POLYOLEFIN TERPOLYMERS, VITRIMERS MADE THEREFROM, AND METHOD OF MAKING THE POLYOLEFIN TERPOLYMERS AND VITRIMERS

Abstract

Terpolymers that include a hydrocarbon unit, an acetoacetate terminated unit and a hydroxy-terminated unit are described. Vitrimers made from these terpolymers are also described.

Claims

1. A random terpolymer comprising a random distribution of: a hydrocarbon unit (A) having the formula ##STR00026## an acetoacetate (ACAC) terminated unit (B) having the formula ##STR00027## and a hydroxy terminated unit (C) having the formula ##STR00028## where R.sub.1 and R.sub.2 are each independently hydrogen (H) or a C.sub.1-5 alkyl group, R.sub.3 is a C.sub.1-10 alkyl group, R.sub.4 is a H or a C.sub.1-5 alkyl group, p is 1 to 9, and p′ is 1 to 9, wherein the hydrocarbon unit (A), the ACAC terminated unit (B), and the hydroxy terminated unit (C) are comprised in the random terpolymer; wherein the random terpolymer is produced by a process comprising contacting a reactant mixture comprising a C.sub.2-5 olefinic monomer and an acetoacetate terminated monomer with a polymerization initiator and a hydroxy-terminated monomer, and reacting the hydroxy-terminated monomer randomly with the hydrocarbon C.sub.2-5 olefinic monomer and the acetoacetate terminated monomer at a temperature of 100° C. to 350° C. and a pressure of 180 MPa to 350 MPa; wherein concentration of the acetoacetate monomer in the reactant mixture is less than 10 mol. %.

2. The random terpolymer of claim 1, wherein R.sub.1 and R.sub.2 are each independently hydrogen (H) or methyl (CH.sub.3).

3. The random terpolymer of claim 1, wherein the random terpolymer includes less than 10 mol. % of the acetoacetate functionality.

4. The random terpolymer of claim 1, wherein the random terpolymer is the random reaction product of an olefin.

5. The random terpolymer of claim 1, wherein the random terpolymer is insoluble in water.

6. A high-pressure free radical process to produce the terpolymer of claim 1, the process comprising contacting a reactant mixture comprising a C.sub.2-5 olefinic monomer and an acetoacetate terminated monomer with a polymerization initiator and a hydroxy-terminated monomer, and reacting the hydroxy-terminated monomer randomly with the hydrocarbon C.sub.2-5 olefinic monomer and the acetoacetate terminated monomer at a temperature of 100° C. to 350° C. and a pressure of 180 MPa to 350 MPa.

7. The process of claim 6, wherein concentration of the acetoacetate monomer in the reactant mixture is less than 1 mol. %.

8. The process of claim 6, wherein the C.sub.2-5 olefinic monomer is ethylene, the acetoacetate terminated monomer is 2-(methacryloyloxy)ethyl acetoacetate, and the polymerization initiator is a peroxide material.

9. The process of claim 6, wherein the hydroxy terminated monomer is hydroxyl-ethyl methacrylate.

10. The process of claim 9, wherein the C.sub.2-5 olefinic monomer is ethylene, the acetoacetate terminated monomer is 2-(methacryloyloxy)ethyl acetoacetate, and the polymerization initiator is a peroxide material.

11. The process of claim 6, wherein the process is a continuous process.

12. An article of manufacture comprising the random terpolymer of claim 1.

13. A vitrimer material comprising at least two polymeric units (D, D′) and a linking moiety (L) having the formula D-L-D, wherein D, D′ or both can have a random distribution of a hydrocarbon unit (A) having the formula ##STR00029## an acetoacetate (ACAC) terminated unit (B) having the formula ##STR00030## and a hydroxy terminated unit (C) having the formula ##STR00031## where R.sub.1 and R.sub.2 are each independently hydrogen (H) or a C.sub.1-5 alkyl group, R.sub.3 is a C.sub.1-10 alkyl group, R.sub.4 is a H or a C.sub.1-5 alkyl group, p is 1 to 9, and p′ is 1 to 9, wherein the vitrimer is recyclable.

14. The vitrimer material of claim 13, wherein L is a polyamino group comprising at least two secondary amines.

15. The vitrimer material of claim 14, wherein the polyamino group is ##STR00032## or any combination thereof, where R.sub.6 and R.sub.7 are each independently an aliphatic group, and R.sub.8, R.sub.9, R.sub.10, and R.sub.11 are each independently an aliphatic group, or an aromatic group, and a is 1 to 20, b is 1 to 20 and c is 1 to 20.

16. The vitrimer material of claim 13, wherein the polymeric unit D, D′ or both, are derived from a random terpolymer comprising a random distribution of: a hydrocarbon unit (A) having the formula ##STR00033## an acetoacetate (ACAC) terminated unit (B) having the formula ##STR00034## and a hydroxy terminated unit (C) having the formula ##STR00035## where R.sub.1 and R.sub.2 are each independently hydrogen (H) or a C.sub.1-5 alkyl group, R.sub.3 is a C.sub.1-10 alkyl group, R.sub.4 is a H or a C.sub.1-5 alkyl group, p is 1 to 9, and p′ is 1 to 9, wherein the hydrocarbon unit (A), the ACAC terminated unit (B), and the hydroxy terminated unit (C) are comprised in the random terpolymer; wherein the random terpolymer is produced by a process comprising contacting a reactant mixture comprising a C.sub.2-5 olefinic monomer and an acetoacetate terminated monomer with a polymerization initiator and a hydroxy-terminated monomer, and reacting the hydroxy-terminated monomer randomly with the hydrocarbon C.sub.2-5 olefinic monomer and the acetoacetate terminated monomer at a temperature of 100° C. to 350° C. and a pressure of 180 MPa to 350 MPa; wherein concentration of the acetoacetate monomer in the reactant mixture is less than 10 mol. %.

