Azido-substituted heteroaromatic additives for making recyclable polymer compositions and for upgrading re-manufactured plastic waste

Abstract

This invention relates to a method for preparing a polymer composition, the method comprising the steps of: (a) processing at a temperature T 混合 (a) Mixing the polymer or polymer blend with the azide derivative of formula (I): N3-Ar(I), wherein Ar is a heteroaromatic group, and (b) heating the mixture from step (a) to a temperature T. R T 混合 The glass transition temperature or melting temperature of the polymer used in step (a) is higher than that of the polymer used in step (a), or the highest glass transition temperature or melting temperature of all polymers present in the polymer blend of step (a) at a content of at least 8% by weight relative to the total weight of the blend, T R Equal to or higher than the decomposition temperature of the azide in formula (I), and T 混合 Strictly below T R The present invention also relates to polymer compositions obtained by the method of the present invention. The present invention further relates to the use of the additive N3-Ar of formula (I) for upgrading recycled plastics or mixtures of plastics.

Description

Technical Field

[0001] This invention relates to a method for preparing polymer compositions by mixing polymers or polymer blends with azido-substituted heteroaromatic derivatives, and to the polymer compositions obtained by said method. The method of this invention enables the provision of polymers and polymer blends with dynamically crosslinked polymers, which can be reprocessed / recycled without altering their mechanical properties. This invention also relates to the use of azido-substituted heteroaromatic derivatives as additives for upgrading recycled plastics (particularly plastic waste and unsorted plastic waste). Background Technology

[0002] Plastics are a ubiquitous feature of modern life due to their low cost, strength, lightweight, durability, and processability. However, the capacity to recycle and reuse end-of-life plastic products remains limited. To address this issue, the European Union has developed an ambitious initiative to transform the plastics industry, emphasizing the need to make plastics easier to recycle in a cost-effective manner. A key component of this initiative is mechanical recycling, which involves sorting, purifying, and grinding the recycled post-consumer plastic waste. Currently, mechanical recycling is only applied on a large scale to polyethylene terephthalate (PET) and polyethylene (PE), but forecasts indicate that mechanical recycling will be the most important method for adding value to global plastic waste.

[0003] The main drawback of mechanical recycling is that the resulting recycled polymer feedstock exhibits inferior mechanical properties compared to the corresponding virgin materials. Therefore, mechanically recycled polymers are limited to low-value applications, which is insufficient to achieve a circular plastics economy. Three main challenges must be addressed before mechanically recycled polymers can be used in a wide range of applications: chain degradation during processing, incompatible blends of different polymer types, and limited applicability to materials containing permanent and non-dynamically crosslinked materials, such as elastomers.

[0004] During machining, most polymers undergo flow-induced and / or thermally induced chain breakage, affecting their processability and physical properties. Even industrial waste (such as runners generated during injection molding) exhibits poor properties during reprocessing. Another unfortunate reality of current recycling technologies is that even the most efficient equipment in the EU produces recycled polymer feedstock containing approximately 5% to 10% polymer contaminants. This problem poses a challenge because almost all the major polymers in post-consumer waste streams are incompatible with each other. When co-mixed in the absence of compatibilizers, polymers undergo phase separation, characterized by poor interfacial adhesion. This phenomenon results in mechanically weak materials that can only be used in applications where mechanical strength is not required.

[0005] Finally, the possibility of mechanically recycling chemically cross-linked materials (such as elastomers used in the automotive, construction, and packaging industries) is inherently limited by the permanent and non-dynamic nature of the cross-linking. The vast majority of elastomer waste is landfilled or incinerated.

[0006] To avoid unwanted side reactions during (re)processing (e.g., shear-induced chain breakage), it is common practice to use stabilizers and chain extenders to adjust the melt viscosity to the desired processing window. However, the use of these additives has several drawbacks (poor thermal stability and high cost). ZOG Schyns , MP Schaver. Macromol. Rapid Commun. 2021, 42, 2000415 Furthermore, these additives are typically only applicable to specific types of polymers.

[0007] Industrial polymer users tend to modify the chemical structure of polymers through reactive processing because this does not require any changes to established polymer synthesis protocols. Macosko, CW; Jeon, HK; Hoye, TR Prog. Polym. Sci. 2005, 30, 939 This strategy is particularly useful for polymers with inherent reactivity (e.g., polyesters that can undergo transesterification). For less reactive polymers (e.g., polyethylene), radical acceptors (e.g., maleic anhydride) are used to bind with organic peroxides to introduce functional groups. The resulting grafted structure can reduce interfacial tension. This strategy is not suitable for polymers that readily undergo radical-initiated side reactions (e.g., polypropylene (PP)).

[0008] Regarding the recyclability of traditional thermoset materials and elastomers, only a few strategies exist for large-scale implementation. Mechanically milled elastomers can be blended with other polymers to reinforce degraded materials. To date, efforts to chemically decrosslink elastomer waste have yielded limited results. Currently, most thermoset waste is landfilled or incinerated.

[0009] Therefore, there is a need for (i) easily reprocessable and recyclable polymer compositions that retain the desired mechanical properties of the original material, or even exhibit new or improved thermomechanical properties, for use in the same applications as the original material or in new applications requiring materials with excellent thermomechanical properties, and (ii) for upgrading polymer blends (e.g., plastics and plastic waste (including unsorted plastic waste)) into polymer compositions with excellent thermomechanical properties.

[0010] Surprisingly, the inventors have developed a method for preparing polymer compositions that combine the mechanical behavior and solvent resistance of thermoset materials with the recyclability of thermoplastic polymers. When this method is applied to plastic waste, the resulting upgraded and recycled polymer compositions possess improved thermomechanical properties, thus allowing them to be used in the same applications as the virgin materials, or even in applications where the thermomechanical properties are unsuitable for plastic waste.

[0011] This invention is based on the preparation of polymers containing heteroaromatic nitrogen-nitrogen bonds that can undergo exchange reactions at high temperatures. Nitrogen-nitrogen bond exchange has been rarely reported. Breton, GW; Martin, KLJ Org. Chem. 2020, 85, 10865） Furthermore, this has not been reported in the context of polymer chemistry. This chemistry is particularly advantageous because the reactive species (i.e., amino radicals) are relatively unreactive to other functional groups. In addition, it is insensitive to moisture.

[0012] This invention can be used to improve the thermomechanical properties of various polymers and polymer blends, including increased melt viscosity, enhanced resistance to environmental stress cracking, adhesion between incompatible polymers, polymer functionalization, self-healing, reversible crosslinking, and enhanced reprocessability. In particular, this invention can be used to prepare dynamically crosslinked thermosetting materials with a high insoluble fraction but still reprocessable, addressing a key challenge in the recyclability of crosslinked materials. To the knowledge of the inventors, no previously published or patented examples of polymer compositions obtained by the methods of this invention (e.g., the methods defined in this disclosure) have been reported.

[0013] Compared to other strategies in the art for improving the properties of polymers and polymer blends, the present invention is characterized by a combination of broad applicability, enhanced physical properties compared to corresponding materials that do not contain heteroaromatic N-N bonds, and unparalleled ease of implementation. Summary of the Invention

[0014] According to a first aspect, the present invention relates to a method for preparing a polymer composition, the method comprising the following steps: (a) At processing temperature T 混合 The following mixtures of polymers or polymer blends with azide derivatives of formula (I): N3-Ar(I) Ar is a heteroaryl aromatic group. Then (b) Heat the mixture from step a) to temperature T. R , in T 混合The glass transition temperature or melting temperature of the polymer used in step (a) is higher than that of the polymer used in step (a), or the highest glass transition temperature or melting temperature of all polymers present in the polymer blend of step (a) at a content of at least 8% by weight relative to the total weight of the blend. T R Equal to or higher than the decomposition temperature of the azide in formula (I), and T 混合 Strictly below T R .

[0015] In most cases, and preferably in all cases, the decomposition temperature of the azide is higher than the glass transition temperature (T0) of the polymer. g ) or melting temperature (T) m When the mixture in step (a) contains a blend of polymers, the relevant T g or T m The highest glass transition temperature (T0) of all polymers present in the blend at a content of at least 8% by weight relative to the total weight of the blend. g ) or melting temperature (T) m ).

[0016] According to a second aspect, the present invention relates to a polymer composition obtained by the method described herein.

[0017] According to a third aspect, the present invention relates to the use of azide derivatives of formula (I) as additives for upgrading recycled plastics or mixtures of plastics (particularly waste plastics or mixtures of waste plastics, such as unsorted plastics, broken plastics, mixtures of broken plastics, or mixtures thereof).

[0018] definition According to the present invention, the article "a" or "an" in expressions such as "a polymer" or "an atom" means, for example, one or more.

[0019] Polymers, linear polymers, branched polymers: A polymer comprises a set of polymer chains with different molecular sizes (particularly different molar masses). The polymer chains are composed of covalently assembled units of a large number of repeating units (called monomer units). The molecular size (characterized by its molar mass) of a polymer chain thus defined is significantly larger than that of a simple molecule, and it is composed of covalently assembled units of more than 5 monomer units, preferably more than 20 monomer units, and even more preferably more than 50 monomer units.

[0020] Polymer chains containing a single type of monomer unit are called homopolymers. Polymer chains containing multiple types of monomer units are called copolymers.

[0021] According to the present invention, the term "polymer" means homopolymer or copolymer.

[0022] According to the present invention, polymer and polymer chain refer to linear polymer chain and branched polymer chain.

[0023] As used in this invention, the term "polymer blend" or "polymer blend" refers to a mixture of at least two polymers (homogeneous polymers or copolymers). Blends can be heterogeneous (the polymers are immiscible), compatible (immiscible polymers exhibiting macroscopically uniform physical properties), or homogeneous (the polymers are miscible).

[0024] As used in this invention, the term "polymer network" generally refers to a polymer or blend of polymers as described above that can be crosslinked, which ultimately further comprises oligomers and / or organic molecules covalently linked to polymer chains or dispersed in a polymer network.

[0025] Thermosetting polymers and thermoplastics By definition, a "thermoset polymer" is a polymer that hardens upon energy input (particularly under the influence of heat). Thermoset materials are generally classified into two categories based on the glass transition temperature (Tg) of their polymer matrix. Thermoset materials with a matrix Tg higher than the operating temperature are called rigid thermosets, while those with a matrix Tg lower than the operating temperature are called elastomers. According to the present invention, thermoset materials refer to both rigid thermosets and elastomers. Materials made from thermoset polymers have the advantage of being able to harden in a manner that imparts high mechanical, heat, and chemical resistance, allowing them to replace metals in certain applications. They are also lighter than metals. They can also be used as matrices for composite materials. Conventional thermoset materials must be manufactured; in particular, they must be molded from the outset and have a suitable shape for their end use. After polymerization, they cannot be transformed except through machining, and even machining is difficult due to their brittleness. Soft and hard parts and composites based on thermoset resins cannot be transformed or molded; they also cannot be recycled. Thermoplastics belong to another class of polymer materials. Thermoplastics can be molded or injected at high temperatures, but their mechanical properties, heat resistance, and chemical resistance are inferior to those of thermosetting materials. Furthermore, the molding of thermoplastics can typically only be performed within a very narrow temperature range. When thermoplastics are heated, they become liquid, and their fluidity changes abruptly around their melting / glass transition temperature, making it impossible to apply a range of conversion methods, such as those used for glass and metals.

[0026] When novel polymer compositions contain crosslinked polymers, they can combine the mechanical properties and insolubility of thermosetting materials while functioning like thermoplastics. In this way, polymer networks can be developed that exhibit the mechanical properties and insolubility of thermosetting materials, but can transform upon heating after curing. Specifically, materials can be developed that can be heated to a temperature that makes them plastic without destroying or degrading their structure. Furthermore, the polymer networks are recyclable.

[0027] Pendant groups: As used herein, the term "dangling group" refers to a side group of a polymer chain that is not a substituent of the oligomer or polymer. The side group is not incorporated into the polymer backbone.

[0028] Free molecules: According to the present invention, a molecule is referred to as "free" if it is not covalently linked to the polymer of the composition.

[0029] Crosslinking: Crosslinking, or polymer chain crosslinking, involves the formation of covalent chemical bonds between polymer chains that were not initially linked to each other by covalent bonds. Crosslinking is accompanied by an increase in the connectivity between the individual chains constituting the polymer through covalent bonds. Crosslinking of linear or branched polymer chains is accompanied by an increase in the molecular size (particularly the molar mass) of the chains and may result in the formation of a crosslinked polymer network. The crosslinking of a crosslinked polymer network is accompanied by an increase in the mass fraction of a good nonreactive solvent that is insoluble according to the definition given below.

[0030] According to the present invention, crosslinking is a result of nitrogen-nitrogen bond formation, among other reasons. The presence of NN bonds in crosslinking arises from the following: grafting of azide derivatives of formula (I) onto repeating units of the polymer, and / or recombination of amino radicals existing as dangling groups, and / or exchange reactions between amino radicals existing as dangling groups and NN bonds.

[0031] Glass transition temperature: The glass transition temperature Tg is defined as the temperature at 1 Hz when the damping coefficient or loss factor tan tan θ is reduced by dynamic mechanical analysis. The temperature at which the value of damping coefficient or loss factor is highest. Defined as the ratio of loss modulus E'' to conservation modulus E' (Mechanical Properties of Solid Polymers, Authors: I.M. Ward, J. Sweeney; Editor: Wiley-Blackwell; Edition: 3rd; Printing ISBN: 9781444319507; DOI: 10.1002 / 9781119967125).

[0032] Polymer composition: A polymer composition is defined as a homogeneous or heterogeneous mixture of linear or branched polymers that can be linked by crosslinking, comprising overhanging links and crosslinking that can be exchanged by nitrogen-nitrogen exchange reactions and / or exchange reactions between N-N bonds and amino radicals and / or recombination of amino radicals, and may have various charges, additives or solvents, as defined below.

[0033] In this way, "polymer composition" refers to solid formulations containing little or no solvent and liquid formulations containing a higher mass fraction of solvent.

[0034] In this way, "preparation" refers to both solid preparations and liquid preparations.

[0035] According to the present invention, the solid formulation may contain less than 30% by mass of solvent, preferably less than 25% by mass of solvent, more preferably less than 20% by mass of solvent, even more preferably less than 15% by mass of solvent, even more preferably less than 5% by mass of solvent, even more preferably less than 2.5% by mass of solvent, even more preferably less than 1% by mass of solvent, and even more preferably less than 0.5% by mass of solvent.

[0036] According to the present invention, the solid preparation is a material.

[0037] According to the present invention, the liquid formulation may contain more than 30% by mass of solvent, preferably more than 50% by mass of solvent, more preferably more than 60% by mass of solvent, even more preferably more than 70% by mass of solvent, and even more preferably more than 75% by mass of solvent.

[0038] According to the present invention, the liquid preparation can be a material.

[0039] A solvent is defined as a molecule or mixture of molecules that is liquid at ambient temperature and has the property of dissolving and / or diluting other substances at ambient temperature without chemically altering them or changing itself. Solvents are distinguished as good solvents and bad solvents. Good solvents exhibit the property of dissolving substances at room temperature without chemically altering them or changing themselves, while bad solvents exhibit the property of diluting substances at ambient temperature rather than dissolving them, without chemically altering them or changing themselves.

[0040] Therefore, a solvent may be a good solvent for one compound and a bad solvent for another.

[0041] Non-limiting examples of solvents include ethyl acetate, butyl acetate, acetone, acetonitrile, benzyl alcohol, acetic anhydride, anisole, benzene, butanol, butanone, chlorobenzene, dichlorobenzene, trichlorobenzene, chloroform, cyclohexane, dichloroethane, dichloromethane, dimethylformamide, dimethyl sulfoxide, dioxane, water, ethanol, ethylene glycol ether, diethyl ether, ethylene glycol, heptane, hexane, mineral oil, natural oil, synthetic oil, hydrocarbons, methanol, pentane, propanol, propoxypropane, pyridine, tetrachloroethane, tetrachloromethane, tetrahydrofuran, toluene, trichlorobenzene, xylene, and mixtures thereof.

[0042] Nitrogen-nitrogen exchange reaction, nitrogen-nitrogen / amino radical exchange reaction, recombination of amino radicals According to the present invention, the nitrogen-nitrogen exchange reaction occurring in the crosslinked polymer or polymer blend enables the exchange between substituents that are attached to each nitrogen atom in the covalent N-N bond contained in the crosslink or as a dangling group.

[0043] As used herein, the term "amino radical" refers to a nitrogen-centered radical. Amino radicals can be monoradicals or diradicals, corresponding to nitrogen atoms carrying one or two unpaired valence electrons, respectively. Triptylic azelaenes are an example of amino radicals carrying two unpaired valence electrons.

[0044] According to the present invention, the nitrogen-nitrogen / amino radical exchange reaction that may occur in the crosslinked polymer or polymer blend enables the exchange of one of the two nitrogen atoms in the covalent NN bond contained in the crosslinking or as a dangling group with the other nitrogen atom of the amino radical. In other words, after the exchange reaction, the new nitrogen atom in the NN covalent bond becomes the nitrogen atom of the amino radical involved in the exchange reaction, while the nitrogen atom initially on the NN bond is now transferred to the amino radical after the reaction.

[0045] According to the present invention, the recombination of amino radicals corresponds to the recombination of two amino radicals to form a covalent N-N bond.

[0046] Figure 1The document provides non-limiting examples of nitrogen-nitrogen exchange reactions, nitrogen-nitrogen / amino radical exchange, and recombination of amino radicals, wherein Sub 1 To Sub 8 Substituents for nitrogen atoms involved in nitrogen-nitrogen exchange reactions, nitrogen-nitrogen / amino radical exchanges, and recombination of amino radicals.

[0047] The substituent may be a heteroaromatic group, polymer chain, or oligomer chain of an azide derivative of formula (I).

[0048] The substituents can be the same or different.

[0049] These substituents are covalently bonded to at least one nitrogen atom before and after the exchange reaction.

[0050] Nitrogen-nitrogen exchange reactions, nitrogen-nitrogen / amino radical exchange reactions, and recombination of amino radicals are carried out under processing conditions (i.e., appropriate temperatures). These reactions can be carried out with or without a catalyst. Preferably, the catalyst is stable, readily available, inexpensive, and non-toxic. Preferably, the reaction is carried out in the absence of a catalyst.

[0051] Nitrogen-nitrogen exchange reactions, nitrogen-nitrogen / amino radical exchanges, and recombination of amino radicals can occur in a solvent or in bulk (i.e., in the absence of a solvent).

[0052] These nitrogen-nitrogen exchange reactions, nitrogen-nitrogen / amino radical exchange reactions, and recombination of amino radicals can yield polymer compositions with properties of both thermosetting and thermoplastic polymers, wherein the polymer compositions may be insoluble and plastic upon heating.

[0053] Group: As used in this article, the term "C1-" y "Alkyl" refers to a straight-chain or branched monovalent saturated hydrocarbon chain containing 1 to y carbon atoms, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, etc.

[0054] As used in this article, the term "C1-C" y "Halogenated alkyl" means C1-C as defined above. y An alkyl chain in which one or more hydrogen atoms are replaced by halogen atoms selected from fluorine, chlorine, bromine and iodine.

[0055] As used in this article, the term "C1-" y "alkyl-aryl" means a C1- group as defined above that is attached to an aryl group as defined above. y Alkyl, the C1- yAlkyl-aryl groups are attached to the rest of the molecule by atoms of the alkyl or aryl moiety.

[0056] As used in this article, “heteroatoms” refers to atoms of sulfur, nitrogen, oxygen, boron, phosphorus, or silicon.

[0057] As used in this article, "aromatic" refers to a monovalent or polyvalent group containing an aromatic hydrocarbon group. The valence of the group will be determined on a case-by-case basis.

[0058] Aromatic groups can contain heteroatoms; in this case, they are called "heteroaromatic" groups. Specifically, they can contain ester, amide, ether, thioether, secondary or tertiary amine, carbonate, carbamate, carbamate, or anhydride functional groups. Aromatic groups can represent one or more fused or covalently linked rings. If applicable, aromatic groups may be specifically substituted with halogen, -Rz, -OH, -NH2, -NHRz, -NRzR'z, -C(O)-H, -C(O)-Rz, -C(O)-OH, -C(O)-NRzR'z, -C(O)-O-Rz, -OC(O)-Rz, -OC(O)-O-Rz, -OC(O)-N(H)-Rz, -N(H)-C(O)-O-Rz, -O-Rz, -SH, -S-Rz, -SS-Rz, -C(O)-N(H)-Rz, -N(H)-C(O)-Rz groups (where Rz and R'z may be the same or different, and represent C1-C). 50 Alkyl groups, or functional groups selected from those that can be polymerized via free radical polymerization, are substituted.

