Vitrimer comprising cyclic structure units, method for preparing the vitrimer, composite comprising the vitrimer and the oligomer

Abstract

This disclosure relates to a vitrimer comprising cyclic structure units and reversible moieties, wherein the vitrimer has an unsaturation degree of no more than 0.01 mol / g, wherein the unsaturation degree is calculated by mol of carbon-carbon unsaturated double bond carrying at least one hydrogen atom per gram of vitrimer, to method for preparing the vitrimer and to composite comprising the vitrimer and to the oligomer.

Description

VITRIMER COMPRISING CYCLIC STRUCTURE UNITS, METHOD FOR PREPARING THE VITRIMER, COMPOSITE COMPRISING THE VITRIMER AND THE OLIGOMERFIELD OF THE INVENTION

[0001] This application claims the benefit of U.S. Provisional Application Serial No.63 / 748,059 entitled “Vitrimer Comprising Cyclic Structure Units, Method for Preparing the Vitrimer, Composite Comprising the Vitrimer and the Oligomer” filed on January 22, 2025, the entirely of which is incorporated by reference herein.FIELD OF THE INVENTION

[0002] This disclosure relates generally to a vitrimer comprising cyclic structure units, method for preparing the vitrimer and composite comprising the vitrimer and the oligomer.BACKGROUND OF THE INVENTION

[0003] Vitrimers are a new class of polymeric materials displaying dynamically crosslinked networks. The topology of such networks is not fixed, as the bonds connecting the different polymer chains undergo associative exchange reactions that allows them to “dissociate” from a given location and “re-associate” in a different location in the network. These exchange reactions are activated at temperatures above the topological freezing transition temperature (Tv). Below Tv, vitrimers behave as solid elastic networks (i.e., as thermosets or vulcanized elastomers), and above Tv, they behave as viscoelastic liquids (i.e., as melts). Therefore, vitrimers represent a very attractive class of polymers that breaks the paradigm of non-recyclability of thermosets and vulcanized rubbers.

[0004] Most unsaturated polymer comprising cyclic structure are thermoset or will become thermoset after heating which led to no reprocessability. Therefore, the development of a vitrimer comprising cyclic structure units with good performance has become a very important issue.SUMMARY OF THE INVENTION

[0005] In a first general aspect, this disclosure provides a vitrimer comprising cyclic structure units and reversible moieties, wherein the vitrimer has an unsaturation degree of no more than 0.01 mol / g, wherein the unsaturation degree is calculated by mol of carbon-carbon unsaturated double bond carrying at least one hydrogen atom per gram of vitrimer.

[0006] In a second general aspect, this disclosure provides method for preparing the vitrimer of this disclosure, comprising reacting an oligomer having a functional group (a) and cyclic structure units with a linking compound capable of forming the reversible structure moieties with the functional group (a).

[0007] In a third general aspect, this disclosure provides an oligomer selected from:(x) an oligomer formed from cyclic olefin by ring-opening metathesis polymerization (ROMP) involving a chain transfer agent and then at least partial hydrogenation;(y) an oligomer formed by degrading a cleavable polymer and then at least partially hydrogenating, wherein the cleavable polymer is formed from cyclic olefin and cleavable comonomer; and(z) a functionalized oligomer comprising the cyclic structure units;wherein the oligomer (x), oligomer (y) and oligomer (z) have an unsaturation degree of no more than 0.01 mol / g, wherein the unsaturation degree is calculated by mol of carboncarbon unsaturated double bond carrying at least one hydrogen atom per gram of oligomer, for example, the weight average molecular weight of the oligomer (x), oligomer (y) and oligomer (z) is in the range from 300 to 60,000 g / mol, such as from 400 to 50,000 g / mol.

[0008] In a fourth general aspect, this disclosure provides a composite material comprising the vitrimer defined in this disclosure.

[0009] Certain aspects of the first, second, third and fourth general aspects may include one or more of the following features.

[0010] In some aspects, the vitrimer has an unsaturation degree of from 0 to 0.009 mol / g or from 0 to 0.008 mol / g or from 0 to 0.006 mol / g or from 0 to 0.004 mol / g, wherein the unsaturation degree is calculated by mol of carbon-carbon unsaturated double bond carrying at least one hydrogen atom per gram of vitrimer.

[0011] In some aspects, the ring system of the cyclic structure units has 4 to 20 ring members, for example 5 to 15 ring members, and / or the ring system of the cyclic structure units has 1, 2 or more rings, such as hydrocarbon ring, optionally the ring system of the cyclic structure units carries one or more substituents selected from the group consisting of OH, halogen, anhydride group, Ci-Ce alkyl, Ci-Ce alkoxy, Ci-Ce alkylthio, C3-C6 cycloalkyl, and C6-C12 aryl, the aforementioned Ci-Ce alkyl, Ci-Ce alkoxy, Ci-Ce alkylthio, C3-C6 cycloalkyl, and C6-C12 aryl can be further substituted by one or more OH.

[0012] In some aspects, the cyclic structure units are derived from(x) an oligomer formed from cyclic olefin by ring-opening metathesis polymerization(ROMP) involving a chain transfer agent and then at least partial hydrogenation;(y) an oligomer formed by degrading a cleavable polymer and then at least partially hydrogenating, wherein the cleavable polymer is formed from cyclic olefin and cleavable comonomer; and(z) a functionalized oligomer comprising the cyclic structure units;wherein the oligomer (x), oligomer (y) and oligomer (z) have an unsaturation degree of no more than 0.01 mol / g, wherein the unsaturation degree is calculated by mol of carboncarbon unsaturated double bond carrying at least one hydrogen atom per gram of oligomer, for example, the weight average molecular weight of the oligomer (x), oligomer (y) and oligomer (z) is in the range from 300 to 60,000 g / mol, such as from 400 to 50,000 g / mol.

[0013] In some aspect, the cyclic olefin (for example mentioned for oligomers (x) and (y)) contains one or more endocyclic double bond and has one or two or more rings, optionally the ring system of the cyclic olefin can carry one or more hetero atoms selected from N, O and S as ring member, optionally the ring system of the cyclic olefin carries one or more substituents selected from the group consisting of OH, halogen, anhydride group, Ci-Ce alkyl, Ci-Ce alkoxy, Ci-Ce alkylthio, C3-C6 cycloalkyl, and C6-C12 aryl, the aforementioned Ci-Ce alkyl, Ci-Ce alkoxy, Ci-Ce alkylthio, C3-C6 cycloalkyl, and C6-C12 aryl can be further substituted by one or more OH.

[0014] In some aspects, the ring system of the cyclic olefin has 4 to 20 ring members, such as 5 to 15 ring members, and the cyclic olefin has one, two or more rings, such as hydrocarbon ring.

[0015] In some aspects, the cyclic olefin is selected from single ring olefins, multi-ring olefins, multi-ring fused ring olefins, and multi-ring fused and bridged ring olefins, or selected from multi-ring olefins, multi-ring fused ring olefins, and multi-ring fused and bridged ring olefins.

[0016] In some aspects, the chain transfer agent is a mono-olefin carrying at least one functional group, for example hydroxyl group, carboxylic group and amino group.

[0017] In some aspects, the cleavable comonomer is an olefin metathesis active comonomers containing cleavable bond, for example selected from Si-containing monomer, a monomer having a bicyclic oxazinone structure containing an endocyclic double bond, substituted or unsubstituted 2,3 -dihydrofuran, a substituted or unsubstituted 2,3 -dihydropyran.

[0018] In some aspects, the oligomer (z) is a functionalized petroleum resin, or a functionalized oligomer derived from ROMP.

[0019] In some aspects, the reversible structure moieties are selected from dissociative and associative reversible structure moieties, for example the reversible structure moieties comprise a moiety selected from ester bond, boronic ester bond, amine, imine, disulfide, carbamate, vinylogous urethane, and bond formed from furan and anhydride.

[0020] In some aspects, the reversible structure moieties comprise a moiety selected from boronic ester bond and imine.

[0021] In some aspects, the amount of cyclic structure units is in the range from 55% to 99% by weight, for example 65% to 98.8% by weight, or 75% to 98.6% by weight, or 85% to 98.5% by weight, based on the total weight of the vitrimer.

[0022] In some aspects, the amount of the reversible moieties is in the range from 0.1 to 5 mmol / g vitrimer, such as 0.15 to 3 mmol / g vitrimer.

[0023] In some aspects, there are or are not connecting groups between the cyclic structure units and the reversible structure moieties, for example, the connecting groups have 1 to 20 or 2 to 10 or 3 to 10 carbon atoms.

[0024] In some aspects, the connecting groups are derived from a compound having one or more hydroxyl groups (e.g. 1 or 2 hydroxyl groups) and a carbon-carbon double bond.

[0025] In some aspects, the flow temperature of the vitrimer is in the range from 90°C to 250°C, such as from 95°C to 220°C, from 100°C to 200°C, or from 100°C to 180°C.

[0026] The vitrimer of this disclosure has following advantages:• Be able to obtain cyclic olefins based (for example Cs based) vitrimers, which have thermoset property and thermoplastic processability;• Be able to obtain hydrogenated crosslinked cyclic polymers,• Be able to incorporate functional groups which couldn’t be copolymerized in ROMP;• Be able to control polymer architecture (liner, brunch, thermoset with tunable crosslink density);• Be able to obtain degradable, recyclable, reprocessable polymer;• having good mechanical properties.DESCRIPTION OF THE DRAWING

[0027] Figure 1 shows in situ 'H NMR spectra for oligomers 1, 2 and 3.

[0028] Figure 2 shows1H NMR spectra for oligomers 4, 11 and 12.

[0029] Figure 3 shows 'H NMR spectrum for oligomer 5.

[0030] Figure 4 shows1H NMR spectrum for oligomer 6.

[0031] Figure 5 shows1H NMR spectrum for oligomer 7.

[0032] Figure 6 show 'HNMR spectra for oligomers 8, 9, 13, 14 and 15.

[0033] Figure 7 shows 'H NMR spectrum for oligomer 10.

[0034] Figure 8 shows pictures of hot pressed polymer 3 (comparative), polymer 4 and oligomer 7.

[0035] Figure 9 shows DMTA curves of polymers 2 and 3 (comparative) and polymer 4.

[0036] Figure 10 shows DMTA curves of polymer 6.

[0037] Figure 11 shows ISO 37 type 3 specimen.DETAILED DESCRIPTION OF THE INVENTION

[0038] Various specific embodiments, versions, and examples are described herein; including exemplary embodiments and definitions that are adopted for purposes of understanding the claimed invention. While the following detailed description gives specific preferred embodiments, those skilled in the art will appreciate that these embodiments are exemplary only and that the invention can be practiced in other ways. For purposes of determining infringement, the scope of the invention will refer to any one or more of the appended claims, including their equivalents, and elements or limitations that are equivalent to those that are recited. Any reference to the “invention” may refer to one or more, but not necessarily all, of the inventions defined by the claims.

[0039] All numerical values within the detailed description and the claims herein are modified by “about” the indicated value, and take into account experimental error and variations that would be expected by those skilled in the art.

[0040] In the context of this disclosure, the term “halogen” denotes in each case F, Br, Cl or I, in particular F, Br or Cl.