17. The vitrimer material of claim 13, wherein the vitrimer comprises a semi-crystalline morphology.

18. A process of producing a vitrimer material of claim 13 using an extruder, the process comprising contacting a reactant mixture comprising a random terpolymer with a polyamino group comprising at least two secondary amines at temperatures from 120° C. to 300° C., wherein the random terpolymer comprises a random distribution of: a hydrocarbon unit (A) having the formula ##STR00036## an acetoacetate (ACAC) terminated unit (B) having the formula ##STR00037## and a hydroxy terminated unit (C) having the formula ##STR00038## where R.sub.1 and R.sub.2 are each independently hydrogen (H) or a C.sub.1-5 alkyl group, R.sub.3 is a C.sub.1-10 alkyl group, R.sub.4 is a H or a C.sub.1-5 alkyl group, p is 1 to 9, and p′ is 1 to 9, wherein the hydrocarbon unit (A), the ACAC terminated unit (B), and the hydroxy terminated unit (C) are comprised in the random terpolymer; the process comprising contacting a reactant mixture comprising a C.sub.2-5 olefinic monomer and an acetoacetate terminated monomer with a polymerization initiator and a hydroxy-terminated monomer, and reacting the hydroxy-terminated monomer randomly with the hydrocarbon C.sub.2-5 olefinic monomer and the acetoacetate terminated monomer at a temperature of 100° C. to 350° C. and a pressure of 180 MPa to 350 MPa.

19. An article of manufacture comprising the vitrimer material of claim 13.

20. (canceled)

21. An article of manufacture comprising the vitrimer material of claim 14.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings.

[0035] FIG. 1 shows high temperature proton nuclear magnetic resonance (HT-.sup.1H NMR) for the PACE polymers and a comparison example made through transesterification.

[0036] FIG. 2 shows dynamic mechanical thermal analysis (DMTA) graphs for PACHE copolymer with varying ACAC content cross-linked with 0.55 molar equivalents of p-xylylene diamine (with respect to ACAC groups). The curves are named according to the ACAC content of the parent polymer.

[0037] FIG. 3 shows graphs of frequency sweep at 160° C. of PACHE copolymers with varying ACAC contents cross-linked with 0.55 molar equivalents of p-xylylene diamine (with respect to ACAC groups) and a pristine sample (no crosslinking). The curves are named according to the ACAC content of the parent polymer.

[0038] FIG. 4 shows graphs of complex viscosity of vitrimers of the present invention and a pristine sample (no crosslinking) as function of frequency measured in the melt at 160° C.

[0039] FIG. 5 shows average results (from quadruplets) of tensile tests on dog bones made from vitrimers (PACHE with 0.94% ACAC and 0.55 equivalents of XYDIA, Break 1) and recycled dog bones made from the tested dog bones processed 2, 3 and 4 times (Breaks 2, 3, and 4).

[0040] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale.

DETAILED DESCRIPTION OF THE INVENTION

[0041] A discovery has been made that provides a solution to at least some of the problems associated with production of vitrimers. The discovery is premised on the idea of a terpolymer that is capable of being extruded in the presence of a crosslinking group at temperatures of 120° C. to 300° C. to produce a vitrimer material. The produced vitrimer material can be semi-crystalline. The terpolymer used to produce the vitrimer material can be a random terpolymer. The random terpolymer can include a hydrocarbon unit, an acetoacetate-terminated unit and a hydroxy-terminated unit (e.g., units A, B and C described above) randomly distributed in the polymeric matrix. Notably, the terpolymer can be water insoluble.

[0042] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

[0043] A. Functionalized Polymers

[0044] The functionalized polymers of the present invention can include a terpolymer or a copolymer. The terpolymers of the present invention are functionalized polymers. Terpolymers of the present invention can be the random reaction products of an olefin (e.g., C.sub.1-5 olefin, preferably, ethylene or propylene), an acetoacetate terminated (meth)acrylate (ACAC), and a hydroxyl terminated (meth)acrylate (HEMA) forming a random terpolymer having non-uniformly distributed units (e.g., containing a PE-ACAC-HEMA or PACHE portion) in the polymeric matrix. The random terpolymer can a random distribution of 3 units coupled together in a non-uniform manner. The three units include a hydrocarbon unit (A) having the formula

##STR00013##

an acetoacetate (ACAC) terminated unit (B) having the formula

##STR00014##

and a hydroxy terminated ester unit (C) having the formula

##STR00015##

where R.sub.1 and R.sub.2 are each independently hydrogen (H) or a C.sub.1-5 alkyl group, R.sub.3 is a C.sub.1-10 alkyl group, R.sub.4 is a H or a C.sub.1-5 alkyl group, p is 1 to 9, and p′ is 1 to 9. Units A, B and C, can be coupled in a random manner at the wavy lines. For example, A can couple to B and/or C, two B units can couple and then couple to an A unit or a C unit, two C units can couple and then couple to an A unit or a B unit, and so on.