[0059] The term "aryl" refers to an aromatic hydrocarbon group, such as phenyl or naphthyl, that preferably contains 6 to 12 carbon atoms and comprises one or more fused rings. Advantageously, it is phenyl.

[0060] Specifically, in the context of this invention, the heteroaromatic group is a heteroaryl. As used herein, the term "heteroaryl" refers to an aromatic group comprising one or more, particularly one or two fused hydrocarbon rings, wherein one or more, particularly one to four, carbon atoms in each fused hydrocarbon ring are advantageously replaced by heteroatoms selected from sulfur, oxygen, and nitrogen atoms, preferably oxygen and nitrogen atoms. It can be furanyl, thiophene, pyrrole, pyridinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, thiazolyl, triazolyl, tetrazolyl, pyridazinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, or indoleyl. Preferably, it is azazinyl, diazinyl, triazinyl, or purineyl, more preferably triazinyl.

[0061] Detailed description azide derivatives of formula (I) The azide derivatives of formula (I) are preferably selected from: , Where R 1 To R x One or two of them, preferably one of which is N3, and the others are each independently selected from hydrogen atoms, halogens, C atoms, etc. 1-12 Alkyl, C 1-12 Halogenated alkyl, aryl, heteroaryl, C 1-12 Alkyl-aryl, bridging oxygen, NR c R d OR e C(O)R f C(O)OR g C(O)NR h R i SR j , CN and NO2, of which R c To R j Each is independently a hydrogen atom, C1-C 12 Alkyl, C 1-6 Alkyl-aryl or aryl, R x It is the group with the highest index on the compound.

[0062] Advantageously, R 1 To R x One or two of them, preferably one of which is N3, and the others are each independently selected from hydrogen atoms, halogen atoms, C1-C6 alkyl groups, aryl groups, bridging oxygen groups, and NR. c R d OR e and SR j , where R c To R e and R j Preferably, they are hydrogen atoms, C1-C, and are independent of each other. 12 Alkyl or aryl.

[0063] Advantageously, R 1 To R x One or two of them, preferably one of which is N3, and at least one of the others is selected from halogens, C 1-12 Alkyl, C 1-12 Halogenated alkyl, aryl, heteroaryl, C 1-12 Alkyl-aryl, bridging oxygen, NR c R d OR e C(O)R f C(O)OR g C(O)NRh R i SR j , CN and NO2, of which R c To R j Each is independently a hydrogen atom, a C1-C6 alkyl group, and a C 1-6 Alkyl-aryl or aryl. More preferably, R 1 To R x One of them is N3, and at least one of the others is selected from halogen atoms, C1-C6 alkyl, aryl, bridging oxygen, NR c R d OR e and SR j , where R c To R e and R j As defined above, and preferably independently of each other, they are hydrogen atoms, C1-C 12 Alkyl or aryl, wherein the aryl group is particularly phenyl.

[0064] In one embodiment, the azide derivative of formula (I) is a triazine selected from the following: , Specifically, the triazine is 1,3,5-triazine of formula (IA): (IA), Where R 2 and R 3 As specified above, and preferably each independently selected from hydrogen atoms, halogens, and C atoms. 1-6 Alkyl, aryl, bridging oxygen, NR c R d OR e SR j , where R c To Re and R j Each is independently a hydrogen atom, C1-C 12 Alkyl, C 1-6 Alkyl-aryl or aryl. More preferably, R 2 and R 3 Each was independently selected from C 1-6 Alkyl, aryl, NR c R d OR e SR j , where R c To R e and R j Each is independently a hydrogen atom, C1-C 12 Alkyl or aryl, wherein the aryl group is particularly phenyl.

[0065] Preferably, R in the compound of formula (IA) 2 and R 3 They are the same.

[0066] In another embodiment, the azide derivative of formula (I) is an azide selected from the following: , Specifically, azazine is a pyridine of formula (IB): (IB), Where R 1 R 2 R 4 and R 5 As specified above, and preferably each independently selected from hydrogen atoms, halogens, and C atoms. 1-6 Alkyl, aryl, bridging oxygen, NR c R d and OR e , where R c To R e Each is independently a hydrogen atom, C1-C 12 Alkyl, C 1-6 Alkyl-aryl or aryl.

[0067] More preferably, in the compound of formula (IB), R 1 R 2 R 4 and R 5 At least one (and in particular all) of them are not hydrogen atoms.

[0068] Even more preferably, R in the compound of formula (IB) 1 R 2 R 4 and R 5 Each is independently selected from halogens (e.g., fluorine), C 1-6 Alkyl, aryl, NR c R d , where R c and R d C1-C are independent of each other. 12 Alkyl or aryl, wherein the aryl group is particularly phenyl. Specifically, R in compounds of formula (IB) 1 R 2 R 4 and R 5 Each is independently selected from halogens (e.g., fluorine) and NR. c R d , where R c and R dThey are independently C1-C6 alkyl (e.g., methyl) or aryl (e.g., phenyl).

[0069] In another embodiment, the azide derivative of formula (I) is a diazine selected from the following: , Specifically, the diazine is a pyrimidine of formula (IC): (IC) Where R 2 To R 4 As specified above, and preferably each independently selected from hydrogen atoms, halogens, and C atoms. 1-6 Alkyl, aryl, bridging oxygen, NR c R d and OR e , where R c To R e Each is independently a hydrogen atom, C1-C 12 Alkyl, C 1-6 Alkyl-aryl or aryl.

[0070] More preferably, in the compound of formula (IC), R 2 To R 4 At least one of them is not a hydrogen atom.

[0071] Even more preferably, R in the compound of formula (IC) 2 To R 4 Each is independently selected from hydrogen atoms and aryl groups (especially phenyl groups).

[0072] In another embodiment, the azide derivative of formula (I) is a purine having the following formula: Especially purines with the formula (ID): (ID) Where R 2 To R 3 R 5 and R 6 As specified above, and preferably each independently selected from hydrogen atoms, halogens, and C atoms. 1-6 Alkyl, aryl, bridging oxygen, NR c R d and OR e , where R c To R e Each is independently a hydrogen atom, C1-C 12 Alkyl, C 1-6 Alkyl-aryl or aryl.

[0073] More preferably, in the compound of formula (ID), R 2 To R 3 R 5 and R 6 At least one (especially one, two, or three) of them is not a hydrogen atom.

[0074] Even more preferably, R in the compound of formula (ID) 2 To R 3 R 5 and R 6 Each was independently selected from C 1-6 Alkyl (e.g., methyl) and NR c R d , where R c and R d Each of them is independently a hydrogen atom, a C1-C6 alkyl group, or an aryl group (e.g., phenyl).

[0075] Preferably, the azide derivative of formula (I) is selected from: (IA) (IB) (IC) and (ID), where R 1 To R 6 As specified above.

[0076] More preferably, the azide derivative of formula (I) is selected from: , , , , , , , , , and .

[0077] Specifically, the azide derivatives of formula (I) are selected from: , and .

[0078] More specifically, the azide derivatives of formula (I) are selected from: (1) and (AT-Ph).

[0079] polymers or polymer blends An advantage of this invention is that the polymers can be selected from a broad group including waste plastics. The polymers can be synthetic, natural, biologically derived, and / or bio-based.

[0080] Advantageously, the polymer used in step (a) of the method of the present invention is selected from polyolefins, polyesters, polystyrene (PS), polyurethane (PU), polyamides, polyvinyl chloride (PVC), natural polymers, copolymers thereof, and blends thereof.

[0081] The polymer blend used in step (a) may comprise two or more polymers selected from polyolefins, polyesters, polystyrene (PS), polyurethane (PU), polyamides, polyvinyl chloride (PVC), natural polymers and their copolymers.

[0082] Preferably, the polymer or polymer blend does not contain polydiene.

[0083] Specifically, the polyolefin is polyethylene, polypropylene (PP or iPP), copolymers thereof, or ethylene propylene diene monomer terpolymer (EPDM rubber). Polyethylene is particularly high-density polyethylene (HDPE) or low-density polyethylene (LDPE) (e.g., linear low-density polyethylene (LLDPE)), and the polyester can be polycaprolactone (PCL) or polyethylene terephthalate (PET) and copolymers thereof.

[0084] Natural polymers can be, in particular, polysaccharides or polycyclic aromatic compounds, which can be selected from starch, chitin, chitosan, alginate, natural gums, cellulose, pectin, polyphenols (e.g., lignin) and proteins (e.g., gluten, corn gluten, casein, collagen and gelatin).

[0085] The polymer or polymer blend used in step (a) may be, in particular, HDPE, LDPE, copolymers thereof, or a blend of HDPE with another polyolefin (e.g., polyethylene, polypropylene, or copolymers thereof).

[0086] Preferably, the number average molecular weight Mn of the polymer or polymer blend used in step (a) before network formation is in the range of 300 g / mol to 3,000,000 g / mol, more preferably 1,000 g / mol to 1,000,000 g / mol, more preferably 5,000 g / mol to 500,000 g / mol, and even more preferably 10,000 g / mol to 300,000 g / mol.

[0087] In certain embodiments, the polymer is a plastic or a mixture of plastics. In the context of this invention, the term "plastic" refers to a material that uses a polymer (including natural polymers, semi-synthetic polymers, and synthetic polymers as defined above) as its main component and may also contain additives (e.g., fillers, antioxidants, etc.). Plastics in the framework of this invention can be wholly or partially bio-based plastics (i.e., "bioplastics"), which means plastics made from or containing renewable polymers (particularly from animal or plant sources). Their plasticity allows plastics to be molded, extruded, or compressed into solid objects of various shapes. The success and dominance of plastics have led to widespread environmental problems because they decompose slowly in natural ecosystems. The plastics of this invention include existing plastics (i.e., polymeric materials as described above) that have already been shaped for their intended use and have ultimately been used. A significant advantage of this invention is that, in the method of this invention, the polymer can be waste plastic or a mixture of waste plastics, which also includes broken plastics, mixtures of broken plastics, unsorted plastics, or mixtures thereof.

[0088] Methods for obtaining polymer compositions The method of the present invention includes the following steps: (a) At processing temperature T 混合 The following mixtures of polymers or polymer blends with azide derivatives of formula (I): N3-Ar(I) Ar is a heteroaryl aromatic group. Then (b) Heat the mixture from step a) to temperature T. R , in T 混合 The glass transition temperature or melting temperature of the polymer used in step (a) is higher than that of the polymer used in step (a), or the highest glass transition temperature or melting temperature of all polymers present in the polymer blend of step (a) at a content of at least 8% by weight relative to the total weight of the blend. T R Equal to or higher than the decomposition temperature of the azide in formula (I), and T 混合 Strictly below T R .

[0089] The method of the present invention may further include one or more processes at a processing temperature T' 混合 Step (a') involves mixing a polymer or polymer blend different from that in step (a) with an azide derivative of formula (I) that is the same as or different from that in step (a). 混合The glass transition temperature or melting temperature of the polymer used in step (a') is higher than that of the polymer used in step (a'), or the highest glass transition temperature or melting temperature of all polymers present in the polymer blend in step (a') at a content of at least 8% by weight relative to the total weight of the blend.

[0090] In such an implementation, the mixing in step (a) and the mixing in step (a') are typically carried out in separate reactors, and then in step (b), the mixture from step (a) is heated to temperature T in the presence of the mixture from step (a'). R According to these embodiments, the method of the present invention includes the following steps: (a) At processing temperature T 混合 The following mixtures of polymers or polymer blends with azide derivatives of formula (I): N3-Ar(I) Ar is a heteroaryl aromatic group. (a') at processing temperature T' 混合 The following mixtures of polymers or polymer blends with azide derivatives of formula (I): N3-Ar(I) Ar is a heteroaryl aromatic group. The polymer or polymer blend and / or azide derivative of formula (I) used in step (a') are different from the polymer or polymer blend and / or azide derivative of formula (I) used in step (a). (b) In the presence of the mixture from step (a'), heat the mixture from step a) to temperature T. R , Where T 混合 T' 混合 and T R As specified above, and T 混合 and T' 混合 Each is strictly below T R .

[0091] Alternatively, when the method of the present invention further includes one or more steps (a'), it may each include heating the mixture of step (a') to a temperature T. R Step (b'). In such an embodiment, steps (a) and (b) are carried out in one reactor, and steps (a') and (b') are carried out in another reactor. The polymer composition obtained from step (b) can then be blended with the polymer composition obtained from step (b'). According to these embodiments, the method of the present invention includes the following steps: (a) At processing temperature T 混合The following mixtures of polymers or polymer blends with azide derivatives of formula (I): N3-Ar(I) Ar is a heteroaryl aromatic group. (a') at processing temperature T' 混合 The following mixtures of polymers or polymer blends with azide derivatives of formula (I): N3-Ar(I) Ar is a heteroaryl aromatic group. The polymer or polymer blend and / or azide derivative of formula (I) used in step (a') are different from the polymer or polymer blend and / or azide derivative of formula (I) used in step (a). T 混合 and T' 混合 As specified above, (b) Heat the mixture from step (a) to temperature T. R T R The decomposition temperature of the azide is equal to or higher than that of formula (I) used in step (a). (b') Heat the mixture from step (a') to temperature T' R , where T' R The decomposition temperature of the azide is equal to or higher than that of formula (I) used in step (a'). Steps (a) and (b) are carried out in one reactor, and steps (a') and (b') are carried out in another reactor. (c) At temperature T'' R The polymer composition obtained in step (b) is blended with the polymer composition obtained in step (b') at a temperature T''. R equal to T R and T' R Higher temperatures in the environment.

[0092] Step (a) Step (a') is the same as step (a), but uses a different polymer or blend and / or a different azide derivative of formula (I). Steps (a) and (a') are carried out in two different reactors. Steps (a) and (a') are specifically carried out concurrently. Although only one parallel step (a') is specifically mentioned, multiple parallel steps (a') can be implemented. In the following, all embodiments disclosed for step (a) also apply to step (a').

[0093] According to a preferred embodiment, the mixture of step (a) comprises, relative to the polymer repeating unit, 0.05 mol% to 10 mol%, preferably 0.1 mol% to 3.5 mol%, more preferably 0.5 mol% to 1.5 mol% of an azide derivative of formula (I). In some embodiments, the mixture of step (a) comprises, relative to the total weight of the mixture, 0.1 wt% to 40 wt%, preferably 0.5 wt% to 20 wt%, more preferably 1 wt% to 15 wt% of a derivative of formula (I).

[0094] The repeating units of a polymer can be determined by a combination of FTIR, Raman spectroscopy, and NMR spectroscopy.

[0095] The azide derivative of formula (I) may be soluble or insoluble in the molten polymer or polymer blend used in step (a). When the azide derivative is completely insoluble or partially soluble, i.e., when phase separation is observed by transmission electron microscopy (TEM) as explained below, it is broadly referred to herein as an insoluble azide derivative.

[0096] The solubility of the azide derivative of formula (I) in the mixture of step (a) can be determined by transmission electron microscopy (TEM) or according to the solubility theoretical model described in detail in the “Methods” paragraph below.

[0097] For a given polymer or blend of polymers, the lower the solubility of the azide derivative of formula (I) in the mixture of step (a), the higher the crosslinking density of the polymer composition. In other words, when the azide derivative is insoluble, the polymer composition obtained after step (b) contains a high proportion of crosslinked polymers, even forming a polymer network. Conversely, when the azide derivative is soluble, the polymer composition obtained after step (b) will contain a high proportion of non-crosslinked polymers and / or weakly crosslinked polymers.

[0098] By performing steps (a) and (a') (where each azide derivative in the mixture of step (a) or (a') has a different solubility (depending on the properties of the polymer or polymer blend or the properties of the azide derivative)), a polymer composition comprising a mixture of crosslinked and non-crosslinked polymers can be obtained.

[0099] Preferably, the azide derivative of formula (I) is insoluble in the molten polymer or polymer blend used in step (a), more preferably it is completely insoluble. Therefore, the polymer composition obtained after step (b) preferably contains a high proportion of crosslinked polymer, more preferably it consists of a polymer network.

[0100] Therefore, step (a) is a premixing step, which is crucial for dispersing azide derivatives (especially insoluble azide derivatives) in polymers or polymer blends. This premixing enables the production of polymer compositions with enhanced thermomechanical properties, which are reprocessable and recyclable. Typically, this reprocessability and recyclability can be demonstrated by comparing the thermomechanical properties after cycles of reprocessing and reshaping. For example, a polymer composition can be described as reprocessable and recyclable when a consistent rubber plateau is observed in dynamic mechanical analysis (DMA), and / or when consistent tensile properties are observed by uniaxial tensile testing, and / or when consistent high-temperature creep resistance is observed by, for example, rheological experiments.

[0101] According to the preferred embodiment, step (a) includes the following successive sub-steps: (a1) Provide polymers or polymer blends, (a2) provides an azide derivative of formula (I), (a3) At the processing temperature T specified above 混合 The polymer or polymer blend of step (a1) is mixed with the azide derivative of formula (I) in step (a2).

[0102] Preferably, the temperature T 混合 The highest glass transition temperature (Ti) of all polymers present in the blend at a content of at least 8% by weight, particularly at least 4% by weight, and especially less than 2% by weight relative to the total weight of the blend. g ) or melting temperature (T) m ).

[0103] Therefore, the glass transition temperature or melting temperature of the polymer present in the blend at a content of less than 8% by weight, particularly less than 4% by weight, and especially less than 2% by weight, will not be considered when setting temperature T. 混合 .

[0104] It should be understood that when the polymer is amorphous, it is called the glass transition temperature (T0). g (This is the melting temperature), and when the polymer is semi-crystalline, it is called the melting temperature.

[0105] The polymer or polymer blend of step (a1) may be provided as is or as a suspension or solution in a solvent. Typically, the suspension or solution may be heated, for example, to the processing temperature T before mixing in step (a3). 混合 .

[0106] In step (a2), the azide derivative may be provided as is or as a masterbatch. "Masterbatch" is understood to mean the azide derivative pre-dissolved or suspended in a solvent or a "diluted" polymer in which the azide derivative is soluble. The "diluted" polymer may be part of the polymer or polymer blend of step (a1), or, when the azide derivative is poorly soluble in the polymer or polymer blend of step (a1), the "diluted" polymer may be a different polymer or polymer blend used in step (a1). Typically, such a masterbatch contains 0.5% to 40% by weight of the azide derivative relative to the total weight of the masterbatch. Providing the azide derivative as a masterbatch facilitates the dispersion of the additive during the melt processing in step (a3). The masterbatch may typically be heated to the processing temperature T before being mixed with the polymer or polymer blend of step (a3). 混合 Or even lower temperatures.

[0107] Alternatively, the polymer or polymer blend of step (a1) and the azide derivative of step (a2) can be provided at room temperature, and the mixture is heated to T only during step (a3). 混合 .

[0108] According to the preferred embodiment, step (a3) ​​is performed at a processing temperature T. 混合 The mixture is carried out for 1 to 10 minutes, preferably 2 to 6 minutes.

[0109] The mixing step (a) is carried out in a reactor (e.g., an extruder, a closed mixer or a die, especially the barrel of an extruder).

[0110] Temperature T in step (b) R and reaction time t R T R This is the reaction temperature at which the mixture from step (a) is heated in step (b). It is the setpoint temperature set by the operator. T R The decomposition temperature of the azide is equal to or higher than that of formula (I).

[0111] The decomposition temperature of the azide derivative of formula (I) is the decomposition temperature of the azide derivative in the mixture of step (a). This decomposition temperature corresponds to the temperature at which the azide derivative in the mixture of step (a) begins to decompose (i.e., when the covalent bonds of the compound begin to break). Therefore, the value of the decomposition temperature will depend on the properties of the polymer or polymer blend provided in step (a) that is mixed with the azide derivative. The decomposition temperature of the azide derivative in the mixture of step (a) is typically determined by TGA or DSC according to the methods described in the “Methods” paragraph below.

[0112] The temperature T equal to the decomposition temperature of the azide derivative R This refers to T compared to the decomposition temperature of the azide derivative in the mixture of step (a). R The temperature range is -5℃ to +5℃.