[0041] The term “alkyl” as used herein and in the alkyl moieties of alkylthio and alkoxyl, denotes in each case a straight-chain or branched alkyl group having usually from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms. Examples of an alkyl group are CH3, C2H5, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3 -methylbutyl, 1,1 -dimethylpropyl, 1.2-dimethylpropyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, 1 -methylpentyl, 2-methylpentyl, 3 -methylpentyl, 4-methylpentyl, 1,1 -dimethylbutyl, 1,2-dimethylbutyl, 1.3 -dimethylbutyl, 2,2-dimethylbutyl, 2,3 -dimethylbutyl, 3, 3 -dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1 -ethyl- 1 -methylpropyl, and l-ethyl-2-m ethylpropyl.

[0042] The term “alkoxy” as used herein denotes in each case a straight-chain or branched alkyl group which is bonded via an oxygen atom and has usually from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of an alkoxy group are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert. -butyl oxy, and the like.

[0043] The term “alkylthio” (alkyl sulfanyl: alkyl-S-) as used herein refers to a straightchain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylthio), more preferably 1 to 3 carbon atoms, which is attached via a sulfur atom. Examples include methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.

[0044] The term “cycloalkyl” as used herein and in the cycloalkyl moieties of cycloalkoxy and cycloalkylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 14 carbon atoms (for example, 3 to 12, 3 to 10, 3 to 8, 3 to 7, 4 to 7, or 5 to 6 carbon atoms), such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl, for example cyclopentyl and cyclohexyl.

[0045] The term “heterocyclyl” or “heterocyclic” refers to a radical of a 3 - to 14-membered (e.g. 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14-membered, for example 4 to 10 or 5 to 10, or 5 to 8 or 5 to 7, or 5 to 6 membered) non-aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms (e.g. 1, 2, 3 or 4 ring heteroatoms), wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“3-14 membered heterocyclyl”). In heterocyclyl groups that contain one or more nitrogen atoms, the point of attachment can be a carbon or nitrogen atom, as valency permits. A heterocyclyl group can either be monocyclic (“monocyclic heterocyclyl”) or polycyclic (e.g. a fused, bridged or spiro ring system such as a bicyclic system (“bicyclic heterocyclyl”) or tricyclic system (“tricyclic heterocyclyl”)), and can be saturated or can contain one or more carbon-carbon double or triple bonds. Heterocyclyl polycyclic ring systems can include one or more heteroatoms in one or both rings. “Heterocyclyl” also includes ring systems wherein the heterocyclyl ring, as defined above, is fused with one or more carbocyclyl groups wherein the point of attachment is either on the carbocyclyl or heterocyclyl ring, or ring systems wherein the heterocyclyl ring, as defined above, is fused with one or more aryl or heteroaryl groups, wherein the point of attachment is on the heterocyclyl ring, and in such instances, the number of ring members continue to designate the number of ring members in the heterocyclyl ring system. Unless otherwise specified, each instance of heterocyclyl is independently unsubstituted (an “unsubstituted heterocyclyl”) or substituted (a “substituted heterocyclyl”) with one or more substituents.

[0046] In some embodiments, a heterocyclyl group is a 5-10 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-10 membered heterocyclyl”). In some embodiments, a heterocyclyl group is a 5-8 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-8 membered heterocyclyl”). In some embodiments, a heterocyclyl group is a 5-6 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-6 membered heterocyclyl”). In some embodiments, the 5-6 membered heterocyclyl has 1-3 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5-6 membered heterocyclyl has 1-2 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5-6 membered heterocyclyl has 1 ring heteroatom selected from nitrogen, oxygen, and sulfur.

[0047] The term “heteroaryl” relates to aromatic heterocycles having either 5 or 6 ring atoms (5- or 6-membered heteroaryl) and being monocyclic or 8, 9 or 10 ring atoms and being bicyclic. Heteroaryl will generally have at least one ring atom selected from O, S and N. In case of N ring atom, N ring atom may be an imino-nitrogen or an amino-nitrogen, which carries hydrogen or a radical different from hydrogen. Heteroaryl may have 1, 2, 3 or 4 further nitrogen atoms as ring members, which are imino nitrogens. Examples of 5- or 6-membered heteroaryl include 2-furyl, 3 -furyl, 2-thienyl, 3 -thienyl, 1 -pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4 pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5 thiazolyl, 1 -imidazolyl, 2-imidazolyl, 4-imidazolyl, 1,3,4-triazol-l-yl, l,3,4-triazol-2-yl, l,3,4-oxadiazolyl-2-yl, l,3,4-thiadiazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl and l,3,5-triazin-2-yl. Examples of 8-, 9- or 10-membered heteroaryl include, for example, quinolinyl, isoquinolinyl, cinnolinyl, indolyl, indolizynyl, isoindolyl, indazolyl, benzofuryl, benzothienyl, benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzimidazolyl, imid-azo[l,2-a]pyridine-2-yl, thieno[3,2-b]pyridine-5-yl, imidazo-[2,l-b]-thiazol-6-yl and l,2,4-triazolo[l,5-a]pyridine-2-yl.

[0048] In some embodiments, a heteroaryl group is a 5-10 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-10 membered heteroaryl”). In some embodiments, a heteroaryl group is a 5-8 membered aromaticring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-8 membered heteroaryl”). In some embodiments, a heteroaryl group is a 5-6 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-6 membered heteroaryl”). In some embodiments, the 5-6 membered heteroaryl has 1-3 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1-2 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1 ring heteroatom selected from nitrogen, oxygen, and sulfur. Unless otherwise specified, each instance of a heteroaryl group is independently unsubstituted (an “unsubstituted heteroaryl”) or substituted (a “substituted heteroaryl”) with one or more substituents.

[0049] The term “aryl” denotes in each case an aromatic carbocyclic radical comprising only one ring or several (e.g. 2 or 3), optionally fused, rings having usually 6 to 12, preferably 6 to 10 ring member atoms, such as phenyl, 1- naphthyl, 2-naphthyl, biphenylyl or ferrocenyl.

[0050] The term “substituted” if not specified otherwise refers to substitutions by 1, 2 or maximum possible number of substituents.Vitrimer comprising cyclic structure units and reversible structure moieties

[0051] In a first general aspect, this disclosure provides a vitrimer comprising cyclic structure units and reversible moieties, wherein the vitrimer has an unsaturation degree of no more than 0.01 mol / g, wherein the unsaturation degree is calculated by mol of carbon-carbon unsaturated double bond carrying at least one hydrogen atom per gram of vitrimer.

[0052] The vitrimer has an unsaturation degree of no more than 0.01 mol / g (e.g.0.009 mol / g, 0.008 mol / g, 0.007 mol / g, 0.006 mol / g, 0.005 mol / g, 0.004 mol / g, 0.003 mol / g, 0.002 mol / g, 0.001 mol / g, 0.0009 mol / g, 0.0008 mol / g, 0.0007 mol / g, 0.0006 mol / g, 0.0005 mol / g, 0.0004 mol / g, 0.0003 mol / g, 0.0001 mol / g, 0.00005 mol / g, 0.00002 mol / g, or 0.00001 mol / g), for example no more than 0.009 mol / g or no more than 0.008 mol / g, or no more than 0.007 mol / g, or no more than 0.005 mol / g, or no more than 0.0025 mol / g, wherein the unsaturation degree is calculated by mol of carbon-carbon unsaturated double bond carrying at least one hydrogen atom per gram of vitrimer. In an embodiment, the vitrimer has an unsaturation degree of from 0 to 0.009 mol / g, or from 0 to 0.008 mol / g, or from 0 to 0.007 mol / g, or from 0 to 0.006 mol / g, or from 0 to 0.005 mol / g, or from 0 to 0.0025 mol / g, wherein the unsaturation degree is calculated by mol of carbon-carbon unsaturated double bondcarrying at least one hydrogen atom per gram of vitrimer. The mol of the carbon-carbon unsaturated double bond can be calculated based on mol of olefin-H measured by1H NMR. For example, if each carbon-carbon unsaturated double bond carries one hydrogen atom, then the amount of carbon-carbon unsaturated double bond is the amount of olefin-H. If each carbon-carbon unsaturated double bond carries two hydrogen atoms, then the amount of carbon-carbon unsaturated double bond is half of the amount of olefin-H. If each carboncarbon unsaturated double bond carries three hydrogen atoms, then the amount of carboncarbon unsaturated double bond is the amount of olefin-H divided by 3. A person skilled in the art could understand that the amount of carbon-carbon unsaturated double bond carrying at least one hydrogen atom does not comprise those in aryl or heteroaryl.

[0053] The carbon-carbon unsaturated double bond can carry 1, 2 or 3 hydrogen atoms. The terminal carbon-carbon unsaturated double bond can carry 3 hydrogen atoms. Usually, the carbon-carbon unsaturated double bond carries 2 hydrogen atoms in the vitrimer prepared from the oligomer derived from the ring-opening metathesis polymerization.

[0054] The vitrimer of this disclosure can contain carbon-carbon unsaturated double bonds without hydrogen atom, which generally do not affect the reprocessability of the vitrimer. In an embodiment, the amount of carbon-carbon unsaturated double bonds without hydrogen atom is no more than 0.005 mol / g vitrimer, or no more than 0.004 mol / g vitrimer, or no more than 0.003 mol / g vitrimer, or no more than 0.002 mol / g vitrimer, or no more than 0.001 mol / g vitrimer, or no more than 0.0005 mol / g vitrimer, or no more than 0.0003 mol / g vitrimer, or no more than 0.0002 mol / g vitrimer, or no more than 0.0001 mol / g vitrimer, or no more than 0.00005 mol / g vitrimer, or no more than 0.00002 mol / g vitrimer. A person skilled in the art could understand that the amount of carbon-carbon unsaturated double bond does not comprise those in aryl or heteroaryl.

[0055] The cyclic structure units can comprise saturated cyclic structure units. According to the present disclosure, the amount of the saturated cyclic structure units is at least 40 mol% (for example 42 mol%, 45 mol%, 48 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 92 mol%, 95 mol%, 98mol%, 99 mol% or 100 mol%), based on the total amount of the cyclic structure units of the vitrimer. In an embodiment, the amount of the saturated cyclic structure units is at least 42 mol%, for example at least 55 mol% or at least 65 mol%, based on the total amount of the cyclic structure units of the vitrimer. In an aspect, the amount of the saturated cyclic structure units is in the range from 40 to 100 mol%, or from 42 to 100 mol%, or from 42 to 99 mol%, or from 50 to 95 mol%, or from 60 to 95mol%, or from 70 to 95 mol%, or from 80 to 95 mol%, based on the total amount of the cyclic structure units of the vitrimer.

[0056] The ring system of the cyclic structure units can have 4 to 20 ring members (e.g. 5, 6, 7, 8, 10, 12, 14, 15, 16, 18 or 20 ring members), for example 5 to 15 ring members or 5 to 10 ring members. The ring system of the cyclic structure unit can have 1, 2 or more rings (for example 3 or 4 rings). The ring system of the cyclic structure units can carry one or more hetero atoms (for example 1, 2 or 3 hetero atoms) selected from N, O and S as ring member. In an embodiment, the ring(s) of the cyclic structure unit is hydrocarbon ring. Optionally, the ring system of the cyclic structure units carries one or more substituents selected from the group consisting of OH, halogen, anhydride group, Ci-Ce alkyl, Ci-C6alkoxy, Ci-Ce alkylthio, C3-C6 cycloalkyl, and C6-C12 aryl, optionally the aforementioned Ci-Ce alkyl, Ci-Ce alkoxy, Ci-Ce alkylthio, C3-C6 cycloalkyl, and C6-C12 aryl can be further substituted by one or more OH.