[0045] A portion of the random terpolymer can also be represented by the formula:

##STR00016##

where R.sub.1 and R.sub.2 can each be independently hydrogen (H) or a C.sub.1-5 alkyl group, R.sub.3 can be a H or C.sub.1-10 alkyl group, R.sub.4 can be a H or a C.sub.1-5 alkyl group, p and p′ are repeating units, and x, y and z are mole percentages of the functional group content. Non-limiting examples of C.sub.1-5 alkyl groups can include methyl, ethyl, n-propyl isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, and any combination thereof. Non-limiting examples of C.sub.1-10 alkyl groups can include methyl, ethyl, n-propyl isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-methylbutan-2-yl, 2,2-dimethylpropyl, 3-methylbutyl, pentan-2-yl, pentan-3-yl, 3-methylbutan-2-yl, 2-methylbutyl, hexyl, heptyl, octyl, nonyl, and decyl. The value for p and/or p′ can be 0 to 9, or 1 to 5 or at least any one of, equal to any one of, or between any two of 1, 2, 3, 4, 5, 6, 7, 8, 9, preferably 1. The value for x can be 0 to 10, or at least any one of, equal to any one of, or between any two of 0, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. The value for y can be 88 to 99, or at least any one of, equal to any one of, or between any two of 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, and 99. The value for z can be 0.1 to 10, or at least any one of, equal to any one of, or between any two of 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. In one embodiment, R.sub.1, R.sub.2 and R.sub.3 are all methyl and R.sub.4 is hydrogen. In another embodiment, R.sub.1 is methyl, and R.sub.2 R.sub.3, and R.sub.4 are hydrogen. In some embodiments, R.sub.1 and R.sub.4 are hydrogen and R.sub.2 and R.sub.3 are methyl. The terpolymers of the present invention can be water insoluble. Without wishing to be bound by theory, the water insolubility is believed to be due to the length of the carbon hydroxyl-terminated chain (i.e., 9 or less chain units) in the terpolymer. This can result in the terpolymers having more hydrophobic or lipophilic characteristics.

[0046] The functionalized random terpolymers of the present invention can be made through a high-pressure free radical process. In a preferred aspect, the high pressure free radical process is a continuous process. In the process, suitable monomers can be polymerized under conditions to produce the functionalized terpolymers of the present invention. By way of example, a C.sub.2-5 olefin monomer (e.g., a precursor material to the hydrocarbon unit A) and an acetoacetate monomer (e.g., a precursor material to ACAC terminated unit B) and an optional hydroxy-terminated monomer can be contacted with a polymerization initiator at polymerization conditions suitable to produce a functionalized terpolymer of the present invention. Suitable hydrocarbon unit precursor materials can include C.sub.2-5 olefinic monomers such as ethylene, propylene, butylene, or pentene, or mixtures thereof. The flow of the reactants can be adjusted to control the degree of polymerization. Polymerization conditions can include temperature and pressures. Reaction temperatures can be at least any one of, equal to one of, or between any two of 100° C., 125° C., 150° C., 175° C., 200° C., 225° C., 250° C., 275° C., 300° C., 325° C. and 350° C. Reaction pressures can be at least any one of, equal to any one of, or between any two of 180 MPa, 190 MPa, 200 MPa, 210 MPa, 220 MPa, 230 MPa, 240 MPa, 250 MPa, 260 MPa, 270 MPa, 280 MPa, 290 MPa, 300 MPa, 310 MPa, 320 MPa, 330 MPa, 340 MPa and 350 MPa. Any peroxide polymer initiator can be used and is available from commercial vendors such as Arkema (France). Non-limiting examples of peroxide initiators include diacyl peroxide, t-butyl peroxypivalate or the like.

[0047] Suitable acetoacetate monomers can include any functionalized diketone material or meth(acrylate) having one or more acetoacetate groups, or ethylenically unsaturated monomers having one or more acetoacetate groups. Non-limiting examples of suitable acetoacetate monomers include 2-(methacryloyloxy)ethyl acetoacetate (AAEM) (CAS No. 21282-97-3), 2-(acryloyloxy)ethyl acetoacetate (CAS No. 21282-96-2). In a preferred instance, 2-(methacryloyloxy)ethyl acetoacetate is used. The acetoacetate monomer concentration in the reactant mixture can be less than 10 mol. %, equal to any one of, or between any two of 9.99 mol. %, 8 mol. %, 7 mol. %, 6 mol. %, 5 mol. %, 4 mol. %, 3 mol. %, 2 mol. %, 1 mol. %, 0.9 mol. %, 0.8 mol. %, 0.7 mol. %, 0.6 mol % or 0.5 mol. %, 0.4 mol. %, 0.3 mol. %, 0.2 mol %, 0.1 mol %, but greater than 0 mol. %. In some instances, the acetoacetate monomer concentration is between 0.1 mol. % to 0.5 mol. %.