[0113] Preferably, T R Strictly above the decomposition temperature of the azide derivatives in the mixture of step (a). Specifically, temperature T. R The range is from the decomposition temperature plus 5°C to the decomposition temperature plus 100°C, and especially from the decomposition temperature plus 10°C to the decomposition temperature plus 90°C.

[0114] In most cases, and preferably in all cases, the decomposition temperature of the azide is higher than the glass transition temperature (T0) of the polymer. g ) or melting temperature (T) m When the mixture in step (a) contains a blend of polymers, the relevant T g or T m The highest glass transition temperature (T0) of all polymers present in the blend at a content of at least 8% by weight relative to the total weight of the blend. g ) or melting temperature (T) m ).

[0115] Therefore, when the mixture in step (a) contains a polymer, the temperature T R Strictly above the polymer's glass transition temperature (Tg) or melting temperature (Tm). m Alternatively, when the mixture in step (a) contains a polymer blend, the temperature T R The content of all polymers present in the blend at a concentration of at least 8% by weight, preferably at least 4% by weight, and more preferably at least 2% by weight, relative to the total weight of the blend, is strictly higher than the highest glass transition temperature (T0) of the polymers present in the blend. g ) or melting temperature (T) m ).

[0116] In all cases, T R All are strictly higher than T 混合 .

[0117] According to the preferred embodiment, in step (b), the temperature T is observed. R The reaction time t R Reaction time t R Corresponding to temperature T RThe time required to decompose 50%, preferably 75%, more preferably 90%, and even more preferably 95% of the azide derivative of formula (I). The percentage is expressed relative to the total amount of the azide derivative of formula (I) provided in step (a). Preferably, the reaction time t... R Less than 60 min, more preferably less than 30 min.

[0118] In other words, choose temperature T R and reaction t R This results in the decomposition of 50%, preferably 75%, more preferably 90%, or even more preferably 95% of the azide derivative of formula (I), preferably within the shortest possible time.

[0119] Reaction time t R It can correspond to temperature T R The mixture in step (a) contains 1 to 10, preferably 2 to 9, more preferably 4 to 8, and even more preferably 5, azide derivative of formula (I). The half-life applies to one azide derivative of formula (I) and varies with the reaction temperature. Temperature T R The higher the value, the shorter the half-life.

[0120] According to the preferred implementation scheme, T is selected. R This results in a half-life for the azide derivative ranging from 1 min to 15 min, preferably from 1 min to 10 min, and more preferably from 2 min to 5 min. Specifically, T is selected... R This results in a half-life of 2 minutes for the azide derivative. Preferably, the reaction time t... R It equals 10 minutes.

[0121] According to some implementation schemes, the mixture in step (a) reaches temperature T. R The required heating time, especially from temperature T 混合 To temperature T R The required time is equal to or less than 5 half-lives, preferably equal to or less than 2 half-lives, and more preferably equal to 1 half-life.

[0122] According to some implementation schemes, step (b) is carried out by reactive extrusion, compression molding, injection molding, or furnace hardening. In particular, the reaction can be carried out in a twin-screw extruder or by compression molding using a hot press.

[0123] Step (b') is the same as step (b), but involves heating the mixture of step (a') (if present). Steps (b) and (b') are carried out in two different reactors. Steps (b) and (b') are specifically carried out concurrently. Although only one parallel step (b') is specifically mentioned, multiple parallel steps (b') can be implemented when multiple steps (a') are performed. All embodiments disclosed herein for step (b) also apply to step (b').

[0124] Grafting of azide derivatives to polymers or polymer blends can be evaluated using conventional techniques known in the art, including NMR, IR, Raman spectroscopy, UV-Vis spectroscopy, EPR spectroscopy, elemental analysis, and mass spectrometry.

[0125] The polymer composition obtained by the method described above The method of the present invention provides a polymer composition that is crosslinked or non-crosslinked, preferably crosslinked, wherein the polymer or polymer blend is grafted with residues of an azide derivative of formula (I) provided in the method. In other words, the polymer composition contains at least one NN bond, which can be demonstrated by Raman spectroscopy, UV-Vis spectroscopy and / or NMR spectroscopy and / or elemental analysis. This NN bond imparts dynamic behavior to the polymer composition. Because such NN bonds can break and then dynamically reform (especially under processing conditions), the entire polymer network can be reconfigured and adapted to processing and forming conditions. This NN bond can be contained in crosslinks between polymer chains of the polymer composition, in dangling groups of polymer chains, and / or in free molecules present in the polymer composition. Therefore, the polymer composition obtained by the method of the present invention can contain crosslinked polymers, non-crosslinked polymers, or mixtures thereof, particularly depending on the solubility of one or more azide derivatives of formula (I) in the mixture of step (a) of the method.

[0126] According to some embodiments, the polymer composition obtained by the method described above comprises groups of formula (II) and / or formula (III): (II) (III) in The bonds between group (II) and / or group (III) and the carbon atoms of the repeating units of the polymer of the composition. x and y are each independent integers ranging from 0 to 10, preferably 0 or 1. Ar is defined as the azide derivative of formula (I) used in the method described above, and *Selected from H and another repeating unit of the polymer of the composition, carbon atoms.

[0127] It should be understood that the Ar groups present in the groups of formulas (II) and (III) correspond to the Ar groups present in the azide derivative of formula (I) provided in step (a) of the method for providing the polymer composition.

[0128] The polymer compositions may comprise crosslinked polymers or polymer blends and mixtures of non-crosslinked polymers or polymer blends. Compared to existing polymer compositions, these polymer compositions disclose improved processability and ductility. Even with lower overall additive content compared to existing polymer compositions, these polymer compositions can achieve interesting macroscopic properties, such as excellent creep resistance above Tg for amorphous polymers, excellent creep resistance above Tg and above Tm for semi-crystalline polymers, improved elongation at break, improved fracture stress, improved toughness, improved solvent resistance, and the ability to induce adhesion between polymer compositions with the same or different chemical properties.

[0129] According to a preferred embodiment, the polymer composition comprises a high proportion of crosslinked polymers or crosslinked polymer blends, particularly due to the insolubility of one or more azide derivatives of formula (I) in the mixture of step (a). Specifically, the polymer composition comprises a proportion of crosslinked polymers or crosslinked polymer blends sufficient to make the composition reprocessable and recyclable. The insoluble fraction of such polymer composition typically exceeds 10% by weight of the total weight of all polymers present in the composition, preferably exceeding 25% by weight, more preferably exceeding 40% by weight. The insoluble fraction is the mass of dried insoluble polymer remaining after immersion of the composition for at least 10 hours in a solvent or solvent mixture in which all polymers present in the composition are completely soluble when uncrosslinked at a given temperature.

[0130] According to this embodiment, the polymer composition comprises groups of formulas (II) and (III) as defined above, wherein the group (II) is preferably a carbon atom of another repeating unit of the polymer of the composition.

[0131] In particular, the inventors have demonstrated that the method of the present invention produces polymer compositions comprising dynamic crosslinking (see Example 4). “Dynamic crosslinking” is understood to mean that the crosslinks that occur between the polymer chains of the composition can break and reform under processing conditions (i.e., at appropriate temperatures and / or high shear).

[0132] As described above, these reversible crosslinks contain at least one N-N bond, particularly a heteroaromatic N-N bond, which can therefore be broken and reformed under the processing conditions. Prior to reformation, the heteroaromatic group helps stabilize the free radical species (e.g., amino radicals) generated by the breaking of the N-N bond.

[0133] The inventors have also demonstrated that long-lived free radicals containing at least one N-N bond (particularly heteroaromatic N-N bonds) may be present in the crosslinked composition. These persistent free radicals can remain in the composition under stable conditions (e.g., during storage or use) and then recombine under future processing conditions to form crosslinks.

[0134] Due to the reversible crosslinking of the composition, such crosslinked polymers or polymer blends are reprocessable and therefore recyclable. According to some other embodiments, the polymer composition comprises a high proportion of non-crosslinked polymers or non-crosslinked polymer blends, particularly due to the high solubility of one or more azide derivatives of formula (I) in the mixture of step (a). Such a polymer composition may contain up to 99.5% by weight of soluble polymer relative to the total weight of all polymers present in the composition. The insoluble fraction of such a polymer composition is typically less than 40% by weight, preferably less than 25% by weight, particularly between 0.1% by weight and 25% by weight, and especially between 0.5% by weight and 10% by weight.

[0135] According to this embodiment, the polymer composition comprises groups of formula (II) and formula (III) as defined above, wherein * in group (II) is preferably H, and thus the group of formula (II) is a pendant group.

[0136] This non-crosslinked polymer composition may also contain long-lived free radicals as defined above.

[0137] In some embodiments, the polymer composition of the present invention (primarily crosslinked or non-crosslinked, preferably crosslinked) further comprises a dangling group of formula -NH(Ar) attached to the carbon atom of the repeating unit of the polymer of the composition, wherein Ar is defined in an azide derivative of formula (I) as used in the methods described above.

[0138] Without being bound by theory, polymer compositions (primarily crosslinked or non-crosslinked, preferably crosslinked) may contain free compounds comprising heteroaromatic Ar groups resulting from the decomposition of unreacted azide derivatives of formula (I) and / or the reaction of azide derivative of formula (I) with a polymer or polymer blend. Such free compounds may be: - Free amines containing the heteroaromatic group Ar, such as primary amines of the formula NH2Ar. - Formula NHAr-[N(Ar)] x -NHAr polyazine, wherein x is from 0 to 10, preferably an integer of 0 or 1, - Formula NHAr-[N(Ar)] x -NAr· polyazine, wherein x is 0 to 10, preferably an integer of 0 or 1, or - Derivatives of the formula (Ar)N=N(Ar).

[0139] Therefore, polymer compositions obtained by the methods of this invention can be recycled under future processing conditions. Processing conditions are those commonly used for processing thermoplastics, including but not limited to extrusion, reactive extrusion, injection molding, thermoforming, blow molding, fiber spinning, powder coating, rotational molding, reactive processing, and compression molding. Recycling, as used herein, includes, but is not limited to, shaping the polymer composition into a novel form, adding additives and charges to recycled materials, and adding virgin polymers to recycled materials.

[0140] In some embodiments, the polymer composition can be recovered by performing reactive extrusion followed by compression molding. In other embodiments, the polymer composition can be recovered by performing compression molding without reactive extrusion.

[0141] Uses of azide derivatives of formula (I) The present invention also relates to the use of azide derivatives of formula (I) as described in this disclosure as additives for upgrading recycled plastics or mixtures of plastics (particularly waste plastics or mixtures of waste plastics, such as unsorted plastics, broken plastics, mixtures of broken plastics, or mixtures thereof). Preferably, the azide derivative is insoluble in the plastic or mixture of plastics to which the azide derivative is added, particularly waste plastics or mixtures of waste plastics, such as unsorted plastics, broken plastics, mixtures of broken plastics, or mixtures thereof.

[0142] Therefore, according to the present invention, a method for upgrading recycled plastics or mixtures of plastics (particularly waste plastics or mixtures of waste plastics, such as unsorted plastics, broken plastics, mixtures of broken plastics, or mixtures thereof) is provided, the method comprising the following steps: (i) A source of mixed plastics or mixtures of plastics (particularly waste plastics or mixtures of waste plastics, such as unsorted plastics, broken plastics, mixtures of broken plastics, or mixtures thereof) and an azide derivative of formula (I) as an additive: N3-Ar(I) Ar is a heteroaromatic group as defined in this disclosure. (ii) Heat the mixture from step (i) to temperature T. R , Where T R The glass transition temperature or melting temperature of the plastic used in step (i) is higher than that of the highest glass transition temperature or melting temperature of all plastics present in the mixture at a content of at least 8% by weight relative to the total weight of the mixture, and is equal to or higher than the decomposition of the azide derivative of formula (I).

[0143] The source of the azide derivative of formula (I) can be the azide derivative of formula (I) itself and / or a polymer composition obtained by the method of the present invention as defined herein, particularly a non-crosslinked or weakly crosslinked polymer composition as defined above. It should be understood that the non-crosslinked polymer comprises a polymer chain grafted with residues of the azide derivative of formula (I), particularly groups of formula (II) and / or formula (III): (II) (III) in The bonds between groups (II) and / or (III) and the carbon atoms of the repeating units of the polymer of the composition. x and y are each independent integers ranging from 0 to 10, preferably 0 or 1. Ar is defined as the azide derivative of formula (I) used in the method described above, and * represents H.

[0144] Sources of azides of formula (I) in the form of non-crosslinked polymer compositions as defined above are particularly helpful in facilitating the storage, handling, and dispersion of additives in plastics, especially in large quantities of the azide derivatives.

[0145] Preferably, the mixing in step (i) is carried out at a temperature T. 混合 The following is achieved, the temperature T 混合 The glass transition temperature or melting temperature of the plastic used in step (i) is higher than that of the highest glass transition temperature or melting temperature of all plastics present in the mixture at a content of at least 8% by weight relative to the total weight of the blend. Below temperature T R .

[0146] Specifically, step (i) includes the following consecutive sub-steps: (i-1) Provide plastics or mixtures of plastics, particularly waste plastics or mixtures of waste plastics, such as unsorted plastics, broken plastics, mixtures of broken plastics, or mixtures thereof. (i-2) provides a source for the azide derivative of formula (I), (i-3) At the processing temperature T specified above混合 The plastic or mixture of plastics from step (i-1) is mixed with the azide derivative of formula (I) from step (i-2).

[0147] Uses of the polymer compositions of the present invention The present invention also relates to materials obtained from polymer compositions obtained by the methods of the present invention (particularly polymer compositions of the present invention as described above). Preferably, the polymer composition from which the material is obtained comprises a high proportion of crosslinked polymers or blends of crosslinked polymers, the insoluble fraction of which generally exceeds 10% by weight of the total weight of all polymers present in the composition, preferably exceeding 25% by weight, more preferably exceeding 40% by weight.

[0148] Another object of the present invention is a method for preparing such a material according to the present invention, the method comprising the following steps: - Prepare a polymer composition according to the method described above, and - The resulting polymer composition is then shaped.

[0149] Molding also includes compounding the polymer composition in granular or powder form, for example, when preparing a finished product. Molding can also be carried out by methods known to those skilled in the art of molding thermoplastic or thermosetting polymers. In particular, methods such as molding, compression molding, injection molding, extrusion molding, and thermoforming may be mentioned. The material will typically be in granular or powder form before being presented in the form of a finished product.

[0150] Advantageously, in the method for preparing the material according to the invention, the preparation step and the forming step can be performed simultaneously.

[0151] The present invention also relates to a formulation comprising a polymer composition obtained by the method of the present invention (particularly the polymer composition of the present invention as described above).

[0152] The present invention also relates to the use of the non-crosslinked polymers or polymer blends of the present invention as compatibilizers.

[0153] Compatibilizers typically reduce the surface tension between incompatible domains in two separated phases (especially between incompatible polymers). This usually leads to an increase in the interfacial area between the incompatible polymers. Compatibilizers function by forming chemical bonds (e.g., N-N bonds) and / or physical bonds between the two polymer phases, thereby facilitating stress transfer at the interface.

[0154] method Determination of the solubility of azide derivatives The solubility of the azide derivative of formula (I) in the mixture of step (a) can be determined by transmission electron microscopy (TEM) performed at room temperature (18°C-22°C), where when the azide derivative is added to the mixture of step (a), visible phase separation can be observed (meaning that the azide is insoluble or partially soluble) or a homogeneous phase without separation can be observed (meaning that the azide derivative is soluble in the mixture of step (a)).

[0155] Alternatively, the solubility of the azide derivative can be estimated based on a solubility theory model. This model implies selecting a model solvent with polarity similar to the polymer or polymer blend provided in step a). The model solvent is then saturated with the azide derivative of interest. Excess azide derivative is removed by filtration, and the solubility is determined by quantitative FITR spectroscopy and / or UV-Vis spectroscopy and / or [other methods] at room temperature (18°C–22°C). 1 H NMR spectroscopy was used to assess the concentration of azide derivatives.

[0156] Determination of the half-life of azide derivatives of formula (I) This can be measured by DSC and analyzed using the Borchardt-Daniels method (BD method; see Swarin, SJ; Wims, AM). Analytical Calorimetry middle ; Porter, RS, Johnson, JF,Eds.; Springer: Boston, MA, 1977; Vol. 4; and ASTM International. Standard Test Method for Estimating Kinetic Parameters by Differential Scanning Calorimeter Using the Borchardt and Daniels Method; ASTM E2041-13. West Conshohocken, PA, 2018. DOI: 10.1520 / E2041-13R18) to determine the half-life of azide derivatives of formula (I). This method can be applied to pure azide derivatives and mixtures of the derivatives from step (a).

[0157] This method assumes Arrhenius kinetics and is able to determine the rate constant ( k ),activation energy( Ea ) and pre-exponential factors ( A Then it can be used to calculate the half-life of azide triazine at a specific temperature.

[0158] For reactions following n-order Arrhenius kinetics, the BD method assumes a general rate equation of the form of Equation 1, where α To convert fractions, k(T) As temperatureT The rate constant of change, n This represents the reaction order. Replace it with the Arrhenius equation (Equation 2; R is the universal gas constant). k(T) After rearranging and applying logarithms, the resulting expression (Equation 3) has the general form. z = a + bx + cy This can be solved using multiple linear regression. Based on data from DSC experiments, the terminology can be analyzed. , ln(1-α) is defined numerically.

[0159] n (1) k(T) =A (2) (3) Therefore, after the DSC measurement, a BD analysis was performed using the change in enthalpy integral over time with respect to the DSC data. The conversion fraction over time was calculated by dividing the value of the integral by the total enthalpy of the transformation. α To avoid erroneous edge effects, the BD method typically only considers the transformation evolution between 10% and 90%. The derivative can be calculated using appropriate software. The value of . Considering these factors, we can limit . , And ln(1-α).

[0160] Then, the predetermined temperature is calculated using the average kinetic parameters. T R Half-life under () t 1 / 2 ), or use Equation 4: (4) For an azide derivative, the kinetic parameters, temperature TR, and half-life value depend on the characteristics of the mixture in which the azide derivative is present, i.e., on the polymer or polymer blend provided in step (a).

[0161] Determination of the decomposition temperature of the azide derivatives of formula (I) The decomposition temperature of the azide derivative of formula (I) in the mixture of step (a) can be determined by thermogravimetric analysis (TGA). In practice, the decomposition temperature is found in the mixture subjected to TGA running at the intersection of a straight line tangent to the TGA curve before the decomposition reaction and a straight line tangent to the TGA curve at the inflection point of the transition, wherein the mixture subjected to TGA running comprises a polymer or polymer blend in which the azide derivative of formula (I) is dispersed, as defined in step (a) of the method of the present invention. This measurement can be performed on pure azide derivative of formula (I).

[0162] An alternative method for determining the decomposition temperature is the onset temperature of decomposition exothermic reaction, as detected in high-pressure DSC experiments. In DSC runs, this temperature corresponds to the intersection of the straight line tangent to the curve at the inflection point and the baseline. This method is applicable to azide derivatives themselves and azide derivatives dispersed in polymers or polymer blends.

[0163] The present invention is illustrated by the following embodiments, but is not limited to the following embodiments.

[0164] Nuclear magnetic resonance (NMR) spectroscopy At 24°C, Bruker Avance-400 and Bruker Avance-Neo 500 spectrometers were used at 400 MHz and 500 MHz, respectively, to obtain... 1 ¹H NMR spectra. Recorded at 100 MHz using a Bruker Avance-400 spectrometer at 24 °C. 13 C10 NMR spectra. Recorded at 50 MHz using a Bruker Avance-Neo 500 spectrometer at 24 °C. 15 NNMR spectrum.

[0165] 1 The residual hydrogen signal from the H NMR spectrum reference deuterated solvent: 7.26 (CDCl3) and 2.50 (DMSO-d6). 13 C NMR spectroscopy reference to residual carbon signal in deuterated solvent: 77.16 (CDCl3) and 39.50 (DMSO-d6).

[0166] Fourier transform infrared (FTIR) spectroscopy FTIR spectra were acquired using a Bruker Tensor 37 spectrometer in attenuated total reflection (ATR) mode.

