Molecular melt and methods for making and using the molecular melt

background

polyolefins and other polymers are often to improve their rheological modified and other physical properties. Various chemical Means for execution Such modifications have been used.

On A method for modifying polymers, such as polyolefins, provides the use of molecules represent that are capable of providing a nitrene reactive group (s) for insertion into provide H bonds on the polymers. An example of such a Class of chemicals are the sulfonyl azides which in WO 99/10424, which on 04 March published in 1990 was disclosed which to herein by reference its considered teaching for azides is. Upon heating to a suitable reaction temperature to decompose these azides to form nitrene which then into CH bonds on the can insert polymers. These sulfonyl azides are in providing nitrene for the introduction in the CH bonds of polymers based on styrene and Polyolefin effectively.

sulfonyl and other azides can However, sensitive to shock be. Therefore, it may be necessary to desensitize the azides or the azides prior to the reaction during the manufacture and processing of the azide and to protect the shipping and handling of the azide. These Method, the commonly used in order chemicals such as azides, prior to reacting to protect, can be expensive and may be having to be modified polymers incompatible. additionally Polymers often used for packaging of foods. Therefore, it is important that adding a protective agent is not an obstacle that the modified polymer for Applications will be accepted as food packaging.

What required is, is a relatively inexpensive and simple manner to a coupling agent phlagmatizing (Adhesive), which also the coupling means not disturbing influenced or the use of the coupling agent for the preparation of modified polymers limits.

As used herein, the following terms have the following significances: <ul><li>(A) "coupling agent" means a chemical Compound containing at least two reactive groups, the are each capable of a carbene or nitrene group to form, which is capable of in the carbon-hydrogen bonds of both aliphatic and / or aromatic CH-, CH₂- or CH₃Groups of a polymer chain to insert. The reactive groups may together couple or crosslink polymer chains. It may be necessary be, a coupling agent with heat, Sonic energy, radiation or other chemical activating to enable energy to the coupling means for coupling and / or crosslinking of the polymer chains is effective.</li><li>(B) "phlagmatizing" refers to A method for reducing the shock sensitivity of a chemical or of a chemical species, which by mixing or combining the reactive Chemical with an inert or less reactive chemical accomplished is.</li><li>(C) "molecular melt" refers to an at least partially amorphous mixture of a coupling agent (Modifying agent) and an antioxidant, which is optionally also contains other polymer additives, at room temperature. Both the coupling agent (modifying agent) and the antioxidant are at least partially contained in the amorphous phase of the mixture. The Coupling means (modifying agent) and the antioxidant also preferably form a complex, wherein the Raman spectra, the refer to the groups forming the nitrene groups, in Compared to the Raman spectra that reflect the groups forming the nitrene groups of the coupling agent alone, moved are.</li><li>(D) "antioxidant" refers to Types or classes of chemical compounds to minimize the oxidation may be used, during the may occur to the processing of polymers. The term covers chemical derivatives of the antioxidants, including hydrocarbyl groups. The term further includes chemical compounds, such as in described below in the description of the antioxidant, which when properly combined with the coupling agent (modifying agent) to form a complex interact therewith, wherein the complex compared to the coupling agent or the modifying agent alone exhibits a modified Raman spectrum.</li><li>(E) "modifying agent" refers to a chemical compound containing a reactive group, the is capable of forming a carbene or nitrene group a, capable of reacting with a polymer chain.</li><li>(F) "target polymer" refers to a polymer, it being provided that the polymer by Kopp&lt;?page 3?&gt;ment is modified or modifiers. The target polymer can be any polymer which aliphatic or aromatic CH-, CH₂- Or CH₃-Groups a polymer chain. Preferably, the target polymer can be any polyolefin (including polyethylene) or be a polymer based on styrene.</li><li>(G) "DSC" refers to dependence of the context in which it is used on a differential scanning calorimeter or Differential scanning calorimetry analysis. DSC is a method is familiar with which a skilled artisan, the crystallinity of a to determine polymer.</li><li>(H) "nitrene" refers to a compound having a structure RN, where N is nitrogen is, which is able by inserting in both aliphatic and / or aromatic carbon-hydrogen bonds of CH, CH₂- Or CH₃-Groups a polymer chain with a polymer chain to respond. It is believed, that the most preferred for inserting into the carbon hydrogen bonds having at least two nitrogen individual electron pairs. R may represent any atom or atoms that inserting the the nitrogen in the carbon-hydrogen bonds described above not adversely interfere influence.</li><li>(I) "carbene" refers to a compound which 'has a structure RCR, where C is carbon, is able by inserting into carbon-hydrogen bonds of both aliphatic and / or aromatic CH-, CH₂- or CH₃Groups of a polymer chain with a polymer chain to respond. It is believed that the Inserting into the carbon hydrogen bonds most preferred carbon comprises a single pair of electrons. R and R 'are independently any atom or Atoms described inserting of the carbon in the above not adversely interfere with carbon-hydrogen bonds.</li><li>(J) "DPO-BSA" refers to the following compound: 4,4'-OXYDIBENZENESULFONYL AZIDE.</li></ul>

Summary

It is surprisingly been discovered that, an antioxidant and a coupling agent (or Modifiers) are mixed together to form a molecular melt can be, and that the formation of this molecular melt the coupling and / or Modifier can desensitize.

It is a composition of a molecular melt reveals that: (A) an antioxidant; and (b) comprises a coupling agent.

A Composition of a molecular melt, comprising: (a) an antioxidant; and (b) a modifying agent is also described.

On A method for desensitizing a coupling agent, in which a liquid is included, is disclosed, comprising the step of: introducing an antioxidant in the liquid comprises. The coupling agent, which is preferably poly (sulfonyl azide), may in the liquid dissolved his or suspended; and the antioxidant may be before or be introduced after the preparation of the coupling agent.

On A method for desensitizing a modifying agent which in a liquid is included, is disclosed, comprising the step of: introducing an antioxidant in the liquid comprises. The modifier can in the liquid dissolved his or suspended. The antioxidant may be before or after the manufacture of the coupling agent are introduced.

According to a Aspect of the invention is a method for producing a molecular melt provided comprising the steps of: introducing an antioxidant in a liquid, the coupling means having at least two reactive groups contains, which are each capable of forming a carbene or nitrene group to form to desensitize the adhesive; and recovering the molecular melt. When recovering the molecular melt is desired in a dry form, can by precipitation from the liquid are obtained, or the molecular melt may alternatively Co-crystallization of the antioxidant and the coupling agent be won.

According to a further aspect of the invention is a process for preparing a coupling polymer, comprising the steps of: Mixing the molecular melt with a polymer; and reacting the Molecular melt with the polymer. Preferably, the polymer is a Polyolefin, more preferably a polymer based on propylene, and the coupling means is preferably a poly (sulfonyl azide). The reaction is usually place in a polymer extruder, which both the molecular melt and the polymer are mixed and providing energy for triggering the the Reaction between the Molekularschmel&lt;?page 4?&gt;ze and the target polymer required is.

Furthermore is surprisingly been discovered that in the formation of the coupling agent (or modifying agent) in a molecular melt, the efficiency of coupling agent increased modification of the polymer can be. Therefore, the molecular melt may to provide a more efficient way of producing modified polymers and the compositions resulting from such a process, be used. Dependent on on the process used, the modifying agent used, the coupling agent used and the concentrations of the coupling agent and / or modifiers can Polymers rheology-modified, functionalized polymers and / or cross-linked polymers (including, but not limited to Thermosets) is provided.

It it is believed that the molecular melt the preparation of Coupling and modifying agents, the for Polymers are to be used, extraordinarily facilitated. It is also believed that the polymer modification processes, use such molecular melts, the previously described far superior method in terms of efficiency and economy are.

Short description the figures

<figref idrefs="S55">1A</figref> is a representation of the Raman spectra of the DPO-BSA, Irganox 1010, a physical mixture of DPO-BSA and Irganox 1010 and a Molecular melt containing DPO-BSA and Irganox 1010 obtained is.

<figref idrefs="S56">1B</figref> is an illustration of these portions of the Raman spectra for DPO-BSA, the molecular melt, the DPO-BSA and Irganox 1010 contains, and the physical mixture of DPO-BSA and Irganox 1010, which is on Azidstreckung for DPO-BSA refers.

<figref idrefs="S57">2</figref> is a graph showing the peak decomposition energy of DPO-BSA in different samples, which only DPO-BSA, DPO-BSA in a physical Mixture with selected Antioxidants or DPO-BSA in a molecular melt with Irganox 1010 included, illustrates.

<figref idrefs="S58">3</figref> is a graph showing the differential scanning calorimetry analysis the for DPO-BSA was obtained, is illustrated. The DSC shows both the Melting point of the DPO-BSA and the peak decomposition energy for DPO-BSA. The data were obtained using a Thermo Analysis Instruments 2920 modulated differential scanning calorimeter using received 2200 Thermo Analysis Instruments software. Samples were contained in aluminum pans, the kept under a nitrogen atmosphere were. The temperature scan rate was 10 ° / minute.

<figref idrefs="S59">4</figref> is a diagram illustrating the differential scanning calorimetry analysis the for Molecular Melt Sample A was obtained. The data were in two runs obtained, wherein in the first pass, the total crystallinity of the sample is determined and a second run, the peak decomposition energy for the Molecular melt shows. The data were obtained using a with a Thermo Analysis Instruments 2920 modulated differential scanning calorimeter obtained using 2200 Thermo Analysis Instruments software. The samples were contained in aluminum pans that kept under a nitrogen atmosphere were. The temperature scan rate was 10 ° C / minute.

<figref idrefs="S60">5</figref> is a diagram illustrating the differential scanning calorimetry analysis the for Molecular Melt Sample B was obtained. The data were in two runs obtained, wherein in the first pass, the total crystallinity of the sample is determined and a second run, the peak decomposition energy for the Molecular melt shows. The data were obtained using a with a Thermo Analysis Instruments 2920 modulated differential scanning calorimeter obtained using 2200 Thermo Analysis Instruments software. The samples were contained in aluminum pans that kept under a nitrogen atmosphere were. The temperature scan rate was 10 ° C / minute.

<figref idrefs="S61">6</figref> is a diagram illustrating the differential scanning calorimetry analysis the for Molecular Melt Sample C was obtained. The data were in a single pass using a Thermo Analysis Instruments DSC V2.6D dual-cell differential scanning calorimeter receive. The endotherm shown was used to determine the crystallinity, the peak decomposition energy is also shown for the sample. Samples were contained in aluminum pans, the kept under a nitrogen atmosphere were. The temperature scan rate was 10 ° C / minute.