[0057] The ring of the cyclic structure unit can be selected from single ring, multi-ring, fused multi-ring, and fused and bridged multi-ring. In an embodiment, the ring of the cyclic structure unit can be selected from alicyclic single ring, alicyclic multi-ring, alicyclic fused multi-ring, and alicyclic fused and bridged multi-ring. For example, the ring system of the (alicyclic) single ring can have 5 to 8 ring members or 5 to 6 ring members. The ring system of the (alicyclic) multi-ring can have 8 to 20 ring members or 10 to 15 ring members. The ring system of the (alicyclic) fused multi-ring can have 8 to 14 ring members or 8 to 10 ring members. The ring system of the (alicyclic) fused and bridged multi-ring can have 10 to 20 ring members or 12 to 15 ring members.

[0058] In an embodiment, the cyclic structure units are derived from:(x) an oligomer formed from cyclic olefin by ring-opening metathesis polymerization (ROMP) involving a chain transfer agent and then at least partial hydrogenation;(y) an oligomer formed by degrading a cleavable polymer and then at least partially hydrogenating, wherein the cleavable polymer is formed from cyclic olefin and cleavable comonomer; and(z) a functionalized oligomer comprising the cyclic structure units;wherein the oligomer (x), oligomer (y) and oligomer (z) have an unsaturation degree of no more than 0.01 mol / g, wherein the unsaturation degree is calculated by mol of carboncarbon unsaturated double bond carrying at least one hydrogen atom per gram of oligomer, for example, the weight average molecular weight of the oligomer (x), oligomer (y)and oligomer (z) is in the range from 300 to 60,000 g / mol, such as from 400 to 50,000 g / mol.

[0059] The oligomer (x), oligomer (y) and oligomer (z) are particularly suitable for preparing the vitrimer of this disclosure.

[0060] Usually, the unsaturation degree of the oligomers (i.e., oligomers (x), (y) and (z)) corresponds to the unsaturation degree of the vitrimer. In this disclosure, the oligomer (x), oligomer (y) and oligomer (z) have an unsaturation degree of no more than 0.01 mol / g (e.g.0.009 mol / g, 0.008 mol / g, 0.007 mol / g, 0.006 mol / g, 0.005 mol / g, 0.004 mol / g, 0.003 mol / g, 0.002 mol / g, 0.001 mol / g, 0.0009 mol / g, 0.0008 mol / g, 0.0007 mol / g, 0.0006 mol / g, 0.0005 mol / g, 0.0004 mol / g, 0.0003 mol / g, 0.0001 mol / g, 0.00005 mol / g, 0.00002 mol / g, 0.00001 mol / g), for example no more than 0.009 mol / g or no more than 0.008 mol / g, or no more than 0.007 mol / g, or no more than 0.005 mol / g, or no more than 0.0025 mol / g, wherein the unsaturation degree is calculated by mol of carbon-carbon unsaturated double bond carrying at least one hydrogen atom per gram of oligomer. In an embodiment, the oligomer (x), oligomer (y) and oligomer (z) have an unsaturation degree of from 0 to 0.009 mol / g, or from 0 to 0.008 mol / g, or from 0 to 0.007 mol / g, or from 0 to 0.006 mol / g, or from 0 to 0.005 mol / g, or from 0 to 0.0025 mol / g, wherein the unsaturation degree is calculated by mol of carbon-carbon unsaturated double bond carrying at least one hydrogen atom per gram of oligomer. The mol of the carbon-carbon unsaturated double bond can be calculated based on mol of olefin-H measured by 'H NMR. For example, if each carbon-carbon unsaturated double bond carries two hydrogen atoms, then the amount of carbon-carbon unsaturated double bond is half of the amount of olefin-H. A person skilled in the art could understand that the amount of carbon-carbon unsaturated double bond does not comprise those in aryl or heteroaryl.

[0061] The oligomer (z.e., oligomers (x), (y) and (z)) can contain carbon-carbon unsaturated double bonds without hydrogen atom. In an embodiment, the amount of carboncarbon unsaturated double bonds without hydrogen atom is no more than 0.005 mol / g oligomer, or no more than 0.004 mol / g oligomer, or no more than 0.003 mol / g oligomer, or no more than 0.002 mol / g oligomer, or no more than 0.001 mol / g oligomer, or no more than 0.0005 mol / g oligomer, or no more than 0.0003 mol / g oligomer, or no more than 0.0002 mol / g oligomer, or no more than 0.0001 mol / g oligomer, or no more than 0.00005 mol / g oligomer, or no more than 0.00002 mol / g oligomer.

[0062] In an embodiment, Mw, i.e., the weight average molecular weight of the oligomers (i.e., oligomers (x), (y) and (z)) can range from 300 to 60,000 g / mol (e.g. 350, 400, 500, 600, 700, 800, 900, 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 8,000, 10,000, 20,000, 30,000, 40,000,50,000, 60,000 g / mol), such as from 400 to 50,000 g / mol, or from 500 to 50,000 g / mol, or from 600 to 50,000 g / mol, or from 800 to 40,000 g / mol, or from 1,000 to 40,000 g / mol, or from 2,000 to 40,000 g / mol, or from 4,000 to 40,000 g / mol, or from 400 to 10,000 g / mol, or from 500 to 8,000 g / mol, or 500 to 5,000 g / mol, or from 500 to 2,000 g / mol.

[0063] Mw / Mn of the oligomers (i.e., oligomers (x), (y) and (z)) can range from 1.5 to 3.5 (e.g. 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, or 3.4), or range from 1.6 to 3.3, or from 1.6 to 2.5, or from 2.0 to 3.3.

[0064] In an embodiment, the oligomers (i.e., oligomers (x), (y) and (z)) carry functional group (a), for example hydroxyl group, carboxylic group and amino group. The amount of the functional group (a) in the oligomers can be in the range from 0.1 to 5 mmol / g oligomer (e.g.0.12, 0.15, 0.18, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.5, 1.8, 2, 2.5, 3, 3.5, 4, 4.5, or 4.8 mmol / g oligomer), such as 0.12 to 4.8 mmol / g oligomer, 0.15 to 4.5 mmol / g oligomer, 0.15 to 4 mmol / g oligomer, 0.15 to 3.5 mmol / g oligomer, 0.15 to 3 mmol / g oligomer, 0.2 to 4.8 mmol / g oligomer, 0.2 to 4.5 mmol / g oligomer, 0.2 to 4 mmol / g oligomer, 0.2 to 3.5 mmol / g oligomer, 0.2 to 3 mmol / g oligomer, 0.2 to 2.5 mmol / g oligomer, or 0.2 to 2 mmol / g oligomer.

[0065] In an embodiment, the cyclic olefin (for example those mentioned for oligomers (x) and (y)) contains one or more (for example 1, 2 or 3) endocyclic double bond and has one or two or more rings, optionally the ring system of the cyclic olefin can carry one or more hetero atoms selected from N, O and S as ring member. For example, the cyclic olefin can contain 1, 2, 3 or 4 endocyclic double bonds and has 1 to 6 (for example 1, 2, 3, 4, 5 or 6) rings or 2 to 4 rings, or 2 to 3 rings.

[0066] In an embodiment, the ring system of the cyclic olefin has 4 to 20 ring members, such as 5 to 15 ring members, and the cyclic olefin has one, two or more rings, such as hydrocarbon ring.

[0067] The ring system of the cyclic olefin can have 4 to 20 ring members e.g. 5, 6, 7, 8, 10, 12, 14, 15, 16, 18 or 20 ring members), for example 5 to 15 ring members or 5 to 10 ring members. The ring system of the cyclic olefin can have 1, 2 or more rings (for example 3 or 4 rings), such as 2 to 4 rings, or 2 to 3 rings. The ring system of the cyclic olefin can carry one or more hetero atoms (for example 1, 2 or 3 hetero atoms) selected from N, O and S as ring member. In an embodiment, the ring(s) of the cyclic olefin is hydrocarbon ring.

[0068] In an embodiment, the cyclic olefin can be selected from single ring olefin, multiring olefin, multi-ring fused ring olefin, and multi-ring fused and bridged ring olefin, orselected from multi-ring olefin, multi-ring fused ring olefin, and multi-ring fused and bridged ring olefin. In an embodiment, the cyclic olefin is selected from single ring alicyclic olefin, multi-ring alicyclic olefin, multi-ring alicyclic fused ring olefin, and multi-ring alicyclic fused and bridged ring olefin, or selected from multi-ring alicyclic olefin, multi-ring alicyclic fused ring olefin, and multi-ring alicyclic fused and bridged ring olefin. For example, the ring system of the single ring alicyclic olefins can have 5 to 12 ring members, 5 to 10 ring members, 5 to 8 ring members or 5 to 6 ring members. The ring system of the multi-ring alicyclic olefin can have 8 to 20 ring members or 10 to 15 ring members. The ring system of the multi -ring alicyclic fused ring olefin can have 8 to 14 ring members or 8 to 10 ring members. The ring system of the multi -ring alicyclic fused and bridged ring olefin can have 10 to 20 ring members or 12 to 15 ring members. Optionally, the ring system of the cyclic olefin carries one or more substituents selected from the group consisting of OH, halogen, anhydride group, Ci-Ce alkyl, Ci-C6alkoxy, Ci-Ce alkylthio, C3-C6 cycloalkyl, and C6-C12 aryl, the aforementioned Ci-Ce alkyl, Ci-Ce alkoxy, Ci-Ce alkylthio, C3-C6 cycloalkyl, and C6-C12 aryl can be further substituted by one or more OH.

[0069] Multi ring generally means 2 or more rings (for example 3 or 4 rings), such as 2 to 4 rings, or 2 to 3 rings.

[0070] In an embodiment, the cyclic olefin can be selected from cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclododecene, cyclopentadiene, cyclohexadiene, cyclooctadiene, and cyclododecadiene, dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, tetrahydroindene, norbornene, norbomadiene, bicyclo- (2.2.1)-hepta-2,5-diene, 7-oxanorbornene, 7-oxanorbomadiene, l,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene (CAS 21635-90-5), 3a,4,7,7a-tetrahydro-lH-4,7-methanoinden-l-one (CAS 5530-96-1), 3a,4,7,7a-tetrahydro-lH-4,7-methanoinden-l-ol (CAS 6814-80-8), their derivatives substituted with one or more substituents selected from the group consisting of OH, halogen, anhydride group, Ci-Ce-alkyl, Ci-Ce-alkoxy, Ci-Ce-alkylthio, Cs-Ce-cycloalkyl or Ce-Ci2-aryl, for example methyl-tetrahydroindene, for example 5-norbornene-2,3-dicarboxylic anhydride and 5-norbornene-2-methanol, and also endo isomers, exo isomers and mixture thereof.

[0071] The single ring olefin (e.g. cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclododecene, cyclopentadiene, cyclohexadiene, cyclooctadiene, and cyclododecadiene) is generally used in a mixture with multi-ring olefin, especially for ring-opening metathesis polymerization (ROMP). Usually, the amount of the single ring olefin is no more than 50%by weight, e.g. no more than 40% by weight, no more than 30% by weight, no more than 20% by weight, no more than 10% by weight or no more than 5% by weight, based on the total weight of the mixture of single ring olefin and multi-ring olefin.