[0167] Raman spectroscopy Fourier transform Raman spectroscopy was performed using near-infrared excitation at 1064 nm provided by an Nd-YAG laser diode coupled to an RFS 100 / S FT Raman spectrometer based on a Michelson-type interferometer. It was equipped with a liquid nitrogen-cooled Ge detector. The spectrometer was coupled to a macroscopic Ramanscope III (Bruker Optics). All materials were recorded using a macroscopic interface with a 90° condenser lens (which allows objects to be placed on a horizontal surface). The sample was placed on a gold mirror to enhance the intensity of the collected Raman signal. The image was viewed at 4 cm⁻¹. -1 Resolution at 3500 cm -1 and 50 cm -1 The spectra were recorded. To optimize the signal-to-noise ratio, the laser power and the number of scans needed to be adjusted for different types of samples. In all cases, the spot size was approximately 100 μm.

[0168] Gas chromatography coupled with mass spectrometry (GC-MS) GC-MS with electron collision (EI) analysis was performed using Shimadzu GCMS-QP 2010s (70 eV) in ethyl acetate, diethyl ether, or tetrahydrofuran.

[0169] High-resolution mass spectrometry (HRMS) HRMS was performed on an ESI-LTQ Orbitrap XL FTMS (Thermo Fischer Scientific). Samples were prepared in acetonitrile. Full scans were performed between 150 m / z and 2000 m / z in positive polarity mode.

[0170] Electron paramagnetic resonance (EPR) EPR spectra were acquired using a JEOL FA300 computerized spectrometer equipped with a microwave source, operating at approximately 9.3 GHz (X-band) and 100 kHz field modulation. Different modulation widths, amplification factors, and microwave powers were used depending on the signal width and amplitude.

[0171] Full-range spectrum: The modulation width is between 0.1 mT and 1.0 mT, the amplification factor is between 10 and 1600, and the microwave power is 2.000 mW.

[0172] Magnified spectrum: The modulation width is between 0.1 mT and 0.2 mT, the amplification factor is between 100 and 1000, and the microwave power is 0.125 mW.

[0173] The sample was introduced into a transparent quartz tube in a solid state. The g-factor was calibrated using a manganese oxide label. For comparison purposes, the signal intensity was normalized by the mass of the triazine unit Tr in the sample (if applicable, calculated from the total mass in the introduction tube and the weight fraction of Tr in the sample), modulation width, amplification factor, and the square root of the microwave power.

[0174] Differential scanning calorimetry (DSC) DSC analysis was performed using a TA Instruments Discovery 250 DSC equipped with an autosampler and liquid nitrogen cooling system. Samples were loaded into sealed disposable aluminum trays. The temperature program consisted of a heating homogenization at +10 °C / min from 0 °C to 250 °C, a cooling homogenization at -10 °C / min from 250 °C to 0 °C, and a second heating homogenization at +10 °C / min from 0 °C to 250 °C. The measured heat flux was normalized by the sample mass. The reported melting temperature (T0) is... m ) and enthalpy of fusion (ΔH) m The crystallinity (χ) was determined from the homogenization during the second heating, and the homogenization during the second heating was corrected for the weight fraction of the polymer in the sample. The reported crystallinity (χ) was calculated by dividing the corrected enthalpy of fusion by the specific enthalpy of fusion of the corresponding polymer (8.06 kJ / mol for polyethylene and 8.75 kJ / mol for polypropylene, Polymer Handbook 1999).

[0175] High-pressure differential scanning calorimetry (DSC) High-pressure DSC analysis was performed using a TA Instruments Discovery 250 DSC equipped with a liquid nitrogen cooling system. The sample was loaded into a reusable, sealed, gold-plated tray. Different temperature programs were used depending on the type of analysis. Thermal decomposition of azide triazine in bulk (full range): Heating uniformly from 0℃ to 320℃ at a rate of +10℃ / min Thermal decomposition of azide triazine in bulk (for calculation): Uniform heating from 30℃ to 120℃ at +10℃ / min, uniform cooling from 120℃ to 0℃ at -10℃, constant temperature for 10 min, and uniform heating from 0℃ to 320℃ at +10℃ / min. Thermal decomposition of azide triazine in polymer matrices (full range): Uniform heating from 0℃ to 320℃ at a rate of +10℃ / min, uniform cooling from 320℃ to 0℃ at a rate of -10℃, and uniform heating from 0℃ to 320℃ at a rate of +10℃ / min. Thermal decomposition of azide triazine in the polymer matrix (for calculation): Heating uniformly from 0℃ to 320℃ at a rate of +10℃ / min The measured heat flux was normalized by the mass of the sample. The enthalpy of fusion and the enthalpy of decomposition were corrected for the weight fraction of azide triazine in the sample (if applicable). The reported temperature and enthalpy values ​​are the average of three measurements.

[0176] Thermogravimetric analysis (TGA) TGA was performed using a Netzsch TG 209 F1 Libra under a nitrogen atmosphere. The temperature program consisted of heating from 30°C to 600°C at a rate of 10°C / min. The sample was loaded into a disposable aluminum tray.

[0177] Size exclusion chromatography (SEC) SEC was performed on a Viscotek GPCmax / VE2001 from Malvern connected to a triple detection array (TDA 305). Samples were prepared and analyzed in tetrahydrofuran.

[0178] High-temperature SEC of polypropylene samples in 1,2-dichlorobenzene was performed using a Freeslate Rapid-GPC apparatus equipped with a PolymerChar IR4 infrared detector. Molecular weight distribution parameters were determined based on universal polystyrene calibration. The reported values ​​of Mn, Mw, and PDI are averages of two measurements.

[0179] Reactive extrusion In the embodiments, the modification of high molecular weight polymers with Tr-N3 was carried out using a DSM Xplore batch twin-screw extruder with a barrel capacity of 5 cc or 15 cc. The system is equipped with a co-rotating conical screw profile and a recirculation channel that allows for controlled residence time. Unless otherwise stated, modification was carried out at a screw speed of 100 rpm under a nitrogen flow.

[0180] Compression molding In the example, after reactive extrusion, the high molecular weight polymer sample was reshaped by compression molding at 180°C for 20 min under a normal force equivalent to 3 tons.

[0181] Separation of the soluble and gel portions of cross-linked polymer samples Unless otherwise stated, in these examples, the high molecular weight polymer samples were separated from the gel fraction after compression molding. Polyolefin-based samples (PE, PP, and blends) were introduced into glass vials at a concentration of approximately 15 mg / mL in xylene. The medium was heated at 130°C for 15 h. The gel fraction (individual solid masses) was then manually separated from the soluble fraction and dried overnight under reduced pressure at 90°C. The remaining soluble fraction was concentrated and dried overnight under reduced pressure at 90°C. The gel fraction was calculated by dividing the mass of the dried insoluble fraction by the initial mass of the sample. The reported gel fraction values ​​are the average of three independent measurements.

[0182] Dynamic Mechanical Analysis (DMA) DMA was performed on a TA Instruments Q800 analyzer in tension mode from 30°C to 250°C at a heating rate of 3°C / min, 1% strain amplitude, and a fixed frequency of 1 Hz. The samples were formed into rectangular rods (30 mm × 5 mm × 1.5 mm) by compression molding.

[0183] Tensile test Tensile stress-strain tests were performed at room temperature at a rate of 10 mm / min on the Instron Universal testing system. For reproducibility, at least five specimens of each sample were tested. For each specimen, Young's modulus was calculated in the linear domain. Dog-bone shaped specimens (ISO 527-2 type 5B) were prepared by compression molding. The reported values ​​are averages of different measurements.

[0184] Rheological measurement Rheological properties were measured using an Anton Paar MCR501 rotational rheometer equipped with a 25 mm parallel plate geometry. The upper and lower geometries were a stainless steel plate and a scrap aluminum plate, respectively. The geometries were enclosed in a convection oven with a nitrogen flow rate of 200 L / h. The oven temperature was controlled to an accuracy of ±0.5 °C.

[0185] Amplitude scan: The applied angular frequency is 1 rad / s, the temperature is 180℃, and the shear strain range is 10. -2 % to 10 3 % Frequency scan: The applied shear strain was 1%, the temperature was 180℃, and the angular frequency range was 10. -2 rad / s to 10 2 rad / s Creep:Apply a continuous shear stress of 1 kPa (or 5 kPa) for 30 min (or 3 h), followed by recovery at 180°C under zero shear stress for 30 min (or 3 h). For all measurements, a normal force of 10 N is applied to the cross-linked sample, or a normal force of 0.1 N is applied to the non-cross-linked sample.

[0186] Rheological samples (disc-shaped, 25 mm in diameter and 1.5 mm thick) were prepared by compression molding.

[0187] Transmission electron microscopy (TEM) The compressed samples were cut into ultrathin sections (60-70 nm) using a Leica Ultracut UCT cryostat equipped with an EM FCS cryostat block and a 35° diamond blade at -30°C. The sections were then stained with RuO4 vapor from a freshly prepared RuO4 aqueous solution (20 mg of ruthenium chloride dissolved in 1 mL of 13% sodium hypochlorite aqueous solution) for 30-45 seconds. The samples were imaged using a JEOL 1011 transmission electron microscope (3 Å resolution) equipped with a tungsten thermal ionizer (100 kV) and a Gatan Orius 4k camera.

[0188] Masterbatch preparation In the embodiments of the invention described below, azidotriazine 1 is provided as a masterbatch for grafting reactions. The masterbatch is a mixture of 40% by weight of azidotriazine prepared by solvent mixing and a portion of the polymer or polymer blend used in the embodiments, thereby promoting the dissolution of azidotriazine in laboratory equipment, maximizing the conservation of azidotriazine content and ensuring the safest conditions.

[0189] Density functional theory calculations The computation was performed using the ORCA 5.0.4 package (Neese, F. "The ORCA program system"). Wiley Interdisciplinary Reviews: Computational Molecular Science, (2012, Vol. 2, No. 1, pp. 73-78). Geometry optimization, harmonic vibrational frequencies, infrared intensity, and Raman activity were calculated using the B97-3c generalized gradient approximation (GGA) functional and polarization valence state-triple-ζ basis set mTZP analysis (Brandenburg, JG; Bannwarth, C.; Hansen, A.; Grimme, S. B97-3c: A revised low-cost variant of the B97-D density functional method). J. Chem. Phys. 2018,148 (No. 064104). Raman spectra were plotted without any frequency scaling. Attached Figure Description

[0190] Figure 1 Examples of nitrogen-nitrogen exchange reactions, nitrogen-nitrogen / amino radical exchange, and recombination of amino radicals.

[0191] Figure 2 High-pressure DSC (downward exothermic) and TGA monitoring (under N2) of the decomposition of various azide triazines.

[0192] Figure 3 : Bulk decomposition of 6-azido- N 2 , N 4 -dimethyl- N 2 , N 4 Size exclusion chromatography (SEC) analysis of diphenyl-1,3,5-triazine-2,4-diamine (black curve; structure 1 shown in Scheme 1, also known as azotriazine 1) and the true standard of the corresponding aminotriazine (grey curve; structure 1' shown in Scheme 16).

[0193] Figure 4 Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis of the bulk decomposition products of azidotriazine 1.

[0194] Figure 5 The decomposition of azidotriazine 1 in HDPE (5 mol%) was followed by TGA (grey curve). The observed 5.1% mass loss was compared with the theoretical 3.1% mass loss from nitrogen release during the decomposition of azidotriazine 1. DSC (black curve) for this sample is also provided.

[0195] Figure 6 The decomposition of azidotriazine 1, followed by TGA.

[0196] Figure 7 The decomposition of azidotriazine 1 in HDPE was monitored by DSC at a loading of 5 mol% (37 wt%). 8.1 mg of the sample was heated from 50 °C to 320 °C at a rate of 10 °C / min in a high-pressure DSC sample cell. The green curve represents the run integral of the decomposition exothermic reaction.

[0197] Figure 8A) Normalized Raman spectra of grafted paraffin (5 mol%), unmodified paraffin, and the model dimer structure (1064 nm laser source), and calculated Raman spectra of the model dimer using density functional theory (DFT). B) Chemical structure of the model dimer. C) Peak assignment of diagnostic bands based on DFT calculations. Figure 9 Electron paramagnetic resonance (EPR) spectra of paraffin grafted with 5 mol% azidotriazine 1. On the left, spectra were obtained at ambient temperature in the solid state (black) or at 77 K in chloroform (gray). On the right, the same sample was precipitated twice in acetone before analysis by EPR spectroscopy in the solid state at ambient temperature.

[0198] Figure 10 : Performed on paraffin products grafted with azide triazine 1 1 H- 1 H-correlation spectroscopy (COSY). Two prominent signals correspond to the correlation between the methylene proton f of paraffin and the adjacent methylene proton δ' of the paraffin skeleton (1) and the correlation between the methylene proton f of paraffin and the NH proton e on the triazine graft (2).

[0199] Figure 11 A) A heating process used to prepare a modified polymer having a matrix. B) Reactive extrusion of HDPE with 1 mol% of azidotriazine to produce HDPE. m The torque curve.

[0200] Figure 12 A) A heating procedure for preparing modified polymers with two matrices. B) Reactive extrusion of HDPE and PP (70:30 weight ratio) with 1 mol% azidotriazine to produce (HDPE-PP). m The torque curve.

[0201] Figure 13 Raw HDPE (black) and HDPE m (Gray) Raman spectrum (1064 nm laser source).

[0202] Figure 14 Original HDPE and HDPE m The DMA curve (top) is compared with the DMA curve (bottom) of PE modified with 0.05 mol%, 0.1 mol%, 0.5 mol% or 1.0 mol% azidotriazine 1.

[0203] Figure 15 : Raw HDPE (top) and HDPE modified with 1 mol% azidotriazine at 180 °C m(Below) Creep and recovery experiments.

[0204] Figure 16 DMA curves of the original HDPE-PP blend (70:30 weight ratio) and (HDPE-PP) m Comparison of DMA curves.

[0205] Figure 17 Creep and recovery experiments of original HDPE and PP blends at 180°C (top) and creep and recovery experiments of HDPE and PP blends modified with 1 mol% azidotriazine 1 (bottom).

[0206] Figure 18 : Raw PE, raw PP, raw PE-PP blend (70:30), HDPE with 1 mol% azidotriazine 1 m HDPE-PP modified with 0.1 mol% or 1 mol% azidotriazine 1 m (70:30), and HDPE m and PP m Representative stress-strain curves of the blends (each was grafted with 1 mol% of azidotriazine 1 before blending).

[0207] Figure 19 HDPE processed at 180℃ m (Above) and (HDPE-PP) m (Below) Strain scanning experiments. Both samples were modified with 1 mol% of azidotriazine 1.

[0208] Figure 20 Used for HDPE m (Left) and (HDPE-PP) m (Right) Schematic diagram of the scheme for conducting the recycling experiment.

[0209] Figure 21 HDPE after each recycling cycle m (Above) and (HDPE-PP) m (Below) DMA.

[0210] Figure 22 HDPE m An overview of the tensile properties during the four reprocessing cycles.

[0211] Figure 23 (HDPE-PP) m An overview of the tensile properties during the four reprocessing cycles.

[0212] Figure 24HDPE modified with 1 mol% azidotriazine 1 after 4 reprocessing cycles m (Left) and (HDPE-PP) m (Right) Creep experiment.

[0213] Figure 25 EPR spectra of PE modified with 1 mol% azidotriazine 1 after direct extrusion (samples marked with X) or after compression molding (samples marked with CS).

[0214] Figure 26 A) Raw PE, B) Blend of HDPE and 1 mol% of azidotriazine 1, C) HDPE m D) Original HDPE-PP blend and E) (HDPE-PP) m TEM micrographs.

[0215] Figure 27 Grafting with azidotriazine 1 and 15 EPR spectrum of oligomeric PS of N-labeled azide triazine 1.

[0216] Figure 28 Modified complete blend (HDPE-LDPE-PP-PETg-PS) m DMA of the corresponding control blends of the original polymer.

[0217] Figure 29 Modified complete blend (HDPE-LDPE-PP-PETg-PS) m Stress-strain curves (obtained at ambient temperature) for the corresponding control blend of the original polymer (top) and (bottom).

[0218] Figure 30 HDPE was reactively extruded with 1 mol% AT-Ph (left) and AT-NBu2 (right) to produce HDPE, respectively. AT-Ph and HDPE AT-NBu The torque curve.

[0219] Figure 31 The modified HDPE depends on the DMA curve of the azidotriazine used for reactive extrusion.

[0220] Figure 32 : Left: HDPE AT-Ph DMA curves for materials recycled through extrusion and compression molding, or materials recycled through compression molding only. Right: HDPE AT-PhEngineering stress-strain curves (20°C, 10 mm / min) for materials recovered through extrusion and compression molding or materials recovered through compression molding only. The curves shown are the closest average values.

[0221] Figure 33 HDPE m DMA curves of Sample 1 and Sample 2 in Example 8.

[0222] Figure 34: A) Reactive extrusion of HDPE with 1 mol% of azidodiazine AD-Ph to produce HDPE AD-Ph Torque curve. B) HDPE AD-Ph The DMA curve. Detailed Implementation

[0223] Example Material All chemicals and reagents were purchased from Merck (Sigma-Aldrich). 15 N-labeled reagents were purchased from Eurisotop. All solvents were purchased from Carlo Erba.

[0224] Unless otherwise specified, all reagents and solvents shall be used without further purification.

[0225] High-density polyethylene (PE, Hostalen 4131B) has a melt flow index (MFI) of 2.2 g / 10 min at 190°C and a density of 0.94 g / cm³ at 5 kg weight. 3 Both the isotactic polypropylene (PP, Moplen HF 501N, with a melt flow index (MFI) of 10 g / 10 min at 2.16 kg weight and 230 °C) were purchased from Albis Plastique France.

[0226] Post-consumer polyethylene and polypropylene samples were derived from household laundry detergent bottles.

[0227] Example 1. Synthesis of azide-substituted heteroaromatic derivatives according to the present invention 1.1 Di(N-methylaniline)azidotriazine 1(6-azido- N2 , N4 -dimethyl- N2 , N4 -diphenyl-1,3, Synthesis and characterization of 5-triazine-2,4-diamine or "azidotriazine 1" Scheme 1 describes the synthesis of azide-1,3,5-triazine (1). The synthesis consists of two steps, both of which are safely carried out on a gram scale. Scheme 1: Synthesis of azidotriazine 1 Synthesis of bis(N-methylaniline)chloro-triazine Cyanurium chloride (9.900 g, 53.68 mmol, 1.00 equivalent) was dissolved in 100 mL of THF (distilled using CaH2) and cooled to 0 °C. DIPEA (6.938 g, 53.68 mmol, 1.00 equivalent) followed by N-methylaniline (5.752 g, 53.68 mmol, 1.00 equivalent) was added dropwise, and the mixture was stirred at 0 °C for 1.5 h. DIPEA (6.938 g, 53.68 mmol, 1.00 equivalent) followed by N-methylaniline (6.040 g, 56.36 mmol, 1.05 equivalent) was added dropwise, and the mixture was stirred at 0 °C for 15 min, then further stirred at 30 °C for 18 h. THF was removed under reduced pressure. 100 mL of distilled water was added, and the mixture was extracted with 4 × 100 mL of ethyl acetate. The organic phase was washed with 5 × 100 mL of 0.05 M HCl aqueous solution, 1 × 100 mL of saturated NaHCO3 aqueous solution, and 1 × 100 mL of brine, dried over MgSO4, and concentrated under reduced pressure to give a pale yellow solid, di(N-methylaniline)chloro-triazine (16.613 g, 50.99 mmol, ). Yield was 95%. Purity: 98.5%-94.3% by weight; impurities: ethyl acetate.

[0228] 1 H NMR (DMSO-d6 400 MHz) δppm: 7.7-7.0 (br m, 10H), 3.39 (br s, 6H) 13 C-{1H} NMR (DMSO-d6 100 MHz) δppm: 168.35, 164.42, 143.20, 128.71, 126.41, 126.23, 37.79 GC / MS (EI): Retention time 9.02 sm / z, molecular peak at 325 (+chlorine isotope) (expected: 325.11) Synthesis of bis(N-methylaniline)azido-triazine (1) Di(N-methylaniline)chlorotriazine (16.613 g, 50.99 mmol, 1.00 equivalent) was dissolved in 30 mL of anhydrous water. NSodium azide (6.630 g, 101.98 mmol, 2.00 equivalent) was slowly added to 100 °C and the mixture was stirred for 66 h. 400 mL of distilled water was added and the mixture was extracted with 3 × 200 mL of diethyl ether. The organic phase was washed with 5 × 200 mL of brine, dried over MgSO4, and concentrated to three aliquots under reduced pressure. The obtained product was dissolved in a 50:50 volume mixture of hexane and ethyl acetate in 150 mL and passed through a double layer of silica and basic alumina. After concentration and drying under reduced pressure, a grayish-white solid di(N-methylaniline)azido-triazine (1) (12.206 g, 36.72 mmol, ...) was obtained. Yield was 72%. Purity: 99.5%-98.2 mol%, impurities: ethyl acetate, hexane.