[0048] In some embodiments, contact of the C.sub.2-5 olefin monomer (e.g., a hydrocarbon unit precursor material) and the acetoacetate monomer with the polymerization initiator produces a hydroxy-terminated acrylate monomer in situ, and the hydroxy-terminated acrylate monomer can react with at least a portion of the polyolefin backbone to form the terpolymer of the present invention. The hydroxy-terminated acrylate monomer is a precursor to the hydroxy-terminated acrylate unit C. By way of example, ethylene and 2-(methacryloyloxy)ethyl acetoacetate can react to form hydroxyethyl methacrylate, which in turn reacts with a portion of the olefin to form the terpolymer(s) of the present invention.

[0049] In another instance, a hydroxy-terminated acrylate monomer (e.g., 2-hydroxyethyl methacrylate) can be added to the reaction mixture that includes the C.sub.2-5 olefin monomer and the acetoacetate monomer with the polymerization initiator. At the reaction conditions, the C.sub.2-5 olefin monomer, the acetoacetate monomer, and the hydroxy-terminated acrylate monomer react to form the terpolymer(s) of the present invention.

[0050] B. Vitrimers

[0051] At least two polymeric units (D) of the present invention can be linked with a linking moiety (L) to form a vitrimer of the formula D-L-D′. The polymeric units D and/or D′ can be any one of the random terpolymers of the present invention. In a preferred instance D and D′ are the terpolymers of the present invention. In some instances, D and/or D′ can be a terpolymer having a random distribution of a hydrocarbon unit (A) having the formula

##STR00017##

an acetoacetate (ACAC) terminated unit (B) having the formula

##STR00018##

and a hydroxy terminated unit (C) having the formula

##STR00019##

where R.sub.1 and R.sub.2 are each independently hydrogen (H) or a C.sub.1-5 alkyl group, R.sub.3 is a C.sub.1-10 alkyl group, R.sub.4 is a H or a C.sub.1-5 alkyl group, p is 1 to 9, and p′ is 1 to 9.

[0052] In another instance, a portion of the random terpolymer can have the following formula:

##STR00020##

where R.sub.1 and R.sub.2 can each be independently hydrogen (H) or a C.sub.1-5 alkyl group, R.sub.3 can be a H or a C.sub.1-10 alkyl group, R.sub.4 can be a H or a C.sub.1-5 alkyl group, p can be 1 to 9, and p′ can be 1 to 9, x can be 0 to 10, y can be 88 to 99, and z can be 0.1 to 10, where p and p′ are repeat units and x, y, z are mole percentage (mol. %) of functional group content. In one instance, the vitrimer can have the following formula:

##STR00021##

where L is the linking group covalently bonded to the vinyl group of the polymer.

[0053] The linking group (L) can be any difunctional group capable of reacting with a carbonyl functional group. In a preferred instance, the linking group is a polyamino group. Polyamino groups can be derived from a di-, tri-, or poly-amine. In some embodiments, polyamines can include amines having the formula (R.sub.5).sub.n—NH.sub.x, in which R.sub.5 can be optionally substituted C.sub.1-20 alkyl, C.sub.3-8 cycloalkyl, C.sub.6-12 aryl, hetero C.sub.1-20 alkyl, heterocycle, heteroaryl, n is 0 to 3, and x is 0 to 2. Non-limiting examples of polyamines include tris(2-aminoethyl)amine, ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dihexylenetriamine, cadaverine, putrescine, hexanediamine, spermine, isophorone diamine, dimerized fatty diamine (such as are available commercially under the trade name Priamine from Croda International and the trade name Versamine from Cognis Corporation), 1,3-cyclohexanebis(methylamine), 1,2-diaminocyclohexane, 1,5-diamino-2-methylpentane, 4,9-dioxa-1,12-dodecanediamine, 1,3-pentanediamine, 2,2-dimethyl-1,3-propanediamine, 2,2′-(ethylenedioxy)bis(ethylamine), tris(2-aminoethyl)amine, tris(2-aminoalkyl)amines, 4,4′-methylenebis(cyclohexylamine); 4,7,10-trioxa-1,13-tridecanediamine; all polyether amines (e.g., JEFFAMINE® products commercially available from Huntsman). Non-limiting examples of aromatic amines include m-xylylene diamine, p-xylylene diamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, methylenebischlorodiethylaniline, or any combination thereof. In some instances p-xylylene diamine, tris(2-aminoalkyl)amines, spermines or any combination thereof can be used. Generic polyamines are illustrated below:

##STR00022##

or any combination thereof,
where R.sub.6 and R.sub.7 are each independently an aliphatic group, and R.sub.8, R.sub.9, R.sub.10, and R.sub.11 are each independently an aliphatic group, or an aromatic group, and a is 1 to 20, b is 1 to 20 and c is 1 to 20. In some embodiments, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, and R.sub.11 are —CH.sub.2— and can be presented in the following illustration:

##STR00023##

or any combination thereof,
where a is 1 to 20, b is 1 to 20 and c is 1 to 20. In a preferred instance, the polyamine is p-xylene diamine.