[0072] The chain transfer agent can be a mono-olefin carrying at least one functional group (a), for example hydroxyl group, carboxylic group and amino group. In an embodiment, the chain transfer agent can carry one, two or three or more functional groups, for example hydroxyl group, carboxylic group and amino group. The mono-olefin carrying at least one functional group (a) as the chain transfer agent can have at least 3 carbon atoms, for example 3 to 20 carbon atoms (e.g. 4, 5, 6, 7, 8, 10, 12, 16 or 18 carbon atoms), or 4 to 16 carbon atoms, or 4 to 12 carbon atoms, or 4 to 8 carbon atoms. For example, the chain transfer agent can butenol and butenediol.

[0073] For the formation of the oligomer (x), the amount of the chain transfer agent can be in the range from 0.8% to 40% by weight (e.g. 1%, 1.2%, 1.5%, 2%, 5%, 8%, 10%, 12%, 15%, 20%, 25%, 30%, 32%, 35% or 40% by weight), for example from 1% to 35% by weight, or from 1.2% to 32% by weight, or from 1.2% to 25% by weight, or from 1.2% to 20% by weight, or from 1.2% to 15% by weight, or from 1.2% to 10% by weight, based on the total weight of the chain transfer agent and the cyclic olefin.

[0074] In some aspects, there are or are not connecting groups between the cyclic structure units and the reversible structure moieties. The connecting groups can derive from the chain transfer agent.

[0075] The ring-opening metathesis polymerization (ROMP) can be carried out in the presence of a catalyst. The catalyst for ring-opening metathesis polymerization of this disclosure is a compound that catalyzes olefin metathesis reactions.

[0076] Examples of the catalyst include metal compounds, preferably compounds of Group 8 metal, more preferably metal compounds of titanium (Ti), molybdenum (Mo), tungsten (W), rhenium (Re), osmium (Os) and ruthenium (Ru).

[0077] In some embodiments of this disclosure, the ring-opening metathesis polymerization catalyst is represented by the formula:wherein:M is a Group 8 metal, preferably Ru or Os, more preferably Ru;X and X1are, independently, any anionic ligand, preferably a halogen (preferably chlorine), an alkoxide or a tritiate, or X and X1can be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non- hydrogen atoms;L and L1are, independently, a neutral two electron donor, preferably a phosphine or a N- heterocyclic carbene, L and L1can be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;L and X can be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;L1and X1can be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 nonhydrogen atoms;R and R1are, independently, hydrogen, halogen, or Ci to C20 substituted or unsubstituted hydrocarbyl (preferably Ci to C20 substituted or unsubstituted alkyl or a substituted or unsubstituted Ce to C20 aryl) which may contain at least one atom selected from halogen, oxygen, nitrogen, sulfur, phosphorus and silicon atoms;R1and L1or X1can be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms; andR and L or X can be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms.

[0078] Preferred alkoxides include those where the hydrocarbyl group is Ci to C10 hydrocarbyl, preferably Ci to C10 alkyl group, preferably methyl, ethyl, propyl, or butyl.

[0079] Preferred phosphines are represented by the formula: PR’ R” R’”, where R’ is a secondary alkyl or cycloalkyl (preferably a C3 to C12 secondary alkyl or cycloalkyl), and R” and R’” are aryl, Ci to C10 primary alkyl, secondary alkyl, or cycloalkyl. R” and R’” can be the same or different. Preferred phosphines include P(cyclohexyl)3, P(cyclopentyl)3, and / or P(isopropyl)3.

[0080] Preferred tritiates are represented by the formula:wherein R2is hydrogen or Ci to C30 alkyl group, preferably Ci to C12 alkyl group, preferably methyl, ethyl, propyl, butyl, or phenyl.

[0081] Preferred N-heterocyclic carbenes are represented by the formulae of:wherein:each R4is independently a hydrocarbyl group or substituted hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl, benzyl, tolulyl, or chlorophenyl; andeach R5is hydrogen, a halogen, or Ci to C12 hydrocarbyl group, preferably hydrogen, bromine, chlorine, methyl, ethyl, propyl, butyl, or phenyl. In other useful embodiments, one of the N atoms bound to the carbene in these formulae can be replaced with an S, O, or P atom, preferably an S atom.

[0082] Other useful N-heterocyclic carbenes include the compounds described in Herrmann, W. A. et. al., (1996) “N-Heterocyclic Carbenes[+]: Generation under Mild Conditions and Formation of Group 8-10 Transition Metal Complexes Relevant to Catalysis**,” Chem. Eur. J., v.2(7), pp. 772-780; Herrmann, W.A. et. al., (1996) “Heterocyclic Carbenes:[+]A High-Yielding Synthesis of Novel, Functionalized N-Heterocyclic Carbenes in Liquid Ammonia**,” Chem. Eur. J., v.2(12), pp. 1627-1636; Enders, D. et al., (1995) “Preparation, Structure, and Reactivity of l,3,4-Triphenyl-4,5-dihydro-U / -l,2,4-triazol-5-ylidene, aNew Stable Carbene* Angew. Chem. Int. Ed., v.34(9), pp. 1021-1023; Alder R. W. etal., (1996) “Bis(diisopropylamino)carbene,” Angew. Chem. Int. Ed., v.35(10), pp. 1121-1123; and Bertrand, G. et al., (2000) “Stable Carbenes,” Chem. Rev., v.100, pp. 39-91.

[0083] In some embodiments of this disclosure, the ring-opening metathesis polymerization catalyst is one or more of tricyclohexylphosphine[l,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][3-phenyl-lH-inden-l-ylidene]ruthenium(II)di chloride, tricyclohexylphosphine[3-phenyl-lH-inden-l-ylidene][l,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-imidazol-2-ylidene]ruthenium(II) dichloride, tricyclohexylphosphine[l,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene] [(phenylthio)methylene]ruthenium(II) dichloride, and l,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(isopropoxy)-5-(N,N- dimethylaminosulfonyl)phenyl]methylene ruthenium(II) dichloride. In some embodiments, the ring-opening metathesis polymerization catalyst is l,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(isopropoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methylene ruthenium(II) dichloride and / or tricyclohexylphosphine[3-phenyl-lH-inden-l-ylidene][l,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene]ruthenium(II) dichloride.

[0084] In some embodiments of this disclosure, the ring-opening metathesis polymerization catalyst is an organoruthenium compound having formula of:

[0085] In an embodiment of this disclosure, the ring-opening metathesis polymerization catalyst is Grubbs 2nd catalyst.

[0086] The weight ratio of the monomers (cyclic olefin and chain transfer agent) to the ring-opening metathesis polymerization catalyst is typically at least 100:1 (e.g. 200:1, 500:1, 800:1, 1000:1, 2,000:1, 3,000:1, 5,000:1, 6000:1, 8,000:1, 10,000:1, 20,000:1, 30,000:1, 40,000:1, or 50,000:1), for example at least 500:1 or at least 800:1. In an embodiment, the weight ratio of the monomers to the ring-opening metathesis polymerization catalyst is in the range from 100:1 to 50,000:1, or from 200:1 to 40,000:1, or from 500:1 to 20,000:1, or from 800:1 to 10,000:1, or from 1000:1 to 8,000:1.

[0087] The polymerization temperature for ROMP can be selected from -30°C to 200°C, such as -25°C, -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, and any temperature between these values. In an embodiment, the polymerization temperature for ROMP is in the range from 0°C to 180°C. In an embodiment, the polymerization temperature for ROMP is in the range from 10°C to 100°C, such as 20°C to 95°C or 40°C to 95°C or 50°C to 95°C.

[0088] The polymerization time for ROMP is usually in the range from Ih to lOOh (e.g. 2h, 4h, 5h, 8h, lOh, 15h, 20h, 25h, 30h, 40h, 50h, 60h, 70h, 80h, or 90h), such as 2h to 90h, or 4h to 80h, or 6h to 60h, or 8h to 50h.

[0089] The ROMP of this disclosure can be carried out in inert solvent or under solvent-free conditions. The term “inert solvent” means that the solvent does not react with the catalyst and for example is capable of dissolving the obtained polymer. Examples of the solvent for polymerization according to the process of this disclosure include alcohols, such as methanol, ethanol or isopropanol; ketones, such as acetone or methyl ethyl ketone; straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, n-hexane, isohexane, heptane, octane or dodecane; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane or methylcycloheptane, such as commercial product (Isopar™); aromatic compounds, such as benzene, toluene, mesitylene, ethyl benzene or xylene; halogenated hydrocarbons, such as dichloromethane, chloroform, di chloroethane, tetrachloroethane, chlorobenzene or trichlorobenzene; ethers, such as tetrahydrofuran; amides, such as dimethylformamide; sulfoxides, such as dimethyl sulfoxide; or mixtures thereof.

[0090] In some embodiments of this disclosure, the solvent for polymerization according to the process of this disclosure can be selected from the group consisting of methanol, ethanol, isopropanol, dichlormethane, chloroform, acetone, n-hexane, isohexane, cyclohexane or tetrahydrofuran.

[0091] After polymerization, the polymerization catalyst and by-products thereof can be removed by a known process if necessary, including a filtration or a process using an adsorbent for adsorptive removal.

[0092] After the removal of the polymerization catalyst and by-products thereof, the obtained oligomer can be precipitated and then be collected by filtration, washed and dried.

[0093] An illustrative scheme for the synthesis of oligomer formed from cyclic olefin by ring-opening metathesis polymerization (ROMP) involving a chain transfer agent is as follows:wherein:cyclic monomer can be a cyclic olefin for example selected from dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, tetrahydroindene, norbomene, norbomadiene, l,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene (CAS 21635-90-5), 3a, 4, 7, 7a-tetrahydro-lH-4,7-methanoinden-l-one (CAS 5530-96-1), 3a,4,7,7a-tetrahydro-lH-4,7-methanoinden-l-ol (CAS 6814-80-8), methyl-tetrahydroindene, 5-norbomene-2,3-dicarboxylic anhydride and 5-norbornene-2-methanol, and also endo isomers, exo isomers and mixture thereof;is the chain transfer agent;Rn and R22 are independently selected from H, Ci-Ce alkyl substituted by OH, or other functional groups (such as carboxylic group and amino group);R33 and R44 are independently selected from H, Ci-Ce alkyl substituted by OH, or other functional groups (such as carboxylic group and amino group);alternatively, R33 and R44 together with the carbon atom to which they are attached form a four- to six-membered (or five to six-membered) saturated or partially unsaturated hydrocarbon ring;m and n independently denote a number > 0 and m and n are not zero at the same time; o denotes a number greater than zero.In an embodiment, at least one of Rn and R22 is Ci-Ce alkyl substituted by OH.

[0094] A specific illustrative reaction scheme (for example for the synthesis of oligomers in example 1) is as follows:wherein a and b independently denote a number of 1 or more.

[0095] Another specific illustrative reaction scheme (for example for the synthesis of oligomers in example 2) is as follows:wherein a and b independently denote a number of 1 or more.

[0096] A further specific illustrative reaction scheme (for example for the synthesis of oligomers in example 3) is as follows:wherein a and b and c independently denote a number of 1 or more.

[0097] A further specific illustrative reaction scheme (for example for the synthesis of oligomers in example 4) is as follows:wherein a and b and c independently denote a number of 1 or more.

