Dibenzylidene sorbitol (dbs) based compounds, composition and method of using said compounds

FIELD: chemistry.

SUBSTANCE: invention relates to novel dibenzylidene sorbitol (DBS) compounds of formula 1: , in which R₁ and R₂ are independently selected from a group consisting of CH₃CH₂CH₂- and CH₃CH₂CH₂O-; and in which R₃ is independently selected from -CH₂CH₂CH₃ and -CH₂-CH=CH₂ groups. According to one version, this invention pertains to a disubstituted DBS based compound having an allyl or propyl group as a substitute at the first carbon atom in the sorbitol chain. The present invention also relates to compositions containing such DBS based compounds and preparation methods thereof.

EFFECT: compounds are characterised by one or more of improved transparency, reduced yellowing and improved organoleptic properties.

11 cl, 3 tbl, 16 ex

The technical field to which the invention relates.

The present invention relates to compounds based dibenzylideneacetone ("DBS"). The compounds of this invention have in particular the advantage that they improve the transparency (lower turbidity), reduce yellowing and improve the organoleptic properties.

The level of technology

Derivatives acetals polyhydric alcohols are useful for several applications, including, for example, use as nuclearpower and brightening agents for polymer resins and as gelling and thickening agents for organic liquids. Connection-based DBS are useful for such applications.

Nuclearmoose and brightening agents are used to reduce the turbidity in the products made from crystalline polyolefin resins. Typical acetals of sorbitol and xylitol, which are used as nuclearpower and brightening agents described in Hamada, et al., United States Patent No. 4,016,118, dibenzylideneacetone; Kawai, et al., United States Patent No. 4,314,039, di(alkylbenzenes)sorbite; Mahaffey, Jr., United States Patent No. 4,371,645, diacetyl sorbitol having at least one bromine or chlorine Deputy; Kobayashi, et al., United States Patent No. 4,954,291, the distribution of diacetals sorbitol and xylitol obtained from a mixture of dimethyl or trimethyl substituted benzaldehyde and the unsubstituted Bansal is Egida. U.S. patent No. 5,049,605 Rekers et al. describes bis(3,4-dialkylanilines)sorbite. As an example of one type of bleach - 1,3-O-2,4-bis(3,4-dimethylbenzylidene)sorbitol (in this description DMDBS), available from Milliken Chemical under the trade name Millad^®3988, provides clarification of the target polypropylene and other polyolefins.

Changes in various alternative groups in the compounds based on DBS can have a significant impact on the properties of the compound in the composition of the plastics. In particular, the replacement of different groups in the position(s) benzyl ring compounds based on DBS can have a significant impact on the suitability of these compounds as nuclearpower and brightening agents. Accordingly, in the past, efforts were made to change the layout of the Deputy (deputies) in benzylidene ring.

Published patent application US 2005-0239926 A1 and US 2005-0239928 A1 Xie et al. describe compositions on the basis of acetals, suitable as nuclearpower and brightening agents. These applications describe, in particular, that benzylideneaniline derivatives, substituted at the first carbon atom chain sorbitol are particularly effective brightening agents.

The percentage of turbidity polyolefin products is usually a measure of the degree of whitening that nuclearmoose or brightening agent gives polyaluminosilicate, to employ such an agent. Typically, the reduction is only one percent (or even parts of a percent) turbidity can be very significant in the industry. Thus, in the production of additives for plastics are constantly trying to find connections, which nuclearfamily or brightening agents that will give the lowest turbidity. Leading, commercially available bleaching agent Millad^®3988, gives 7-8% of the turbidity of 50 mil (1.27mm millimeters) statistical copolymer polypropylene products made by injection molding. Long-term goal of industry is to develop a brightening agent, which would have reduced the degree of turbidity under the same conditions and with the same degree of concentration.

Low turbidity is not only an important factor in determining the suitability of an additive to the plastic. Low thermal stability can cause undesirable yellowing and contamination during high temperature processing. This yellowing is undesirable.

Nuclearmoose or brightening agent should not give excessive unwanted taste of plastic products, in which it is introduced. Thus, it is desirable nuclearmoose and brightening agents, which contributes to overcoming organoleptic the definition of problems. "Organoleptic" refers to the taste, which is undesirable, can be transmitted to polymeric containers for storage of food and beverages connection - nuclearpower or brightening agent introduced into the plastic.

These are worthy of attention problems has necessitated industry polyolefin clarifiers provide such compounds which do not cause these problems and give excellent transparency target polyolefin products. Today best known for this purpose, compounds the problems mentioned above, has not been solved.

