3-methylbenzaldehyde, 5,6,7,8- tetrahydro-2-naphthaldehydebenzylidene, 3-methylbenzaldehyde, 4- propylbenzaldehyde, 4-butylbenzaldehyde, 4-methoxybenzaldehyde, 3- chlorobenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5-difluorobenzaldehyde, 3-fluorobenzaldehyde, 4-fluorobenzaldehyde, 3-bromo-4- fluorobenzaldehyde, 3-methyl-4-methoxybenzaldehyde, 2,4,5- trimethylbenzaldehyde, 4-chloro-3-fluorobenzaldehyde, 4- methylbenz
• Preferred di-acetals of the present invention include 1 ,3:2,4-bis(4-ethylbenzylidene)-1 -allyl-sorbitol, 1 ,3,2,4-bis(3'-methyl-4'- fluoro-benzylidene)-1 -propyl-sorbitol, 1 ,3,2,4-bis(5',6',7',8'-tetrahydro-2- naphthaldehydebenzylidene)-1 -allyl-xylitol, bis-1 ,3,2-4-(3',4'- dimethylbenzylidene)-1 "-methyl-2"-propyl-sorbitol, 1 ,3,2,4-bis(3',4'- dimethylbenzylidene)-1-propyl-xylitol.
• the di-acetals and mono-acetals 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 substituted alditol (such as allyl-sorbitol, propyl-sorbitol, allyl-xylitol, propyl-xylitol and the like) with 2 moles of aldehyde (for diacetals), with 1 mole of aldehyde (for monoacetals), or with 3 moles of aldehyde (for triacetals) in the presence of an acid catalyst (inorganic acid such as hydrochloric acid or organic acid such as p-toluenesulfonic acid (pTSA)). Further, an organic solvent is employed that is miscible with water (such as low alkyl alcohols, N-N-dimethylformamide, or acetic acid) at room temperature. In the practice of the invention, it is possible to have any number of substitute
• DBS moities on the structure It is common to have one, two, or three DBS (i.e. aryl-containing) moities on the hydrocarbon backbone.
• DBS i.e. aryl-containing
• Ar, An and Ar 2 are independently selected from substituted or unsubstituted aryl-containing groups;
• R is selected from the group consisting of: alkenyls, alkyls, alkoxy, hydroxyl alkyls, alkyl-halides and derivatives thereof.
• co-additives may be combined with said polyolefin composition. Examples of co-additives that can be used are set forth below in (1 ) - (3). Example 21 below shows yet another example of a co-additives lauryl sulfuric acid Na, that may be employed. Many other examples could be employed, and the co-additives below could be used with essentially any of the nucleating agent structures or compositions disclosed herein. Also, more than one co-additive set forth below could be employed, and the amount or concentrion employed would vary for a given application.
• Co-additives for inhibiting migration of odor and taste Alkali metal salts of amino acids (at least one amino acid chosen from the following: glycine, L-alanine, L-phenyl-alanine, L-isoleucine, L- valine, L-leucine, L-proline, L-arginine, L-asparatic acid, L-cystine, L- glutamic acid, L-serine, L- histidine, L-tryptophan, L-lysine, L-threonine, L- methionine, DL-ethionine, L-cysteine, L-tyrosine, L-asparagine, L- glutamine, L-norvaline, and L-a-amino butyric acid.) and 0.1 to 100 parts by weight of at least one fatty acid with 8-32 carbon atoms (octane acid, capric acid, lauric acid, myristic acid, palmitic acid,
• Co-additives for inhibiting migration of odor and taste and depression the melting point of DBS A: At least a saturated or unsaturated aliphatic alcohol with 6-32 carbon atoms (for example: lauric alcohol). B: and at least a saturated or unsaturated aliphaltic carboxylic acid with 8-32 carbon atoms having at least one hydroxy group within the molecule (for example: 12-hydroxy stearic acid), C: at least one type chosen from the following groups: lithium salt, sodium salt, or potassium salt of a saturated or unsaturated fatty acid with 8-32 carbon atoms that may have at least one hydroxyl group within the molecule, or D: at least one type sulfuric acid ester salt chosen from the following group: lauryl sulfuric acid salt, stearyl sulfuric acid salt, oleyl sulfuric acid salt, and polyoxyethylene stearyl ether sulfuric acid salts.