[0098] The oligomer obtained from ROMP is an unsaturated oligomer. In this disclosure, the oligomer obtained from ROMP is subjected to hydrogenation. The hydrogenation can be carried out in the presence of a metal catalyst for hydrogenation.

[0099] The catalyst for hydrogenation can be selected from palladium, platinum, rhodium, Ruthenium, nickel or cobalt, such as in the form of RuClH(CO)(PPh3)3, Co(acac)3 / Bu3Al, nickel silica alumina, nickel / tungsten sulfides, Co-octanoate / EtsAl, platinum / palladium, Pd / C, Rh(PPh3)3Cl, and the like. (In these formulas, Ph is phenyl, acac is acetyl acetonoate, Bu is butyl and Et is ethyl). Such hydrogenation catalysts may be homogenous or heterogeneous (e.g. supported on silicates or aluminum oxides) in form. Suitable hydrogenation catalysts, catalyst systems, and catalyst supports are described in greater detail in U.S. Pat. Nos.6,191,243 and 6,476,153, both of which are incorporated herein by reference.

[0100] The amount of the catalyst can be 0.1% to 20% by weight (e.g. 0.2%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 8%, 10%, 12%, 15% or 18% by weight), or 1% to 20% by weight, or 5% to 20% by weight, for example 6% to 15% by weight, based on total weight of the oligomer.

[0100] In an embodiment, an oligomer solution is purged with hydrogen. Hydrogen pressures of from 10 bar to 120 bar (e.g. 20 bar, 25 bar, 30 bar, 40 bar, 50 bar, 60 bar, 70 bar, 80 bar, 90 bar, 100 bar, or 110 bar), for example from 20 bar to 80 bar or from 25 bar to 70 bar may be employed. Hydrogenation temperatures can range, for example, from 60°C to 300°C (e.g. 80°C, 100°C, 120°C, 150°C, 180°C, 200°C, 250°C or280°C), or from 80°C to 250°C, or from 90°C to 220°C.

[0101] Hydrogenation level can be at least 35% (e.g. 40%, 45%, 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9% or 100%), for example at least 40%, or at least 50%, or at least 60% or at least 80%, of the residual double bonds which are present within oligomer prior to the hydrogenation. In an embodiment, hydrogenation level can range from 35% to 100%, from 40% to 100% or from 40% to 99.9%, from 50% to 100% or from 50% to 99.5%, from 60% to 100% or from 60% to 99.5%, from 70% to 100% or from 70% to 99.5%, from 80% to 100% or from 80% to 99.5% or from 80% to 95%, of the residual double bonds which are present within oligomer prior to the hydrogenation.

[0102] In an embodiment, a hydrogenation is performed for a time of from Ih to lOOh (e.g.2h, 5h, 8h, lOh, 12h, 15h, 18h, 20h, 25h, 3 Oh, 40h, 5 Oh, 60h, 70h, 80h, 90h, or95h), for example from 2h to 80h or from 2h to 50h, from 5h to 80h or from lOh to 50h.

[0103] In an embodiment, the hydrogenated oligomer is filtered through celite to remove the catalyst. In an embodiment, the hydrogenated oligomer is added to methanol to obtain a solid precipitate.

[0104] Oligomer (y) can be formed by degrading a cleavable polymer, wherein the cleavable polymer can be formed from cyclic olefin and cleavable comonomer.

[0105] The cyclic olefin is as described above.

[0106] The formation of cleavable polymer can be carried out by ROMP of cyclic olefin and cleavable comonomer. Details of ROMP, such as the catalysts, polymerization conditions are as mentioned above.

[0107] The cleavable comonomer can be selected from Si-containing monomer, a monomer having a bicyclic oxazinone structure containing an endocyclic double bond, substituted or unsubstituted 2,3 -dihydrofuran, a substituted or unsubstituted 2,3 -dihydropyran.

[0108] The Si-containing monomer can contain Si-0 bond and carbon-carbon double bond, especially the Si-containing monomer can contain Si-0 bond and carbon-carbon double bond in a ring, for example such ring can containing 6 to 12 ring members (for example 6, 7, 8, 9, 10, 11 or 12 ring members) or 6 to 8 ring members.

[0109] The Si-containing monomer are described for example in US2023 / 0416283A, US2024 / 0294555A1 and US11,897, 905B2, all of which are incorporated herein by reference.

[0110] In an embodiment, the Si-containing monomer has the following structure:wherein:Y is O or C(RQ)2;each instance of RQis independently hydrogen, halogen, or substituted or unsubstituted, Ci-6 alkyl;each instance of RKis independently hydrogen, halogen, substituted or unsubstituted, Ci-io alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or — ORN;each instance of RNis independently hydrogen, substituted or unsubstituted acyl, substituted or unsubstituted, Ci-io alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or an oxygen protecting group;j is 1, 2, or 3; andk is 0, 1, 2, or 3.

[0111] An example of Si-containing monomer can be 2,2-diisopropyl-4,7-dihydro-l,3,2-dioxasilepine.

[0112] The monomer having a bicyclic oxazinone structure containing an endocyclic double bond is described in US9,206,271B2, which is incorporated herein by reference.

[0113] Substituted or unsubstituted 2, 3 -dihydrofuran, a substituted or unsubstituted 2,3 -dihydropyran are described in WO2022 / 212752A1, which is incorporated herein by reference.

[0114] In an embodiment, the amount of the cleavable comonomer can range from 5% to 25% by weight (e.g. 6%, 8%, 10%, 12%, 15%, 18%, 20% or 22% by weight), for example 6% to 22% by weight, or 8% to 20% by weight, or 8% to 18% by weight, based on the total weight of the cyclic olefin and cleavable comonomer.

[0115] The degradation of the cleavable polymer can be carried out in the presence of a cleaving agent or by heating. For example, for the Si-containing monomer, the cleaving agent can be a cleaving agent having fluoride ion, especially when a Si-containing monomer is used for the formation of the cleavable polymer. The cleaving agent having fluoride ion can be selected from tetrabutylammonium fluoride, tetraethylammonium fluoride, tetramethylammonium fluoride, HF and trifluoroacetic acid. In an embodiment, the cleaving agent having fluoride ion is tetrabutylammonium fluoride. For the monomer having a bicyclic oxazinone structure containing an endocyclic double bond, the cleaving agent can be selected from acid or base. For Substituted or unsubstituted 2,3 -dihydrofuran, and a substituted or unsubstituted 2,3 -dihydropyran, the cleaving agent can be selected from acid.

[0116] In an embodiment, the cleavable polymer is a cleavable thermoset polymer.

[0117] An illustrative scheme for degrading cleavable polymer is as follows:wherein:X is a structure unit derived from the cleavable monomer;Rn and R22 are independently selected from H, Ci-Ce alkyl substituted by OH, or other functional groups (such as carboxylic group and amino group);a and b independently denote a number > 0 and a and b are not zero at the same time; andc denotes a number of at least 1.In an embodiment, at least one of Rn and R22 is Ci-Ce alkyl substituted by OH.

[0118] A specific illustrative reaction scheme for the preparation of cleavable polymer and degrading cleavable polymer (for example for the synthesis of the oligomer in example 5) is as follows:wherein a and b independently denote a number of 1 or more.

[0119] The oligomer obtained from degradation is an unsaturated oligomer. In this disclosure, the oligomer obtained from degradation is subjected to hydrogenation. The details of the hydrogenation are as discussed above.

[0120] Oligomer (z) is a functionalized oligomer comprising the cyclic structure units, for example a functionalized petroleum resin, or a functionalized oligomer derived from ROMP.The oligomer derived from ROMP can be selected from oligomer (x), oligomer (y), oligomer (x’) formed from cyclic olefin by ring-opening metathesis polymerization (ROMP) involving a chain transfer agent (t’), and oligomer (y’) formed by degrading a cleavable polymer, wherein the oligomer (x) and oligomer (y) still comprise carbon-carbon unsaturated double bond. The chain transfer agent (t’) can be a mono-olefin carrying at least one functional group (a), for example hydroxyl group, carboxylic group and amino group, or a mono-olefin (i.e., without the functional group (a)). The oligomer (x) and oligomer (y) are as mentioned above, but still comprise carbon-carbon unsaturated double bond, i.e., oligomer (x) and oligomer (y) are not fully hydrogenated. The cyclic olefin and cleavable polymer are as mentioned above.

[0121] A person skilled in the art could understand that the petroleum resin is different from the oligomer derived from ROMP. In an embodiment, the petroleum resin is unsaturated cyclic based hydrocarbon resin. In an embodiment, the petroleum resin is Escorez 8400 from ExxonMobil Chemical Company.

[0122] The oligomer to be functionalized has carbon-carbon unsaturated double bond, for example in its structure units. The amount of the structure units having carbon-carbon unsaturated double bond can be at least 5 mol% (e.g. 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 40 mol%, 50 mol%, 60 mol%, 70 mol%, 80 mol%, 90 mol%, or 95 mol% or 100 mol%), for example at least 20 mol%, or at least 50 mol%, or at least 80 mol%, based on the total amount of the structure units in the oligomer to be functionalized.

[0123] In an embodiment, the oligomer comprising the cyclic structure units to be functionalized has carbon-carbon unsaturated double bond, the functionalization can be carried out in single-stage or multistage reactions known in principle to a person skilled in the art.

[0124] The functionalization of the oligomer can comprise:i) reacting aromatic hydroxy compounds in the presence of an alkylating catalyst to give aromatic hydroxy compounds alkylated with the oligomer,ii) reacting the oligomer with a peroxy compound to give an epoxidized petroleum resin,iii) reacting the oligomer with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to give a hydroformyl ated petroleum resin,iv) reacting the oligomer with a borane, followed by oxidative cleavage, to give a hydroxylated oligomer, and / orv) reacting the oligomer with oxides of nitrogen, followed by hydrogenation, to give an oligomer containing terminal amino groups.

[0125] In an embodiment, the functional group of the oligomer (z) is carbonyl or aldehyde group, the functionalization can be carried out by hydroformylation. For example, the oligomer can be reacted with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to give a hydroformylated petroleum resin.

[0126] An illustrative scheme for functionalizing petroleum resin having the cyclic structure units is as follows:wherein R a functional group which is reactive to the other functional group to form the reversible structure moieties. In an embodiment, R is carbonyl or aldehyde group or hydroxyl group.

[0127] A specific illustrative reaction scheme (for example for the synthesis the oligomer in example 7) is as follows:

[0128] The vitrimer of the present disclosure comprising cyclic structure units and reversible structure moieties.

[0129] In an embodiment, the reversible structure moieties are selected from dissociative and associative reversible structure moieties, for example the reversible structure moieties comprise a moiety selected from ester bond, boronic ester bond, amine, imine, disulfide, carbamate, vinylogous urethane, and bond formed from furan and anhydride.

[0130] In an embodiment, the reversible structure moieties comprise a moiety selected from boronic ester bond and imine.

[0131] In this disclosure, oligomers, such oligomers (x), (y) and (z) can have a functional group (a), which is reactive to a linking compound capable of forming the reversible structure moieties.

[0132] In an embodiment, the boronic ester bond may derived from a linking compound such as a BOH-containing compound or its ester derivative, for example if the oligomer (x),(y) and (z) contains hydroxyl group. In an embodiment, said BOH-containing compound contains two or more B-OH moieties.

[0133] The BOH-containing compound or its ester derivative can be selected from a compound containing at least two B-0 ester bonds, a compound containing at least one B(OH)2 group, boric acid, and pyroboric acid.