Detailed description of the invention

This invention relates to new compounds nuclearfusion or brightening agents, providing unexpectedly, one or more of the characteristics of the range: the lower the turbidity, yellowing and improved organoleptic properties. According to the first variant implementation is provided by the derived benzylideneamino (DBS), which is the disubstituted compound based on the DBS, having allyl group or n-sawn group as substituent at the first carbon atom chain sorbitol (C-1 position). The present invention also relates to compositions containing such compounds based on the DBS, and methods of use thereof. The compounds of this invention can be represented HUF who Ulai I:

in which R₁and R₂independently selected from the group consisting of: CH₃CH₂CH₂- (i.e. n-propyl) and CH₃CH₂CH₂O- (i.e. n-propoxy); and

in which R₃independently selected from the group consisting of: -CH₂CH₂CH₃(n-propyl)- CH₂-CH=CH₂(allyl).

Applicants investigated a number of nuclearpower and brightening agents, including those described in US 2005-0239926 A1 and US 2005-0239928 A1 Xie et al. It was found that the compounds of formula I provide unexpectedly improved, i.e. reduced turbidity, improved organoleptic properties and/or reduced yellowing compared to other tested nuclearfamily and brightening agents, including some of those that are closely related structure.

In one embodiment, the present invention provides a compound of formula I, in which R₃is n-sawn group (-CH₂CH₂CH₃). In an alternative embodiment, R₃is the allyl group (-CH₂CH=CH₂). In one embodiment of this invention R₁and R₂are n-cuts. In an alternative embodiment, R₁and R₂are n-propoxy.

In another embodiment of this invention R₁and R₂are Odie is akovali: ie the compound of formula I is symmetric. In another embodiment, R₁and R₂are different: i.e. the compound of formula I is asymmetric.

In another embodiment of this invention R₃is allyl and R₁and R₂independently selected from the group consisting of n-propyl and n-propoxy.

In another embodiment of this invention R₃is n-propylene and R₁and R₂independently selected from the group consisting of n-propyl and n-propoxy.

According to one variant of implementation of the present invention, the compound of formula I is compound 1:

Connection 1.

According to another variant implementation of the invention, the compound of formula I is the compound 2:

Connection 2.

According to another variant implementation of the invention, the compound of formula I is compound 3:

Connection 3.

According to another variant implementation of the invention, the compound of formula I is the compound 4:

Connection 4.

The compounds of formula I of the present invention are useful for several applications, including, for example, the use as the e nuclearpower and brightening agents for polymer resins and as gelatinosa and a thickening agent for organic liquids.

According to another variant implementation of the invention the present invention provides nuclearfamily or bleaching compositions containing a compound of formula I.

According to one variant of implementation of the present invention nuclearmoose or brightening compositions contain a mixture of compounds of formula I. In one embodiment, the composition contains a mixture of asymmetric compounds of formula I. In another embodiment, nuclearia or bleaching composition comprises a mixture of symmetrical compounds of formula I.

In one embodiment, nuclearia or bleaching composition comprises compound 1. In another preferred embodiment, nuclearia or bleaching composition comprises compound 2. In another embodiment, nuclearia or bleaching composition contains a compound 3. In yet another embodiment, nuclearia or bleaching composition contains the compound 4.

According to a variant implementation of the present invention provides a method of nucleation olefin polymer, including the state Association olefin polymer with the compound of the formula I.

According to another variant implementation of the present invention provides a polyolefin composition comprising a compound of formula I and leinaweaver.

Olefin polymers that can be used in this invention include polymers and copolymers of aliphatic monoolefins containing from 2 to about 6 carbon atoms, which have an average molecular weight of from about 10,000 to about 2000000, preferably from about 30,000 to about 300000, such as, for example, polyethylene, including linear low density polyethylene, low density polyethylene and high density polyethylene, polypropylene, crystalline ethylene/propylene copolymer (statistical or block), poly(isobutene) and polymethylpentene.

Examples of other olefin polymers that can be used in this invention include, for example, a complex polyester, poly(ethyleneterephthalate) (PET) and poly(butylene terephthalate) and polyamide, including nylon 6 and nylon 6,6, poly(phenylindole), syndiotactic polystyrenes and polyketone having a carbonyl group in the structure of the skeleton.

In a desirable embodiment, this invention the polyolefin compositions contain polypropylene.

According to one variant of implementation of the present invention, the polyolefin compositions contain a compound of formula I at a concentration of from about 0.005-about 3 percent by weight, preferably from approximately 0.01 to approximately 1 is recent by weight and more preferably from about 0.025 to about 0.5 percent by weight, and even more preferably from about 33 percent by weight or less, as in concentrated masterbatches.