&lt;?page 5?&gt;

<figref idrefs="S62">7</figref> is a diagram illustrating the differential scanning calorimetry analysis the for Molecular Melt Sample D was obtained. The data were in a single pass using a Thermo Analysis Instruments DSC V2.6D dual-cell differential scanning calorimeter receive. The endotherm shown was used to determine the crystallinity, the peak decomposition energy is also shown for the sample. Samples were contained in aluminum pans, the kept under a nitrogen atmosphere were. The temperature scan rate was 10 ° C / minute.

<figref idrefs="S63">8</figref> is a diagram illustrating the differential scanning calorimetry analysis the for Molecular Melt Sample E was obtained. The data were in a single pass using a Thermo Analysis Instruments DSC V2.6D dual-cell differential scanning calorimeter receive. The endotherm shown was used to determine the crystallinity, the peak decomposition energy is also shown for the sample. Samples were contained in aluminum pans, the kept under a nitrogen atmosphere were. The temperature scan rate was 10 ° C / minute.

<figref idrefs="S64">9</figref> is a graph showing the differential scanning calorimetry analysis, the for the Molecular Melt Sample F was obtained shows. The data were in a single pass using a Thermo Analysis Instruments DSC V2.6D dual-cell differential scanning calorimeter receive. From DSC No endotherm was seen and the total crystallinity was therefore determined to be 0%. The peak decomposition energy for the sample shown. The samples were contained in aluminum pans that kept under a nitrogen atmosphere were. The temperature scan rate was 10 ° C / minute.

<figref idrefs="S65">10</figref> is a diagram of the Yoshida Correlation with the experimental value for the Peak decomposition energy, which the molecular melt from the applied sample B was released.

<figref idrefs="S66">11</figref> is a graph showing the differential scanning calorimetry analysis, the for the Molecular Melt Sample G was obtained shows. The data were in a single pass using a Thermo Analysis Instruments DSC V2.6D dual-cell differential scanning calorimeter receive. The endotherm shown was used to determine the crystallinity, the peak decomposition energy is also shown for the sample. Samples were contained in aluminum pans, the kept under a nitrogen atmosphere were. The temperature scan rate was 10 ° C / minute.

<figref idrefs="S67">12</figref> is an illustration of Raman spectra from a molecular melt were obtained, the DPO-BSA and Chimassorb 944 contains.

<figref idrefs="S68">13</figref> is a graph showing the Difterentialrasterkalorimetrie analysis, for the Molecular Melt Sample H was obtained shows. The data were in a single pass using a Thermo Analysis Instruments DSC V2.6D dual-cell differential scanning calorimeter receive. The endotherm shown was used to determine the crystallinity, the peak decomposition energy is also shown for the sample. Samples were contained in aluminum pans that were maintained under a nitrogen atmosphere. The temperature scan rate was 10 ° C / minute.

<figref idrefs="S69">14</figref> is an illustration of Raman spectra from a molecular melt were obtained, the DPO-BSA and Irganox HP 136 contains.

<figref idrefs="S70">15</figref> is a graph showing the differential scanning calorimetry analysis, the for the Molecular Melt Sample I was obtained, showing. The data were in a single pass using a Thermo Analysis Instruments DSC V2.6D dual-cell differential scanning calorimeter receive. The endotherm shown was used to determine the crystallinity, the peak decomposition energy is also shown for the sample. Samples were contained in aluminum pans that were maintained under a nitrogen atmosphere. The temperature scan rate was 10 ° C / minute.

<figref idrefs="S71">16</figref> is an illustration of Raman spectra from a molecular melt were obtained, the DPO-BSA and Irganox I-245 contains.

<figref idrefs="S72">17</figref> is a graph showing the differential scanning calorimetry analysis, the for the Molecular Melt Sample J was obtained shows. The data were in a single pass using a Thermo Analysis Instruments DSC V2.6D- dual cell differential scanning calorimeter receive. The endotherm shown was used to determine the crystallinity, the peak decomposition energy is also shown for the sample. Samples were contained in aluminum pans that were maintained under a nitrogen atmosphere. The temperature scan rate was 10 ° C / minute.

&lt;?page 6?&gt;

<figref idrefs="S73">18</figref> is an illustration of Raman spectra from a molecular melt were obtained, the DPO-BSA and Irganox I-1425 contains.

<figref idrefs="S74">19</figref> is a graph showing the differential scanning calorimetry analysis, the for the Molecular Melt Sample K was obtained shows. The data were in a single pass using a Thermo Analysis Instruments DSC V2.6D dual-cell differential scanning calorimeter receive. The endotherm shown was used to determine the crystallinity, the peak decomposition energy is also shown for the sample. Samples were contained in aluminum pans that were maintained under a nitrogen atmosphere. The temperature scan rate was 10 ° C / minute.

<figref idrefs="S75">20</figref> is a graph showing the differential scanning calorimetry analysis, the for the Molecular Melt Sample L was obtained shows. The data were in a single pass using a Thermo Analysis Instruments DSC V2.6D dual-cell differential scanning calorimeter receive. The endotherm shown was used to determine the crystallinity, the peak decomposition energy is also shown for the sample. Samples were contained in aluminum pans that were maintained under a nitrogen atmosphere. The temperature scan rate was 10 ° C / minute.

Detailed description

While these Invention in many embodiments is applicable, are in the figures, specific embodiments of the invention shown and detail described herein. It is understood, however, that the present Revelation as exemplification of the principles of Invention is to be considered and that it is not intended that the Disclosure limit the invention to specific illustrated embodiments and examples limits.

Of the large part the following discussion refers to a molecular melt, a mixture of a coupling agent and an antioxidant represents. While the molecular melt comprised of a modifying agent and a Antioxidant is, will not be discussed in detail, detects a skilled person, that unless otherwise stated, discussed below Discussions and information for Molecular melt comprised of a coupling agent and an antioxidant composed, for the molecular melt is valid and out of a modifying agent is composed of an anti-oxidant.

molecular melt

The Molecular melt is at least partially amorphous, assuming is that this amorphous nature, the ability of the molecular melt for the desensitization of the coupling agent improves. It will also believed that this amorphous nature, the efficiency of Molecular melt improved to modify a target polymer. In many cases it is preferred that the solubility the molecular melt higher than the solubility in the target polymer the coupling agent in the target polymer.

Prefers forms at least a portion of the present in the molecular melt Coupling agent (modifying agent) and antioxidant a complex comprising the use of the coupling agent for modifying the polymers do not adversely interfere influenced, and the Raman spectra relating to the nitrene forming group (s) (s) reflect, compared to the Raman spectra by the nitrene forming Groups of the coupling agent alone shown, shifted are.

<figref idrefs="S55">1A</figref> shows the Raman spectra for DPO-BSA alone, IRGANOX-1010 alone, DPO-BSA, with IRGANOX-1010 in a physical mixture with a molar ratio of DPO-BSA to IRGANOX-1010 of 1 is combined;: 1 and for a molecular melt from a molar ratio of DPO-BSA to IRGANOX-1010 composed 1: of Figure 1. <figref idrefs="S56">1B</figref> shows the regions of the Raman spectra in more detail (for the DPO-BSA alone, the physical Mixture of DPO-BSA / IRGANOX-1010 molecular melt and the DPO-BSA / IRGANOX-1010) relating to the azide stretch for DPO-BSA relate. As is apparent from the FIG.en, the Raman spectra for the molecular melt, which relate to the azide stretch, compared to the Raman spectra for the DPO-BSA alone and for the physical mixture of DPO-BSA / IRGANOX-1010 and widened shifted. It is also to note that the portion of the Raman spectra near 2700-3200 cm^-1 for the DPO-BSA molecular melt the same in shape and size Section of the Raman spectra for the IRGANOX-1010 similar is.

The molar ratio of coupling agent to antioxidant in the molecular melt is übli&lt;?page 7?&gt;cherweise 1:10 to 10: 1, preferably 1: 2 to 8: 1, more preferably 1: 1 to 4: 1. It has surprisingly been found that the overall crystallinity of the molecular melt typically with the molar ratio of coupling agent to antioxidant is related. In most cases it is preferred that the ratio of coupling agent to antioxidant in the molecular melt is set so that a molecular melt having a total crystallinity weighted average of 99 weight percent or less (as determined by DSC determined and as shown in Example 2 cases), more preferably less than a weighted average of 95 weight percent, furthermore preferably less than a weighted average of 60 weight percent, the strongest preferably provided is less than a weighted average of 40 weight percent is. In some cases, with special consideration the shock sensitivity of the molecular melt, it is also preferable to provide a molecular melt provide that a crystallinity with a weighted average of 20 weight percent or less, more preferably with a weighted Agent of 10 weight percent or less, even more preferably with a weighted average of 5 weight percent or less, most preferably with a weighted average of from 1 percent by weight or less, as determined by DSC, has. For a molecular melt of 4,4'-OXYDIBENZENESULFONYL AZIDE and tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] is, is the molar ratio of coupling agent to antioxidant is preferably between 1: 2 and 4: 1. In some cases can low melting polymer additives, such as polyethylene glycol Contain and / or polypropylene glycol in the molecular melt be. It is believed that these types of connection, the crystallinity of the molecular melt can reduce and / or the shock sensitivity the molecular melt may decrease.

The Molecular melt can be prepared by melt blending the coupling agent and the antioxidant, by Mitausfällen of the coupling agent and of the antioxidant from a common solvent or be formed by another any method an at least partially amorphous molecular melt provides.

Other compounds optionally additionally to the coupling agent and the antioxidant in the molecular melt present. Preferably, the additional compounds put not adversely with either the coupling agent or the antioxidant to and cause no significant increase in crystallinity of the molecular melt. In some cases However, it may be desirable, For example, if the blocking of the molecular melt to be considered is additional add links, which increase the resulting crystallinity of the molecular melt. As discussed above, low melting Materials, such as polyethylene glycol and polypropylene glycol, optionally to reduce shock sensitivity and / or crystallinity of the molecular melt be included in the molecular melt. It is preferred that the molecular melt any compounds based on phosphite (Such as anti-oxidant on the basis of phosphite) contains, since it is believed that these compounds on the basis of Phosphite adversely with the coupling agent in the molecular melt implement. In general, should the additional compounds adds to the molecular melt will be polymer additives that usually during Polymerization process or polymer processing process added will.