[0054] Vitrimers of the present invention can be produced through a condensation reaction of the linking group with the functionalized polyolefin. The vitrimers can be manufactured by various methods known in the art. By way of example, the vitrimers can be produced using an extrusion process. The functionalized polymer (e.g., terpolymer) can be contacted with an amount of linking material (e.g., a polyamine) under conditions sufficient to react the linking material with the carbonyl group to form the vitrimer (e.g., a urethane linkage). In some instances, the functionalized polymer and linking material can be blended in a high speed mixer or by hand mixing. The blend can then be fed into the throat of a twin-screw extruder via a hopper. Alternatively, the linking material can be contacted with the functionalize polymer by feeding it directly into the extruder at the throat or downstream through a side port into the extruder. The extruder is generally operated at a temperature higher than that necessary to cause the functionalized polyolefin to flow and sufficient to promote the condensation reaction. Reaction conditions can include temperatures from 120° C. to 300° C., preferably 140° C. to 160° C., or at least any one of, equal to any one of, or between any two of 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., 190° C., 200° C., 210° C., 220° C., 230° C., 240° C., 250° C., 260° C., 270° C., 280° C., 290° C. and 300° C. At least a slight excess of linking material amount is used during an extrusion process. The extrudates can be immediately quenched in a water bath and pelletized. Such pellets can be used for subsequent molding, shaping, or forming. A non-limiting example of preparation of vinylogous urethane polyolefin vitrimers with a polyamine is shown in the following reaction scheme (A), where x, y and z are defined above and R.sub.5 is the hydrocarbon moiety (linking group) derived from the polyamine (R.sub.5).sub.nNH.sub.x defined above. The asterisk represent continuing polymeric portions.

##STR00024##

[0055] The vitrimers and random terpolymers of the present invention can be produced as films, sheets, foams, particles, granules, beads, rods, plates, strips, stems, tubes, etc. via any process known to those skilled in the art. By way of example, extrusion, casting, compression molding can be used. These elemental components based on the terpolymers and/or vitrimers of the present invention, are easy to store, transport and handle.

[0056] The components can be subjected to heat and/or mechanical constraint through blending, extrusion, molding (injection or extrusion), blow-molding, or thermoforming to form an article of manufacture. This transformation can include mixing or agglomeration with one or more additional components chosen from: one or more polymers, pigments, dyes, fillers, plasticizers, fibers, flame retardants, antioxidants, lubricants.

[0057] C. Articles of Manufacture

[0058] The random terpolymers and/or vitrimers of the present invention can be used in all types of applications and articles of manufacture. Non-limiting examples of the types of applications that the materials of the present invention can be used in include motor vehicles, airplanes, boats, aeronautical construction or equipment or material, electronics, sports equipment, construction equipment and/or materials, printing, packaging, biomedical, and cosmetics. Non-limiting examples of articles of manufacture can include leak tight seals, thermal or acoustic insulators, tires, cables, sheaths, footwear soles, packagings, coatings (paints, films, cosmetic products), patches (cosmetic or dermopharmaceutical), furniture, foams, systems for trapping and releasing active agents, dressings, elastic clamp collars, vacuum pipes, pipes and flexible tubing for the transportation of fluids. Examples of packaging materials include films and/or pouches, especially for applications such as food and/or beverage packaging applications, for health care applications, and/or pharmaceutical applications, and/or medical or biomedical applications. The materials can be in direct contact with an item intended for human or animal use, such as for example a beverage, a food item, a medicine, an implant, a patch or another item for nutritional and/or medical or biomedical use.

[0059] The articles of manufacture can exhibit good resistance to tearing and/or to fatigue. The articles of manufacture can include rheological additives or additives for adhesives and hot-melt adhesives. In these applications, the materials according to the invention can be used as such or in single-phase or multiphase mixtures with one or more compounds such as petroleum fractions, solvents, inorganic and organic fillers, plasticizers, tackifying resins, antioxidants, pigments and/or dyes, for example in emulsions, suspensions or solutions.

[0060] In an embodiment, an article based on the terpolymers or vitrimers of the present invention can be manufactured by molding, filament winding, continuous molding or film-insert molding, infusion, pultrusion, RTM (resin transfer molding), RIM (reaction-injection molding), 3D printing, or any other method known to those skilled in the art. The means for manufacturing such an article are well known to those skilled in the art. In some embodiments, the terpolymers or vitrimers of the present invention and/or other ingredients can be mixed and introduced into a mold and the temperature raised.

[0061] Films that include the terpolymers and/or vitrimers of the present invention can have various thicknesses. For example, films can be from 1 micrometer to 1 mm thick. Multilayer films of the present invention can be produced by co-extrusion or other bonding methodology.

[0062] In some embodiments, the vitrimers of the present invention, on account of their particular composition, can be transformed, repaired, and/or recycled by raising the temperature of the article. Below the glass transition (Tg) temperature, the vitrimers are vitreous-like and/or have the behavior of a rigid solid body. Above the Tg temperature (or Tm for semi-crystalline polymers), the vitrimers become flowable and moldable. Below the Tg or the solidification temperature, in case of semi-crystalline materials, the material behaves like a hard glassy solid, whereas above, the material is soft and rubber like. The other temperature of importance is related to the exchange reactions of the vitrimer network called the topology freezing temperature (Tv). Until exchange reactions become fast enough, the network is set, and the topology cannot change. The convention is to place Tv at the solid to liquid transition point where a viscosity of 10.sup.12 Pa.Math.s is reached. The vitrimer will first behave like a glassy solid below Tg in case of amorphous materials, then like an elastomer above Tg, and finally, when Tv is reached, the viscosity will decline following the Arrhenius law because viscosity is predominantly controlled by the exchange reactions. For semi-crystalline polymers, also the melting temperature (Tm) and the crystallization temperature (Tc) has to be considered. For sufficiently crystalline polymers (crystalline network leading to elastic network response), Tm/Tc will have a similar influence as Tg, below which the topology is frozen due to the physical connections provided by the crystals inhibiting flow and therefore the ability to measure Tv.