[0134] A person skilled in the art could understand that two or three B-OH moieties can share one B atom, and two or three B-0 ester moieties can also share one B atom.

[0135] The compound containing at least two B-0 ester bonds comprises a compound containing three B-0 ester bonds. The term B-0 ester bond refers to a -B-O-C- structure. Preferably, the compound containing three B-0 ester bonds has the following structure:wherein Ra, Rb and Rcare independently hydrocarbyl, preferably alkyl or aryl. Ra, Rb and Rc can be same or different. The hydrocarbyl can have 1 to 20 carbon atoms, preferably 1 to 10 or 1 to 6 or 1 to 4 carbon atoms. The alkyl can have 1 to 20 carbon atoms, preferably 1 to 10 or 1 to 6 or 1 to 4 carbon atoms. The aryl can have 6 to 10 carbon atoms. The typical example of such compound comprises trimethyl borate, triethyl borate, tri-n-propyl borate, tri-isopropyl borate, tri -butyl borate, and tri -tert-butyl borate.

[0136] In an embodiment, the compound containing at least one B(OH)2 group is selected from benzen-l,4-diboronic acid, 3-carboxyphenylboronic acid, aminobenzeneboronic acid, and tetrahydroxy diboron.

[0137] The imine moiety may derive from a linking compound such as an amine, for example if the oligomers such as oligomers (x), (y) and (z) contain carbonyl group or aldehyde group.

[0138] Amine of this kind typically has at least two primary amino groups, and generally has 2 to 6, more particularly 2 to 4, for example 2, 3 or 4 primary amino groups.

[0139] Examples of customary amine are:aliphatic polyamines such as ethylenediamine, 1,2- and 1,3 -propanediamine, neopentanediamine, hexamethylenediamine, octamethylenediamine, 1,10-diaminodecane, 1,12-diaminododecane, diethylenetriamine, and the like;cycloaliphatic diamines, such as 1,2-diaminocyclohexane, l,3-bis(aminomethyl)-cyclohexane, 1 -methyl-2,4-diaminocy clohexane, 4-(2-aminopropan-2-yl)- 1 -methylcyclohexane- 1 -amine, isophoronediamine, 4,4'-diaminodicyclo-hexylmethane,3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,8-diaminotricyclo[5.2.1.0]decane, norbornanediamine, menthanediamine, menthenediamine, and the like;aromatic diamines, such as tolylenediamine, xylylenediamine, especially meta-xylylenediamine, Diethyltoluenediamine, bi s(4-aminophenyl)m ethane (MDA or methylenedianiline), bis(4-aminophenyl) sulfone (also known as DADS, DDS or dapsone), and the like;and also mixtures of the aforesaid amine.

[0140] The amount of the reversible moieties in the vitrimer can be in the range from 0.1 to 5 mmol / g vitrimer (e.g. 0.12, 0.15, 0.18, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.5, 1.8, 2, 2.5, 3, 3.5, 4, 4.5, or 4.8 mmol / g vitrimer), such as 0.12 to 4.8 mmol / g vitrimer, 0.15 to 4.5 mmol / g vitrimer, 0.15 to 4 mmol / g vitrimer, 0.15 to 3.5 mmol / g vitrimer, 0.15 to 3 mmol / g vitrimer, 0.2 to 4.8 mmol / g vitrimer, 0.2 to 4.5 mmol / g vitrimer, 0.2 to 4 mmol / g vitrimer, 0.2 to 3.5 mmol / g vitrimer, 0.2 to 3 mmol / g vitrimer, 0.2 to 2.5 mmol / g vitrimer, or 0.2 to 2 mmol / g vitrimer. In an embodiment, the reversible structure moiety is boronic ester bond, the amount of the reversible moieties in the vitrimer can be in the range from 0.1 to 4 mmol / g vitrimer, 0.15 to 3.5 mmol / g vitrimer, 0.2 to 3 mmol / g vitrimer, or 0.2 to 2.5 mmol / g vitrimer. In an embodiment, the reversible structure moieties comprise a reversible moiety other than boronic ester bond, for example imine moiety, the amount of the reversible moieties in the vitrimer can be in the range from 1 to 5 mmol / g vitrimer, 1.5 to 5 mmol / g vitrimer, 2.5 to 5 mmol / g vitrimer, or 2.5 to 4.5 mmol / g vitrimer.

[0141] If boric acid is used as the linking compound, boric acid and hydroxyl of the oligomer can form three boronic ester bonds, i.e., form three reversible structure moieties. If diamine is used as the linking compound, the diamine and carbonyl or aldehyde group of the oligomer can form two imine moieties, i.e. form two the reversible structure moieties. The amount of reversible structure moieties can be calculated according to the amount of functional group (a) in the oligomer, for example when the amount of the linking compound is used in excess.

[0142] The amount of cyclic structure units can range from 82% to 99.7% by weight (e.g.83% by weight, 84% by weight, 85% by weight, 88% by weight, 90% by weight, 92% by weight, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight, 99.2% by weight, 99.5% by weight), such as from 75% to 99.6% by weight, from 90% to 99.6% by weight, from 96% to 99.6% by weight, or from 72% to 92% by weight, or from 75% to 88% by weight, based on the total weight of the vitrimer.

[0143] In an embodiment, there are or are not connecting groups between the cyclic structure units and the reversible structure moieties, for example, if present, the connecting groups can have 1 to 20 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) carbon atoms or 2 to 10 carbon atoms, or 3 to 10 carbon atoms or 4 to 10 carbon atoms or 4 to 8 carbon atoms or 4 to 6 carbon atoms. In an embodiment, the connecting groups can derive from the chain transfer agent, for example the connecting groups can derive from a compound having one or more hydroxyl groups (e.g. 1 or 2 hydroxyl groups) and a carbon-carbon double bond. The amount of the connecting groups can be in the range from 0.8% to 40% by weight (e.g. 1, 1.2, 1.5, 2, 5, 8, 10, 12, 15, 20, 25, 30, 32, 35 or 40% by weight), for example from 1% to 35% by weight, or from 1.2% to 32% by weight, or from 1.2% to 25% by weight, or from 1.2% to 20% by weight, or from 1.2% to 15% by weight, or from 1.2% to 10% by weight, based on the total weight of the connecting groups and the cyclic structure units.

[0144] In some aspects, the connecting groups are derived from a compound having one or more hydroxyl groups (e.g. 1 or 2 hydroxyl groups) and a carbon-carbon double bond.

[0145] The glass transition temperature (Tg) of the vitrimer can range from 50°C to 250°C (e.g. 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 215°C, 220°C, 230°C, 240°C or245°C). In some embodiments, the glass transition temperature (Tg) of the vitrimer can range from 60°C to 240°C, or from 70°C to 230°C, or from 80°C to 220°C, or from 85°C to 200°C, or from 90°C to 210°C, or from 100°C to 200°C, or from 100°C to 190°C, or from 100°C to 180°C, or from 100°C to 170°C, or from 100°C to 160°C. The glass transition temperature can be measured by dynamic mechanical thermal analysis (DMTA). The testing was performed in torsion fixture at a frequency of 1 Hz in the temperature range from 35°C to 350°C with a heating rate of 5°C / min in N2 atmosphere.

[0146] The flow temperature (Tf) of the vitrimer of this disclosure can range from 90°C to 300°C (e.g. 95°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, or 240°C, 250°C, 260°C, 270°C, 280°C, or 290°C), such as from 90°C to280°C, from 90°C to 250°C, from 95°C to 220°C, from 100°C to 210°C, or from 100°C to 200°C. The flow temperature can be measured by dynamic mechanical thermal analysis (DMTA). The testing was performed in torsion fixture at a frequency of 1 Hz in the temperature range from 35°C to 350°C with a heating rate of 5°C / min in N2 atmosphere. The vitrimer goes to the visco-elastic region at a temperature higher than flow temperature. In a DMTA curve of the vitrimer, the value of loss modulus is above the value of storage modulus at the flow temperature.

[0147] The tensile modulus of the vitrimer can range from 1500 MPa to 3500 MPa (e.g.1550 MPa, 1580 MPa, 1600 MPa, 1650 MPa, 1700 MPa, 1800 MPa, 1900 MPa, 2000 MPa, 2100 MPa, 2200 MPa, 2300 MPa, 2400 MPa, 2450 MPa, 2500 MPa, 2600 MPa, 2700 MPa, 2800 MPa, 2900 MPa, 3000 MPa, 3100 MPa, 3200 MPa, 3300 MPa, or 3400 MPa,). In some embodiments, the tensile modulus of the vitrimer can range from 1550 MPa to 3400 MPa, 1550 MPa to 3200 MPa, 1550 MPa to 3000 MPa, 1550 MPa to 2800 MPa, 1550 MPa to 2500 MPa, 1550 MPa to 2400 MPa, or from 1580 MPa to 2300 MPa, or from 1600 MPa to 2300 MPa, or from 1700 MPa to 2300 MPa, or from 1800 MPa to 2300 MPa. The tensile modulus is measured by INSTRON 5966 Universal Testing Systems at 25°C under a tensile rate of 50 mm / min.

[0148] The tensile stress of the vitrimer can range from 40 MPa to 100 MPa (e.g. 42 MPa, 45 MPa, 48 MPa, 50 MPa, 55 MPa, 60 MPa, 65 MPa, 68 MPa, 70 MPa, 75 MPa, or 78 MPa, 80 MPa, 85 MPa, 90 MPa, 95 MPa, or 98 MPa). In some embodiments, the tensile stress of the vitrimer can range from 42 MPa to 98 MPa, 42 MPa to 95 MPa, 42 MPa to 90 MPa, 42 MPa to 85 MPa, 42 MPa to 80 MPa, 42 MPa to 78 MPa, or from 45 MPa to 75 MPa, or from 48 MPa to 75 MPa, or from 50 MPa to75 MPa, or from 55 MPa to 75 MPa, or from 55 MPa to 70 MPa, or from 55 MPa to 68 MPa. The tensile stress was measured by INSTRON 5966 Universal Testing Systems at 25°C under a tensile rate of 50 mm / min.

[0149] The vitrimer of this disclosure has thermoplastic property, for example is able to be processed by pressing, injection molding, extrusion molding, blow molding, calendering, foaming, solvent plasticizing, mold pressing, casting, reaction molding, for example by granulation and further hot press or extrusion. By "thermoplastic polymer(s)" is meant a polymer that can be melted by heat and then cooled without appreciable change in solid-state properties before and after heating.Oligomer

[0150] One aspect of this disclosure relates to the oligomers (x), (y) and (z) as defined in this disclosure.Method for preparing the vitrimer

[0151] A further aspect of this disclosure is directed to method for preparing the vitrimer of this disclosure, comprising reacting an oligomer having a functional group (a) and cyclic structure units with a linking compound capable of forming the reversible structure moieties with the functional group (a).

[0152] In an embodiment, the oligomer is selected from oligomer (x), oligomer (y) and oligomer (z) defined in this disclosure.

[0153] Therefore, the method can further comprise a step of preparing oligomer (x), a step of preparing oligomer (y) and / or a step of preparing oligomer (z).

[0154] Oligomer (x) can be formed from cyclic olefin by ring-opening metathesis polymerization (ROMP) involving a chain transfer agent and then at least partial hydrogenation. Details of the ROMP, cyclic olefin and chain transfer agent and hydrogenation are as mentioned above.