According to another variant implementation of the invention, the polyolefin compositions contain a compound of formula I at a concentration of up to 50 percent by weight, as in the case of the song "Royal mixture". In a preferred embodiment, the polyolefin composition may contain more than one olefinic polymer.

In various embodiments, the implementation of the compounds of formula I of this invention provide improved transparency (reduced turbidity) polyolefin compositions in which they are entered. In alternative embodiments, the implementation of the compounds of formula I provide reduced yellowing of the polyolefin composition. In yet another embodiment, the compounds of formula I provide enhanced transparency, yellowing and organoleptic properties of olefinic composition.

According to another variant implementation of the invention, the polyolefin composition is formed into or ekstragiruyut to form various polymer products.

According to one variant of implementation of the present invention the polyolefin composition ekstragiruyut many times before making it in the final product. Appropriate ways extrusion polyolef the new composition include, but not limited to, injection pressing, pneumotropica with extrusion, injection molding, injection blow, oriented blow molding, extrusion in the form of a centrifugal molding, the molding of shaped products, manufacture of sheet extrusion, thermal molding, film extrusion and extrusion film orientation.

The synthesis methods

The compounds of formula I can be synthesized in various ways. Such methods can be those described herein or those known in the art. Typically these methods use the reaction of 1 mole of substituted Aldata (such as allylboronic, n-profilarbed, allelectric, n-propixel and similar) with 2 moles of aldehyde in the presence of an acidic catalyst (inorganic acid, such as chloromethane acid, or organic acids such as p-toluensulfonate (pTSA)). Then use an organic solvent, i.e. miscible with water (such as lower alkalemia alcohols,N,N-dimethylformamide or acetic acid)at room temperature.

One method that can be used to prepare the compounds of formula I, described in U.S. patent No. 5,106,999 Gardlik et al., introduced into this description by reference.

Methods of synthesis alditol with different long chain described in Kim, Gordon,Schmid, and Whitesides, Tin and Indium Mediated Allylation in Aqueous Media: Application to Unprotected Canbohydrates, J. Org. Chem, 5500-5507, 58 (1993), and Whitesides, Journal of the American Chemical Society, 113, 6674-6675 (1991). Whitesides was referred to the reaction of glucose with allylbromide/tin.

According to one variant of implementation of the scheme of synthesis to obtain the compounds shown below. Experts clear that these diagrams are merely examples, and that you can use other methods to prepare the compounds of formula I.

Scheme 1 illustrates a method for obtaining intermediate compounds C and D.

In scheme 1, the intermediate compound C is obtained by reaction of A sugar and alkenylphenol group B.

Scheme 1

Scheme 2 illustrates a typical example for producing compounds of the formula I, in which R₃is allyl or propylene.

When R₃is allyl, as shown in scheme 2, are provided with a polyhydric alcohol and allyl-containing group B. At the next stage, a polyhydric alcohol and allyl-containing group B react with the formation of the first allyl-containing compounds C. Then compound C reacts in the condensation reaction with substituted benzaldehyde F with the formation of compound G.

In an alternative embodiment, R₃is propylene. This method is used a polyhydric alcohol and allyl group B. a Polyhydric alcohol and allyl-with the holding group B react with the formation of compound C. The allyl - containing compound C restore with the formation of n-propyl-substituted compound E, which then reacts in the condensation reaction with substituted aromatic aldehyde F with the formation of compound H.

Scheme 2

Thus, the present invention provides a method for obtaining compounds of formula I in which R₃is allyl, including the stage of (a) providing a polyhydric alcohol and allyl groups; (b) the reaction of a polyhydric alcohol and allyl groups with the formation of the first allyl-containing compounds; (c) the reaction of the first allyl-containing compounds in the condensation reaction with substituted benzaldehyde.

In another embodiment, the present invention provides a method for obtaining compounds of formula I in which R₃is n-propylene, comprising the stages of (a) providing a polyhydric alcohol and allyl groups, (b) reaction mentioned polyhydric alcohol and the above-mentioned allyl group with the formation of the first allyl-containing compounds; (c) recovery mentioned allyl-containing compounds with the formation of n-propyl-substituted compounds, and (d) the condensation reaction of the mentioned n-propyl-substituted compounds with substituted aromatic aldehyde.

As shown in scheme 2, compounds of formula I mo is but to get the reaction of condensation, using the appropriate benzaldehyde. Professionals it is clear that in the condensation reaction are obtained mixture diacetate (compound of formula (I), triacetate and monoacetate. Although delete triacetate and monoacetal not always necessary (especially if they are present in very small amounts) before the introduction of the compounds of formula I in the polyolefin composition, it may turn out to be desirable, and this treatment can be used in order to increase the transparency of the produced polymer.