Examples the additional Compounds that may be present in the molecular melt include: Internal Lubricants, such as polyethylene glycol (PEG), polypropylene glycol (PPG), calcium stearate, glycerol monostearate (GMS); compatibilizer, such as Titandi (dioctylpyrophosphosat) oxyacetate, di (dioctylpyrophosphosat) ethylene, Isopropyltricumylphenyl, tetra (2,2-diallyloxymethyl) butyl, di (ditridecyl) phosphiozirconat, Glycidoxypropyltrimethoxysilane; Separating Mitel, such as Oleamide, stearamide, zinc stearate, erucamide, aminopropyltrimethoxysilane, bis (glycidoxypropyl) tetramethyldisiloxane, Bis (3-triethoxysilyl) propyl) tetrasulfide, Bis (trimethylsilyl) urea; Plasticizers, for example, triisooctyl trimellitate, epoxidized soybean oil, Di (2-ethylhexyl) adipate, Acetyl, acetyl, Diisocecyladipat, triethylcitrate, polybutene, Oleylpalitamid, N-stearylerucamide, distearyl thiodipropionate; Ultraviolet stabilizers, such as 2-hydroxy-4-n-octoxybenzophenone; 2-hydroxy-4-methoxy-benzophenone; Natriumdicyclohexylsulfosuccinat; Catalyst-neutralizing agent, such as metal stearates (such as calcium stearate), Hydrotalcites, calcium lactate, and metal oxides; and combinations thereof.

compounds contain phosphorus with the oxidation number +3, may in limited quantities that do not adversely with the coupling agent implement or the modifying agent to the molecular melt added will.

&lt;?page 8?&gt;

The Molecular melt can in a convenient form, which are liquid or may be fixed, are formed. The molecular melt is usually formed into particles in a process for modifying the Polymers, such as polyolefins, can be used. It is generally important to ensure that the coupling means in the target polymer prior to or during the reaction can be sufficiently dispersed. Applicants have discovered that to improve the dispersion of the coupling agent in the target polymer, the particle size according to the molar ratio of Coupling agent to antioxidant in the molecular melt can be modified. The optimum particle size depends to be used by the equipment implementing the molecular melt with a target polymer from. To the is example the average diameter of the particles of molecular melt for a Molecular melt of 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) and <u>tetrakis</u>[Methylene (3,5-di-<u>t</u>-butyl-4-hydroxyhydrocinamat)] with a molar ratio of 1: 1, wherein a co-rotating ZSK-40 twin-screw extruder, manufactured by Werner Pfleiderer Corporation was used is preferably 3000 microns or less, more preferably 2000 microns Or less. For ease of processing and handling have the particles preferably have an average diameter of at least 200 micrometers.

The particles from a flowable melt using methods such as rotoforming, are formed, which provides particles of uniform size and shape. alternative can A method such as prilling or spray drying, or any other process, such as grinding, coarse comminution be or tableting used to particles of the desired to generate size. When a highly amorphous molecular melt is desired, the use a method preferred that the resulting crystallinity of the molecular melt minimized. If Block (or agglomeration) of the molecular melt considered is, it is desirable produce a molecular melt having a relatively high crystallinity. This high crystallinity minimizes or prevents the agglomeration of the particles of the molecular melt. An example of a compound that alters the crystallinity of the molecular melt increase can, is Octacecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, a primary sterically hindered phenolic antioxidant, available from Ciba Specialty Chemicals Company under the trade name IRGANOX 1076 (I-1076) is available. I-1076 can be optionally as the second antioxidant with a further, more amorphous antioxidant as the first antioxidant in a molecular melt, as described in Example 14 below used will.

coupling agent and modifiers

As discussed above, are the modifier and coupling means of the invention chemical compounds having at least one reactive group included which is capable of forming a carbene or nitrene group to form. A modifier, such a reactive group on. A coupling agent has two or more such reactive groups on.

Examples of chemical compounds containing at least a reactive group included which is capable of forming carbene groups, include as diazoalkane, germinal-substituted methyl groups, Ketenes and metal carbenes.

Examples of chemical compounds containing at least a reactive group included which is capable of forming a nitrene group, include For example, silyl azides, Phosphazenazide, sulfonyl, Formylazide, Azides, salts of N-Chlorsulfonamiden, NN-Dichlorsulfonamide and 2-trialkyl-1-sulfonyl (internal Salts).

in the Generally, the coupling agents and modifying agents a structure RX_n , wherein each X is independently a reactive Group which is capable of a carbene or nitrene group to form, and wherein R represents a substituted, unsubstituted or inertly substituted hydrocarbyl, hydrocarbyl ether, Hydrocarbylpolyether-, represents sulfur or silicon-containing group. Possibly R has more than one oxygen, sulfur, or silicon in its Main chain. Silicon-containing groups include silanes and Siloxanes, preferably siloxanes. The term substituted inert refers to a substitution with atoms or groups which not desired (n) Reaction (s) or desired undesirably interfere with properties of the resulting modified polymer.

For a modifying agent is n = 1. For a modifying agent, R is preferably a hetero atom, or a -group functionalized. The functional group is selected from Groups that do not undesirably with the reactive implement group is capable of the carbene and / or nitrene to form. In some cases it may be necessary, the functional group with a protecting group to protect, the interactions of the heteroatoms with the reactive group (Or the azide or Car&lt;?page 9?&gt;ben obtained by the reactive group is formed) minimized. This protecting group, by subsequent Reaction be removed. In some embodiments, R is preferably to increase the solubility of the Modifying agent in the target polymer sufficiently large. In these make has R preferably at least 10 total carbon, oxygen, Sulfur and silicon atoms, more preferably at least 20 carbon, oxygen, sulfur, and silicon atoms on. The strongest Preferably, the modifier is a long aliphatic or substituted aliphatic chain of at least 30 atoms, stronger preferably of at least 40 atoms. It is believed that increasing solubility of the modifying agent, the dispersion of the modifying agent increases in the target polymer.

Examples of functional heteroatoms or groups that in one modifier may be contained, include the following, but are not limited to these:

<img img-content="cf" img-format="tif" he="44" wi="95" file="00170001.tif" />

Which respectively an amino, a hydroxy, a carboxylic acid, an ester, an isocyanate, a quaternary Ammonium salt, an acrylate, an amide, an anhydride and an epoxy group represent. Wherein R '' 'any atom, or any represents atomic group inserting a reactive carbon a carbene group (or a reactive nitrogen of a nitrene group) not adversely in the carbon hydrogen bond of a target polymer disturbing affected; represents and N nitrogen, O represents oxygen, H represents hydrogen, represents C is carbon and Y is a counterion group, which after introduction of the group in a modifying agent may be present or not. Imides are another example of a group, which can be incorporated into a modifying agent.

A coupling agent n is greater than One. For a coupling agent, R preferably represents an unsubstituted or inertly substituted hydrocarbyl, hydrocarbyl ether or silicon-containing Group. While it for the length of R is no ultimate limit decreed each R preferably have sufficient carbon, Sulfur, oxygen, or silicon atoms to the reactive groups be separated sufficiently so that a slight reaction between the (n) Target polymer (s) and the sulfonyl is possible, more preferably at least 1, most preferably at least 2, about more preferably at least 3 carbon, oxygen, sulfur, or silicon atoms between the reactive groups. Preferably separate Carbon atoms, the reactive Groups. R preferably has less than 50 carbon, Sulfur, oxygen, or silicon atoms in the main chain, the reactive Groups separated, more preferably less than 20, most preferably less than 15 total carbon, sulfur, oxygen or silicon atoms. In some respects, the use of a Backbone be preferred to the more is and therefore the solubility the coupling agent increases in the target polymer. In this regard, it is preferred that the main chain at least a total of 10 carbon, Sulfur, oxygen, or silicon atoms, more preferably at least a total of 20 carbon, sulfur, oxygen, or silicon atoms, most preferably at least a total of 30 carbon, sulfur, oxygen or Silicon atoms. In some embodiments, it is preferred that R is a long aliphatic side group or substituted aliphatic chain contains. Preferably comprises the chain at least a total of 10 carbon, sulfur, oxygen or Silicon atoms, more preferably at least 20 total carbon, sulfur, oxygen or silicon atoms, most preferably at least 30 total carbon, sulfur, oxygen or S iliciumatome. It is believed that this site group the dispersion of the coupling agent increases in the target polymer.

Around to reduce the cost of manufacturing the coupling agent, may it may be advantageous that the reactive groups (X's) for a given Coupling means are equal. In other situations it may be desirable be that a coupling agent, two or more different types of reactive groups (X's) contains. To the For example it may be desirable be if two target polymers having different melting temperatures are to be coupled, using a coupling agent, the two different reactive includes groups, which are activated at different temperatures. In&lt;?page 10?&gt;one preferred embodiment, the invention is a the target polymer is a polyolefin and the coupling agent Poly (sulfonyl azide). A poly (sulfonyl azide) is any compound having at least two reactive Groups (the sulfonyl azide groups (-SO₂N₃)), Which are reactive with the polyolefin. Preferably the poly (sulfonyl azide) s to a structure XRX wherein each X is SO₂N₃ is and R represents an unsubstituted or inertly substituted hydrocarbyl, Hydrocarbyl ether or silicon-containing represents group, preferably a group having sufficient carbon, Oxygen or silicon, preferably carbon atoms, the sulfonyl azide groups to sufficiently separate so that a slight reaction between the Polyolefin and the sulfonyl azide is made possible. Examples of include atoms or groups that may be inertly substituted into R, Groups, such as fluorine, aliphatic or aromatic ethers, Siloxane as well as sulfonyl azide groups when more than two polyolefin chains to connect are. R is suitably aryl, alkylene, aryl alkaryl, Arylalkylsilan-, Siloxane or heterocyclic groups, and other groups are, which are inert and the sulfonyl azide groups as described, separates. Stronger preferably R includes at least one aryl group between the sulfonyl groups, the strongest preferably at least two aryl groups (such as when R 4,4'-diphenyl ether or 4,4'-biphenyl represents). When R is an aryl group, it is preferred that the group having more than one ring, as in the case of Naphthylenbis (sulfonyl azides). Poly (sulfonyl) azides include such compounds as 1,5-Pentanbis (sulfonyl azide), 1,8-octane bis (sulfonyl azide), 1,10-Decanbis (sulfonyl azide), 1,10-Octadecanbis (sulfonyl azide), 1-octyl-2,4,6-benzoltris (sulfonyl azide), 4,4'-Diphenyletherbis (sulfonyl azide), 1,6-bis (4'-sulfonazidophenyl) hexane, 2,7-naphthalene bis (sulfonyl azide), and mixed sulfonyl azides of chlorinated aliphatic hydrocarbons, average per molecule 1 to the contain eight chlorine atoms and 2 to 5 sulfonyl azide groups, and mixtures from that. Preferred poly (sulfonyl azide) s include oxy-bis (4-sulfonylazidobenzene), 2,7-naphthalene bis (sulfonyl azido), 4,4'-bis (sulfonyl azido) biphenyl, 4,4'-Diphenyletherbis (sulfonyl azide) and bis (4-sulfonyl azidophenyl) methane, and mixtures thereof.

sulfonyl conveniently be the reaction of sodium azide with the corresponding sulfonyl chloride manufactured while Nitrosation and dehydration of sulfonyl hydazines with various reagents (Nitrous acid, Dinitrogen tetroxide, nitrosonium tetrafluoroborate) has been used is.