[0229] 1 H NMR (DMSO-d6 400 MHz) δppm: 7.7-7.0 (br m, 10H), 3.37 (br s, 6H) 13 C-{1H} NMR (DMSO-d6 100 MHz) δppm: 167.97, 165.05, 143.47, 128.45, 126.35, 125.82, 37.39 FTIR (ATR): 2125 cm -1 (N3) TLC (silica, ethyl acetate / hexane 50:50, volume): Rf = 0.5 1.2 6-Azide-N 2 N 2 N 4 N 4 -Tetrabutyl-1,3,5-triazine-2,4-diamine or "azidotriazine AT- Synthesis and characterization of “NBu2” N 2 N 2 N 4 N 4 Synthesis of tetrabutyl-6-chloro-1,3,5-triazine-2,4-diamine (intermediate A) (A) Option 2: N 2 N 2 N 4 N 4 Synthesis of tetrabutyl-6-chloro-1,3,5-triazine-2,4-diamine (intermediate A) Cyanuronic acid (10.0 g, 53.7 mmol) was dissolved in 100 mL of THF in a round-bottom flask and cooled in an ice bath. Dipinea (7.02 g, 53.7 mmol, 1.00 equivalent) and di-n-butylamine (6.98 g, 53.7 mmol, 1.00 equivalent) were added dropwise, and the mixture was stirred for 30 min. Then, additional Dipinea (7.02 g, 53.7 mmol, 1.00 equivalent) and di-n-butylamine (6.98 g, 53.7 mmol, 1.00 equivalent) were added dropwise, the medium was heated to 30 °C, and the mixture was allowed to stand with stirring for 18 h. THF was removed under reduced pressure. 200 mL of distilled water was added, and the mixture was extracted with 3 × 100 mL of ethyl acetate. The organic phase was washed with 5 × 100 mL of 0.05 M HCl aqueous solution, 2 × 100 mL of saturated NaHCO3 aqueous solution, and 1 × 100 mL of brine. The product was dried over MgSO4 under reduced pressure to obtain a pale yellow viscous liquid product (18.6 g, 50.2 mmol, 94% separation yield).

[0230] 1 H NMR (CDCl3, 400 MHz) δppm: 3.49-3.43 (m, 8H), 1.55 (m, 8H), 1.31 (m, 8H), 0.93 (t, 12H).

[0231] 13 C NMR (CDCl3, 400 MHz) δ ppm: 168.9, 164.5, 47.4, 30.5, 20.2, 14.0.

[0232] 6-Azide-N 2 N 2 N 4 N 4 Synthesis of Tetrabutyl-1,3,5-triazine-2,4-diamine (AT-NBu2) Option 3: 6-azido-N 2 N 2 N 4 N 4 Synthesis of Tetrabutyl-1,3,5-triazine-2,4-diamine (AT-NBu2) Intermediate A (15.0 g, 40.2 mmol) was dissolved in 30 mL of N-methylpyrrolidine in a round-bottom flask. Sodium azide (5.25 g, 80.4 mmol, 2.00 equivalent) was slowly added, and the mixture was stirred at 100 °C for 66 h. The reaction was cooled at room temperature and poured into 300 mL of distilled water. The mixture was extracted with 3 × 200 mL of Et₂O. The organic phase was washed with 5 × 200 mL of brine, dried over MgSO₄ under reduced pressure, and then further dried overnight under reduced pressure at 50 °C to obtain a pale yellow viscous liquid AT-NBu₂ (14.5 g, 3.86 mmol, 96% separation yield).

[0233] 1 H NMR (CDCl3, 400 MHz) δppm: 3.48-3.46 (m, 8H), 1.55 (m, 8H), 1.31 (m, 8H), 0.93 (t, 12H).

[0234] 13 C NMR (CDCl3, 400 MHz) δ ppm: 168.1, 165.1, 47.4, 30.5, 20.2, 14.0.

[0235] 1.3 Synthesis of 2-azido-4,6-diphenyl-1,3,5-triazine or "azidotriazine AT-Ph" Scheme 4: Synthesis of 2-azido-4,6-diphenyl-1,3,5-triazine AT-Ph 2-Chloro-4,6-diphenyl-1,3,5-triazine (10.0 g, 36.6 mmol) was dissolved in 30 mL of N-methylpyrrolidine in a round-bottom flask. Sodium azide (0.24 g, 36.7 mmol, 1.1 equivalents) was slowly added, and the mixture was stirred at room temperature for 2 h. The mixture was then poured into 300 mL of distilled water. The mixture was extracted with 3 × 400 mL of Et₂O. The organic phase was washed with 5 × 300 mL of brine, dried over MgSO₄ under reduced pressure, and then further dried overnight under reduced pressure at 50 °C to give a white solid AT-Ph (14.5 g, 3.86 mmol, 96% separation yield).

[0236] 1 H NMR (CDCl3, 400 MHz) ppm: 7.53 (t, 4H), 7.61 (tt, 2H), 1.31 (d, 4H).

[0237] 13C NMR (CDCl3, 400 MHz) ppm: 128.7, 129.2, 133.2, 135.0, 170.4, 173.1.

[0238] 1.4 Synthesis of 2-azido-4,6-diphenyl-1,3-diazine or "azido-diazine AD-Ph" Scheme 5: Synthesis of 2-azido-4,6-diphenyl-1,3-diazine or azido-diazine AD-Ph 2-Chloro-4,6-diphenyl-1,3-diazine (0.5 g, 1.84 mmol) was dissolved in 30 mL of NMP in a round-bottom flask. Sodium azide (0.24 g, 3.67 mmol, 2 equivalents) was slowly added, and the mixture was stirred at 80 °C for 16 h. The mixture was then poured into 30 mL of distilled water. The mixture was extracted with 3 × 40 mL of Et₂O. The organic phase was washed with 5 × 30 mL of brine, dried over MgSO₄ under reduced pressure, and then further dried overnight at 80 °C under reduced pressure to give a white solid (0.271 g, 0.993 mmol, 54% separation yield).

[0239] 1 H NMR (DMSO-d6, 400 MHz) ppm: 8.46 (dd, 2H, tetrazolium), 8.37 (s, 2.5H, azido), 8.35 (s, 1H, tetrazolium), 8.32 (m, 12.4H, azido / tetrazolium), 7.76-7.5 (m, 22.9H, azido / tetrazolium).

[0240] 13 C NMR (DMSO-d6, 400 MHz) ppm: 166.6 (azido), 164.8 (tetrazozo), 162.1 (azido), 156.3 (tetrazozo), 146.5 (tetrazozo), 136.0 (azido), 132.8 (tetrazozo), 132.1 (azido), 129.6 (tetrazozo), 129.4 (azido), 129.3 (tetrazozo), 128.9 (tetrazozo), 127.9 (azido), 109.1 (azido, tetrazozo).

[0241] 1.5 Synthesis of other triazines 1.5.1 Synthesis of Precursors a) Monosubstituted triazine Tr-Cl2 Scheme 6: Synthesis of Tr-Cl2 4,6-Dichloro-N-methyl-N-phenyl-1,3,5-triazine-2-amine Tr-Cl2 Cyanurium chloride (9.900 g, 53.68 mmol, 1.00 equivalent) was dissolved in 100 mL of THF and cooled to 0 °C. DIPEA (6.938 g, 53.68 mmol, 1.00 equivalent) was added dropwise at 0 °C, followed by N-methylaniline (5.752 g, 53.68 mmol, 1.00 equivalent), and the mixture was stirred at 0 °C for 3 h. THF was removed under reduced pressure, 80 mL of distilled water was added, and the aqueous phase was extracted with 3 × 50 mL of ethyl acetate. The organic phase was washed with 1 × 50 mL of 0.05 M HCl aqueous solution, 1 × 50 mL of saturated NaHCO3 aqueous solution, and 1 × 50 mL of brine, dried over MgSO4, and concentrated under reduced pressure. A pale yellow solid, Tr-Cl2 (13.150 g, 51.55 mmol, 96% yield), was obtained.

[0242] 1 H NMR (CDCl3 400 MHz) ppm: 7.46 (tt, J=8.0 Hz, J=1.7 Hz, 2H), 7.36 (m, 1H), 7.25 (tt, J=7.4 Hz, J=1.8 Hz, 2H), 3.56 (s, 3H) 13 C-{ 1 H NMR (CDCl3 100 MHz) ppm: 170.52, 170.10, 165.27, 142.18, 129.67, 127.94, 126.20, 39.33 GC-MS (EI): Retention time 6.539 sm / z, 253 (+chlorine isotope) molecular peak (expected: 254.01) b) Tr(aniline)-Cl Scheme 7: Synthesis of Tr (aniline)-Cl 6-Chloro-N 2 -Methyl-N 2 N 4 -Diphenyl-1,3,5-triazine-2,4-diamineTr(aniline)-Cl The compound Tr-Cl2 (2.991 g, 11.72 mmol, 1.00 equivalent) was dissolved in 50 mL of THF and cooled to 0 °C. DIPEA (1.515 g, 11.72 mmol, 1.00 equivalent) was added dropwise at 0 °C, followed by aniline (1.638 g, 17.59 mmol, 1.50 equivalent). The mixture was stirred at 0 °C for 15 min and then at 30 °C for 20 h. THF was removed under reduced pressure, 50 mL of distilled water was added, and the aqueous phase was extracted with 3 × 50 mL of ethyl acetate. The organic phase was washed with 1 × 50 mL of 0.05 M HCl aqueous solution, 1 × 50 mL of saturated NaHCO3 aqueous solution, and 1 × 50 mL of brine, dried over MgSO4, and concentrated under reduced pressure. The white solid compound Tr(aniline)-Cl (3.306 g, 10.60 mmol, 90% yield) was obtained.

[0243] 1 H NMR (THF-d8 400 MHz) ppm: (a mixture of rotational isomers was observed) 9.13 (br s, α×1H), 8.98 (br s, (1-α)×1H), 7.8-6.7 (br m, 10H), 3.50 (br s, 3H) 13 C-{ 1 H NMR (THF-d8 100 MHz) ppm: (A mixture of rotational isomers was observed) 169.89, 166.62, 164.20, 144.95, 139.94, 129.62, 128.93, 127.66, 127.15, 123.20, 121.07, 120.11, 38.39, 38.01 GC-MS (EI): Retention time 9.508 sm / z, 310 (+chlorine isotope) molecular peak (expected: 311.09) TLC (silica, hexane / AcOEt 95:5 volume): Rf 0.1 c) Tr(isopropylamine)-Cl Scheme 8: Synthesis of Tr (isopropylamine)-Cl 6-Chloro-N 2 -Isopropyl-N 4 -Methyl-N 4 -Phenylacet-1,3,5-triazine-2,4-diamineTr(isopropylamine)-Cl The compound Tr-Cl2 (1.496 g, 5.86 mmol, 1.00 equivalent) was dissolved in 25 mL of THF and cooled to 0 °C. DIPEA (0.758 g, 5.86 mmol, 1.00 equivalent) was added dropwise at 0 °C, followed by isopropylamine (0.520 g, 8.79 mmol, 1.50 equivalent). The mixture was stirred at 0 °C for 15 min and then at 30 °C for 21 h. THF was removed under reduced pressure, 30 mL of distilled water was added, and the aqueous phase was extracted with 3 × 30 mL of ethyl acetate. The organic phase was washed with 2 × 30 mL of 0.05 M HCl aqueous solution, 1 × 30 mL of saturated NaHCO3 aqueous solution, and 1 × 30 mL of brine, dried over MgSO4, and concentrated under reduced pressure. The white solid compound Tr(isopropylamine)-Cl (1.081 g, 3.89 mmol, yield 66%) was obtained.

[0244] 1 H NMR (DMSO-d6 400 MHz) ppm: (70:30 mixture of rotational isomers observed) 7.89 (br s, 0.7 × 1H), 7.72 (br s, 0.3 × 1H), 7.5-7.1 (br m, 5H), 4.03 (sept, J = 6.61 Hz, 0.7 × 1H), 3.85 (app br s, 0.3 × 1H), 3.40 (s, 0.7 × 3H), 3.35 (s, 0.3 × 3H), 1.09 (br s, 0.3 × 6H), 1.07 (br s, 0.7 × 6H) 13 C-{ 1 H NMR (DMSO-d6 100 MHz) ppm: (A mixture of rotational isomers was observed) 168.55, 167.92, 164.84, 164.67, 164.34, 164.08, 143.77, 143.54, 128.99, 128.70, 126.89, 126.63, 126.34, 126.23, 42.15, 41.92, 38.14, 37.82, 22.19, 21.81 GC-MS (EI): Retention time 7.497 sm / z 276 (+chlorine isotope) molecular peak (expected: 277.11) TLC (silica, hexane / AcOEt 95:5 volume): Rf 0.1 d) Tr(phenol)-Cl Scheme 9: Synthesis of Tr(phenol)-Cl 4-Chloro-N-methyl-6-phenoxy-N-phenyl-1,3,5-triazine-2-amine Tr(phenol)-Cl Compound Tr-Cl2 (2.000 g, 7.82 mmol, 1.00 equivalent) was dissolved in 20 mL of THF and cooled to 0 °C. Phenol (1.478 g, 15.63 mmol, 2.00 equivalent) was slowly added at 0 °C, followed by crushed NaOH (0.516 g, 7.82 mmol, 1.00 equivalent). The suspension was stirred at 0 °C for 30 min and then at 30 °C for 18 h. THF was removed under reduced pressure. 40 mL of water was added, and the mixture was extracted with 3 × 30 mL of ethyl acetate. The organic phase was washed with 3 × 40 mL of 1 M NaOH aqueous solution and 2 × 30 mL of brine, dried over MgSO4, and concentrated under reduced pressure. A white solid compound Tr(phenol)-Cl (1.721 g, 5.50 mmol, 70% yield) was obtained.

[0245] 1 H NMR (DMSO-d6 400 MHz) ppm: 7.6-7.0 (br m, 10H), 3.45 (br s, 3H) 13 C-{ 1 H NMR (DMSO-d6 100 MHz) ppm: 170.18, 165.88, 161.59, 151.46, 142.50, 129.48, 129.20, 128.86, 126.42, 125.81, 121.52, 38.40 GC-MS (EI): Retention time 8.618 sm / z, molecular peak at 311 (+chlorine isotope) (expected: 312.08) TLC (silica, hexane / AcOEt 90:10 volume): Rf 0.2 e) Tr (isopropanol)-Cl Scheme 10: Synthesis of Tr (isopropanol)-Cl 4-Chloro-6-isopropoxy-N-methyl-N-phenyl-1,3,5-triazine-2-amine Tr(isopropanol)-Cl Sodium hydride (0.616 g, 15.41 mmol, 2.10 equivalents) was suspended in 60 mL of dry THF and stirred under nitrogen at room temperature for 20 min. The supernatant was removed and neutralized in a mixture of heptane and isopropanol. The defatting step was repeated three times. 50 mL of dry THF was added, and the suspension was cooled to 0 °C. Isopropanol (0.466 g, 7.76 mmol, 1.05 equivalents, distilled using CaH2) was dissolved in 5 mL of dry THF and added dropwise to the reaction vessel at 0 °C. The medium was stirred from 0 °C to room temperature for 1.5 h until bubbling stopped. The medium was then cooled to -15 °C. Compound Tr-Cl2 (1.890 g, 7.39 mmol, 1.00 equivalents) was dissolved in 30 mL of dry THF and cooled to -15 °C. The alcohol was transferred dropwise to a triazine container using a tubing (the alcohol was quantitatively transferred using an additional 30 mL of dry THF). The mixture was stirred at -15 °C for 45 min, and the reaction was quenched by transferring the reaction medium dropwise to 200 mL of 0.1 M NH4Cl aqueous solution at 0 °C. The aqueous phase was extracted with 3 × 70 mL of dichloromethane. The organic phase was washed with 2 × 50 mL of saturated NaHCO3 aqueous solution and 1 × 50 mL of brine. The solution was dried over MgSO4 and concentrated under reduced pressure to give a yellow, viscous, oily compound Tr(isopropanol)-Cl (1.466 g, 5.26 mmol, 71% yield).

[0246] 1 H NMR (DMSO-d6 400 MHz) ppm: 7.44 (br t, J=7.5 Hz, 2H), 7.35 (br d, J=7.4Hz, 2H), 7.31 (br t, J=7.3 Hz, 1H), 5.4-4.7 (app br m, 1H), 3.44 (s, 3H), 1.5-1.0 (br m, 6H) 13 C-{ 1 H NMR (DMSO-d6 100 MHz) ppm: 165.84, 142.85, 129.05, 128.73, 126.97, 126.68, 126.54, 126.23, 71.28, 38.35, 21.56, 21.32 GC-MS (EI): Retention time 7.017 sm / z 278 (+chlorine isotope) molecular peak (expected: 278.09) TLC (silica, hexane / AcOEt 95:5 volume): Rf 0.2 f) Tr (isopropylthiol)-Cl Scheme 11: Synthesis of Tr (isopropylthiol)-Cl 4-Chloro-6-(isopropylthio)-N-methyl-N-phenyl-1,3,5-triazine-2-amine Tr(isopropylthiol)-Cl The compound Tr-Cl2 (2.000 g, 7.82 mmol, 1.00 equivalent) was dissolved in 20 mL of THF and cooled to 0 °C. Isopropyl mercaptan (0.921 g, 11.72 mmol, 1.50 equivalent) was slowly added at 0 °C, followed by crushed NaOH (0.516 g, 7.82 mmol, 1.00 equivalent). The suspension was stirred at 0 °C for 30 min and then at 30 °C for 18 h. THF was removed under reduced pressure. 40 mL of water was added, and the mixture was extracted with 3 × 30 mL of ethyl acetate. The organic phase was washed with 2 × 30 mL of 1 M NaOH aqueous solution and 1 × 30 mL of brine, dried over MgSO4, and concentrated under reduced pressure. The resulting pale yellow solid, Tr(isopropyl mercaptan)-Cl (1.982 g, 6.72 mmol, 86% yield), was obtained.

[0247] 1 H NMR (DMSO-d6 400 MHz) ppm: 7.44 (m, 2H), 7.38 (m, 2H), 7.32 (tt, J=7.3 Hz, J=1.3 Hz, 1H), 3.9-3.3 (br m, 1H), 3.45 (s, 3H), 1.4-0.9 (br m, 6H) 13 C-{ 1 H NMR (DMSO-d6 100 MHz) ppm: 180.74, 167.66, 163.18, 142.60, 129.03, 127.10, 126.71, 126.51, 37.99, 35.52, 22.51 GC-MS (EI): Retention time 7.798 sm / z, molecular peak at 294 (+chlorine isotope) (expected: 294.07) TLC (silica, hexane / AcOEt 90:10 volume): Rf 0.4 g) Tr(phenyl)-Cl Scheme 12: Synthesis of Tr(phenyl)-Cl 4-Chloro-N-methyl-N,6-diphenyl-1,3,5-triazine-2-amine Tr(phenyl)-Cl Compound Tr-Cl2 (0.499 g, 1.95 mmol, 1.00 equivalent) was dissolved in 10 mL of THF (distilled using CaH2) in a Schlenk tube and cooled to 0 °C under nitrogen. Phenyl magnesium bromide (1 M solution in THF, 2.7 mL, 2.7 mmol, 1.4 equivalent) was added dropwise with stirring at 0 °C. The mixture was stirred at 0 °C for 30 min and then at 15 °C for 45 h. The reaction mixture was slowly added to 30 mL of distilled water at 0 °C, and THF was removed under reduced pressure. The suspension was extracted with 3 × 20 mL of ethyl acetate. The organic phase was washed with 1 × 20 mL of 0.1 M HCl aqueous solution, 1 × 20 mL of saturated NaHCO3 aqueous solution, and 1 × 20 mL of brine, dried over MgSO4, and concentrated under reduced pressure. The compound Tr(phenyl)-N3 was purified by silica gel column chromatography (hexane / AcOEt 99:1 to 90:10) to give a pale yellow solid (0.204 g, 0.69 mmol, yield 35%).