According to another variant implementation of the invention, the purification of the compounds of formula I can be carried out by removing any present triacetate extraction of its relatively non-polar solvent. As one non-limiting example, the composition of the present invention contains a compound of the formula I, in which the composition has a purity of at least 95 to 98 percent depending on the application.

In this paper refer to various alternative embodiments of the present invention, one or more of the examples described below. Each example is by way of explanation of this invention, but not limit the present invention. Professionals it is clear that the present invention can make various modifications and variants without going beyond the scope or substance of the data of the invention.

Example 1

1-allylboronic

In a three-liter three-neck round bottom flask equipped with a mantle, a stirrer, a hole for the nitrogen and the fridge was loaded with 900 ml of ethanol, 150 ml of water, 180 g (1.00 mol) of D-glucose, 119 g (1.00 mol) of powdered tin (-100 mesh) and 121 g (1.00 mol) of allylbromide. The mixture was stirred and slowly heated to 60°C. the Grey suspension was stirred at this temperature for 24 hours, during which time the reaction mixture had become a light yellow color. Heating was stopped and cooled to room temperature. The reaction mixture was neutralized to pH 7 by adding about 200 ml of 5 M aqueous NaOH solution. The suspension was filtered to remove solids, and the yellow solution was decolorized by repeated treatment with activated charcoal. Activated charcoal was removed by filtration, and the solvent was removed by evaporation on the rotor to get a white syrup. Standard output was 200 g ratio threo-Erythro 6:1 on the basis of GC-MS. Syrup 1-allylcarbamate used without further purification.

Example 2

Bis-1,3,2,4-(4`-propylbenzamide)-1-allylboronic

Connection 1

In a two-liter reaction vessel equipped with a stirrer and outlet for nitrogen, downloaded the solution and 48.8 g (0.22 mol) of syrup of 1-allylbromide in 400 ml of methanol. Was added in the reaction with the UD 97,7 g (0.44 mol) of 4-propylbenzenesulfonyl and 4.3 g of the monohydrate of p-toluenesulfonic acid. A clear solution was stirred for 24 hours, during which formed a significant amount of sediment. Were isolated by filtering white powder and washed with 250 ml of 1 M aqueous NaOH solution. White powder suspended in water and optionally neutralized to pH 7 with a small amount of NaOH. The suspension was heated to boiling, then filtered. The white powder was washed 7×with 500 ml of boiling water. The washed powder was dried overnight. The powder is then stirred in 500 ml of cyclohexane was heated to boiling, filtered and washed with 2×250 ml of boiling cyclohexane. Selected white powder was dried in a vacuum oven to get to 44.5 g of the product, TPL 223-225°C. Purity was approximately 99% based on GC-MS.¹H NMR(500 MHz, DMSO-d₆, h/m), 0,86-of 0.90 (m, 6H₁-CH₂CH₂CH₃), 1,53-to 1.61 (m, 4H, -CH₂CH₂CH₃), 2,41 is 2.44 (t, 2H, -CH₂-CH=CH₂), 2,55-to 2.57 (m, 4H, -CH₂CH₂CH₃), 3,42-4.09 to (m, 7H, sugar H), 4,37-4,39 (t, 1H, -CH₂OH), 4,79-4,80 (d, 1H, -CHOH), 5,08-5,18 (square, 2H, -CH₂CH=CH₂), the ceiling of 5.60 (s, 1H, acetal), 5,64 (s, 1H, acetal), of 5.84-to 5.93 (m, 1 H, -CH₂-CH=CH₂), 7,17-7,21 (m, 4H), 7,34-7,37 (t, 4H).