• Co-Additives having a granular or powdery diacetal composition wherein the binder is selected from the group consisting of monocarboxylic acids, polycarboxylic acids, partial salts of polycarboxylic acids, esters of phosphoric acid and at least one member selected from the group consisting of C1-C30 monohydric aliphatic alcohols and C2-C30 polyhydric aliphatic alcohols, esters of phosphorous acid and at least-one member selected from the group consisting of C1-C30 monohydric aliphatic alcohols and C2-C30 polyhydric aliphatic alcohols, esters of phosphoric acid and at least one member selected from the group consisting of C6-C30 monohydric aromatic alcohols and C6-C30 polyhydric aromatic alcohols, esters of phosphorous acid and at least one member selected from the group consisting of C6-C30 monohydric aromatic alcohols and C6-C30 polyhydric aromatic alcohols, taurine, salts of sulfuric acid ester, s,
• an acetal compound formed by the process of: (a) reacting a carbohydrate and an alkenyl group to form a first compound; and (b) reacting in a condensation reaction said first compound with an aromatic aldehyde to form an acetal compound.
• the alkenyl group comprises an allyl.
• This general reaction pathway may be used in various forms to synthesize carbohydrates in the manufacture of the compositions of the invention.
• One embodiment of the invention relates to the use of carbohydrate synthesis reactions in combination with other acetal formation reactions to prepare compositions of the invention.
• Substituted sorbitol diacetals, triacetals, and monoacetals may be prepared. These structures contain mixtures of any correlated types of acetals (such as the related di-, tri-, and/or mono-acetals of the target acetal).
• a di-acetal may be accomplished, in one embodiment of the invention, by removal of any present 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 95 percent and even up to 98 percent di-acetal or more, depending upon the application.
• a more complete synthesis pathway is shown below, which is merely illustrative, and not limited to only those species or reactions shown: Synthesis Pathwav(s)
• R may be selected from a wide variety of compounds, including without limitation and by way of example: -CH 3 ; -CH 2 CH 3 ; -CH2CH2CH3; -CH 2 CH 2 CH 2 CH 3 ; -CH2CH-X-CH2-X' ; -CH2CH2-X -CH2-CH3 ; -CH 2 CH-X"'-CH2 ⁇ H; -CH-OH-CH-OH-CH 2- OH.
• X, X', X" , and X'" comprise independently selected halide groups in those selected compounds, if they are employed.
• Examples 3-8 A variety of allyl-substituted dibenzylidene-based (DBS) molecules were synthesized using the procedures similar to the one described in
• Example 2 above. Structures are shown in Table I, with measured values for melting point. All derivatives had NMR consistent with the indicated structures, and purities of at least 95%, based on GC-MS.
• the mixture was stirred and slowly heated to reflux - a significant exotherm and gas evolution was observed at 60°C.
• the gray suspension was stirred at reflux for three days, in which time the reaction mixture turned an orange/brown color. Heat was removed and the mixture was allowed to cool to room temperature.
• Example 10 Bis-1.3:2,4-(5'.6'.7'.8'-tetrahvdro-2- naphthaldehvdebenzylidene) 1 -Allyl Xylitol
• allyl DBXs were synthesized using the procedure similar to the one described in Example 2.
• the structures of example 10 and 11 are shown in Table 1. All derivatives had NMR consistent with the indicated structures, and purities of at least 95%, based on GC-MS.
• Example 15 Bis-1.3:2.4-(3'.4'-Pimethylbenzylidene) 1 '-Methyl-2'-PropenylSorbitol
• Example 16 Bis-1.3.2,4-Dibenzylidene 2'.3'-Dibromopropyl Sorbitol/ Bis-1.3.2.4-Dibenzylidene 2'-Bromo-3'-Hvdroxypropyl Sorbitol
• An aqueous solution of 90 g allyl sorbitol syrup (Example 1) in 110 g of methanol was titrated with bromine until a light yellow solution. Small amount of NaHS0 3 was added to give a colorless solution. 1.9 g of p- toulenesulfonic acid monohydrate was added. The clear solution was stirred overnight, during which time a significant amount of white precipitate formed.
• the powder was isolated by filtration and washed with 1 M NaOH aqueous solution.
• the suspension was heated to boiling, then filtered.