[0248] 1 H NMR (DMSO-d6 400 MHz) ppm: 8.6-7.3 (br m, 10H), 3.56 (br s, 3H) 13 C-{ 1 H NMR (DMSO-d6 100 MHz) ppm: 171.18, 169.82, 165.04, 142.86, 134.36, 133.03, 129.11, 128.76, 128.41, 127.05, 126.47, 38.43 GC-MS (EI): Retention time 8.629 sm / z 295 (+chlorine isotope) molecular peak (expected: 296.08) TLC (silica, hexane / AcOEt 95:5 volume): Rf 0.2 1.5.2 Synthesis of the azide triazine according to the present invention i. Tr(aniline)-N3 Scheme 13: Synthesis of Tr (aniline)-N3 6-Azide-N 2 -Methyl-N 2 N 4-Diphenyl-1,3,5-triazine-2,4-diamineTr(aniline)-N3 The compound Tr(aniline)-Cl (0.984 g, 3.16 mmol, 1.00 equivalent) was dissolved in 3 mL of DMF. Sodium azide (0.285 g, 4.73 mmol, 1.50 equivalent) was suspended in 3 mL of DMF and added dropwise to the triazine solution. The mixture was stirred at 100 °C for 24 h and then transferred to 40 mL of distilled water at 0 °C. The aqueous phase was extracted with 3 × 30 mL of ethyl acetate. The organic phase was washed with 5 × 30 mL of brine, dried over MgSO4, and concentrated under reduced pressure. The compound was purified by Tr(aniline)-N3 purification through a silica pad (hexane / AcOEt 90:10) to give a white solid (0.762 g, 2.39 mmol, 76% yield).

[0249] 1 H NMR (THF-d8 400 MHz) ppm: (a mixture of rotational isomers was observed) 8.91 (br s, 1H), 7.9-6.6 (br m, 10H), 3.47 (br s, 3H) 13 C-{ 1 H NMR (THF-d8 100 MHz) ppm: (A mixture of rotational isomers was observed) 169.62, 167.18, 165.10, 145.20, 140.36, 129.45, 128.85, 127.71, 126.85, 122.83, 120.15, 37.98 FTIR (ATR) σcm -1 : 3345, 3309, 3056, 3037, 2944, 2224, 2131, 1615, 1601, 1575, 1556, 1525, 1489, 1441, 1388, 1348, 1298, 1238, 1193, 1114, 1076, 1031, 1019, 971, 899, 829, 799, 767, 746, 689, 629 TLC (silica, hexane / AcOEt 90:10 volume): Rf 0.2 HRMS (ESI-MS): 319.1418 [M+H] + (Expected value: 319.1414) ii. Tr (isopropylamine)-N3 Scheme 14: Synthesis of Tr (isopropylamine)-N3 6-Azide-N 2 -Isopropyl-N 4 -Methyl-N 4 -Phenylacetyl-1,3,5-triazine-2,4-diamine Tr (isopropylamine)-N3 Compound Tr(isopropylamine)-Cl (0.799 g, 2.88 mmol, 1.00 equivalent) was dissolved in 1 mL of DMF. Sodium azide (0.346 g, 5.75 mmol, 2.00 equivalent) was suspended in 2 mL of DMF and added dropwise to the triazine solution. The mixture was stirred at 100 °C for 47 h and then transferred to 30 mL of distilled water at 0 °C. The aqueous phase was extracted with 3 × 20 mL of diethyl ether. The organic phase was washed with 5 × 20 mL of brine, dried over MgSO4, and concentrated under reduced pressure. Compound Tr(isopropylamine)-N3 was purified by silica gel column chromatography (hexane / AcOEt 98:2 to 85:15) to give a white solid (0.479 g, 1.68 mmol, 58% yield).

[0250] 1 H NMR (DMSO-d6 400 MHz) ppm: (Observed 60:40 mixture of rotational isomers) 7.58 (br d, J=7.5 Hz, 0.6×1H), 7.47 (br d, J=7.5 Hz, 0.4×1H), 7.4-7.1 (m, 5H), 4.04 (sept, J=6.6Hz, 0.6×1H), 3.89 (app br s, 0.4×1H), 3.41 (s, 0.6×3H), 3.37 (s, 0.4×3H), 1.08 (m, 6H) 13 C-{ 1 H NMR (DMSO-d6 100 MHz) ppm: (A mixture of rotational isomers was observed) 167.99, 167.70, 165.45, 165.31, 165.05, 164.75, 144.04, 143.81, 128.73, 128.44, 126.82, 126.55, 125.92, 125.79, 41.94, 41.81, 37.76, 37.41, 22.23, 21.98 FTIR (ATR) σcm -1: 3269, 3162, 3119, 2970, 2930, 2872, 2156, 2127, 1566, 1532, 1487, 1451, 1396, 1344, 1296, 1258, 1205, 1174, 1131, 1105, 1078, 1028, 997, 971, 806, 770, 739, 694, 639 TLC (silica, hexane / AcOEt 90:10 volume): Rf 0.1 HRMS (ESI-MS): 285.1573 [M+H] + (Expected value: 285.1571) iii. Tr(phenol)-N3 Scheme 15: Synthesis of Tr(phenol)-N3 4-Azide-N-methyl-6-phenoxy-N-phenyl-1,3,5-triazine-2-amine Tr(phenol)-N3 Compound Tr(phenol)-Cl (1.200 g, 3.81 mmol, 1.00 equivalent) was dissolved in 2 mL of DMF. Sodium azide (0.460 g, 7.62 mmol, 2.00 equivalent) was suspended in 3 mL of DMF and added dropwise to the triazine solution. The mixture was stirred at 100 °C for 47 h and then transferred to 50 mL of distilled water at 0 °C. The aqueous phase was extracted with 3 × 50 mL of diethyl ether. The organic phase was washed with 5 × 50 mL of brine, dried over MgSO4, and concentrated under reduced pressure. Compound Tr(phenol)-N3 was purified by silica gel column chromatography (hexane / AcOEt 92:8), dried under reduced pressure overnight at 50 °C, and a white solid (0.409 g, 1.28 mmol, 34% separation yield) was obtained.

[0251] 1 H NMR (DMSO-d6 400 MHz) ppm: 7.6-6.9 (m, 10H), 3.31 (s, 3H) 13 C-{ 1 H NMR (DMSO-d6 100 MHz) ppm: 171.50, 167.02, 166.38, 151.69, 151.57, 142.85, 142.74, 129.29, 129 .23, 128.77, 128.63, 126.36, 126.26, 125.56, 125.38, 121.58, 37.95, 37.80 FTIR (ATR) σcm -1 : 3061, 2932, 2879, 2163, 2127, 1606, 1570, 1525, 1489, 1456, 1418, 1358, 1291, 1255, 1198, 1162, 1112, 1064, 1028, 1002, 911, 808, 798, 767, 689 TLC (silica, hexane / AcOEt 90:10 volume): Rf 0.2 HRMS (ESI-MS): 320.1260 [M+H] + (Expected value: 320.1254) iv. Tr (isopropanol)-N3 Scheme 16: Synthesis of Tr (isopropanol)-N3 4-Azide-6-isopropoxy-N-methyl-N-phenyl-1,3,5-triazine-2-amine Tr(isopropanol)-N3 The compound Tr(isopropanol)-Cl (1.617 g, 4.23 mmol, 1.00 equivalent) was dissolved in 5 mL of DMF. Sodium azide (0.512 g, 8.47 mmol, 2.00 equivalent) was suspended in 3 mL of DMF and added dropwise to the triazine solution. The mixture was stirred at 100 °C for 69 h and then transferred to 50 mL of distilled water at 0 °C. The aqueous phase was extracted with 3 × 50 mL of diethyl ether. The organic phase was washed with 5 × 50 mL of brine, dried over MgSO4, and concentrated under reduced pressure. The compound Tr(isopropanol)-N3 was purified by silica gel column chromatography (hexane / AcOEt 90:10), dried under reduced pressure overnight at 40 °C, and a white solid (0.391 g, 1.37 mmol, 33% separation yield) was obtained.

[0252] 1 H NMR (DMSO-d6 400 MHz) ppm: 7.42 (br t, J=8.1 Hz, 2H), 7.35 (br d, J=8.8Hz, 2H), 7.29 (br t, J=7.3 Hz, 1H), 5.4-4.7 (app br s, 1H), 3.44 (s, 3H), 1.24 (app br s, 6H) 13 C-{ 1 H NMR (DMSO-d6 100 MHz) ppm: 170.01, 166.47, 143.16, 128.85, 126.63, 126.58, 70.53, 37.97, 21.44 FTIR (ATR) σcm -1 : 3066, 3022, 2999, 2978, 2930, 2872, 2213, 2131, 1676, 1599, 1556, 1525, 1513, 1450, 1418, 1382, 1360, 1334, 1317, 1288, 1255, 1219, 1179, 1105, 1064, 1026, 918, 803, 763, 740, 699, 660, 615 TLC (silica, hexane / AcOEt 90:10 volume): Rf 0.3 HRMS (ESI-MS): 286.1414 [M+H] + (Expected value: 286.1411) v. Tr (isopropylthiol)-N3 Scheme 17: Synthesis of Tr (isopropylthiol)-N3 4-Azide-6-(isopropylthio)-N-methyl-N-phenyl-1,3,5-triazine-2-amine Tr(isopropylthiol-N3) Compound Tr(isopropylthiol)-Cl (1.499 g, 5.08 mmol, 1.00 equivalent) was dissolved in 2 mL of DMF. Sodium azide (0.611 g, 10.17 mmol, 2.00 equivalent) was suspended in 3 mL of DMF and added dropwise to the triazine solution. The mixture was stirred at 100 °C for 47 h and then transferred to 50 mL of distilled water at 0 °C. The aqueous phase was extracted with 3 × 50 mL of diethyl ether. The organic phase was washed with 5 × 50 mL of brine, dried over MgSO4, and concentrated under reduced pressure. Tr(isopropylthiol)-N3 was purified by silica gel column chromatography (hexane / AcOEt 95:5), dried under reduced pressure overnight at 50 °C, and a white solid (0.694 g, 2.30 mmol, 45% separation yield) was obtained.

[0253] 1 H NMR (DMSO-d6 400 MHz) ppm: 7.41 (m, 2H), 7.35 (m, 2H), 7.29 (m, 1H), 4.1-3.5 (app br s, 1H), 3.44 (s, 3H), 1.22 (app br s, 6H) 13 C-{ 1 H NMR (DMSO-d6 100 MHz) ppm: 181.05, 167.10, 163.68, 142.87, 128.79, 126.69, 126.50, 37.79, 35.18, 22.36 FTIR (ATR) σcm -1 : 3062, 6042, 2961, 2925, 2865, 2184, 2132, 1604, 1534, 1492, 1449, 1408, 1341, 1302, 1281, 1238, 1220, 1193, 1155, 1099, 1054, 1026, 988, 969, 927, 902, 799, 765, 739, 696, 632 TLC (silica, hexane / AcOEt 90:10 volume): Rf 0.5 HRMS (ESI-MS): 302.1186 [M+H] + (Expected value: 302.1182) vi. Tr(phenyl)-N3 Scheme 18: Synthesis of Tr(phenyl)-N3 4-Azide-N-methyl-N,6-diphenyl-1,3,5-triazine-2-amine Tr(phenyl)-N3 Compound Tr(phenyl)-Cl (0.155 g, 0.52 mmol, 1.00 equivalent) was dissolved in 1 mL of DMF. Sodium azide (0.047 g, 0.78 mmol, 1.50 equivalent) was suspended in 2 mL of DMF and added dropwise to the triazine solution. The mixture was stirred at 100 °C for 22 h and then transferred to 30 mL of distilled water at 0 °C. The aqueous phase was extracted with 3 × 20 mL of ethyl acetate. The organic phase was washed with 5 × 20 mL of brine, dried over MgSO4, and concentrated under reduced pressure. Tr(phenyl)-N3 was purified by silica gel column chromatography (hexane / AcOEt 90:10), dried under reduced pressure overnight at 40 °C, to give a white solid (0.022 g, 0.07 mmol, 14% separation yield).

[0254] 1 H NMR (DMSO-d6 400 MHz) ppm: 8.7-7.2 (br m, 10H), 3.58 (br s, 3H) FTIR (ATR) σcm -1 : 3092, 3064, 3035, 2975, 2956, 2920, 2906, 2856, 2425, 2141, 2125, 1602, 1587, 1539, 1501, 1494, 1454, 1444, 1415, 1389, 1341, 1301, 1291, 1236, 1196, 1184, 1129, 1109, 1095, 1071, 1026, 1004, 992, 973, 940, 914, 902, 820, 801, 777, 742, 717, 696, 658, 629, 615 TLC (silica, hexane / AcOEt 90:10 volume): Rf 0.4 vii. Tr (isopropyl sulfone)-N3 Scheme 19: Synthesis of Tr (isopropyl sulfone)-N3 4-Azide-6-(isopropyl sulfone)-N-methyl-N-phenyl-1,3,5-triazine-2-amine Tr(isopropyl sulfone-N3) Compound Tr(isopropylthiol)-N3 (0.250 g, 0.83 mmol, 1.00 equivalent) was dissolved in 5 mL of THF, and m-chloroperoxybenzoic acid (0.358 g, 2.07 mmol, 2.50 equivalent) was slowly added at room temperature. The mixture was stirred at 40 °C for 18 h, and then concentrated under reduced pressure. Tr(isopropyl sulfone)-N3 was purified by silica gel column chromatography (hexane / AcOEt 70:30), and a white solid was obtained after concentration. The product was degraded by drying under reduced pressure overnight at 50 °C to show altered... 1 A grayish-white, viscous paste-like substance as measured by 1H NMR.

[0255] TLC (silica, hexane / AcOEt 70:30 volume) at 50°C before drying: Rf 0.3 Figure 2 High-pressure DSC (downward exothermic) and TGA monitoring (under N2) are shown for the decomposition of azidotriazine 1, Tr(aniline)-N3, Tr(isopropylamine)-N3, Tr(phenol)-N3, Tr(isopropanol)-N3 and Tr(isopropylthiol)-N3.

[0256] Tables 1 and 2 below summarize the temperature, enthalpy, and kinetic parameters for the melting and bulk decomposition of the aforementioned azidotriazines obtained from high-pressure DSC. All azidotriazines shown in this study were microcrystalline solids with similar onset decomposition temperatures (between 192 °C and 199 °C). The measured enthalpies ranged from 111 kJ / mol (Tr(phenol)-N3) to 235 kJ / mol (Tr(isopropylthiol)-N3). Generally, higher enthalpies were observed for azidotriazine grafts containing aliphatic CH and NH bonds. Regarding kinetics, all decomposition reactions were found to be first-order. These parameters allowed for the calculation of the half-life of each individual azidotriazine at the desired processing temperature.

[0257] Table 1. Temperatures and enthalpies of bulk melting and decomposition of azide-substituted heteroaromatic derivatives of the library obtained by high-pressure DSC. a na = Not applicable Table 2. Kinetic parameters of azide-substituted heteroaromatic derivatives from the library calculated from high-pressure DSC data. Table 3. Explosion probability (based on Yoshida and Pfizer correlations and the highest storage temperature (TD24) calculated based on high-pressure DSC measurements, according to literature (especially as described in Green, SP et al., J. Org. Chem. 2019, 84, 5893-5898). Negative correlation values ​​between Yoshida and Pfizer indicate stable compounds.

[0258] Example 2. Decomposition of azidotriazine 1 2.1 Bulk decomposition of azidotriazine 1 Compared to HDPE and PP, azidotriazine 1 is more polar, and therefore it is not expected to be fully compatible with these polyolefins in the molten state. Therefore, understanding how azidotriazine 1 reacts to predict the structures that will form during reactive extrusion is crucial. Scheme 16 illustrates the reaction scheme for the model decomposition of azidotriazine. The reaction temperature and time were selected based on kinetic studies performed by differential scanning calorimetry (DSC). The molecule has a half-life of approximately 2 min at 215 °C. The reaction was set to proceed for 5 half-lives (10 min), corresponding to a conversion of approximately 97%. Based on 1H NMR spectroscopy, approximately 9% of the product was converted to the corresponding aminotriazine, while the remaining 91% was a triazine derivative. The broad resonances observed in the 1H NMR spectroscopy hindered further structural insights. Scheme 20: Reaction scheme for the bulk decomposition of azidotriazine 1 Product distribution was studied using size exclusion chromatography (SEC) and matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS).

[0259] Through the SEC Figure 3 The response of the crude product (black curve) was compared with that of the true standard of aminotriazine 1' (grey curve; the aminotriazine structure is shown as one of the products in Scheme 16). The signal of the decomposition product appeared to be a mixture of aminotriazine 1' (retention volume 33.5 mL) and a broadly distributed higher molecular weight product (retention volumes between 30 mL and 33.5 mL). This was determined by MALDI-TOF-MS (…). Figure 4 The higher molecular weight products were found to be oligomer species, characterized by repeating units at 304.14 m / z, which is consistent with... Figure 4 The polyazine structure shown in the upper left corner is consistent.

[0260] 2.2 Decomposition temperature of azidotriazine 1 The decomposition temperature of 5 mol% azidotriazine 1 in HDPE was determined using TGA measurements (see [reference]). Figure 5 Based on the method described above, the decomposition temperature of 206℃ was found.

[0261] The same method applies to samples containing bulk azide triazine 1. Figure 6 The TGA was reported to be running, and a decomposition temperature of 196°C was found.

[0262] 2.3 Kinetics of the decomposition of azidotriazine 1 To rationally select the temperature and time for the grafting reaction, the kinetic parameters of the decomposition of azidotriazine 1 were determined by DSC measurement and the application of the Borchardt-Daniels (BD) analytical method (as described in the "Methods" paragraph above). This method is applicable to bulk samples of azidotriazine 1 and mixtures of azidotriazine 1 with the polymer to be grafted or polymer blends.

[0263] The decomposition of azidotriazine 1 loaded at 5.0 mol% in HDPE was investigated by DSC. Figure 7 An 8.1 mg sample was decomposed in a high-pressure, sealed gold DSC sample cell by heating the sample from 50 °C to 320 °C at a constant rate of 10 °C / min. After the polyethylene (PE) melted at 126 °C, azidotriazine 1 underwent an exothermic decomposition reaction with an onset temperature of 195 °C and a peak temperature of 227 °C. The integral of this signal yielded a total enthalpy of 172 J / (g sample), corresponding to 154 kJ / (mol azidotriazine).

[0264] For this measurement, a BD analysis was performed using the time-enthalpy integral data. In this embodiment, the obtained coefficients can be calculated. A, Ea, and n The values ​​of 2.366 × 10¹⁵, 164.9 kJ / mol, and 1.140 kJ / mol were given respectively. 。

[0265] Similar analyses were performed on the bulk azide triazine (i.e., the pure compound not dispersed in the polymer) and a range of other matrices. Table 3 provides the main calorimetric characteristics for each experiment. All reported kinetic parameters used in this study were calculated based on three DSC measurements and averaged from results obtained through three separate BD analyses. Table 4 provides a summary of these analyses.

[0266] In all cases, the decomposition of azide-triazine 1 was found to follow first-order kinetics. The desired temperature was then calculated using the average kinetic parameters. T R Half-life under () t1 / 2), or conversely, using Equation 4. In Table 5, the calculations will correspond to 2 min 24 s. t1 / 2 of T R As an example, each sample is grafted with 5 half-lives, and the two temperatures will then give total grafting times of 10 min and 2 min, respectively.

[0267] (4) Table 4. Summary of calorimetric characterization of azidotriazine 1 dispersed in the matrix and as bulk. PETg = polyethylene glycol, ethylene glycol modified; PCL = polycaprolactone; PS = polystyrene; PP = polypropylene; PE = polyethylene; PB = polybutadiene; bulk = pure azidotriazine, not dispersed in the matrix). Table 5. Summary of kinetic parameters of azidotriazine 1 determined by DSC measurements using the Borchardt-Daniels (BD) method. All parameters are based on the average of three DSC runs and three BD analyses. Table 6. Half-life of azidotriazine 1 decomposition calculated based on BD kinetic parameters in each matrix Example 3. Model grafting of azidotriazine 1 onto paraffin wax Due to the low solubility of high molecular weight polyolefins in organic solvents, it is generally difficult to directly study the structure of high molecular weight polyolefins after grafting. Therefore, according to the following scheme 17, a model grafting reaction of azidotriazine 1 was carried out using paraffin (which is essentially an oligomeric analog of HDPE). One equivalent of azidotriazine 1 was reacted with excess paraffin at 214 °C for 13 minutes. Scheme 21: Reaction scheme for model grafting of azidotriazine 1 onto paraffin.