Example 3

Bis-1,3,2,4-(4`-propoxybenzene)-1-allylboronic

Connection 2

to 65.2 g (0.29 mol) of syrup of 1-allylcarbamate (made in example 1) was dissolved in 500 ml of methanol. Added 104 g of 4-propoxybenzaldehyde to 0.63 mol). The solution was brought to pH 1 by addition of acid. The reaction mixture was stirred at room temperature for 5 hours. Collected by filtering the resulting solid was washed with an aqueous solution of KOH to pH>10. The suspension was heated to boiling, then filtered. The white powder was washed 7×with 500 ml of boiling water. The washed powder was dried overnight. Then the powder was stirred in 500 ml of cyclohexane was heated to boiling, filtered and washed with 2×250 ml of boiling cyclohexane. Selected white powder was dried in a vacuum oven to obtain 78.5 per g of product, m.p. 206-208°C. Purity was approximately 99% based on GC-MS.¹H NMR(500 MHz, DMSO-d₆, ppm): 0,95-0,98 (m, 6H, -OCH₂CH₂CH₃), by 1.68 to 1.76 (m, 4H, -OCH₂CH₂CH₃), 2,40-to 2.42 (t, 2H, -CH₂-CH=CH₂), 3,41-3,82 (m, 5H, sugar H), 3,90-3,93 (m, 4H, -OCH₂CH₂CH₃), Android 4.04-4,07 (m, 2H, sugar H), 4,36-to 4.38 (t, 1H, -CH₂OH), 4,78-rate 4.79 (d, 1H, -CHOH), 5,07-5,18 (square, 2H, -CH₂CH=CH₂), to 5.56 (s, 1H, acetal), the ceiling of 5.60 (s, 1H, acetal), of 5.84-of 5.92 (m, 1H, -CH₂-CH=CH₂), 6,90-6,93 (t, 4H), 7,33-7,37 (t, 4H).

Example 4

1-profilarbed

30 g (is 0.135 mol) syrup 1-allylcarbamate (made as in example 1) was dissolved in 300 ml of ethanol. Was added 1.0 g of platinum (5% by weight on activated carbon)and the mixture was first made at room temperature under hydrogen pressure of 60 psi. The reaction was stopped at the moment when no observation is whether the pressure drop of the hydrogen. The solid residue was filtered. Allyl group in the solution is completely transformed in various group on the basis of NMR.

Example 5

Bis-1,3,2,4-(4^`-propylbenzamide)-1-profilarbed

Connection 3

In one litre reaction vessel equipped with a stirrer and outlet for nitrogen, loaded ethanol solution popularite. Was added to the reaction vessel, 40 g (0.27 mol) of 4-propylbenzamide and 2.6 g of the monohydrate of p-toluenesulfonic acid. A clear solution was stirred for 24 hours, during which formed a significant amount of sediment. A white powder was isolated by filtration and washed with 250 ml of 1 M aqueous NaOH solution. White powder suspended in water and optionally neutralized to pH 7 with a small amount of NaOH. The suspension was heated to boiling, then filtered. The white powder was washed 7×with 500 ml of boiling water. The washed powder was dried overnight. Then the white powder was stirred in 500 ml of cyclohexane was heated to boiling, filtered and washed with 2×250 ml of boiling cyclohexane. Additional purification was carried out using Ace Glass 6810 Giant Soxhlet Extraction Apparatus (size F) and the tip of the cellulose fibers (58×170 MM OD) 2000 ml of methanol. White powder suspended in 250 ml of methanol was poured into the tip and were extracted for 5 days while boiling. P is obtained in the extract was cooled to 5°C and filtered, to collect a white solid, which was suspended in 1000 ml of petroleum ether, filtered and air-dried. Selected white powder was dried in a vacuum oven to get to 20.1 g of product, m.p. 244-245°C. Purity was approximately 99%, based on GC-MS.¹H NMR (500 MHz, DMSO-d₆, ppm): 0,86-to 0.89 (m, 6H, Ph-CH₂CH₂CH₃), 0,91-of 0.94 (t, 3H, sugar-CH₂CH₂CH₃), 1,35-1,49 (m, 2H, sugar-CH₂CH₂CH₃) 1,54-to 1.60 (m, 4H, Ph-CH₂CH₂CH₃), 1,61-1,71 (m, 2H, sugar-CH₂CH₂CH₃), 2,53-of 2.56 (t, 4H, Ph-CH₂CH₂CH₃), 3,41-Android 4.04 (m, 7H, sugar H), 4,36-4,39 (t, 1H, -CH₂OH), 4,78-rate 4.79 (d, 1H, -CHOH), the ceiling of 5.60 (s, 1H, acetal), 5,62 (s, 1H, acetal), 7,17-7,20 (DD, 4H), 7,32-7,37 (DD, 4H).