• the white powder was washed with 7 x 500 ml of boiling water.
• the washed powder dried overnight.
• the powder was then stirred in 50 mL of cyclohexane, heated until boiling, filtered, and washed with 2 x 25 ml of boiling cyclohexane.
• the product was dried in a vacuum oven to give 7.3 g of white powder, m.p. 188-190°C.
• Example 17 Asymmetric benzylidene/2,4-dimethylbenzylidene 1 -Allyl Sorbitol
• 9.5 g of pTSA, 53 g (0.5 mol) of benzaldehyde and 67 g (0.50 mol) of 2,4-dimethylbenzaldehyde were added to the reaction vessel.
• the clear solution was stirred for 48 hours, during which time a significant amount of white precipitate formed.
• Example 18 Tri-1.3:2.4:5.6-benzylidene-1 -AIM Sorbitol 111 g (0.50 mol) of 1 -allyl sorbitol syrup (product of Example 1) was dissolved in 111 g of water. The solution was mixed with 50 g of ice. With an ice cooling bath, 90 mL of 93% of sulfuric acid was added slowly so the temperature was below 20°C. 106 g (1.0 mol) of benzaldehyde was added. A dark pink suspension was formed. The reaction was allowed to stand at room temperature overnight. The resultant yellow solid was collected by filtration, neutralized with 10% NaOH solution.
• Example 19 Bis-1.3: 2,4-(3'-bromo-4'-ethylbenzylideneM-AIM Sorbitol/ Mono 2. 4-(3'-bromo-4'-ethylbenzylidene)-1 -Allyl Sorbitol
• To this vessel was added 335.2 mL of a 0.4M methanolic solution of 1-allyl sorbitol (30.07g, 134.1 mmol) (product of example 1 ) and 60.00g (281.6 mmol) of 3- bromo-4-ethylbenzaldehyde.
• the crude solids were isolated by Buchner funnel vacuum filtration and washed with 800 ml of boiling D.I. H 2 O. To remove unreacted sugar, the material was dried overnight, ground to a fine powder, and suspended in 1000 mL of D.I. H 0. The slurried mixture was brought to a boil and stirred for 30 minutes. The solids were ' captured via Buchner funnel filtration and further washed with boiling D.I. H 2 0 (3 x 1000 mL). To remove residual aldehyde, the aforementioned procedure was repeated utilizing boiling methanol as wash solvent.
• Example 22 Compositions containing various levels of the acetal of examples 2-21, coadditives (0.05 wt. % Irganox 1010, 0.1 wt. % Irgafos 168, and 0.08 wt. % calcium stearate) and the balance polypropylene homopolymer or polypropene random copolymer (3% ethylene content) were dry blended in a mechanical mixer, extruded through a single screw extruder at 240°C and pelletized. Plaques were prepared (1.27 mm thick) by injection molding the pellets at 220°C. The Tc and haze were measured, and the results are reported in
• Millad 3988® is a registered trademark of Milliken and Company of Spartanburg, South Carolina. Millad 3988® is a commercially distributed clarifying agent product that employs bis(3,4- dimethylbenzylidene sorbitol)("DMDBS”), as shown and described in United States Patent No. 5,049,605.
• the nucleating agent composition may be added to the polymer resin at a concentration of from about 0.005 to about 3 weight percent. In other applications, a concentration of between about 0.01 and about 1 weight percent may be employed. In other applications, a concentration of between about 0.025 and about 0.5 weight percent of the composition is useful. Concentrates of up to 50 weight percent of the nucleating agent in resin may also be prepared for blending with additional resin prior to molding. Typically, concentrates containing 33 weight percent or less of the nucleating agent in resin are used commercially.
• the resin may be extruded a second time immediately before being processed into a finished article by, for example, injection molding, extrusion blow molding, injection blow molding, stretch blow molding, compression molding, rotational molding, profile extrusion, sheet extrusion, thermal forming, film extrusion, and film extrusion with orientation.
• Gel Formation and Testing Solid gels also were produced comprising the inventive substituted- alditol derivatives through recognized, simple methods. In particular, 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.
• inventive substituted-alditol derivatives provide excellent gelling capabilities for solvents, depending upon their concentration without the target solvents. It is understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention, which broader aspects are embodied in the exemplary constructions. The invention is shown by example in the appended claims.

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