[0268] Upon heating, the mixture releases a gas (likely N2) and turns red. Based on NMR spectroscopy, 24% of the azide triazine 1 is converted to the corresponding aminotriazine derivative, while the remaining 76% is covalently grafted onto paraffin.

[0269] Multiple techniques were used to elucidate the product distribution of grafted paraffin structures; the three most important findings are described below.

[0270] Through Raman spectroscopy ( Figure 8This confirmed the presence of key functional groups in the grafted paraffin. Peak assignment was performed by comparing the spectrum of the model dimer structure with the spectrum calculated using density functional theory. (975 cm⁻¹) -1 The signal (ν1) at this point was attributed to in-phase radial bending of the triazine ring stretching mode. Two other bands were also observed in this range: 1003 cm⁻¹. -1 The signal at (ν2) (which is attributed to the in-phase radial bending of the benzene ring) and 1030 cm -1 The signal at (ν3) (which is attributed to the out-of-plane bending of the phenyl CH group) (Lin-Vien, D.; Colthup, NB; Fateley, WG; Grasselli, JG) The Handbook of Infrared and Raman Characterisitic Frequencies of Organic Molecules Academic Press, 1991.

[0271] These materials were also studied using electron paramagnetic resonance (EPR) spectroscopy. Figure 9 The grafted material exhibits singlet resonances in both the solid and solution states. The observed resonances correspond to approximately 2. g Factors that are consistent with organic free radical species (Weil, JA; Bolton, JR) Electron Paramagnetic Resonance, Elementary Theory and Practical Applications ; 2nd ed.; John Wiley & Sons: Hoboken, NJ, USA, 2007). This resonant singlet characteristic indicates that the radical is delocalized on the triazine structure. To ensure the covalent grafting of radical-containing species onto the paraffin chain, the grafted material was purified by sequential precipitation. Figure 9 (Right). The purified material still exhibited a singlet EPR signal; this result indicates that radical species are grafted onto the paraffin chain. It should be noted that these measurements were performed on samples stored in air for more than two weeks without special precautions, indicating that the radicals are long-lived.

[0272] The grafted paraffin was further analyzed using 1D and 2D NMR spectroscopy. Figure 10 In the study, 1H-1H correlation spectroscopy (COSY) revealed the key proton coupling, which clearly identified the covalent bond between the paraffin chain and the monomeric aminotriazine graft.

[0273] Example 4. Grafting of azidotriazine 1 onto HDPE, PP, and HDPE-PP blends via reactive processing. 4.1 Grafting of azide-triazine 1 onto HDPE, PP, and HDPE-PP blends according to the method of the present invention The grafting of azide triazine 1 was incorporated into the reactive processing scheme. Figure 11 Figure A schematically illustrates a general scheme for grafting a single substrate, and Figure 11 B shows the experimental torque curves for grafting HDPE with 1 mol% of azide triazine.

[0274] In the first step, a masterbatch of azidotriazine 1 in HDPE was prepared according to the following procedure: 6.000 g of azidotriazine 1 was dissolved in xylene (15 mL), and the solution was preheated to 100 °C. 9.000 g of HDPE was suspended in xylene (250 mL), and nitrogen was bubbled in for 5 min. The suspension was heated and stirred under nitrogen at 140 °C. When the polymer was completely dissolved, the azidotriazine solution was added, and the mixture was further stirred under nitrogen at 140 °C for 5 min. The xylene was evaporated under reduced pressure at 90 °C, and the resulting masterbatch was dried overnight under the same conditions (mass obtained: 15.090 g, final loading of azidotriazine: 40 wt%).

[0275] Then, in the second step, the masterbatch of azide-triazine 1 is co-loaded with the virgin HDPE and subjected to a processing temperature of 160°C. T 混合 The mixture was extruded in a 15 cubic centimeter (cc) twin-screw extruder. This mixing stage was introduced to ensure the homogenization of the melt prior to grafting (the half-life of azidotriazine 1 at this temperature is close to 3 h). After mixing for 5 min at a screw speed of 100 rpm, the temperature was rapidly increased to the reaction temperature. T R (In the case of HDPE, it is 214℃). For example... Figure 11 As can be seen in B, upon reaching... T R Subsequently, the torque immediately increased, indicating an increase in viscosity. Considering that the half-life of azidotriazine 1 at this temperature is 2 minutes, the material extruded from the barrel (referred to as HDPE)... m Before that, the reaction is carried out for 10 minutes (5 half-lives, approximately 97% conversion).

[0276] A similar approach was used to graft PP with azide triazine 1, thereby obtaining a product called PP. m Materials.

[0277] A similar approach was applied to graft HDPE-PP blends (70:30 weight ratio) with azidotriazine 1. Figure 12 A). Figure 12B illustrates an example of the torque curve for the reactive grafting of this blend with 1 mol% of azidotriazine 1. This HDPE / PP ratio was chosen because it represents the weight ratio of polyethylene to polypropylene in a typical municipal waste stream (“Plastics The Facts 2017.” PlasticsEurope, 2018, Accessed on 4 Nov. 2018, https: / / www.plasticseurope.org / application / files / 5715 / 1717 / 4180 / Plastics_the_facts_2017_FINAL_for_website_one_page.pdf). The resulting material is referred to as (HDPE-PP). m .

[0278] The obtained HDPE m and (HDPE-PP) m Both are cross-linked materials, exhibiting gel fractions of 63% and 58%, respectively. To determine whether the cross-linking is chemically composed of triazine units, Raman spectroscopy was performed on the paraffin as described above. Figure 13 ). In HDPE m The same diagnostic signal as that observed in grafted paraffin was detected. This vibration mode was not observed in the original HDPE.

[0279] To further determine whether the crosslinking is due to triazine group linkages rather than solely due to chain coupling formed via C-C bonds, HDPE m The reaction was subjected to numerous reaction conditions under which the aminotriazine bond was expected to be chemically decomposed. Two reaction conditions were successfully determined: HDPE treated at 160 °C with a) 1-naphthol and KOH or b) 1-aminodecane and triazabicyclodecene (TBD). m This leads to the complete dissolution of the material. These results indicate that the aminotriazine bond is indeed used to link polymer chains, rather than for irreversible C-C bond chain coupling.

[0280] In (HDPE-PP) m In this case, another key issue is whether covalent bonds will form between the HDPE and PP chains, as this structural feature is expected to have a significant impact on the mechanical properties of the material. Therefore, a systematic gel fraction experiment was conducted on a series of HDPE-PP blends modified in different ways. As shown in Table 6, the first column gives the expected theoretical gel fraction for each blend based on the gel fraction of each pure component (e.g., for pristine HDPE, pristine PP, HDPE...). m and PP mThe gel fractions were determined to be 0%, 0%, 63%, and 0%, respectively. As expected, the blends of virgin HDPE and virgin PP did not exhibit an insoluble portion (entry 1). In (HDPE-PP) m In this case, the gel fraction was higher than expected for a 70:30 mixture, which is consistent with the formation of covalent bonds between HDPE and PP chains (Item 2). HDPE m With PP m The blends also produced a higher gel fraction than theoretically expected, indicating that crosslinking is reversible during melt processing at high temperatures (Item 3). As a control experiment to verify this method, HDPE... m The blend with PP gives the expected gel fraction, assuming it is in HDPE. m There are no new connections between the original PP chain and the original PP chain (entry 4).

[0281] Table 7. Gel fraction experiments of control and PE-PP modified blends a (All have a 70:30 weight ratio). a Three experiments were conducted using xylene at 130℃ for 16 hours. b Calculation based on the gel fraction of each component Calculation (original PE and original PP are 0%; HDPE) m 63%; PP m (0%) 4.2 HDPE m and (HDPE-PP) m Thermomechanical properties of (polymer compositions according to the present invention) It is worth noting that, although HDPE m and (HDPE-PP) m They exhibit high gel fractions, yet can be reshaped via compression molding, a characteristic consistent with the systematic gel fraction experiments shown in Table 7, indicating that crosslinking is reversible under processing conditions. This behavior allows for simple shaping and analysis via dynamic mechanical analysis (DMA) and rheology. Figure 14 (At the top) HDPE m The DMA exhibits a distinct rubber plateau (black curve) above the melt transition temperature of the HDPE matrix, consistent with the formation of the crosslinked network. This behavior contrasts with that of the original HDPE control (gray curve), which flows at its own weight above the melt transition. When the loading of azidotriazine 1 varies from 0.05 mol% to 1 mol%, ( Figure 14 (Bottom), the elastic modulus of the rubber platform increased from 0.05 mol% to 0.5 mol%; the rubber platform of the 0.5 mol% sample had essentially the same elastic modulus as the 1 mol% sample, indicating "saturation" of crosslinking. Compared to the original HDPE control, HDPEm The triazine-based crosslinking imparts excellent creep resistance at 180°C. Figure 15 ).

[0282] For (HDPE-PP) m A very similar trend was observed because DMA exhibited a distinct rubber plateau above the melting temperature of PE and PP matrices. Figure 16 Compared to the original HDPE-PP control blend, triazine-based crosslinking also endows this material with excellent creep resistance. Figure 17 For (HDPE-PP) m It also emphasized its tensile properties measured at ambient temperature. Figure 18 (The representative stress-strain curves are shown in the figure). Although virgin HDPE and virgin PP are ductile materials, the untreated blend has a fracture strain of approximately 30%, making it too brittle for practical use. It is worth noting that (HDPE-PP) m Its elongation at break exceeds 300%. Treatment with azidotriazine 1 results in a significant recovery of ductility—combined with its processability at high temperatures and creep resistance, this material represents an impressive step toward upgrading and remanufacturing this plastic blend.

[0283] 4.3 HDPE m and (HDPE-PP) m The flow properties of the polymer composition according to the invention Although it is covalently crosslinked, HDPE m and (HDPE-PP) m Both can be passed through a twin-screw extruder and can be reshaped by compression molding, indicating that crosslinking is reversible under high shear and high temperature. As an example of an experiment illustrating the flow properties of the obtained material, Figure 19 HDPE is shown in the figure. m (Top) and (HDPE-PP) m(Bottom) Strain scanning experiments. These measurements were performed at 1 rad / s at 180 °C (a typical temperature used in compression molding). The two materials behave similarly: at strains up to approximately 80%, a linear response approximating the storage modulus above the loss modulus is observed. Above 80%, both materials reach a critical strain value of approximately 120%, at which a crossover between the storage modulus and loss modulus is observed. This material exhibits melt fracture at high strains and temperatures, but this fracture is rapidly healed through cross-linking reforming. This flow behavior is comparable to that of polyethylene glass polymers based on the metathesis of dioxaborolane (see Ricarte, RG; Tournilhac, F.; Cloître, M.; Leibler, L. Linear Viscoelasticity and Flow of Self-Assembled Vitrimers: The Case of a Polyethylene / Dioxaborolane System). Macromolecules 2020, 53 (1852-1866).

[0284] 4.4. Recyclability of Modified HDPE and HDPE-PP Blends like Figure 20 As shown, by applying HDPE m and (HDPE-PP) m Recycling experiments were conducted to test the recyclability of modified HDPE and HDPE-PP blends. In each cycle, the material was compressed into an appropriate shape for analysis using a series of techniques (DMA, tensile testing, Raman spectroscopy, and EPR spectroscopy; rheological testing was performed in the first and last cycles). After analysis, and before compression re-forming, the test samples from the tensile tests were recycled, cut, and re-extruded. Based on DMA (… Figure 21 ) and tensile test ( Figures 22 to 23 ), HDPE m and (HDPE-PP) m Significant stability was observed in all four cycles. Through DMA, it is evident that the effective crosslinking density of both materials did not change with recycling. Except for Young's modulus, which may increase with recycling cycles, the tensile properties remained essentially constant with recycling. High-temperature creep-recovery experiments were performed on each material after the final cycle. Figure 24 The performance after the fourth iteration is essentially the same as that after the first iteration (e.g., ...). Figure 15 and Figure 17 (As shown).

[0285] This performance stability after multiple cycles is significant for cross-linked materials and provides direct evidence of the reversible nature of N-N bond cross-linking. To further understand the mechanism of reprocessing, EPR spectra were acquired after each recycling cycle following extrusion and compression molding. Normalizing the signal intensity to the sample weight allowed for qualitative comparisons of radical concentrations. Clearly, the EPR signal became stronger after each cycle, indicating that N-N bonds broke after each cycle. However, the radical concentration appeared to decrease after compression molding, consistent with radical coupling reactions.

[0286] 4.5. Morphology of modified HDPE and HDPE-PP blends The morphology was comprehensively studied using transmission electron microscopy (TEM). Figure 26 The TEM results are shown, in which HDPE m and (HPDE-PP) m Comparisons were made with their respective original precursors. All samples were cryosectioned and stained with RuO4. Figure 26 In A, the fine texture of crystalline HDPE extends across the entire field of view (the visible inhomogeneity is due to mechanical creases in the sliced ​​film). At low temperatures (i.e., at... T 混合 (Below) Blending azide-based triazine 1 with molten HDPE yields a phase-separated mixture. Figure 26 B). Azide-triazine 1 is dispersed in the HDPE matrix as large droplets (dark areas). In contrast, HDPE m It is characterized as an additional phase that appears as dark nodules within the HDPE matrix. The nodules are characterized by a clear and smooth interface with the HDPE matrix. The size distribution is wide, ranging in diameter from approximately 10 nm to over 100 nm.

[0287] In the case of the original HDPE-PP 70:30 blend ( Figure 26 (D) Clearly, coarse macroscopic phase separation between HDPE and PP is observed. The lighter-colored droplets correspond to PP, while the darker matrix corresponds to HDPE. The interface between HDPE and PP is sharp and fragile—it appears that the HDPE phase has delaminated to some extent from the surface of the PP droplets due to slicing. In contrast, (HDPE-PP) m It exhibits characteristics similar to HDPE m Similar morphology ( Figure 26 E). Dark nodules of the triazine-rich phase are distributed in the HDPE / PP blend. In this case, the interface between the HDPE and PP phases is not clearly observed.

[0288] Example 5. Azide-triazine 1 in blends with LDPE, PETg, PS, PCL and HDPE as models of waste plastics grafting on objects use Figure 11 The method described in section A modifies low-density polyethylene (LDPE), glycol-modified polyethylene terephthalate (PETg), polystyrene (PS), and polycaprolactone (PCL) polymers respectively via reactive processing using 1 mol% of azidotriazine 1. Blends of these polymers with HDPE (70:30 weight ratio) are shown below. Figure 12 A is prepared by grafting 1 mol% of azidotriazine 1, or by mixing separately modified materials (e.g., HDPE). m With LDPE m Blending to produce HDPE m -LDPE m Finally, use Figure 12 An improved version of the method illustrated in A also uses a five-component mixture (18:26:28:12:9) of 1 mol% azidotriazine grafted onto HDPE, LDPE, PP, PETg and PS.

[0289] A brief understanding of these materials can be obtained by carefully considering the gel fraction experiments shown in Table 7. In one component composition, LDPE... m and PCL m Both are cross-linked networks that can be further processed, while PETg m and PS m This produces soluble thermoplastics. For the latter two matrices, PETg... m and PS m The 1H NMR spectra of the precipitated samples showed grafting rates of 50% and 61%, respectively. Based on SAXS measurements, PETg m and PS m Neither exhibited phase separation. In the case of PS, analysis using EPR spectroscopy confirmed the presence of PS. m Includes long-lived free radicals ( Figure 27 Therefore, it is believed that PETg m and PS m The lack of crosslinking may be due to the higher miscibility of the azidotriazine 1 grafting agent in the polymer. To generate N-N bonds, a high local concentration of radical-containing grafts is naturally required, and nanophase separation is an effective means to meet this requirement.

[0290] Regarding blends with HDPE, all examples yielded insoluble networks. Interestingly, both methods used to produce the blends—i.e., direct grafting of the blends or blending of two pre-grafted components—resulted in gel fractions higher than the theoretical gel fraction calculated based on the gel content of a single component. As described above in the cases of HDPE and PP, this finding strongly suggests the formation of N-N bonds between the different matrices during processing.

[0291] Regarding the five-component mixture (HDPE-LDPE-PP-PETg-PS) m It also exhibits a gel fraction that is superior to the theoretical gel fraction. Figure 28 and Figure 29 The figures show the comparisons between the corresponding blends of the original polymers (HDPE-LDPE-PP-PETg-PS). m DMA and tensile properties. For (HDPE-LDPE-PP-PETg-PS) m A distinct rubber plateau was observed, consistent with the formation of a chemical network. Tensile properties were slightly improved, with elongation at break nearly doubling. Despite no optimization, these results demonstrate the attractiveness of this strategy for upgrading complex blends of recycled plastics.

[0292] Table 8. Gel fraction experiments of control and PE-PP modified blends a (All have a 70:30 weight ratio). a Three experiments were conducted using xylene at 130℃ for 16 hours. b Calculation based on the gel fraction of each component Calculate. c not applicable. d The weight ratio is 70:30. e The weight ratio is 18:26:28:12:9.

[0293] Example 6. Applicable to other polymers and polymer blends All modified high molecular weight materials were prepared by reactive extrusion using a DSM Xplore twin-screw extruder with a barrel volume of 5 cc or 15 cc. The apparatus includes a co-rotating conical screw profile and a recirculation channel that allows for controlled residence time. All extrusions were performed under a nitrogen flow.

[0294] Table 9. Half-life of azidotriazine 1 at various temperatures Measurements were taken by DSC and analyzed using the Borchardt-Daniels method (see Swarin, SJ; Wims, AM In). Analytical Calorimetry; Porter, RS, Johnson, JF, Eds.; Springer: Boston, MA, 1977; Vol. 4; and ASTM International. Standard Test Method for Estimating Kinetic Parameters by Differential Scanning Calorimeter Using the Borchardt and Daniels Method; ASTM E2041-13. West Conshohocken, PA, 2018. DOI: 10.1520 / E2041-13R18) was used to determine the half-life of azidotriazine 1 at various temperatures.

[0295] 6.1. Single-component commercial thermoplastics Reactive processing by extrusion using a 15 cc extruder At temperature T 混合 The barrel was preheated and purged with nitrogen for 5 minutes. The screw speed was set to 50 rpm, and 40% by weight of the masterbatch of virgin polymer P and azide triazine 1 in P was sequentially loaded into the barrel over approximately 5 minutes. The screw speed was then increased to 100 rpm, and the temperature was maintained at a constant level. T 混合 Continue mixing for another 5 minutes. Then, heat the drum to the desired temperature over approximately 2 minutes. T R Subsequently, at temperature T R After a residence time of 10 minutes, the material is extruded and cooled at room temperature.

[0296] Reactive processing by extrusion using a 5 cc extruder At temperature T 混合 The barrel was preheated and purged with nitrogen for 5 minutes. The screw speed was set to 100 rpm, and 40% by weight of the masterbatch of virgin polymer P and azide triazine 1 in P was sequentially loaded into the barrel over approximately 5 minutes. At a temperature... T 混合 Continue mixing for another 5 minutes. Then, heat the drum to the desired temperature over approximately 2 minutes. T R Subsequently, at temperature T R After a residence time of 10 minutes, the material is extruded and cooled at room temperature.

[0297] Table 10. Experimental parameters for the reaction of single-component commercial thermoplastics with azidotriazine 1. a In the case of P=iPP, stabilizers were added directly as a dry blend with the original polymer pellets (0.05 wt% Irganox 1010, 0.10 wt% Irgafos 168). bTU represents the triazine unit, which is the loading (mol%) compared to the polymer repeating unit.

[0298] 6.2. In-situ reactive processing of blends of commercial thermoplastics Reactive processing by extrusion using a 15 cc extruder At temperature T 混合 The barrel was preheated and purged with nitrogen for 5 minutes. The screw speed was set to 50 rpm, and the dry blend of the original polymers P1 and P2 was loaded into the barrel over approximately 2 minutes. The screw speed was then increased to 100 rpm, and the temperature was maintained at a constant level. T 混合 Continue mixing for another 5 minutes. Then, load 40% by weight of the masterbatch of azidotriazine 1 in P1 over approximately 2 minutes, and mix at a temperature of [temperature missing]. T 混合 Continue mixing for another 5 minutes. Then, heat the drum to the desired temperature over approximately 2 minutes. T R Subsequently, at temperature T R After a residence time of 10 minutes, the material is extruded and cooled at room temperature.