[0063] Transforming at least one article made from a vitrimer of the present invention can include application to the article of a mechanical constraint at a temperature (T) above the Tm of the material. The mechanical constraint and temperature are selected to enable transformation within a time that is compatible with industrial application of the process. By way of example, a transformation can include applying a mechanical constraint at a temperature (T) above the Tm of the material of which the article is composed, and then cooling to room temperature, optionally with application of at least one mechanical constraint. By way of example, an article of manufacture such as a strip of material can be subjected to a twisting action. In another example, pressure can be applied using a plate or a mold onto one or more faces of an article of the invention. Pressure can also be exerted in parallel onto two articles made of material in contact with each other so as to bring about bonding of these articles. In yet another example, a pattern can be stamped in a plate or sheet made of material of the invention. The mechanical constraint may also consist of a plurality of separate constraints, of identical or different nature, applied simultaneously or successively to all or part of the article or in a localized manner. Raising of the temperature of the article or manufacture or of any terpolymer or vitrimer of the present invention can be performed by any known means such as heating by conduction, convection, induction, spot heating, infrared, microwave or radiant heating. The means for bringing about an increase in temperature can include an oven, a microwave oven, a heating resistance, a flame, an exothermic chemical reaction, a laser beam, a hot iron, a hot-air gun, an ultra-sonication tank, a heating punch, etc. In some embodiments, application of a sufficient temperature and a mechanical constraint to an article of manufacture that includes a vitrimer of the present invention, a crack or damage caused in a component formed from the material or in a coating based on the material can be repaired.

[0064] In some embodiments, an article made of vitrimer material of the invention may also be recycled, for example, by direct treatment of the article or by size reduction. For example, the broken or damaged article of manufacture can be repaired by means of a transformation process as described above and can thus regain its prior working function or another function. In another example, the article of manufacture can be reduced to particles by application of mechanical grinding, and the particles thus obtained can then be used in a process for manufacturing an article. In some embodiments, the reduced particles can be simultaneously subjected to a raising of temperature and a mechanical constraint; allowing them to be transformed into an article. The mechanical constraint that allows the transformation of particles into an article can include compression molding, blending or extrusion. Thus, molded articles can be made from the recycled material that includes the terpolymers and/or vitrimers of the present invention.

[0065] In some embodiments, transforming the components or articles of manufacture can be performed by a final user without chemical equipment (no toxicity or expiry date or VOC, and no weighing out of reagents).

EXAMPLES

[0066] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.

Example 1

High Pressure Copolymerization

[0067] A continuous stirred autoclave reactor was used to produce the material at an average of 0.6 kg-LDPE/h, operated at 180 to 220° C., pressure of 2000 barg (˜200 MPa), and ethylene flow rate of 4 kg/h with a single monomer and peroxide injection. Total volume was 110 ml, effective volume was 99 ml. Table 1 lists the polymerization conditions and results.

[0068] Raw Materials Used [0069] Ethylene: purity >99.9%—Oxygen<5 ppm. [0070] 2-(Methacryloyloxy) ethyl acetoacetate (AAEM): purity about 95%. [0071] Isopropanol: purity>99%.

[0072] Polymerization Parameters: [0073] Pressure: 2000 bars (200 MPa). [0074] Wall temperature: 200° C.-220° C. [0075] Ethylene flow rate was fixed at around 4 kg/h (residence time ˜45 s). [0076] The impeller velocity was fixed at 1540 rpm. [0077] Peroxide: t-butyl peroxypivalate (Luperox® 11M75, Arkema). [0078] Temperature of polymerization: 180° C.-220° C. [0079] Comonomer flow: 0.05 to 0.4 mol. % of AAEM in the ethylene feed.

TABLE-US-00001 TABLE 1 Pres- Conver- sure Temp sion MFR Run Polymers MPa ° C. % g/10 min 1 Ethylene with 0.05 mol % 200 180 8.46 0.03 AAEM in the feed 2 Ethylene with 0.05 mol % 200 200 10.13 0.18 AAEM in the feed 3 Ethylene with 0.1 mol % 200 180 8.09 0.05 AAEM in the feed 4 Ethylene with 0.1 mol % 200 200 10.88 0.72 AAEM in the feed 5 Ethylene with 0.2 mol % 200 180 9.72 0.28 AAEM in the feed 6 Ethylene with 0.2 mol % 200 200 11.66 2.12 AAEM in the feed 7 Ethylene with 0.4 mol % 200 180 9.97 0.52 AAEM in the feed 8 Ethylene with 0.4 mol % 200 200 12.38 2.85 AAEM in the feed

[0080] During the reaction, a portion of the ACAC hydrolysed to form HEMA in situ, which reacted with the remaining olefin to form the terpolymer. Table 2 lists the amount of HEMA generated in situ due to the hydrolysis of ACAC.