The following discussion with respect to the mechanism of the coupling reaction presents current theories the inventors prepared, but it is not intended that they the scope of the invention limits.

sulfonyl decompose in several ways, but it takes to carry out the Invention that the reactive species the singlet nitrene is represented by the desired Insertion is detected in C-H bonds. It is reported, that thermal decomposition an intermediate singlet sulfonyl nitrene results, which directly by insertion into carbon-hydrogen bonds reacted. The measures necessary for efficient formation of the sulfonyl nitrene Temperatures are usually more than 150 ° C. US Patent Application No. 09 / 133.576, which filed on August 13, 1998 was, contains additional Teach in view of sulfonyl azides and their use for modifying of polyolefins. US Patent Application 09 / 133.576 which is incorporated herein in its entirety by way of reference.

If the target polymer to be strongly linked, for example, when it desirable is a thermoset or a thermoplastic vulcanate (TPV) to form, it may be preferred to use a coupling agent, containing more than two reactive groups capable of forming nitrene and / or carbene groups are capable of.

Antioxidant:

The Antioxidants of the invention include chemicals that as Antioxidants for Polymers and chemical derivatives of such antioxidants, including hydrocarbyl radicals, are suitable. Preferably, the antioxidant is not a phosphite-containing Compound or no compound which has a phosphorus radical having the +3 Oxidation state includes, since it is assumed from these compounds that they are usual with the Coupling agents used in this invention are extremely reactive. An example of an antioxidant on the basis of phosphite represents tris represents (2,4-di-tert-butylphenyl) phosphite, available from the Ciba Specialty Chemicals Company under the trade name Irgafos 168 is available.

The include antioxidants that can be used in the invention, also chemical compounds which with the coupling agent or Modifying agent form a complex, which use the the coupling or Modifier not adversely modifying polymers disturbing influenced and wherein the Raman spectra relating to the groups refer forming the nitrene group (s) of the complex, as compared to the Raman spectra, which are represented by the groups the nitrene group (s) of the coupling agent or the modifying agent have alone moved &lt;?page 11?&gt;are.

It is preferred, but not necessary, that the chemical compounds the for the antioxidant of the invention may be used in the Are capable of acting as antioxidants when the molecular melt added to the target polymer is.

The Antioxidants are preferably used have the ability to insist in an amorphous state. The antioxidant is preferred among the usual Processing conditions during the modification of the target polymer present, more soluble in the target polymer as the coupling agent. The coupling agent should also chemically and sterically be compatible with the antioxidants, making it a partially amorphous molecular melt forming, wherein the reactive groups the coupling agent is not significantly detrimental to the antioxidant implement.

During the Manufacture of the molecular melt, it is of importance, the probability that dry crystalline coupling agent in purified form present, to minimize, if the coupling means sensitive to shock is.

desensitization can by dilution the coupling agent with non-shock sensitive materials be achieved. Desensitization is achieved when the total energy which is released by the molecular melt (per weight of the Molecular melt) during a DSC is sufficiently low so that the molecular melt is not shock sensitive, as described by Yoshida in Kogyo Kayaku, Vol. 48 (no. 5), 1987, pp 311-316, taught. Preferred sinks during a DSC released total energy below the shock sensitivity line, as shown in the Yoshida Correlation described in which the same reference is shown. <figref idrefs="S65">10</figref> shows a diagram of the Yoshida Correlation with the experimental value for the peak decomposition energy, represented by the molecular melt the applied sample B is released. It is from<figref idrefs="S65">10</figref> appreciated that the plotted data from sample b is well below the shock sensitivity line lie.

The amorphous nature of the molecular melt minimizes and / or prevents the separation of the coupling agent and antioxidant Mitel while of the transport and handling of the molecular melt.

Examples of classes of antioxidants that used in the invention can be, include compounds which as either carbon radical scavengers and / or as an oxygen scavenger can act, such as phenolic compounds and derivatives thereof, sterically hindered amines, Aminhydroxide, thioester compounds and sterically hindered phenol compounds. Additionally, lactones, of which it is believed that they both carbon radical scavengers as also act as oxygen free radical scavengers can, also encompassed by the antioxidants of the invention in which can be used. In some cases it may be preferable that the molecular melt is a mixture of Antioxidants contains. An example of a lactone suitable for use in the invention is appropriate, 5,7-bis (1,1-dimethylethyl) -3-hydroxy-2 (3H) -benzofuranone reaction products with o-xylene (Chemical Abstracts # 181314-48-7) is that of Ciba Specialty Chemicals Company under the trade name IRGANOX HP-136 is sold.

The Antioxidant based on phenol and derivatives thereof and the lactones are preferred. Examples of antioxidants on the basis of phenol and substituted antioxidants on Based on phenol include 2,2'-methylenebis (6- (1-methylcyclohexyl) -p-cresol and 2,6-ditertiary Butyl-4-methylphenol. It is believed that these classes of antioxidants are capable, highly amorphous (less than 10% crystallinity) molecular melts to form and are capable of fusing with a molecular high molar ratio of Coupling agent to antioxidant (greater than 1: 1) to form. to Formation of the molecular melt are more preferably hindered Phenol compounds. An example of a hindered Phenol compound for the use is useful in the invention provides <u>tetrakis</u>[Methylene (3,5-di-<u>t</u>-butyl-4-hydroxyhydrocinnamate)] which from Ciba Specialty Chemical Company under the trade name Irganox 1010 (sometimes referred to as "I-1010" hereinafter) is available.

Azidschutz before reaction:

The Antioxidant in the molecular melt protects at least partly the coupling agent prior to reaction with itself and with other chemical compounds, such as compounds which containing a phosphorous in the +3 oxidation state, which detrimental to the coupling means to&lt;?page 12?&gt;can set. By protecting the Coupling agent increases the antioxidant is the percentage of the coupling agent, the for the response is available to the target polymer. This increases the coupling efficiency the coupling agent (ie, it is less coupling agent by Side reactions consumed).

table 1 provides the decomposition peak energy (in Joules per gram of sample (J / g)), which is released from different samples under Using a modulated using a Thermo Analysis Instruments 2920 Differential scanning calorimeter using 2200 Thermo Analysis Instruments software was obtained. The samples were in aluminum pans that were maintained under a nitrogen atmosphere. The temperature scan rate was 10 ° C / minute.

&lt;?page 13?&gt;

<img img-content="tb" img-format="tif" he="223" wi="160" file="00240001.tif" />

The total samples were of approximately equivalent size and contained either DPO-BSA alone (baseline DSC is set forth in Table 1) or DPO-BSA with an additive. The samples used were all physical mixtures of BSA with said additive, wherein The dry ingredients were mixed together physically. The final Sample set used provided all molecular melts of the DPO-BSA with Irganox 1010. For some of the runs If more than one sample is analyzed, and the obtained from the samples Average value was recorded.

&lt;?page 14?&gt;

table 1 also provides for each sample has a value of peak decomposition energy ready which was released from the sample, wherein the value normalized to Joule was that per gram of DPO-BSA present in the given sample was released. This was calculated by multiplying the energy of Decomposition peak per gram of sample multiplied by 1 / weight of Component of the present in the particular sample DPO-BSA calculated. This represents a value for the peak decomposition energy ready immediately with the energy is the decomposition peak comparable to that released by a sample is, containing 100% DPO-BSA. These normalized values ​​for the liberated energy of decomposition peaks in <figref idrefs="S57">2</figref> applied.

As out <figref idrefs="S57">2</figref> can be seen, the normalized decomposition peak energy, which is released by a sample of molecular melt DPO-BSA and Irganox 1010 receives, higher than the normalized decomposition peak energy, which through a sample is released, which consists of a physical mixture of DPO-BSA and Irganox 1010 is released, the equivalent percentage includes shares of DPO-BSA and Irganox 1010th It is believed that the higher Energies of the decomposition peak for indicate the molecular melt that the molecular melt the self-reaction of the DPO-BSA and / or the reaction between the DPO-BSA and Irganox 1010 as compared to the sample that a physical Mixture of DPO-BSA and Irganox 1010 is minimized. If Molecular Melt used to modify a target polymer will be raised this protective Effect the coupling efficiency of the coupling agent for modifying the target polymer.

In addition, show from the physical admixture of the DPO-BSA and Irgafos 168 obtained data shows that the presence of a compound, containing a phosphorous in the +3 oxidation state, the Peak decomposition energy is reduced, which by the DPO-BSA is released, and therefore, the coupling efficiency of the coupling agent reduced, unless other steps to reduce this effect be made. It is believed that adding a Coupling agent to the target polymer together with an antioxidant at least partially, the coupling agent from reacting with itself protects itself and other chemical compounds, such as compounds, containing a phosphorous in the +3 oxidation state, even when it is not added as a molecular melt.

polymers which have been modified by molecular melt the molecular melt can be used to modify any target polymer. Preferably, the target polymer based polymers of styrene or polyolefin (including Ethylene). In polyolefins by means which are common in the art, educated. The alpha olefin monomers and optionally other additional polymerizable monomers under conditions which are customary in the art, polymerized, for example as described by Galli et al., Angew. Macromol. Chem., Vol. 120, p 73 (1974) or EP More, et al. in Polypropylene Handbook, Hanser Publishers, New York, 1996, especially pages 11-98, discloses.