[0299] Reactive processing by extrusion using a 5 cc extruder At temperature T 混合 The barrel was preheated and purged with nitrogen for 5 minutes. The screw speed was set to 100 rpm, and the dry blend of the original polymers P1 and P2 was loaded into the barrel over approximately 2 minutes. At temperature T... 混合 Continue mixing for another 5 minutes. Then, load 40% by weight of the masterbatch of azidotriazine 1 in P1 over approximately 2 minutes, and mix at a temperature of [temperature missing]. T 混合 Continue mixing for another 5 minutes. Then, heat the drum to the desired temperature over approximately 2 minutes. T R Subsequently, at temperature T R After a 10-minute dwell time, the material is extruded and cooled at room temperature.

[0300] Table 11. Experimental parameters for in-situ processing of blends of commercial thermoplastics with azidotriazine 1. aWith P2=iPP, stabilizers were added directly as a dry blend with the original polymer pellets (0.05 wt% Irganox 1010, 0.10 wt% Irgafos 168). b TU represents the triazine unit, which is the loading (mol%) compared to the polymer repeating unit.

[0301] Reactive processing using a hot press through compression molding. This process is illustrated using HDPE as the matrix. First, a 10% by weight mixture of azidotriazine 1 in HDPE was prepared by compounding 40% by weight of a masterbatch of azidotriazine 1 in HDPE with virgin HDPE for 5 min at 160°C in a 5 cc extruder. The resulting material was then cured in a hot press by heating to 214°C for 10 min under 3 T pressure inside a stainless steel die. After curing, the material was cooled to room temperature on a worktable and then removed from the die.

[0302] 6.3. Reactive blending of modified single-component materials Reactive blending extruded using a 5 cc extruder At temperature T R The barrel was preheated and purged with nitrogen for 5 minutes. The screw speed was set to 100 rpm, and the modified single-component material P1 was fed into the machine over approximately 2 minutes. m (a) and P2 m The dry blend is loaded into the machine barrel. Then, at a temperature... T R After a residence time of 10 minutes, the material is extruded and cooled at room temperature.

[0303] (a) P x m This indicates the grafted azide triazine 1 and the original polymer P x The materials obtained.

[0304] Table 12. Experimental parameters for reactive blending of modified single-component materials a TU represents the triazine unit, which is the loading (mol%) compared to the polymer repeating unit.

[0305] 6.4. Preparation of control materials Processing of a single-component control material extruded using a 15 cc extruder. At temperature T 混合The barrel was preheated and purged with nitrogen for 5 minutes. The screw speed was set to 50 rpm, and the raw polymer P was loaded into the barrel in approximately 5 minutes. The screw speed was then increased to 100 rpm, and the temperature was maintained at a constant level. T 混合 Continue mixing for another 5 minutes. Then, heat the drum to the desired temperature over approximately 2 minutes. T R Subsequently, at temperature T R After a 10-minute dwell time, the material is extruded and cooled at room temperature.

[0306] Table 13. Experimental parameters for preparing single-component control materials. a With P=iPP, stabilizers were added directly as a dry blend with the original polymer pellets (0.05 wt% Irganox 1010, 0.10 wt% Irgafos 168). Processing of two-component control materials extruded using a 15 cc extruder. At temperature T 混合 The barrel was preheated and purged with nitrogen for 5 minutes. The screw speed was set to 50 rpm, and the dry blend of the original polymers P1 and P2 was loaded into the barrel over approximately 2 minutes. The screw speed was then increased to 100 rpm, and the temperature was maintained at a constant level. T 混合 Continue mixing for another 5 minutes. Then, heat the barrel to temperature T over approximately 2 minutes. R Subsequently, at temperature T R After a residence time of 10 minutes, the material is extruded and cooled at room temperature.

[0307] Table 14. Experimental parameters for preparing two component control materials. a With P2=iPP, stabilizers were added directly as a dry blend with the original polymer pellets (0.05 wt% Irganox 1010, 0.10 wt% Irgafos 168). Modified single-component material P1 m Control blend with the original polymer P2 At temperature T RThe barrel was preheated and purged with nitrogen for 5 minutes. The screw speed was set to 100 rpm, and the modified single-component material P1 was fed into the machine over approximately 2 minutes. m The dry blend of the original polymer P2 was loaded into the drum. Subsequently, at a temperature... T R After a residence time of 10 minutes, the material is extruded and cooled at room temperature.

[0308] Table 15. Experimental parameters for preparing two-component control blends of the modified polymer and the original polymer. a With P2=iPP, stabilizers were added directly as a dry blend with the original polymer pellets (0.05 wt% Irganox 1010, 0.10 wt% Irgafos 168). b TU represents the triazine unit, which is the loading (mol%) compared to the polymer repeating unit.

[0309] Example 7. Grafting of azide triazine AT-Ph and AT-NBu2 onto HDPE via reactive processing 7.1. Grafting of azide-triazine AT-Ph and AT-NBu2 onto HDPE according to the method of the present invention. AT-Ph and AT-NBu2 were grafted using the same reactive processing scheme as that used for azidotriazine 1 in Example 4 (see [link to example]). Figure 11 A). Figure 30 Zuohe Figure 30 The right side shows the experimental torque curves for grafting HDPE with 1 mol% AT-Ph and 1 mol% AT-NBu2, respectively.

[0310] In the first step, a masterbatch of AT-Ph in HDPE was prepared according to the following steps: AT-Ph (1.6 g) was dissolved in xylene (5 mL), and the solution was preheated to 100 °C. HDPE (2.4 g) was suspended in xylene (50 mL), and nitrogen was bubbled in for 5 min. The suspension was heated and stirred under nitrogen at 140 °C. When the polymer was completely dissolved, an azide triazine solution was added, and the mixture was stirred again under nitrogen at 140 °C for 5 min. The xylene was evaporated under reduced pressure at 90 °C, and the resulting masterbatch was dried overnight under the same conditions (mass obtained: 4.05 g, final loading of AT-Ph: 40% by weight).

[0311] Then, in the second step, the AT-Ph masterbatch is co-loaded with the virgin HDPE at a processing temperature of 160°C. T 混合The mixture was extruded in a 15 cubic centimeter (cc) twin-screw extruder. This mixing stage was introduced to ensure the melt was homogenized prior to grafting. After mixing for 5 minutes at a screw speed of 100 rpm, the temperature was rapidly increased to the reaction temperature. T R (In the case of HDPE, it is 214℃). For example... Figure 30 As can be seen in the middle left, upon reaching T R Subsequently, the torque immediately increased, indicating an increase in viscosity. Following the method used for azidotriazine 1, the reaction proceeded for 10 minutes, after which the material (referred to as HDPE) was extruded from the barrel. AT-Ph Using the same scheme applied to AT-NBu2, a solution known as HDPE is obtained. AT-NBu The material. The obtained HDPE AT-Ph and HDPE AT -NBu Both are cross-linked materials, exhibiting gel fractions of 58% and 60%, respectively (Table 16).

[0312] Table 16. Gel fraction experiments of control and modified HDPE a . a Three experiments were conducted using xylene at 130℃ for 16 hours.

[0313] To further determine whether the crosslinking is due to triazine group linkages rather than solely due to chain coupling formed via C-C bonds, HDPE AT-Ph and HDPE AT-NBu Under the reaction conditions expected to chemically decompose the aminotriazine bond, HDPE was treated with 1-aminodecane and triazabicyclodecene (TBD) at 160°C. AT-Ph and HDPE AT-NBu This leads to the complete dissolution of the material. These results indicate that the aminotriazine bond is indeed used to link polymer chains, rather than for irreversible C-C bond chain coupling.

[0314] 7.2. HDPE AT-Ph HDPE m and HDPE AT-NBu Thermomechanical properties of (polymer compositions according to the present invention) Despite HDPE AT-Ph It has a high gel fraction, but it can be molded using compression molding. HDPE AT-NBu Reforming can be achieved through a two-step reforming process involving reactive extrusion followed by compression molding. This behavior allows for simple forming and analysis via dynamic mechanical analysis (DMA). HDPE AT-Ph HDPE m and HDPE AT-NBuThe DMA exhibits a distinct rubber plateau at temperatures above the melt transition temperature of the HDPE matrix, which is consistent with the formation of the crosslinked network. Figure 31 This behavior is compared to the behavior of the original HDPE (gray curve); Figure 31 In contrast, the original HDPE control flowed under its own weight above the melt transition.

[0315] 7.3 HDPE AT-Ph recyclability HDPE AT-Ph The recyclability of this material is achieved through direct compression molding or, as... Figure 20 The ability to be reshaped via compression molding after additional extrusion cycles is further evaluated. The material is compressed into a suitable shape for DMA and tensile testing. After tensile fracture testing, the tested samples are recycled, cut, and reshaped directly via compression molding, or extruded and then reshaped via compression molding. As demonstrated by DMA and tensile testing, HDPE... AT-Ph Both tested schemes demonstrated excellent recyclability. Figure 32 With DMA, it is evident that a cross-linked material was obtained after recycling, exhibiting a plateau above the melt transition. The tensile properties remained substantially constant after recycling (Table 17).

[0316] In addition, HDPE AT-Ph HDPE that remains insoluble after recycling, such as that recycled through extrusion and compression molding. AT -Ph The insoluble fraction of the substance in xylene at 130°C after 16 hours was 49±7%.

[0317] Table 17. HDPE AT-Ph And the tensile properties of materials recycled through extrusion and compression molding or materials recycled solely through compression molding. Example 8. Comparative Example of a Method Implemented Without Step (a) 8.1. Sample 1: Reactive extrusion without a mixing step The raw HDPE (73.5 wt%) and masterbatch of azidotriazine 1 (26.5 wt%) were loaded into a 15 cubic centimeter (cc) twin-screw extruder at 100 rpm screw speed and 160 °C. This composition corresponds to 1 mol% of azidotriazine 1 in the HDPE. After all materials were introduced, the temperature was rapidly increased to 214 °C. The reaction proceeded for 10 min, and then the material designated as Sample 1 was extruded from the barrel.

[0318] 8.2. Sample 2: Reactive compression molding without melt homogenization The raw HDPE (73.5 wt%) received as commercial granules and the masterbatch of azidotriazine 1 in granule form (26.5 wt%) with a diameter of approximately 5 mm were introduced into a plastic box, covered, and manually shaken for approximately 1 minute. This composition corresponds to 1 mol% of azidotriazine 1 in the HDPE. The mixture was then introduced into a stainless steel mold, which was subsequently placed on a preheated benchtop manual Carver press. Compression molding was performed at 214°C under a normal force of 3 tons for 10 minutes. The sample, designated Sample 2, was then cooled to ambient temperature on the workbench.

[0319] After immersion in xylene at 130℃ for 15 hours, Sample 1 and Sample 2 showed insoluble fractions of 78±2% and 67±2%, respectively, which were higher than those of HDPE. m The insoluble fraction was 63 ± 2%. However, despite the high insoluble fractions, samples 1 and 2 still exhibited poor thermomechanical properties, such as those found in HDPE. m Compared to HDPE, the lower E' value of DMA and the lower melting temperature of HDPE m Compared to the lack of evidence from a rubber platform ( Figure 33 ).

[0320] Example 9. Grafting of azidotriazine AD-Ph onto HDPE via reactive processing 9.1 Grafting of azide-triazine AD-Ph onto HDPE according to the method of the present invention AD-Ph grafting was performed according to the same reactive processing method described in Examples 4 and 7 (see...). Figure 11 A). In the first step, a masterbatch of AD-Ph in HDPE was prepared according to the following steps: AD-Ph (2.02 g) was dissolved in xylene and purged with nitrogen for 5 min. HDPE (3.015 g) was suspended in xylene (50 mL) and purged with nitrogen for 5 min. The suspension was heated and stirred under nitrogen at 140 °C. When the polymer was completely dissolved, an azide diazine solution was added, and the mixture was stirred again under nitrogen at 140 °C for 5 min. The xylene was evaporated under reduced pressure at 90 °C, and the resulting masterbatch was dried overnight under the same conditions (mass obtained: 5 g, final AD-Ph loading: 40% by weight).

[0321] Then, in the second step, the AD-Ph masterbatch (2.692 g) and virgin HDPE (9.308 g) are co-loaded into a processing temperature of 180°C. T 混合The mixture was extruded in a 15 cubic centimeter (cc) twin-screw extruder. This mixing stage was introduced to ensure the melt was homogenized prior to grafting. After mixing for 5 minutes at a screw speed of 100 rpm, the temperature was rapidly increased to the reaction temperature. T R (In this case, it is 240°C). Compared with the one used for azidotriazine 1... T 混合 and T R Compared to the value (Example 4), the value used for AD-Ph in this example is... T 混合 and T R The higher values ​​are based on the slower decomposition kinetics of AD-Ph, which can be rationalized based on the Borchardt-Daniels kinetic parameters (Table 2); at 240 °C, the half-life of AD-Ph is 2 min. As can be seen in Figure 34A, at reaching T R Subsequently, the torque increased, indicating an increase in viscosity. The reaction proceeded for 10 minutes, after which the material (referred to as HDPE) was extruded from the barrel. AD-Ph The obtained HDPE AD-Ph It is a cross-linked material with a gel fraction of 79±6%.

[0322] 9.2 HDPE AD-Ph thermomechanical properties Despite HDPE AD-Ph It has a high gel fraction, yet it can be easily reshaped via compression molding. This behavior allows for simple molding and analysis using DMA. HDPE AD-Ph The DMA exhibits a distinct rubber plateau at temperatures above the melt transition temperature of the HDPE matrix, consistent with the crosslinked network (Figure 34B).

Claims

1. A method for preparing a polymer composition, the method comprising the following steps: (a) At processing temperature T 混合 The following mixtures of polymers or polymer blends with azide derivatives of formula (I): N3-Ar(I) Ar is a heteroaromatic group. Then (b) Heat the mixture from step a) to temperature T. R , in T 混合 The glass transition temperature or melting temperature of the polymer used in step (a) is higher than that of the polymer used in step (a), or the highest glass transition temperature or melting temperature of all polymers present in the polymer blend of step (a) at a content of at least 8% by weight relative to the total weight of the blend. T R Equal to or higher than the decomposition temperature of the azide in formula (I), and T 混合 Strictly below T R .

2. The method according to claim 1, wherein, The azide derivatives of formula (I) are selected from: ， Where R 1 To R x One or two of them, preferably one of which is N3, and the others are each independently selected from hydrogen atoms, halogens, C atoms, etc. 1-12 Alkyl, C 1-12 Halogenated alkyl, aryl, heteroaryl, C 1-12 Alkyl-aryl, bridging oxygen, NR c R d OR e C(O)R f C(O)OR g C(O)NR h R i SR j , CN and NO2, of which R c To R j Each is independently a hydrogen atom, C1-C 12 Alkyl, C 1-6 Alkyl-aryl or aryl, R x It is the group with the highest index on the compound.

3. The method according to claim 2, wherein, The azide derivatives of formula (I) are selected from: , , and , Preferably selected from , , , , , , , , , and , More preferably, the azide derivative is (1) or (AT-Ph).

4. The method according to any one of claims 1 to 3, wherein, The polymer or polymer blend is selected from polyolefins, polyesters, polystyrene (PS), polyurethane (PU), polyamides, polyvinyl chloride (PVC), natural polymers and their copolymers or blends.

5. The method according to claim 4, wherein, The polymer or polymer blend is a plastic or a mixture of plastics, particularly waste plastics or mixtures of waste plastics, such as unsorted plastics, broken plastics, mixtures of broken plastics, or mixtures thereof.

6. The method according to any one of claims 1 to 5, wherein, The decomposition temperature of the azide derivative of formula (I) is higher than the glass transition temperature (Ta) of the polymer in step (a). g ) or melting temperature (T) m ), provided that when the mixture in step (a) contains a blend of polymers, the relevant T g or T m It is the highest glass transition temperature (T0) of all polymers present in the blend at a content of at least 8% by weight relative to the total weight of the blend. g ) or melting temperature (T) m ).

7. The method according to any one of claims 1 to 6, wherein, In step (b), observe temperature T. R The reaction time t R , t R Corresponding to temperature T R The time required to decompose 50%, preferably 75%, more preferably 90%, or even more preferably 95% of the azide derivative of formula (I).

8. The method according to any one of claims 1 to 7, wherein, The mixture of step a) contains, relative to the polymer repeating unit, 0.05 mol% to 10 mol%, preferably 0.1 mol% to 3.5 mol%, more preferably 0.5 mol% to 1.5 mol% of the azide derivative of formula (I).

9. The method according to any one of claims 1 to 8, wherein, The azide derivatives of formula (I) are soluble, partially soluble or insoluble in the molten polymer or polymer blend used in step (a).

10. The method according to any one of claims 1 to 9, wherein, Step b) is performed by reactive extrusion, compression molding, injection molding, or oven curing.

11. The method according to any one of claims 1 to 10, wherein the method comprises step (a') prior to step (b): (a') at processing temperature T' 混合 The following mixtures of polymers or polymer blends with azide derivatives of formula (I): N3-Ar(I) in, Ar is a heteroaromatic group. The polymer or polymer blend and / or azide derivative of formula (I) used in step (a') are different from the polymer or polymer blend and / or azide derivative of formula (I) used in step (a). Among them, T' 混合 T' is higher than the glass transition temperature or melting temperature of the polymer used in step (a'), or higher than the highest glass transition temperature or melting temperature of all polymers present in the polymer blend in step (a') at a content of at least 8% by weight relative to the total weight of the blend. 混合 Strictly below T R , And step (b) includes heating the mixture from step (a) to temperature T in the presence of the mixture from step (a'). R .

12. The method according to any one of claims 1 to 10, the method comprising steps (a'), (b') and (c): (a') at processing temperature T 混合 The following mixtures of polymers or polymer blends with azide derivatives of formula (I): N3-Ar(I) in, Ar is a heteroaromatic group. The polymer or polymer blend and / or azide derivative of formula (I) used in step (a') are different from the polymer or polymer blend and / or azide derivative of formula (I) used in step (a). Among them, T' 混合 T' is higher than the glass transition temperature or melting temperature of the polymer used in step (a'), or higher than the highest glass transition temperature or melting temperature of all polymers present in the polymer blend in step (a') at a content of at least 8% by weight relative to the total weight of the blend. 混合 Strictly below T R , (b') Heat the mixture from step (a') to temperature T' R , where T' R The decomposition temperature of the azide is equal to or higher than that of formula (I) used in step (a'). Steps (a) and (b) are carried out in one reactor, and steps (a') and (b') are carried out in another reactor. (c) At temperature T'' R The polymer composition obtained in step (b) is blended with the polymer composition obtained in step (b') at a temperature T''. R equal to T R and T' R Higher temperatures in the environment.

13. A polymer composition obtained by the method according to any one of claims 1 to 12.

14. The polymer composition according to claim 13, wherein the polymer composition comprises groups of formula (II) and / or formula (III): (II) (III) in The bond between the group and the carbon atom of the repeating unit of the polymer in the composition. x and y are each independent integers ranging from 0 to 10, preferably 0 or 1. Ar is defined as the azide derivative of formula (I) used in the method described above, and *Selected from -H and another repeating unit of the polymer chain of the composition, carbon atoms.

15. The polymer composition of claim 14, further comprising a dangling group of formula -NH(Ar) attached to the carbon atom of the repeating unit of the polymer of the composition, wherein Ar is defined as an azide derivative of formula (I) used in the method of any one of claims 1 to 13.

16. The polymer composition according to any one of claims 13 to 15, further comprising a free compound comprising a heteroaromatic group Ar obtained by the decomposition of an unreacted azide derivative of formula (I) and / or the reaction of an azide derivative of formula (I) with a polymer or polymer blend, said free compound being selected, for example, from: - Free amines containing the heteroaromatic group Ar, such as primary amines of the formula NH2Ar. - Formula NHAr-[N(Ar)] x -NHAr polyazine, wherein x is from 0 to 10, preferably an integer of 0 or 1, - Formula NHAr-[N(Ar)] x -NAr· polyazine, wherein x is 0 to 10, preferably an integer of 0 or 1, or - Derivatives of the formula (Ar)N=N(Ar).

17. The additive of formula (I) as defined in any one of claims 1 to 3 N3-Ar(I) Used for upgrading recycled plastics or mixtures of plastics, particularly waste plastics or mixtures of waste plastics, such as unsorted plastics, broken plastics, mixtures of broken plastics, or mixtures thereof.

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