TABLE-US-00002 TABLE 2 AAEM Feed Temp. MFR HEMA ACAC Combined Entry (mol %) (° C.) (g/10 min) (mol %) (mol %) (mol %) 1 0.05 180 0.03 0.37 0.15 0.53 2 0.1 180 0.05 0.4 0.45 0.85 3 0.2 180 0.28 0.5 1.1 1.6 4 0.4 180 0.52 0.63 2.73 3.36 5 0.05 200 0.18 0.17 0.12 0.29 6 0.1 200 0.72 0.2 0.38 0.58 7 0.2 200 2.12 0.23 1.11 1.34 8 0.4 200 2.85 0.62 2.4 3.02

[0081] The presence of HEMA was confirmed by high temperature proton nuclear magnetic resonance (HT-′H-NMR) at 100° C. by comparing the spectra to PACHE made through transesterification of a PE-HEMA as shown in reaction scheme (B). FIG. 1 depicts the HT-.sup.1H-NMR of the compounds made using the two different methodology, where the top spectrum is the terpolymer and the bottom spectra the PACHE made through conventional transesterification reactions to produce vitrimer material of the present invention. The transesterification reaction is shown in scheme (B) and the ingredients are listed in Table 3. The transesterification of PE-HEMA was carried out in solution, by first dissolving PE-HEMA polymers with varying amounts of HEMA in toluene, then adding methyl acetoacetate and 4-(dimethylamino)pyridine (DMAP), which was used as a transesterification catalyst. The reaction was carried out under atmospheric pressure to ensure that the developing methanol could evaporate. The polymers could be easily recovered via precipitation. By using PE-HEMA polymers with different amounts of HEMA, PACHE polymers with varying amounts of ACAC were be obtained. Three grades of PE-HEMA were used, obtaining a maximum degree of substitution of 67% (determined via nuclear magnetic resonance (NMR)).

##STR00025##

TABLE-US-00003 TABLE 3 HEMA cont. Polymer Toluene t Func. Entry (Mol %) mass (g) (ml) ACAC Cat. (min) (NMR) 1 16.5 8 160 10 EQ DMAP, 1 EQ 420 67 2 16.5 8 160 10 EQ CsF, 0.1 EQ 1320 64 3 1.65 16.1 160 10 EQ DMAP, 1 EQ 240 58 4 12.4 40 530  5 EQ DMAP, 1 EQ 240 54 5 7.5 30 400  5 EQ DMAP, 1 EQ 240 53

[0082] As shown in the NMR spectra, the methodology of transesterification does not produce polymers with complete functionalization. Thus, the high-pressure polymerization methodology provides more efficient and highly functionalized polymers.

Example 2

Preparation of PACHE Vinylogous Urethane Polyolefins

[0083] PACHE (polymeric unit “A” described above where R.sub.1 is CH.sub.3, and R.sub.2, R.sub.3, and R.sub.4 are H) was reacted with linking (L) material of XYDIA, (structure III, where R.sub.6 and R.sub.7 are CH.sub.2, and a and b are equal to 1), using the following general procedure to produce PACHE vinylogous urethane polyolefins and PACHE vitrimers of the present invention. The polymer (PACHE) was melted at 140° C. inside a Haake™ PolyLab™ compounding machine until the observed torque was constant. Then, the machine was opened, and 0.55 equivalents of XYDIA (with respect to the ACAC groups in the PACHE) was added slowly using a syringe. Then, the machine was closed and allowed to react for 15 min or until the observed torque was constant. The screws were stopped, and the machine opened and the vitrimer material of the present invention was removed and processed into a film. Table 4 lists an overview of the prepare materials.

TABLE-US-00004 TABLE 4 ACAC (mol %) HEMA (mol %) Type EQ Entry Material In polymer In polymer of Amine amine 1 PACHE 0.12 0.53 XYDIA 0.55 2 PACHE 0.34 0.93 XYDIA 0.55 3 PACHE 0.66 1.34 XYDIA 0.55 4 PACHE 0.94 1.50 XYDIA 0.55

Example 3

Characterization of Vitrimers of the Present Invention

[0084] The vitrimers from Example 2 were made into films using compression molding methodology. The vitrimer material was placed in a mold and compressed at 140° C. to 160° C. at 2000 kN to a thickness of 1 to 1.2 mm and tested using dynamic mechanical thermal analysis (DMTA) and rheology testing.

[0085] DMTA. Rectangular samples suitable for DMTA were cut to dimension of 3×5×0.5 mm (length×width×thickness). Samples were measured on a TA Instruments Q800 (TA Instruments, USA) in tensile mode. The storage modulus (E′) and loss modulus (E″) were monitored while screening the samples during a temperature sweep from −100 to 200° C. at 3 K/min. An oscillation frequency of 1 Hz with an oscillation amplitude of 10 μm were applied.

[0086] Results. DMTA measurement of PACHE vinylogous urethane polyolefins with different contents of ACAC. FIG. 2 shows DMTA graphs for PACHE vitrimers (Entries 1˜4 of Example 2). The curves are named according to the ACAC content of the parent polymer. Entry 1 (square monikers) had 0.12 mol % ACAC, entry 2 (circle monikers) had 0.34 mol. % ACAC, and entry 3 (diamond monikers) had 0.66 mol. % ACAC, and entry 4 (rectangle monikers) had 94 mol. % ACAC. From the curves it is apparent that 0.12 mol. % of ACAC within the polymer was not sufficient to obtain a fully cross-linked polymer system that provided a rubber plateau after melting of the crystalline regions above about 120° C. The material with 0.34 mol. % of ACAC retained a modulus after melting, revealing the characteristic rubber plateau for semi-crystalline vitrimers Further increasing the ACAC content increased the cross-link density, which in turn raised the observed modulus during DMTA analysis.