Examples the preferred target polymers include polymers based on Ethylene, propylene and other olefins, as well as on the basis of Styrene, substituted styrene and / or ethylene-styrene copolymers, as described in US Pat. No. 5,703,178, which issued on 30 December 1997. was disclosed, whose teachings with respect to ethylene-styrene copolymers and methods for making such copolymers herein by reference are involved. The most preferred target polymers are Polymers based on polyolefin, including propylene homopolymer, and statistical and impact copolymers of propylene and polyethylene polymers, such as high density polyethylenes (HDPE), medium Density (MDPE), linear low density polyethylenes (LLDPE) and linear low density polyethylenes (LDPE). Such polymers include terpolymers, tetrapolymers and higher order polymers of propylene, ethylene and other olefins, optionally dienes and / or trienes.

impact-resistant Propylene copolymers are commercially available and within the department well known, for example from EP Moore, Jr in Polypropylene Handbook, Hanser Publishers, 1996, pp 220-221 and US Patent 3,893,989 and 4,113,802 described. The term "impact copolymer" is used herein to Designation of heterophasic propylene copolymers used, where polypropylene is the continuous phase and a elastomeric phase is uniformly dispersed therein. The impact-resistant Copolymers stem more from an in-reactor process as from physical Mix. are usually the impact copolymers in a two- or multi-step process formed, which is optionally a single reactor with at least two process steps that take place therein, or optionally comprises multiple reactors. Advantageously, the impact-resistant Copolymers at least 5 weight percent, preferably at least 10, preferably up to 40, more preferably up to 25 weight percent, and most preferably up to 20 Weight percent of polymer units derived from ethylene. Illustrative impact-resistant copolymer propylene polymers include those by The Dow Che&lt;?page 15?&gt;ical Company under the trade names propylene impact-resistant Copolymers Dow C104-01 PP, Dow C105-02 PP, Dow C107-04 PP, and Dow DC-111 PP Available are each fluidity rates of 1,2,4 and 0.8 g / 10 minutes under a weight of 2.16 kg at a have temperature of 230 °.

The Molecular melt can be used for modification of polymer mixtures including mixtures are used, wherein more than one of the polymers, which in the Mixture is present, is capable of acting as a target polymer. It it is believed that the coupling agent is at least partially a Coupled polymer in a mixture with another polymer of the mixture. Here, a compatibilizer is formed, which the compatibility of the polymers the mixture improves each other.

The the following discussion is specifically concerned with the reaction of the coupling agent with polyolefins, an expert, however, recognize that the teachings herein the reaction of a coupling agent and / or modifier relate with other target polymers of interest.

The reactive Groups of the coupling agent are usually by heat, sonic energy, Radiation or other chemical activating energy to generate activated by nitrene and / or carbene groups, which is able are reacting with the target polymer. When the coupling agent reacted with a polyolefin, at least two separate polyolefin chains advantageously linked and the molecular weight of the polymer chain is increased. In a preferred embodiment, of the invention, wherein the coupling agent is a bis (sulfonyl azide) is, two polyolefin chains are linked advantageously.

The stronger preferred method for activating a coupling agent is heating the coupling agent is to the decomposition of the reactive groups the formation of carbene (s) and / or nitrene (s) cause. Each Coupling agent has a characteristic temperature curve on, under which it decomposes. This temperature profile can are determined by differential scanning calorimetry analysis. Each coupling means has temperatures of decomposition peak or series of peaks in which the decomposition of a particular reactive group correspond. For example, shows the temperature record of Differential scanning calorimeter (DSC) of the bis (sulfonyl azide) diphenyl oxide of a broad exothermic peak that begins at 130 ° C and its peak at 185 ° C comprising (referred to herein as the peak decomposition temperature referred to) and at 200 ° C completely. The total amount of due to decomposition of the sulfonyl azide energy released in DPO-BSA is 1500 Joules / gram.

The However, most coupling agents also decompose at temperatures which is below the peak decomposition temperature. Prefers the target polymers and the molecular melt are well mixed, while the reaction between the coupling agent and the target polymer takes place. In some embodiments, the invention, it is preferred that the mixture of molecular melt and the target polymer as long below the peak decomposition temperature hold until desired is that the coupling reaction takes place.

A any equipment is suitably used for modifying the target polymer. Preferred is an equipment used that sufficient mixing and sufficient temperature control in the same equipment providing, performing However, the invention preferably takes place in such devices, such as an extruder, melt mixer, pump conveyor or other devices instead, or a polymer blend device, such as a Brabender melt mixer. The term extruder includes in its broadest sense, such devices, which extrude articles, including strands or Pellets. allows Preference equipment a sequence of temperatures or zones having different temperatures. The reaction is an extruder particularly suitable, since the embodiment of the invention in a held single vessel can (that is any single piece of equipment, the may contain the polymer). Suitably finds at least one step the method of the invention, while the melt extrusion step takes place when a melt extrusion step between production of the target polymer and its use lies. While It is within the scope of the invention that the reaction in a solvent or takes place in another medium, it is preferred that the reaction in step is present in excess to downstream Steps to remove the solvent or other media to prevent. For this purpose, a polymer above the softening even mixing and for reaching a reaction temperature advantageously (which is far below the Peak decomposition temperature, by the coupling means for may DSC is determined lie).

&lt;?page 16?&gt;

In a preferred embodiment, is the method of the present invention in a single Vessel instead, ie place mixing the molecular melt and the target polymer in the same vessel as the Heat to the decomposition temperature of the coupling agent instead. The vessel is on most preferably a twin-screw extruder, but preferably a single-screw extruder or advantageously a melt mixer, including a batch mixer. The reaction vessel has stronger preferably at least two different temperature ranges over which a reaction mixture is performed, wherein the first region is advantageously a temperature represents, which is sufficiently low to any reaction between the coupling agent and the target polymer should be minimized. preferably embodiment mixed the first region, the molecular melt and the target polymer mechanically, they while are simultaneously transported to a second area. Prefers the target polymer is not substantially reacted in this first section. For propylene polymers the target polymer is not significantly melted in this first section. The second region is preferably arranged so that the molecular melt and the target polymer are mixed quickly, while sufficiently Heat is added, by reacting the coupling agent to cause the target polymer.

Usually is an extruder arranged and is in such a way and As operated such that a temperature profile is produced across the extruder. The term "temperature profile" is used herein, to denote a temperature range, which exposed the polymer is. Each temperature depends Generally, together with a section of the extruder. As discussed above, comprises the temperature range is preferably a first temperature in the range, in which the target polymer and the molecular melt in the extruder enter. In this area, the molecular melt and the Target polymer preferably physically mixed, adding heat and However, temperature is preferably low enough so that no causes reaction between the coupling agent and the target polymer is or that the reaction between the coupling agent and the The objective polymer minimized. For a system as of polypropylene as the target polymer and DPO-BSA Coupling means is, it has been found that this first temperature , More preferably preferably at or below 170 ° C at or below of 140 ° C, the strongest preferably at or below 130 ° C and in some cases or below 120 ° C should be.

Of the Temperature profile also preferably comprises a second temperature, which usually related to the second section of the extruder. For the second area Sufficient heat added, to a more significant reaction between the coupling agent and causing the target polymer. This second area is preferably at a temperature of at least the peak decomposition temperature represents the coupling agent. At the second area close preferably, more preferably four, most preferably at least five additional Areas on, wherein the polymer is mixed and the temperature is controlled. Within the second and subsequent portions there is at least a temperature which is at least 5, most preferably at least 20, even more preferably at least 35 ° C above the peak decomposition temperature of the coupling agent lies. For a system as of polypropylene as the target polymer and DPO-BSA Coupling agent is, flow temperatures of greater than 250 ° C preferred avoided, while unreacted DPO-BSA in the reaction mixture in substantial Degree is present. In the description of the temperature profile of the extruder for the invention the temperatures, unless otherwise specified, the flow temperatures, ie more temperatures within the polymer stream or polymer melt as temperatures of the equipment, which by a specialist due to incomplete heat transfer into the polymer or probably due to induced shear heating of the polymer as lower or higher as the flow temperatures be considered. A skilled artisan can the relationship between the flow temperature and the equipment or the temperature measuring instruments the specific equipment without undue experimentation determine. It is known in the art that the temperature of the Polymer stream advantageously close to the temperature of the machine set located at the entrances of an extruder, the temperature of the However, the polymer stream may in the latter portions of the extruder often greater than Be the temperatures of the machine set as the outlet nozzle of the extruder approach due to the mechanically induced shear stress heating.

Coupling means for modifying rheology

On Skilled artisans will recognize that the reactivity of the coupling agent, the Coupling agent, and the desired or predetermined rheology or amount of chain coupling the amount to put in the coupling agent determined. The determination of these Amount is within the department. In this aspect of the invention the formation of substantially crosslinked networks should prevents , since the resulting material is not treatable; therefore is poly (sulfonyl azide) are preferred to that amount be&lt;?page 17?&gt;borders, which to a polyolefin with linked chain or rheology-modified (But never substantially crosslinked) leads. Some applications tolerate However, a certain degree of Crosslinking (such as foam applications). In general is the amount of azide used preferably less than 1.6 mole coupling agent per mole of target polymer. For Movies is the amount preferably less than 0.5 weight percent, more preferably less than 0.20 weight percent, most preferably less than 0.10 Weight percent of the preferred coupling agent poly (sulfonyl azide) based on the total weight of polyolefin, preferably polypropylene or polypropylene / ethylene copolymer blend.

Networking is evidenced by gel formation, which in the case of polypropylene by measuring the amount of gel in a cast film, either is measured by eye or with a camera.

If Poly (sulfonyl azide) used in the practice of the invention is advantageously at least 0.005 weight percent poly (sulfonyl azide) to achieve measurable results, preferably at least 0.01 Weight percent, more preferably at least 0.02 weight percent is used. In some cases, it is preferred, at least 0.05 weight percent poly (sulfonyl azide) with respect to use on the total weight of polymer (s).

Coupling agent for crosslinking:

As in modifying the rheology detects a skilled person that the Reactivity, the coupling agent used and the desired degree of crosslinking Amount of coupling agent used is determined. However, it is, In contrast to modifiers of rheology for applications of crosslinking required, sufficient to form cross-linked networks Coupling agent directory. This requires a higher Concentration of reactive Groups to form carbene or nitrene capable are, for which each polymer molecule be used. Usually the molar ratio of reactive Groups to target polymers from 0.9 to 6.0, respectively. In some embodiments, it is preferred to use coupling agents that are more than two reactive comprise groups per coupling agent molecule. This reduces the amount to be used of coupling agent. It is usually for applications crosslinking desirable the amount of antioxidant that is added to the target polymer, to minimize. Therefore, it is preferable in these applications that Molecular Melt used a relatively higher molar ratio of Coupling agent to antioxidant than the molecular melt, usually is used for modifying the rheology.