Example 6

Bis-1,3,2,4-(4`-propoxybenzene)-1-profilarbed

Connection 4

Was added to a solution of 17.0 g (0,076 mol) of profilarbed (made in example 4) in 200 ml of methanol, 25 g (0.15 mol) of 4-propoxybenzaldehyde, followed by the addition of 1.5 g of the monohydrate of p-toluenesulfonic acid. The reaction mixture was stirred at room temperature overnight. The resulting solid was collected by filtration, washed with an aqueous solution of KOH to pH>10. The suspension was heated to boiling, then filtered. The white powder was washed 7×with 500 ml of boiling water. The washed powder was dried overnight. Then white parasociological in 500 ml of cyclohexane, was heated to boiling, filtered and washed with 2×250 ml of boiling cyclohexane. Selected white powder was dried in a vacuum oven to get to 22.3 g of the product, TPL 215-217°C. Purity was approximately 99% based on GC-MS.¹H NMR (500 MHz, DMSO-d₆, h/m): 0,90-of 0.93 (t, 3H, -CH₂CH₂CH₃), 0,95-0,98 (m, 6H, -OCH₂CH₂CH₃), of 1.36 to 1.47 (m, 2H, -CH₂CH₂CH₃), 1,53 is 1.60 (m, 2H, -CH₂CH₂CH₃), and 1.63 and 1.75 (m, 4H₁-OCH₂CH₂CH₃), 3,40-3,81 (m, 5H, sugar H), 3,90-3,93 (t, 4H, -OCH₂CH₂CH₃), 3,97-was 4.02 (m, 2H, sugar H), 4,37-and 4.40 (t, 1H, -CH₂OH), 4,79-4,80 (d, 1H, -CHOH), to 5.56 (s, 1H, acetal), 5,59 (s, 1H, acetal), 6,90-6,93 (m, 4H), 7,31-7,37 (DD, 4H).

Comparative example 7

Bis-1,3,2,4-(4`-ethylbenzamide)-1-allylboronic

This compound is prepared according to the methods described in US Patent Publication 2005-0239928 A1.

Comparative examples 8-14

Various allyl - and propoxyphene DBS derivatives, including examples from US 2005-0239926 A1 and US 2005-0239928 A1, and DBS derivatives, which are most similar in structure to the compounds of the present invention, obtained according to the methods of US 2005-0239928 A1. The patterns shown in table 1. All derivatives had NMR mapping with the specified structures and purity of at least 95%, based on GC-MS.

Example 16

Comparing the turbidity of the compounds of the invention and compounds to compare

Each is th of songs, containing compounds of examples 2, 3, 5, 6 and comparative examples 7 to 14, was separately mixed with 1000 grams of 11 MFR (the flow rate of the melt) polypropylene statistical copolymer resin (RCP, 3% ethylene content) and the standard composition of the additive (i.e. 500 ppm Irganox 1010, 1000 ppm lrgafos 168, and 800 ppm of calcium stearate, CaSt), using a mixer with a ribbon screw blade Gardner for five minutes at approximately 200-220 about/M. the mixture is Then melted on the prism with a diameter of 16 mm, 25:1 L/D twin screw extruder, in which the screws rotate in the same direction. The molten resin was subjected to injection molding using a 40-ton Arburg AIIRounder 221K to get twenty-51 mm×76 mm×1.27 mm test drive, which was collected in sequential order. Each resin was processed in a forming machine, using the temperature of the drum with a uniform profile 230⁰C and not using backpressure.

Sample Millad 3988® also mixed for sensory research. Millad 3988® is a registered trademark of Milliken and Company of Spartanburg, South Carolina. Millad 3988® is a commercially available bleaching agent, which is also known as bis(3,4-dimethylbenzylidene)("DMDBS") and described in United States Patent No. 5,049,605.

The percentage of turbidity was measured using a turbidity meter BYK Gardner Hazegard Plus according to ASTM D1003. The results are presented in table 1.

Each of US 2005-0239926 A1 and US 2005-0239928 A1 describe the connection of comparative example 7 above (allyl if R₃with ethyl when both R₁/R₂). Allyl with ethyl (CH 2CH₃) is the best performance of the comparative groups shown above, in terms of the percentage of turbidity. However, the examples of the invention 2, 3, 5 and 6 above, all show the best results regarding the percentage of turbidity, even when compared with allylation compound of comparative example 7. These excellent properties are unexpected.

As shown in table 1, the compounds of the invention give unexpected results from the point of view of the significant improvement brightening properties when compared with the comparative examples with a similar chemical structure. Indeed, suppose that the compounds of this invention are such well-known compounds that give less than about 5% turbidity 50 miles statistical copolymer polypropylene products obtained by standard injection molding, when the concentration loading 5000 h/million These improved properties turbidity are very desirable and can not be predicted by experts in the field of technology.

For example, the compounds of comparative examples 7, 8 and 9, in which R₃=allyl and R₁, R₂=ethyl, methyl, n-butyl, respectively, are similar in structure to the compound of this invention of example 2 (in which propyl use in both R₁/R₂). In the compound of the present invention use the 2 use the lower alkyl n-propyl for R ₁and R₂and , therefore, is "from the point of view of the structure between the ethyl and n-bootrom from the point of view of the number of carbon atoms in the lower alkyl. Unexpectedly, however, this connection example 2 gives significantly reduced turbidity when compared with their respective comparative examples with large (1)and less (2) the number of carbon atoms in R₁/R₂the provisions. I.e. the results of turbidity are not between the 5.2 and 6.0, as might be expected from consideration of the properties of the comparative examples, but instead, the turbidity of example 2 is significantly lower at 5.2. Indeed, the turbidity of the compounds of the present invention is only approximately 4.5. This unusually low value of turbidity is unexpected. I believe that these findings represent a significant and unexpected discovery.