[0155] Oligomer (y) can be formed by degrading a cleavable polymer and then at least partially hydrogenating, wherein the cleavable polymer is formed from cyclic olefin and cleavable comonomer. In an embodiment, the cleavable polymer is formed from cyclic olefin and cleavable comonomer by ROMP. Details of the ROMP, cyclic olefin, cleavable comonomer, degradation of the cleavable polymer and hydrogenation are as mentioned above.

[0156] For the preparation of oligomer (x) and / or oligomer (y), hydrogenation level can be for example at least 35% (e.g. 40%, 45%, 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9% or 100%), for example at least 40%, or at least 50%, or at least 60% or at least 80%, of the residual double bonds which are present within oligomer prior to the hydrogenation. In an embodiment, hydrogenation level can range from 35% to 100%, from 40% to 100% or from 40% to 99.9%, from 50% to 100% or from 50% to 99.5%, from 60% to 100% or from 60% to 99.5%, from 70% to 100% or from 70% to 99.5%, from 80% to 100% or from 80% to 99.5%, or from 80% to 95%, of the residual double bonds which are present within oligomer prior to the hydrogenation.

[0157] As mentioned above, the oligomer (x), oligomer (y) and oligomer (z) can have an unsaturation degree of no more than 0.01 mol / g (e.g. 0.009 mol / g, 0.008 mol / g, 0.007 mol / g, 0.006 mol / g, 0.005 mol / g, 0.004 mol / g, 0.003 mol / g, 0.002 mol / g, 0.001 mol / g, 0.0009 mol / g, 0.0008 mol / g, 0.0007 mol / g, 0.0006 mol / g, 0.0005 mol / g, 0.0004 mol / g, 0.0003 mol / g, 0.0001 mol / g, 0.00005 mol / g, 0.00002 mol / g, 0.00001 mol / g), for example no more than 0.009 mol / g or no more than 0.008 mol / g, or no more than 0.007 mol / g, or no more than 0.005 mol / g, or no more than 0.0025 mol / g, wherein the unsaturation degree is calculated by mol of carbon-carbon unsaturated double bond carrying at least one hydrogen atom per gram of oligomer. In an embodiment, the oligomer (x), oligomer (y) and oligomer (z) have an unsaturation degree of from 0 mol / g to 0.009 mol / g, or from 0 mol / g to 0.008 mol / g, or from 0 mol / g to 0.007 mol / g, or from 0 mol / g to 0.006 mol / g, or from 0 mol / g to 0.005 mol / g, or from 0 mol / g to 0.0025 mol / g, wherein the unsaturation degree is calculated by mol of carboncarbon unsaturated double bond carrying at least one hydrogen atom per gram of oligomer. The mol of the carbon-carbon unsaturated double bond can be calculated based on mol ofolefin-H measured by1H NMR. For example, if each carbon-carbon unsaturated double bond carries two hydrogen atoms, then the amount of carbon-carbon unsaturated double bond is half of the amount of olefin-H. A person skilled in the art could understand that the amount of carbon-carbon unsaturated double bond does not comprise those in aryl or heteroaryl.

[0158] Oligomer (z) can be formed by functionalizing an oligomer comprising the cyclic structure units, such as petroleum resin or an oligomer derived from ROMP. The functionalization of the oligomer comprising the cyclic structure units and petroleum resin are as mentioned above.

[0159] As mentioned above, the reversible structure moieties are selected from dissociative and associative reversible structure moieties, for example the reversible structure moieties comprise a moiety selected from ester bond, boronic ester bond, amine, imine, disulfide, carbamate, vinylogous urethane, and bond formed from furan and anhydride, the functional group (a) and the linking compound can be selected to form such reversible structure moieties.

[0160] As mentioned above, if reversible structure moieties comprise boronic ester bond, the functional group (a) of the oligomer can be a hydroxyl group and the linking compound can be a BOH-containing compound or its ester derivative. In this scenario, the vitrimer can be prepared by mixing the oligomer and the BOH-containing compound or its ester derivative and polymerizing the resulted mixture. The polymerizing temperature can range from 90°C to 250°C (e.g. 95°C, 98°C, 100°C, 105°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 180°C, 200°C, 220°C, 230°C or 240°C), for example from 95°C to 240°C, or from 95°C to 220°C, or from 98°C to 210°C. The polymerization time can range from 3 minutes to 30 hours (e.g. 4 minutes, 5 minutes, 8 minutes, 10 minutes, 20 minutes, 30 minutes, 45 minutes, 1 hour, 2 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, 25 hours, 28 hours, or 29 hours), or from 4 minutes to 25 hours. In an embodiment, the polymerization is carried out at temperature ranging from 90°C to 150°C, or from 95°C to 120°C and the polymerization time ranges from 5 hours to 30 hours, or from 12 hours to 28 hours. In an embodiment, the polymerization is carried out at temperature ranging from 160°C to 250°C, or from 180°C to 230°C and the polymerization time ranges from 3 minutes to 30 minutes, or from 4 minutes to 15 minutes. Optionally, the vacuum can be applied to remove the volatile during the polymerization.

[0161] As mentioned above, if reversible structure moieties comprise imine moiety, the functional group (a) of the oligomer can be a carbonyl group or aldehyde group and the linking compound can be an amine. In this scenario, the vitrimer can be prepared by mixing the oligomer and the amine and polymerizing the resulted mixture. The polymerizing temperaturecan range from 90°C to 150°C (e.g. 95°C, 98°C, 100°C, 105°C, 110°C, 120°C, 130°C, or 140°C), for example from 95°C to 140°C, or from 95°C to 120°C, or from 98°C to 110°C. The polymerization time can range from 5 hours to 30 hours (e.g. 6 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, 25 hours, 28 hours, or 29 hours), or from 12 hours to 28 hours.

[0162] Usually, the amount of the linking compound can range from 0.1% to 28% by weight (e.g. 0.15% by weight, 0.2% by weight, 0.25% by weight, 0.3% by weight, 0.35% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.8% by weight, 1% by weight, 2% by weight, 5% by weight, 8% by weight, 10% by weight, 12% by weight, 15% by weight, 18% by weight, 20% by weight, 22% by weight, 25% by weight or 26% by weight), such as from 0.15% to 25% by weight, from 0.2% to 25% by weight, from 0.3% to 25% by weight, from 0.4% to 25% by weight, from 0.3% to 10% by weight or from 0.4% to 6% by weight or from 8% to 28% weight, or from 12% to 25% by weight, based on the total weight of the oligomer and linking compound. In an embodiment, the reversible structure moieties comprise boronic ester bond, and the amount of the linking compound such as BOH-containing compound or its ester derivative can range from 0.1% to 10% by weight (e.g. 0.15% by weight, 0.2% by weight, 0.25% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.8% by weight, 1% by weight, 2% by weight, 5% by weight, 8% by weight, 10% by weight), for example from 0.15% to 6% by weight, from 0.2% to 6% by weight, from 0.3% to 6% by weight, from 0.4% to 6% by weight, based on the total weight of the oligomer and linking compound. In an embodiment, the reversible structure moieties comprise a reversible moiety other than boronic ester bond, for example imine moiety, the amount of the linking compound such amine can range from 8% to 28% weight (e.g. 8% by weight, 10% by weight, 12% by weight, 15% by weight, 18% by weight, 20% by weight, 22% by weight, 25% by weight or 26% by weight), for example from 12% to 25% by weight, based on the total weight of the oligomer and linking compound.

[0163] Usually, the linking compound is used in stoichiometric excess of from 5% to 50%, or from 5% to 30%, or from 10% to 20% in relative to the functional group (a) of the oligomer.Composite material

[0164] A further aspect of this disclosure is directed to a composite material comprising a substrate and the vitrimer as defined in this disclosure. The substrate can comprise fiber and fillers.

[0165] The fibers can be selected from glass fibers, carbon fibers, aramid fibers or basalt fibers, or mixtures thereof. Particular preference is given to glass fibers and carbon fibers. Thefibers can be used in the form of single fibers, fiber filaments, fiber rovings, or combinations thereof. The fibers may take the form, for example, of short fiber having a length of a few mm to a few cm (for example 2mm to 5 cm). The amount of the substrate can be in the range from 0.1% to 70% by weight (for example 0.2%, 0.5%, 0.8%, 1%, 1.5%, 1.8%, 2%, 4%, 6%, 8%, 10%, 15%, 20%, 25%, 30%, 40%, 50% or 60% by weight), or from 0.5% to 60% by weight, 1% to 50% by weight, 1.5% to 40% by weight, or from 2% to 30% by weight, or from 5% to 30% by weight, or from 10% to 25% by weight, based on the total weight of the composite material.

[0166] The composite material of this disclosure has thermoplastic property. The composite material of this disclosure is able to be processed by pressing, injection molding, extrusion molding, blow molding, calendering, foaming, solvent plasticizing, mold pressing, casting, reaction molding, for example by granulation and further hot press or extrusion.

[0167] The composite material may further comprise at least one additive. Such additives are well known in the art, and can include, for example: fillers; antioxidants (e.g. hindered phenolics such as IRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites (e.g. IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates and hydrogenated rosins; UV stabilizers; heat stabilizers; antiblocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; fillers; talc; modifier; and the like.Blending and Processing of vitrimer and the composite material

[0168] The vitrimer and composite material described herein may be processed or formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twinscrew extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process. Additionally, additives may be included in the polymer, blend, in one or more components of the blend, and / or in a product formed from the blend, such as a film, as desired. Examples of additives are as described above.

[0169] The vitrimer can be in any physical form. In one embodiment, reactor granules, defined as the granules of polymer that are isolated from the polymerization reactor prior to any processing procedures, are used. In another embodiment, the polymer is in the form of pellets that are formed from melt extrusion. The polymers can be in above mentioned physical form when used to blend with the additive.

[0170] The components of the present disclosure can be blended by any suitable means, and are typically blended to yield an intimately mixed composition which may be a homogeneous, single-phase mixture. For example, they may be blended in a static mixer, batch mixer, extruder, or a combination thereof, that is sufficient to achieve an adequate dispersion of additive in the polymer.

[0171] The mixing step may involve first dry blending using, for example, a tumble blender, where the vitrimer and additive are brought into contact first, without intimate mixing, which may then be followed by melt blending in an extruder. Another method of blending the components is to melt blend the vitrimer pellets with the additive directly in an extruder or batch mixer. It may also involve a "master batch" approach, where the final additive concentration is achieved by combining neat polymer with an appropriate amount of additive that had been previously prepared at a higher additive concentration. The mixing step may take place as part of a processing method used to fabricate articles, such as in the extruder on an injection molding machine or blown-film line or fiber line.

[0172] The vitrimer and the composite material can be used in building and construction, agriculture, automotive, aerospace, energy, wind energy, electrical and electronics, consumer goods.ExamplesMaterials and abbreviation

[0173] 2ndgeneration Grubbs catalyst: Chemical formula C46H65CI2N2PRU, CAS No.246047-72-3, the structure is as follows:DCPD: di cyclopentadiene,TDTBPP: Tris(2,4-di-tert-butylphenyl)phosphite, CasNo. 31570-04-4,TBAF: tetrabutylammonium fluoride.Escorez 8400: an unsaturated cyclic based hydrocarbon resin sold by ExxonMobil Chemical Company, Mn 311, Mw 610, Mw / Mn 1.961, Unsaturated olefin CH: 0.011 mol / g.Method

[0174] DMTA: Dynamic mechanical thermal analysis (DMTA) experiment was performed to evaluate the Tg and flow temperature (Tf) of the material. DMTA was carried out by ARES-G2 according to EM method. The testing was performed in torsion fixture at a frequency of 1 Hz in the temperature range from 35°C to 250°C with a heating rate of 5°C / min in N2 atmosphere. For flowable polymers, the testing was performed with 8 mm parallel plate at a frequency of 1 Hz in the temperature range from 35°C to 250°C with a heating rate of 5°C / min in N2 atmosphere.