EXAMPLES

Example 1: 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA)

production method

DPO-BSA is in a batchwise process, using a glass lined stirred reactor, which is provided with a housing for cooling / heating, Bottom drain valve, condenser, thermowell and a nitrogen pad is equipped prepared. toluene from the circuit (186.83 g) (which consists of washing the DPO-BSA product crystals is obtained) and obtained from the compounding process, toluene (66.9 g) is charged into the reactor. This is heated to 50 ° C and 96.1 g of 4,4'-Oxydibenzolsulfonylchlorid (DPO-BSC) is added with stirring added. To the reactor is then 87.78 g circulation water from the wash step of the preceding added reaction and the stirrer is set to 150 rpm. 0.24 g NaHCO₃ becomes subsequently added to neutralize any acid in the solution. If a pH paper confirms that the water phase is neutral, followed by 0.24 g of tetra-n-butyl-ammonium chloride (PTC) added. To this mixture is added over fifteen minutes 35 g of sodium azide. The Rpm of the stirrer can be increased to 300 be to ensure sufficient mixing of the phases. The reactor temperature is about 30 minutes from 50 ° C to 65 ° C elevated. The reaction is converted in 75 minutes 100% as measured by flüssigkeitschromatografische Analysis determined. The stirrer is turned off and the phases for 10 minutes to separate ditched. The lower aqueous / salt phase is removed using the bottom drain valve and to the local Incinerator ships. In addition, 29.33 g water of 55 ° C added and the stirrer, the for 5 minutes is set at 250 rpm, is subsequently shut off and the layers to separate left (10 minutes). The bottom phase is again removed and the water extraction step is repeated two more times (2 x 29.33 g of water at 55 ° C). The rpm the stirrer is for subsequent extractions is reduced to 200 to ensure that no lasting emulsion. All three washes are combined and for the next Charge Retired in circulation&lt;?page 18?&gt;leads. If the water phases have been removed, the temperature is cooled to 10 ° C and there for held for 60 minutes before the bottom valve is opened and the precipitated DPO-BSA slurry to transmitted a filter is where they gathered and under nitrogen to a cake a moisture is dried from 40% toluene. Approximately 101.4 g DPO-BSA is with the other 5.60 g, which remain in the toluene filtrate obtained. This toluene filtrate is in the next Reaction in the circulation returned. Of the Cake with a moisture content of 40% toluene is directly in the compounding process used. <figref idrefs="S58">3</figref> represents a DSC of DPO-BSA represent.

Example 2: 4,4-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) Melt Blend Compounding Process to manufacture DPO-BSA: I-1010 in a weight ratio of 1: 3.3 (molar ratio of 1.0: 1.066) molecular melt (Molecular Melt Sample A).

DPO-BSA, which was obtained from Example 1, is in a batchwise Process using a glass lined stirred reactor, which is provided with a housing for cooling / heating, Bottom drain valve, condenser, thermowell and a nitrogen sparger is equipped compounded. 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) (101.4 g) as a wet cake (the total weight is the wet cake 168.2 g, the wet cake contains 40% toluene) is charged into the reactor, stirring commenced and the Temperature is maintained at 88 ° C elevated, resulting in a clear solution leads. IRGANOX^® 1010 (I-1010) (334.6 g) is added into the mixture and stirred until at 94 ° C a clear solution results. The reactor is sealed and on increasing the Temperature to 97 ° C evacuated while Toluene (66.7 g) from the overhead (2 hours) is collected and for returning to the DPO-BSA manufacturing process is won. A is exploiting founding subsurface nitrogen sparge while the final hour to aid the removal of the toluene used. When the batch is dry, is the formulation of the compounded polymer additive in 97 ° C and kept dropwise dropped into 3000 g rapidly converted agitated water on and cooled to -25 ° C and a Coarse frit filtered. The product is then using 500 washed ml of water and in a tumble dryer at 40 ° C / 10 mm Hg dried. The product is a free-flowing powder which does not sensitive to shock is and can be handled without special precautions. Analysis by high pressure liquid (HPLC) shows that the composition of this molecular melt 23.7 wt .-% DPO-BSA and 76.3 wt .-% IRGANOX^® I-1010 is. Differential scanning calorimetry analysis showed that by this A method formed DPO-BSA: Irganox-1010 molecular melt, a total crystallinity having a weighted average of 0.42 percent by weight. The weighted average of the percentage weight is calculated by dividing the integrated melt endotherm (in J / g) by the sum of the products of Melting endotherms of the pure components multiplied by their individual percentages by weight of the total molecular melt calculated. <figref idrefs="S59">4</figref> shows the results of differential scanning calorimetry for the Molecular Melt Sample A.

Example 3: DPO-BSA with coprecipitation Process to manufacture DPO-BSA: I-1010 in a weight ratio of 1: 3.3 (molar ratio of 1.0: 1.066) molecular melt (Molecular Melt Sample B)

DPO-BSA, which was obtained as in Example 1, is in a batchwise Process using a glass lined stirred reactor, which is provided with a housing for cooling / heating, Bottom drain valve, condenser, thermowell and a nitrogen sparger is equipped compounded. 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) (25.6 g) and subsequently 100 g acetonitrile is charged to the reactor, stirring commenced and the Temperature is maintained at 60 ° C elevated, resulting in a clear solution leads. IRGANOX^® 1010 (84.37 g) is added into the mixture and stirred until a clear solution at 60 ° C results. The reactor is sealed and at maintaining the temperature at 67 ° C evacuated while Acetonitrile (90 g) from the overhead (2 hours) is collected and recovered for recycle is. A below the surface nitrogen sparge is during the last hour for promotion the removal of the acetonitrile used. At this time, the melted formulation of compounded polymer additive dropwise dropped into 3000 g rapidly converted agitated water on and cooled to -25 ° C and over a coarse frit filtered. The product is then using 500 washed ml of water and in a tumble dryer at 40 ° C / 10 mm Hg dried. The product is a free-flowing powder which does not sensitive to shock is and can be handled without special precautions. Analysis by HPLC shows that the composition of this molecular melt 23.7 wt .-% DPO-BSA and 76.3 wt .-% IRGANOX^® I-1010 is. Differential scanning calorimetry analysis showed that by this A method formed DPO-BSA: Irganox-1010 molecular melt a total crystallinity weighted average of 43.7 weight percent was obtained. <figref idrefs="S60">5</figref> shows the results of differential scanning calorimetry results for Molecular Melt Sample B.

&lt;?page 19?&gt;

Example 4: 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) Melt Blend Compounding Process to manufacture DPO-BSA: I-1010 in a weight ratio of 1: 1.7 (molar ratio of 1.82: 1) molecular melt (Molecular Melt Sample C)

DPO-BSA, which was obtained as in Example 1, is in a batchwise Process using a glass lined stirred reactor, which is provided with a housing for cooling / heating, Bottom drain valve, condenser, thermowell and a nitrogen sparger is equipped compounded. Methylene chloride (3664 g) and then 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) (567.84 g) and IRGANOX^® 1010 (965.32 g) is loaded into the reactor, stirring commenced and the Temperature is maintained at 88 ° C elevated, to give a clear solution results. Methylene chloride is from the top product of the mixture removed until a clear melt results at 94 ° C. The reactor is sealed and increase the temperature to 97 ° C evacuated while Methylene chloride (3600 g) is collected from the overhead (1.5 Hours) and for returning to obtained the DPO-BSA compounding. A under the surface nitrogen sparge is during the last hour for promotion the removal of the methylene chloride used. When the batch dried is the formulation of the compounded polymer additive is at 97 ° C and kept in a boiler poured (32 × 18 × 4 inches), cooled to 25 ° C and ground in a Franklin Miller grinder to particles in the to obtain the range of 200 to 2000 microns. The product was subsequently in a tumble dryer at 40 ° C / 10 mm Hg dried. The product is a free-flowing powder which does not sensitive to shock is and can be handled without special precautions. Analysis by HPLC shows that the composition of this molecular melt 37.04 wt .-% DPO-BSA and 62.69 wt .-% IRGANOX^® I-1010 is. Differential scanning calorimetry analysis revealed that the formed by this method DPO-BSA: Irganox-1010 molecular melt a total crystallinity having a weighted average of 48.15 percent by weight. <figref idrefs="S61">6</figref> shows the results of differential scanning calorimetry results for Molecular Melt the sample C.

Example 5: 4,4-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) Melt Blend Compounding Process to manufacture DPO-BSA: I-1010 in a weight ratio of 1: 0.825 (molar ratio of 3.75: 1) molecular melt (Molecular Melt Sample D)

DPO-BSA, which was obtained as in Example 1, is in a batchwise Process using a glass lined stirred reactor, which is provided with a housing for cooling / heating, Bottom drain valve, condenser, thermowell and a nitrogen sparger is equipped compounded. Methylene chloride (4130 g) and then 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) (640.14 g) and IRGANOX^® I-1010 (528.10 g) is loaded into the reactor, stirring commenced and the Temperature is maintained at 88 ° C elevated, to give a clear solution results. Methylene chloride is from the top product of the mixture removed until a clear melt results at 94 ° C. The reactor is sealed and increase the temperature to 97 ° C evacuated while Methylene chloride (4022 g) from the overhead (1.5 hours) collected is and returning to the DPO-BSA compounding obtained. A is exploiting founding subsurface Nitrogen sparge, during the final hour to aid the removal of the methylene chloride used. When the batch is dry, is the formulation of the compounded polymer additive in kept 97 ° C and in a boiler poured (32 × 18 × 4 inches), cooled to 25 ° C and ground in a Franklin Miller grinder to particles in the to obtain the range of 200 to 2000 microns. The product was subsequently in a tumble dryer at 40 ° C / 10 mm Hg dried. The product is a free-flowing powder which does not sensitive to shock is and can be handled without special precautions. Analysis by HPLC shows that the composition of this molecular melt 54.79 wt .-% DPO-BSA and 45.21 wt .-% IRGANOX^® I-1010 is. Differential scanning calorimetry analysis revealed that the formed by this method DPO-BSA: Irganox-1010 molecular melt a total crystallinity having a weighted average of 51.09 percent by weight. <figref idrefs="S62">7</figref> shows the results of differential scanning calorimetry results for Molecular Melt the sample D.