When there is structural similarity between the compounds of this invention and the compounds of comparative examples, these results are unexpected.

Example 15

Test taste (organoleptic properties)

This example illustrates the low transmission characteristics of taste compounds of the present invention. When such compounds are used as additives to plastics, it is important that the additive did not give an undesirable taste the plastic, which is used for the manufacture of containers for storing the deposits of food and drinks and such. Believe that the organoleptic properties of DBS derivatives are determined aldehyde components.

The test Protocol was after the General guidelines defined in: ASTM STP 434 (Manual on Sensory Testing Methods) and ASTM STP 758 (Guidelines for the Selection and Training of Sensory Panel Members). The experimental design method is based on the statistics of the pairwise comparisons on the basis of 95% or larger of the limits of validity.

Sample preparation

Additives introduced during melting in polypropylene weighing and high-intensity mixing. In addition to 3500 ppm of bleach weighed and mixed in polypropylene the following supplements: 500 ppm Irganox 1010, 1000 ppm lrgafos 168, and 800 ppm of calcium stearate. These studies have added the following bleach:

1. Example 2 at 3500 ppm

2. Example 3 at 3500 ppm

3. Comparative example 7 at 3500 ppm

4. Di(3,4-dimethylbenzylidene)sorbitol (commercial Millad 3988®) at 2000 h/million Then the samples of the resin were introduced during melting in a single screw extruder and molded into tablets. Tablets were formed under the pressure plate, having a thickness - 0,050 inch, width of 2.0 inches and a length of 3.0 inches.

Processing samples

It is believed that water is the best medium for conducting organoleptic measurements because it provides the least sense of taste taster to minimiz is its effect on the material, want to explore. The samples are mixed and molded polypropylene resin was placed in a transparent glass vessels, separated by glass pipette and covered with water. Standard surface to volume ratio used for the samples is 675 cm²/liter Containers tightly closed and kept in the oven for about five days at 50⁰C. Then the resulting water was cooled to evaluate the measurement panel.

Assessment tasters

Tap water was given to each taster to find out the taste before and between each test. The possible error of the order of tasting samples was eliminated by balancing the design of the experiment with respect to the order of presentation in pairs (each additive was uniformly applied both the first and the second when tasting). In addition, the order of the pairs presented in the session tasting is random for tasters. Thus, the plan of the experiment was trying to eliminate sources of possible bias, and experimental Protocol and test conditions sought to reduce other sources of bias and influence. The experiment was performed with double anonymity, so no taster, or the Chairman of the trials did not know the name of the sample you want to examine.

Statistical analyses

Results the ATA tests were analyzed statistically, using the method of paired comparison Herbert A. David. Used a confidence level of 95% for data evaluation. Depending on the plan of the experiment each additive must be interval required number of units to be considered statistically excellent when the degree of reliability of 95%. Execution of samples and required a separate unit when the degree of reliability of 95% is given below.

In this measurement the samples 2, 3 and comparative example 7 were separately compared with Millad® 3988 when paired comparison, as described, 15 tasters. The results were as follows.

Organoleptic results PR is a measure of 2

Millad 3988® was chosen as having the least taste in comparison with the compound of example 2 with a score of 8-7 (ie 8 tasters chose Millad 3988, as having the least taste, while 7 tasters chose the sample 2 as having the least taste), which is statistically insignificant at the 95%confidence intervals. Thus, in addition to remarkable degrees of turbidity example 2 is suitable organoleptic properties.

Organoleptic results of example 3

Millad 3988® was chosen as having the least taste in comparison with the compound of example 3 with a score of 10-5 (i.e. 10 tasters chose Millad 3988, as having the least taste, whereas 5 tasters chose the sample 2 as having the least taste), which is statistically insignificant at the 95%confidence intervals. Thus, in addition to remarkable degrees of turbidity example 3 is suitable organoleptic properties.

Organoleptic results of example 5

Millad 3988® was chosen as having the least taste in comparison with the compound of example 5 with a score of 10-5 (i.e. 10 tasters chose Millad 3988, as having the least taste, whereas 5 tasters chose the sample 2 as having the least taste), which is statistically insignificant at the 95%confidence intervals. Thus, in addition to a remarkable degree any turbidity, example 5 has a suitable organoleptic properties.