[0087] Rheology. Samples for rheology were prepared via compression molding to obtain disk shaped specimens (diameter 25 mm, thickness 1 mm). Samples were measured using a TA Instruments DHR-2, equipped with a parallel plate geometry. Samples were measured with a frequency sweep from 100-0.01 rad/s using a strain amplitude of 0.4% at a temperature of 150° C.

[0088] Frequency sweep of PACHE vinylogous urethane polyolefins with different contents of ACAC: Referring to FIG. 3, the crosslinking of the material was analyzed. The curve of the pristine sample (no crosslinking, square monikers) corresponded to the comparison of PACHE copolymer with 0.34 mol. % of ACAC (and no XYDIA) and was taken as a general representation of a low-density polyolefin. Even though cross-linking of the 0.12 mol. % of ACAC (entry 1) containing polymer was not enough to observe a rubber plateau modulus of the vitrimer during DMTA, partial cross-linking and chain extension was determined to have occurred, as the rheology of this sample (square filled and non-filled monikers) was severely altered in comparison to the comparison polymer (black line). This was apparent from the increased moduli and observed crossover frequency where G′>G″, which was not observed for the comparison polymer in the melt within the same measurement range. From the data of Entry 2 with 0.34 mol % of ACAC (filled and unfilled triangle monikers), a solid character over the entire frequency range, with G′>G″ within the available measurement range was observed, although the material was not fully cross-linked, because G′ was still dependent on the time scale (frequency dependent). Raising the cross-link density (Entry 3), resulted in a further increased storage modulus, but a frequency dependence persisted. Entry 4, having 0.94 mol. % of ACAC (filled and unfilled diamond monikers) exhibited the expected rheology for a fully cross-linked polymer, with G′>G″ over the measured frequency range and a completely frequency independent storage modulus G′.

[0089] Complex viscosity as function of frequency of PACHE vinylogous urethane copolymers with different contents of ACAC: The complex viscosity determined during rheology experiments (See, FIG. 4) provided a similar picture as was observed from the storage and loss moduli. Usually a constant at low shear rates/low frequency for polymer melts (known as zero shear), the melt viscosity increased linearly for the cross-linked species with greater increases for higher cross-link densities. No zero shear was observed or expected for the cross-linked materials within the available measurement range.

[0090] Determination of crosslinking. The presence of crosslinking in the polymers was determined using gel fraction methodology, based on the solubility of the polymers in xylene at 100° C. as compared to the pristine non-crosslinked polymer, which is fully soluble in xylene.

[0091] Gel Fraction Method. Extruded pieces (mass of each sample approximately 190 mg) were first placed in a 50 mL vial, 10 mL of xylene was added to the vial, the vial closed, heated to 100° C., and kept for 24 h. After cooling to room temperature, the liquid was removed with a syringe and the solid residue washed at least three times with methanol. The samples were dried in a vacuum oven (80° C.) until the weight was constant. The gel fraction was determined according to the equation (1) and the average from at least 6 specimens. The results are listed in Table 5.

Gel fraction (%)=(m.sub.final/m.sub.initial)*100  (1)

TABLE-US-00005 TABLE 5 Gel content Entry Sample (in %) 1 PACHE with 0.66% ACAC 0% 2 PACHE with 0.66% ACAC and 0.55 EQ XYDIA 43.1 ± 1.2% 3 PACHE with 0.94% ACAC 0% 4 PACHE with 0.94% ACAC and 0.55 EQ XYDIA 65.3 ± 4.4%

[0092] Entries 1 and 3 represent the pristine polymer, which were fully soluble in xylene. Entries 2 and 4 represent vitrimers of the present invention. When the amount of crosslinker was increased, the gel fraction went from 0% to 43.1±1.2% for vitrimers with 1.9 crosslinks/chain and 65.3±4.4% for vitrimers with 2.6 crosslinks/chain.

[0093] Recyclability. Recyclability was illustrated by reprocessing experiments using injection molded dog bones made from the vitrimers of the present invention. Tensile performance of the injection molded dog bones was measured. Tensile tests were performed with a Zwick type Z020 tensile tester equipped with a 1 kN load cell. The tests were performed on injection molded dog bones with dimensions of 75 mm×4 mm×2 mm. A grip-to-grip separation of 30 mm was used. The samples were pre-stressed to 0.5 N and then loaded with a constant cross-head speed of 50 mm.Math.min.sup.−1. The maximum tensile strength of extruded dog bones was determined. Then, the tested (broken) dog bones were employed for successive extrusion steps to obtain recycled dog bones, which were subsequently tested in their tensile strength. This process was repeated three times. FIG. 5 shows average results (from quadruplets) of tensile tests on PACHE with 0.94% ACAC and 0.55 EQ XYDIA processed 1, 2, 3 and 4 times. From the data, it was determined that the vitrimers are recyclable minimal loss of tensile strength was observed.

[0094] Adaptability of the vitrimers of the present invention was apparent from being able to compression mold defect free rectangular disks and by the ability to reprocess these disks if necessary.

[0095] Although embodiments or aspects of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein can be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.