Example 6: 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) Melt Blend Compounding Process to manufacture DPO-BSA: I-1010 in a weight ratio of 1: 6.6 (molar ratio 1: 2.13) molecular melt (Molecular Melt Sample E)

DPO-BSA, which was obtained as in Example 1, is in a batchwise Process using a glass lined stirred reactor, which is provided with a housing for cooling / heating, Bottom drain valve, condenser, thermowell and a nitrogen sparger is equipped compounded. Methylene chloride (2580 g) and then 4,4'-Oxydibenzolsulfonyl&lt;?page 20?&gt;azide (DPO-BSA) (400.00 g) and IRGANOX^® I-1010 (2640.00 g) is loaded into the reactor, stirring commenced and the Temperature is maintained at 88 ° C elevated, to give a clear solution results. Methylene chloride is from the top product of the mixture removed until a clear melt results at 94 ° C. The reactor is sealed and increase the temperature to 97 ° C evacuated while Methylene chloride (2376 g) from the overhead (1.5 hours) collected and returning to obtained the DPO-BSA compounding. A under the surface nitrogen sparge is during the last hour for promotion the removal of the methylene chloride used. When the batch is dry, is the formulation of the compounded polymer additive in kept 97 ° C and in a boiler poured (32 × 18 × 4 inches), cooled to 25 ° C and ground in a Franklin Miller grinder to particles in the to obtain the range of 200 to 2000 microns. The product was subsequently in a tumble dryer at 40 ° C / 10 mm Hg dried. The product is a free-flowing powder which does not sensitive to shock is and can be handled without special precautions. Analysis by HPLC shows that the composition of this molecular melt 13.16 wt .-% DPO-BSA and 86.84 wt .-% IRGANOX^® I-1010 is. Differential scanning calorimetry analysis revealed that the formed by this method DPO-BSA: Irganox-1010 molecular melt a total crystallinity having a weighted average of 0.82 percent by weight. <figref idrefs="S63">8</figref> shows the results of differential scanning calorimetry results for Molecular Melt the sample E.

Example 7: 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) Melt Blend Compounding Process to manufacture DPO-BSA: I-1010 in a weight ratio of 1: 3.3 (molar ratio of 1: 1.066) the molecular melt sample in a commercial scale (Molecular Melt Sample F)

DPO-BSA, which was obtained as in Example 1, is in a batchwise Process using a glass lined stirred reactor, which is provided with a housing for cooling / heating, Bottom drain valve, condenser, thermowell and a nitrogen sparger is equipped compounded. Methylene chloride (129.42 kg) and then 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) (20.06 kg) and IRGANOX^® I-1010 (66.20 kg) is loaded into the reactor, stirring commenced and the Temperature is at 38 ° C elevated, to give a clear solution results. Methylene chloride is from the top product of the mixture removed until a clear melt results at 94 ° C. The reactor is sealed and increase the temperature to 97 ° C evacuated while collected methylene chloride (128.2 kg) from the overhead (1.5 hours) is and returning to the DPO-BSA compounding obtained. A is exploiting founding subsurface Nitrogen sparge, during the final hour to aid the removal of the methylene chloride used. When the batch is dry, is the formulation of the compounded polymer additive in kept 97 ° C and in ten poured boiler (32 × 18 × 4 inches), cooled to 25 ° C and ground in a Franklin Miller grinder to particles in the to obtain the range of 200 to 2000 microns. The product was subsequently in a tumble dryer at 40 ° C / 10 mm Hg dried. The product is a free-flowing powder which does not sensitive to shock is and can be handled without special precautions. Analysis by HPLC shows that the composition of this molecular melt 23.26 wt .-% DPO-BSA and 76.74 wt .-% IRGANOX^® I-1010 is. Differential scanning calorimetry analysis particular that formed by this method DPO-BSA: Irganox-1010 molecular melt a total crystallinity having a weighted average of 0.00 percent by weight. <figref idrefs="S64">9</figref> shows the results of differential scanning calorimetry results for Molecular Melt the sample F.

The following examples describe additional compounds which act as antioxidant of the compositions of the molecular melt can act.

Example 8: 4,4'-OXYDIBENEZENESULFONYL AZIDE (DPO-BSA) Melt Blend Compounding Process to manufacture DPO-BSA: Chimassorb 944 in a weight ratio of 1: 6.575 (molar ratio of 1: 1) molecular melt (Molecular Melt Sample G)

The The following example demonstrates that chemical compounds that usually not be referred to as antioxidants, but as an antioxidant be considered for use in the molecular melt.

DPO-BSA, which was obtained as in Example 1, is in a batchwise Process using a glass lined stirred reactor, which is provided with a housing for cooling / heating, Bottom drain valve, condenser, thermowell and a nitrogen sparger is equipped compounded. Toluene (20.00 g) followed by 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) (2.00 g) and (poly - [(6- (1,1,3,3-tetramethylbutyl) amino] -s-triazine-2,4-diyl] [2,2,6,6-tetramethyl-4 -pi&lt;?page 21?&gt;peridyl) imino]) (13.15 g) (a hindered amine light stabilizers, which from Ciba Specialty Chemicals Company under the trade name Chimassorb^® 944 available is) is loaded into the reactor, stirring commenced and the Temperature is maintained at 80 ° C elevated, to give a clear solution results. Toluene is from the overhead under vacuum of taken mixture till a clear melt results at 85 ° C. When the batch is dry, the formulation of the compounded is Polymer additive at 85 ° C held and cast on a watch glass and cooled to 25 ° C. The Product was then in a vacuum oven at 40 ° C / 1.0 mm Hg dried. The product is a free flowing powder which is not shock sensitive is and can be handled without special precautions. Analysis by HPLC shows that the composition of this molecular melt 13.16 wt .-% DPO-BSA and 86.84 wt .-% Chimassorb^® 944 is. Differential scanning calorimetry analysis showed that by this Process formed DPO-BSA: Chimassorb^® 944 molecular melt a total crystallinity amounted to a weighted average of 13.3 percent by weight. <figref idrefs="S66">11</figref> shows the results of differential scanning calorimetry results for Molecular Melt the sample G.

As from the Raman spectra of <figref idrefs="S67">12</figref> apparent is, the composition of the molecular melt sample G. at approximately 2100 a doublet on. The left peak of the doublet due to the DPO-BSA, the right peak of the doublet is due to the interaction of the DPO-BSA with Chimassorb^® 944 due.

Example 9: 4,4'-OXYDIBENEZENESULFONYL AZIDE (DPO-BSA) Melt Blend Compounding Process to manufacture DPO-BSA: Lactone (HP 136) in a weight ratio of 1: 0.925 (molar ratio of 1: 1) molecular melt (Molecular Melt Sample H)

DPO-BSA, which was obtained as in Example 1, is in a batchwise Process using a glass lined stirred reactor, which is provided with a housing for cooling / heating, Bottom drain valve, condenser, thermowell and a nitrogen sparger is equipped compounded. Toluene (20.00 g) followed by 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) (2.00 g) and reaction products of (5,7-bis- (1,1-dimethylethyl) -3-hydroxy-2 (3H) -benzofuranone with o-xylene) (1.85 g) (an antioxidant based on a Lactone, available from the Ciba Specialty Chemicals Company under the Trade name IRGANOX HP 136^® Available is), is in the reactor Loading, stirring is started and the temperature is raised to 80 ° C, resulting in a clear solution. Toluene is from the top product of the mixture under vacuum removed until a clear melt results at 85 ° C. When the batch dry is the formulation of the compounded polymer additive is at 85 ° C kept and poured into a 100 ml bottle and cooled to 25 ° C. The Product was then in a vacuum oven at 40 ° C / 1.0 mm Hg dried. The product is a free-flowing powder which does not sensitive to shock is and can be handled without special precautions. Analysis by HPLC shows that the composition of this molecular melt 52.0 wt .-% DPO-BSA and 48.0 wt .-% HP 136^® is. Differential scanning calorimetry analysis revealed that the formed by this method DPO-BSA: HP 136^®-Molekularschmelze a total crystallinity amounted to a weighted average of 0.0 percent by weight. <figref idrefs="S68">13</figref> shows the results of differential scanning calorimetry for the Molecular Melt Sample H.

As from the Raman spectra of <figref idrefs="S69">14</figref> apparent is, the composition of the molecular melt sample of H a doublet at approximately 2100 cm^-1 on. The left peak of the doublet is due to the DPO-BSA, the right peak of the doublet is due to the interaction of the DPO-BSA with the HP 136th

Example 10: 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) Melt Blend Compounding Process to manufacture DPO-BSA: I-245 in a weight ratio of 1: 1.543 (molar ratio of 1: 1) molecular melt (Molecular Melt Sample I)

DPO-BSA, which was obtained as in Example 1, is in a batchwise Process using a glass lined stirred reactor, which is provided with a housing for cooling / heating, Bottom drain valve, condenser, thermowell and a nitrogen sparger is equipped compounded. Toluene (20.00 g) followed by 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) (3.00 g) and ethylenebis (oxyethylene) bis (3 (5-tert-butyl-4-hydroxy-m-tolyl) propionate)) (1.85 g) (an antioxidant available from the Ciba Specialty Chemicals Company under the trade name IRGANOX^® I-245 available is), is loaded into the reactor, stirring commenced and the Temperature is raised to 80 ° C, wherein a clear solution results. Toluene is from the overhead under vacuum of taken mixture till a clear melt results at 85 ° C. When the batch is dry, the For will&lt;?page 22?&gt;formulation of the compounded Polymer additive at 85 ° C kept and poured into a 100 ml bottle and cooled to 25 ° C. The Product was then in a vacuum oven at 40 ° C / 1.0 mm Hg dried. The product is a free flowing powder, which does not is shock sensitive and without special precautions can be handled. Analysis by HPLC shows that the composition this molecular melt 39.3 wt .-% DPO-BSA and 60.6 wt .-% IRGANOX^® I-245 is. Differential scanning calorimetry analysis showed that by this Process formed DPO-BSA: I-245 molecular melt a total crystallinity weighted average of 0.0 percent by weight, respectively. <figref idrefs="S70">15</figref> shows the results of differential scanning calorimetry results for Molecular Melt the sample I.

As from the Raman spectra of <figref idrefs="S71">16</figref> apparent is, the composition of the molecular melt sample of I a doublet at approximately 2100 cm^-1 on. The left peak of the doublet is due to the DPO-BSA, while the right peak of the doublet due to the interaction of the DPO-BSA with Irganox I-245.

Example 11: 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) Melt Blend Compounding Process to manufacture DPO-BSA: I-1425 in a weight ratio of 1: 0.55 (molar ratio of 1: 1) molecular melt (Molecular Melt Sample J)

DPO-BSA, which was obtained as in Example 1, is in a batchwise Process using a glass lined stirred reactor, which is provided with a housing for cooling / heating, Bottom drain valve, condenser, thermowell and a nitrogen sparger is equipped compounded. Toluene (20.00 g) followed by 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) (3.00 g) and (Calciumdiethylbis (((3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl) phosphonate) (5.48 g) (an antioxidant available from the Ciba Specialty Chemicals Company under the trade name IRGANOX^® I-1425 available is), is loaded into the reactor, stirring commenced and the Temperature is maintained at 80 ° C elevated, to give a clear solution results. Toluene is from the overhead under vacuum of taken mixture till a clear melt results at 85 ° C. When the batch is dry, the formulation of the compounded is Polymer additive at 85 ° C kept and poured into a 100 ml bottle and cooled to 25 ° C. The Product was then in a vacuum oven at 40 ° C / 1.0 mm Hg dried. The product is a free-flowing powder which does not sensitive to shock is and can be handled without special precautions. Analysis by HPLC shows that the composition of this molecular melt 35.37 wt .-% DPO-BSA and 64.63 wt .-% IRGANOX^® I-1425 is. Differential scanning calorimetry analysis showed that by this Process formed DPO-BSA: I-1425 molecular melt a total crystallinity weighted average of 68.76 percent by weight, respectively. <figref idrefs="S72">17</figref> shows the results of differential scanning calorimetry results for Molecular Melt the sample J.