Organoleptic results of comparative example 7

Millad 3988® was chosen as having the least taste in comparison with the compound of comparative example 7 with a score of 15-0 (i.e. 15 tasters chose Millad 3988, as having the least taste, while 0 tasters chose the compound of comparative example 7 as having the least taste), which is statistically significant at the 95%confidence intervals. Thus, the compound of comparative example 7 (connection with R₃as the allyl, and R₁/R₂as ethyl) possesses unsuitable organoleptic properties (for tanks that are in contact with food).

Millad 3988®, which offers excellent organoleptic properties, is a leading commercial bleach. Its organoleptic properties are considered industry standard polyolefin bleach. Believe that bleach, which is not statistically different from Millad 3988® in research on taste, meet the requirements of organoleptic properties, whereas bleach, which is statistically different from Millad 3988®, is considered to be less desirable for many industrial applications. The data suggest that the examples of the present invention ablauts is comparable organoleptic properties with Millad 3988®, and comparative example 7 (allyl, p-adelaidian) is less desirable and probably not suitable for use in a wide range of applications.

When there is structural similarity between the compounds of the present invention and comparative examples, the results of the organoleptic properties of the compounds of this invention are unexpected and useful.

Example 16

The yellowness index of the resin is controlled rheology (CR) resin

Controlled rheology (CR) is the process used for the manufacture of polypropylene to reduce the average molecular weight of the polymer. The decrease in molecular weight leads to an increase in the rate of melt flow and a range of benefits in processing, such as rapid processing cycle, better flowing properties and improved form. CR process is usually carried out by introducing peroxides that act as catalysts to degrade the polypropylene under controlled conditions to produce a polymer with a unique and desired distribution of molecular weight. Certain bleaches can interact with peroxides and result in increased undesirable yellowing. Yellowing is undesirable for industrial applications.

Each composition containing compounds sravnitel the different examples 5,6 and comparative example 7, separately mixed with 1000 grams of 11 MFR (the flow rate of the melt or index) polypropylene statistical copolymer resin (RCP, 3% ethylene content) and the standard composition of the additive (i.e. 500 ppm Irganox 1010, 1000 ppm lrgafos 168, and 800 ppm of calcium stearate, CaSt), using a mixer with a ribbon screw blade Gardner, for five minutes at approximately 200-220 rpm meters, and the Mixture was fused to the lens with a diameter of 16 mm, 25:1 L/D twin screw extruder, in which the screws rotate in the same direction. Introduced Lupersol^®101 (2,5-dimethyl-2,5-di-tert-butylperoxide; Atofina Chemicals) in polypropylene melt in the extrusion process. The disks were collected. We measured the rate of melt flow index and yellowness. The yellowness index was measured by Gretag MacBeth Coloreye 6000 according to ASTM E313-73. The data are shown in table 3.

The results clearly show that the compounds of this invention of examples 5 and 6 show excellent color (low yellowness), whereas comparative example 7 (allyl; ethyl) - has a tendency to turn yellow during the CR process. This yellowing is undesirable. When there is structural similarity between the compounds of the present invention (i.e. R₁/R₂- n-propyl for example 5 and R₁/R₂- n-propoxy for example 6 and comparative example (R₁/R₂- ethyl)such appropriate results without yellowing are unexpected and desirable.

Specialists in the art should be onate, that the present description is only a rough description of a variant of implementation, and is not intended to limit the broader aspects of the present invention, where the broader aspects covered in the claims. This invention shown by example in the accompanying claims.

1. The compound corresponding to the structure below:

in which R₁and R₂independently selected from the group consisting of CH₃CH₂CH₂and CH₃CH₂CH₂O-; and
in which R₃independently selected from the group-CH₂CH₂CH₃and CH₂- CH=CH₂.

2. The compound according to claim 1, in which R₃is-CH₂CH₂CH₃.

3. The compound according to claim 1, in which R₃is-CH₂-CH=CH₂.

4. The compound corresponding to the structure below:

5. The compound corresponding to the structure below:

6. The compound corresponding to the structure:

7. The compound corresponding to the structure below:

8. Nuclearia or bleaching composition comprising a compound according to claim 1.

9. Polyolefin composition comprising a compound according to claim 1, in combination with the olefin polymer.

11. Way of clarification olefin polymer by combining the olefin polymer with a compound having the structure

in which R₁and R₂independently selected from the group consisting of CH₃CH₂CH₂and CH₃CH₂CH₂O-; and
in which R₃independently selected from the group-CH₂CH₂CH₃and CH₂-CH=CH₂.