As from the Raman spectra of <figref idrefs="S73">18</figref> apparent is, the composition of the molecular melt sample J a doublet at approximately 2100 cm^-1 on. The left peak of the doublet is due to the DPO-BSA, while the right peak of the doublet on the interaction of the DPO-BSA with IRGANOX^® I-1425 is due.

Example 12: 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) Melt Blend Compounding Process to manufacture DPO-BSA: I-1010 in a weight ratio of 1: 3.3 (molar ratio of 1: 1,066) molecular melt (Molecular Melt Sample K)

in the Below is presented a method for the preparation of a Molecular melt with a higher percentage of crystallinity than that in the previous Examples obtained molecular melt can be used. The Example also demonstrates that the DPO-BSA never isolated in purified form is, I-1010 is added to the DPO-BSA, while suspended in the toluene is to desensitize DPO-BSA, making it easy and safe can be recovered from the toluene.

DPO-BSA is in a batchwise process, using a glass lined stirred reactor, which is provided with a housing for cooling / Heat, a bottom drain valve, condenser, thermowell and a nitrogen pad is equipped prepared. toluene from the circuit (186.83 kg) and fresh toluene (66.9 kg) is in the reactor loaded. This mixture is heated to 95 ° C and 96.1 kg of 4,4'-Oxydibenzolsulfonylchlorid (DPO-BSC) we stirring added. To the reactor is then 87.78 kg circulation water from the washing step of the previous reaction added and the stirrer is set to 150 rpm. 0.24 kg of NaHCO₃ becomes subsequently added to neutralize any acid in the solution. As soon as a pH paper confirms that the water phase is neutral, followed by 0.24 kg of tetra-n-butyl-ammonium chloride (PCT) added. to this &lt;?page 23?&gt;Mixture is added sodium azide over 15 minutes 35 kg. The Rpm of the stirrer is increased to 300, a sufficient mixing of the phases to ensure. The reactor temperature is over 30 minutes from 50 ° C to 65 ° C elevated. The reaction is accomplished within 75 minutes to 100%, such as by flüssigkeitschromatografische Analysis is determined. The stirrer is switched off and the phases are available for 10 minutes for separation calmly. The bottom water / salt phase is determined using the Bottom drain valve is removed and the local incinerator shipped. additionally is 29.33 kg of water added by 55 ° C and the stirrer is at 250 rpm for is 5 minutes, then off and the phases allowed to separate (10 mins). The bottom phase is again removed and the water extraction step is repeated two more times (2 x 29.33 kg of 55 ° C water). The stirrer rpm is for the subsequent Extractions reduced to 200 to ensure that no permanent emulsion. All three washes are combined and returning to Upcoming Charge collected.

IRGANOX^® I-1010 (334.6 kg) is added to the mixture and stirred until a clear solution at 94 ° C results. The reactor temperature is raised to 97 ° C while toluene (186.83 kg) of the overhead (2 hours) and is collected for return to obtained the DPO-BSA manufacturing process. Methanol (600 kg) will be added and the remaining toluene over azeotropic distillation away with the methanol. When the batch is free of toluene, the formulation is cooled to 5 ° C and the crystals are allowed to stand to form, which subsequently Centrifugation is collected. The product is then in a drum dryer at 40 ° C / 10 mm Hg dried. The product is a free-flowing powder which does not sensitive to shock is and can be handled without special precautions. Analysis by HPLC shows that the composition of this molecular melt 23.26 wt .-% DPO-BSA and 76.74 wt .-% IRGANOX^® I-1010 is. Differential scanning calorimetry analysis showed that by this Process formed DPO-BSA: Irganox^® I-1010 molecular melt a total crystallinity amounted to a weighted average of 76.87 percent by weight. <figref idrefs="S74">19</figref> shows the results of differential scanning calorimetry results for this Molecular Melt.

example 13: Preparation of polymer rheology-modified under Use of DPO-BSA: I-1010 in a Gewichtsverhältni s of 1: 3.3 (molar ratio of 1: 1,066) molecular melt

Base polypropylene resin

The Base polypropylene which to prepare the samples in all was used following examples, used is isotactic Polypropylene pellets is, among which from The Dow Chemical Company the name Dow H700-12PP and Dow C105-02PP are available. Dow H700-12PP is a homopolymer of propylene having a melt flow rate (MFR) = 12 dg / min at 230 ° C / 2.16 kg. Dow C105-02PP is an impact copolymer of propylene with 16-22 Weight percent ethylene and a melt flow rate (MFR) = 1.7 dg / min at 230 ° C / 2.16 kg.

manufacturing modified polypropylenes

polymer samples A1, B1, and CA are produced as follows. 1500 grams of polymer were in a container weighed. 1.5 grams of oil was added and the container was then for 30 tumbled minutes. At this time, the desired Amounts of molecular melt (weight ratio of DPO-BSA: Irganox 1010 from 1: 3.3) and additives (see Table 2) was added and the container was for additional tumbled for 30 minutes. The mixture was tumbled directly into a 20 mm extruder using a single vibratory feeder supplied. The rate of feeding was adjusted so that a Torque was achieved of 80%.

polymer samples A2, B2 and CB were measured using a powder-Vormischungsverfahrens prepared as follows. Two feeders were used, one for feeding a powder premix for feeding the additives to the extruder and the second for feeding the Base polymer. The feeders were adjusted so that in a weight ratio of base polymer to Pulvervormischung of 95: 5 feed. The base polymer was positioned in a vibratory feeder and directly in the Extruder fed. The powder premix was by weighing 100 g of an isotactic homopolymer polypropylene powder (®Profax 6301 for Example A2 and ®Profax 6501 for Example B2 and CB available from Bassel) in a container produced. The desired Amounts of the molecular melt (weight ratio of DPO-BSA: Irganox 1010 from 1: 3.3) and the additive (see Table 2) were added so that the final concentration was reached in the product and the container was for 30 tumbled minutes. The base polymer and the Speisevorichtung to Premixing of the powder were adjusted so that &lt;?page 24?&gt;they in a weight ratio of base polymer to powder premix of 95: 5 and a feed reach torque of 80%.

The in all cases Extruder used represented a 20 mm Welding Engineers twin screw extruder . The extruder was operated at 200 rpm is. The temperature variation over the was twin-screw extruder from the inlet opening to the outlet opening 170, 180, 190, 200, 210, 220 and 230. The temperatures listed put the barrel temperatures are in the extruder. One of the outlet opening the last region positioned die had a temperature of 240 ° C on, to the full Reaction of the BSA and ensure the propylene polymer. That I resulting melt-extruded polymer entered through the nozzle and subsequently pelleted.

Among Referring to Table 2, the fluidity rate (MFR) which resulting modified polymers (Polymer Samples A1, A2, B1, and B2), which according to ASTM method D 1238 at 230 ° C were measured using a weight of 2.16 kg, in comparison to the unmodified polymer samples decreased. This suggests out that the polymer samples by the reaction of DPO-BSA with Base polypropylene polymer in terms of its rheology successfully have been modified. It is believed that the molecular melt efficiently to the base polymer coupled as an equivalent amount BSA alone.

&lt;?page 25?&gt;

<img img-content="tb" img-format="tif" he="250" wi="129" file="00480001.tif" />

&lt;?page 26?&gt;

Example 14: 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) Melt Blend Compounding Process to manufacture DPO-BSA: I-1010: I-1076 in a weight ratio of 1: 1.4 (molar ratio: 3.3 1: 1: 1) molecular melt (Molecular Melt Sample L)

DPO-BSA, which was obtained as in Example 1, is in a batchwise Process using a glass lined stirred reactor, which is provided with a housing for cooling / heating, Bottom drain valve, condenser, thermowell and a nitrogen sparger is equipped compounded. Methylene chloride (2500 g) and then 4,4'-OXYDIBENZENESULFONYL AZIDE (DPO-BSA) (250.00 g) IRGANOX^® I-1010 (<u>tetrakis</u>- (Methylene (3,5-di-<u>t</u>-butyl-4-hydroxyhydrocinnamate))) (852.0 g) and IRGANOX^® I-1076 (Octacecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (349.02 g) was charged to the reactor, stirring was started and the Temperature was raised to 81 ° C elevated, to give a clear solution revealed. Methylene chloride was continued under vacuum the top product removed the mixture till a clear melt yielded at 93 ° C. When the batch is dry, the formulation of the compounded is Polymer additive at 96 ° C maintained and in a stainless steel vessel (32 × 18 × 4 inch) cast and cooling down to 25 ° C. allowed to stand and then ground in a Franklin Miller grinder to particles in the to obtain the range of 200 to 2000 microns. The product was then in a vacuum oven at 40 ° C / 1.0 mm Hg dried. The product is a free flowing powder which is not shock sensitive is and can be handled without special precautions. Analysis by HPLC shows that the composition of this molecular melt 17.56 wt .-% DPO-BSA, 57.93 wt% IRGANOX® I-1010 and 24.51 wt .-% IRGANOX^® I-1076 is. Differential scanning calorimetry analysis showed that by this Process formed DPO-BSA: I-1010: I-1076 molecular melt a total crystallinity amounted to a weighted average of 24.7 percent by weight. <figref idrefs="S75">20</figref> shows the results of differential scanning calorimetry results for Molecular Melt the sample L. An expert can derive from <figref idrefs="S75">20</figref> determine, that the mass of the I-1076 is crystalline, whereas the DPO-BSA and I-1010 in this molecular melt are amorphous.

It it is believed that a molecular melt from DPO-BSA, I-1010 and I- 1076 is, in Reacting with a target polymer a more uniform coupling product results, which in production in a cast film, a lower having number of gel. About that , this molecular melt advantageously exhibits high amorphous nature of a conventional high amorphous DPO-BSA: I-1010 molecular melt, and it has also increased resistance opposite to Agglomeration, whereby any blocking of the molecular melt in comparison to a conventional high amorphous DPO-BSA: I-1010 molecular melt is reduced.