[0175] Tensile test: To test the tensile and flexural behaviors, samples bars were prepared (ISO 37 type 3 specimen, shown in Figure 11) and conditioned at 25°C for 48 hours before tests. The stress-strain curve was collected by INSTRON 5966 Universal Testing Systems at 25°C under a tensile rate of 50 mm / min. The flexural testing method is developed based upon ASTM D790, Method A, denoted as EM method.

[0176] GPC: The solid were dissolved in THF at a concentration of 2 mg / mL. The material was then filtered through a 0.22 pm nylon filter before analysis. Gel permeation chromatography (GPC) analyses were performed on an EcoSEC HLC-8320GPC system with TSKgel SuperMultiporeHZ-M + TSKgel SuperMultiporeHZ-M(21488) columns using a THF mobile phase at a flow rate of 0.35 mL / min. The molecular weight (g / mol) and distribution were analyzed with refractive index detector. The standard curve was recorded with narrow MWD polystyrene.Example 1- preparation of oligomers 1, 2, and 3

[0177] According to the amounts in table 1, DCPD was mixed with 3-buten-l-ol in glass vial. 2ndgeneration Grubbs catalyst was added under N2 and the reaction mixture was heated at 80°C for 20 hours.1H NMR and GPC spectra were recorded for the generated oligomers, and 'H NMR spectra were shown in figure 1, GPC results were summarized in Table 1.Table 1

[0178] Almost all carbon-carbon double bonds in the oligomers synthesized in the example part of this disclosure carry two hydrogen atoms, therefore, the amount of the carbon-carbon double bond carrying hydrogen atoms in the oligomers is half of the amount of olefin-H.

[0179] Figure 1 shows in situ 'HNMR spectra for oligomers 1, 2, and 3. Characterization of the reagent: 3-buten-ol: 'H NMR (500 MHz, CDC13) 6 6.01 - 5.60 (m, 1H), 5.35 - 4.87 (m, 2H), 3.68 (q, = 6.1 Hz, 2H), 2.33 (qt, = 6.4, 1.3 Hz, 2H), 1.66 (m, 1H). DCPD: 'HNMR (700 MHz, CDCI3) 6 5.95 (d, J= 32.8 Hz, 2H), 5.49 (d, J= 13.9 Hz, 2H), 3.21 (m, 1H), 2.87 (s, 1H), 2.78 (s, 1H), 2.72 (m, 1H), 2.18 (d, J= 17.3 Hz, 1H), 1.62 (d, J= 17.3 Hz, 1H), 1.48 (d, J = 8.0 Hz, 1H), 1.30 (d, J = 8.0 Hz, 1H). Peaks from 4.8 ppm - 6.2 ppm indicate the unsaturated olefin bonds (carbon-carbon double bonds). Oligomers 1, 2, and 3 are formed because new peaks are generated in this range. The spectrum of oligomer 1 shows that the reagents are all consumed to form the oligomer containing cyclic unit. With the NMR interal standard: Methyl 3,5-dinitrobenzoate, the mol of -OH per gram of oligomer 1 was calculated to be 0.0013 mol / g and the unsaturated olefin -H was calculated to be 0.032 mol / g and thus the amount of carbon-carbon double bond carrying hydrogen atoms is 0.016 mol / g.Example 2: preparation of oligomers 4, 11, and 12

[0180] According to the amount in Table 2, DCPD was mixed with cis-2-Butene-l,4-diol in 250 mL dry THF. 2ndgeneration Grubbs catalyst was added under N2 and the reaction mixture was heated at 80°C for 20 hours. The resulting solution was added to 5000 mL methanol dropwise for precipitation. The white solid was collected and dried under vacuum at 40°C for 24 hours.1H NMR spectra of the oligomers were shown in figure 2, GPC results were summarized in Table 2.Table 2

[0181] Figure 2 shows 'H NMR spectra of oligomers 4, 11, and 12. Peaks from 4.8 ppm - 6.2 ppm indicate the unsaturated olefin bonds formed after ROMP. Peaks from 4.5-4.0 ppm indicate the CH2 connected to -OH and double bonds (overlapped with internal standard sharp peak at 3.99 ppm). With the NMR internal standard: methyl 3,5-dinitrobenzoate, the mol of -OH per gram of oligomers and the unsaturated olefin -H was calculated andsummarized in Table 2. The amount of the carbon-carbon double bond carrying hydrogen atoms in the oligomers is half of the amount of olefin-H.Example 3: preparation of oligomer 5

[0182] 40.45 g DCPD was mixed with 38 g 5-norbornene-2 -methanol and 5.39 g cis-2-Butene-l,4-diol in 153 mL dry THF. 2ndgeneration Grubbs catalyst: 34.8 mg was added under N2 protection, and the reaction mixture was stirred at 80°C for 20 hours. The resulting solution was added to 2000 mL water dropwise for precipitation. The white solid was collected and dried under vacuum at 40°C for 48 hours. Products: 77.4 g, yield: 95%.XH NMR spectra of the oligomer 5 was shown in Figure 3, GPC results were as follows: oligomer 5: Mn 4634, Mw 8374, Mw / Mn 1.807.

[0183] Figure 3 showsXH NMR Spectrum for oligomer 5. Peaks from 4.8 ppm - 6.2 ppm indicate the unsaturated olefin bonds. Oligomer 5 contains two types of -OH groups. Peaks from 4.5-4.0 ppm indicate the CHi connected to -OH and double bonds (overlapped with internal standard sharp peak at 3.99 ppm). Broad peak at 3.52 ppm indicates the CHi from the NBCH2OH after ROMP. With the NMR interal standard: Methyl 3,5-dinitrobenzoate, the mol of -OH per gram of oligomer 5 was calculated to be 0.0029 mol / g and the unsaturated olefin -H was calculated to be 0.025 mol / g. The amount of the carbon-carbon double bond carrying hydrogen atoms in the oligomers is half of the amount of olefin-H, z.e., 0.0125 mol / g.Example 4: preparation of oligomer 6

[0184] 60 g DCPD was mixed with 18.6 g 5-norbomene-2,3-dicarboxylic anhydride and 5.01 g cis-2 -Butene- 1,4-diol in 150 mL Dry THF. 0.0321 g 2ndgeneration Grubbs catalyst was added under N2 and the reaction mixture was stirred at 80°C for 20 hours. The resulting solution was added to 1500 mL methanol dropwise for precipitation. The white solid, 72 g, was collected and dried under vacuum at 40°C for 24 hours (yield 86%).1H NMR spectra of the oligomer 6 was shown in figure 4, GPC results were as follows: oligomer 6: Mn 3901, Mw 6704, Mw / Mn 1.719.

[0185] Figure 4 shows 'H NMR Spectrum for oligomer 6. Peaks from 4.8 ppm - 6.2 ppm indicate the unsaturated olefin bonds. Peaks from 4.5-4.0 ppm indicate the CHi connected to -OH and double bonds. Broad peak at 3.43 ppm indicates the CH connected to MA C=O bond that copolymerized with DCPD after ROMP. With the NMR interal standard: Methyl 3,5-dinitrobenzoate, the mol of -OH per gram of oligomer 6 was calculated to be 0.00059 mol / g and the unsaturated olefin -H was calculated to be 0.028 mol / g. The amount of the carbon-carbon double bond carrying hydrogen atoms in the oligomer is half of the amount of olefin-H, i.e., 0.014 mol / g.Example 5: preparation of oligomer 7

[0186] 45 g DCPD and 5 g 2,2-diisopropyl-4,7-dihydro-l,3,2-dioxasilepine were mixed in 60 mL vial at ambient conditions, and later transferred to mix with 48 mg 2ndgeneration Grubbs catalyst in ultrasonic, during which the process was operated without exposure to air and moisture. The mixture was reacted under 120°C for 0.5 hours. The resulting thermoset material was mixed with 50 mL TBAF (IM THF solution) for degradation. The degraded solution was added to methanol dropwise for precipitation. The resulting white solid was characterized byXH NMR and GPC.XH NMR spectra of the oligomer 7 was shown in Figure 5, GPC results were as follows: oligomer 7: Mn 6171, Mw 20204, Mw / Mn 3.274.

[0187] The oligomer 7 was hot pressed at 150°C with the ISO 37 type 3 specimen mold to achieve sample bars. Figure 8 shows pictures of hot-pressed oligomer 7, wherein cracked sample bars were obtained from oligomer 7, which means a very poor mechanical performance.

[0188] Figure 5 showsXH NMR Spectrum for oligomer 7. Peaks from 4.8 ppm - 6.2 ppm indicate the unsaturated olefin bonds. Peaks from 4.5-4.0 ppm indicate the CH connected to -OH and double bonds. With the NMR interal standard: Methyl 3,5-dinitrobenzoate, the mol of -OH per gram of oligomer 7 was calculated to be 0.00040 mol / g and the unsaturated olefin -H was calculated to be 0.030 mol / g. The amount of the carbon-carbon double bond carrying hydrogen atoms in the oligomer is half of the amount of olefin-H, i.e., 0.015 mol / g.Example 6: preparation of oligomers 8, 9, 13, 14, 15 by hydrogenation

[0189] According to table 3, the unsaturated oligomer was mixed with hydrogenation catalyst and solvent in a high-pressure hydrogenation reactor for hydrogenation reaction at the set time and temperature. After hydrogenation, the mixture was passed through celite to remove hydrogenation catalyst and precipitated in methanol to yield white solid as the product. The yield of oligomers 8, 9, 13, 14 and 15 were 40%, 90%, 89%, 65% and 90%, respectively. 'H NMR spectra of the oligomers 8, 9, 13, 14, 15 were shown in Figure 6. The properties of the hydrogenated oligomers were summarized in Table 3.Table 3. reaction conditions and results of the hydrogenation reaction.

[0190] Figure 6 shows 'H NMR Spectra for oligomers 8, 9, 13, 14, and 15. Peaks from 4.8 ppm - 6.2 ppm indicate the remaining unsaturated olefin bonds after hydrogenation. Peaks from 4.5 ppm - 4.0 ppm indicate the CH 2 connected to -OH and double bonds (overlapped with internal standard sharp peak at 3.99 ppm). Peaks from 4.0 ppm - 3.5 ppm indicate the CH2 connected to -OH and the hydrogenated C-C unit. With the NMR internal standard: methyl 3,5-dinitrobenzoate, the mol of -OH per gram of oligomers and the unsaturated olefin -H was calculated and summarized in Table 3. The amount of the carbon-carbon double bond carrying hydrogen atoms (unsaturated degree) in the oligomers is half of the amount of olefin-H. The unsaturated degree of the polymer prepared in the examples below corresponds to the unsaturated degree of the oligomer used for the preparation of the polymer, since the amount of the carbon-carbon unsaturated double bond remains basically unchanged and the amount of linking compound ( / .< ., boric acid) is very low in the preparation of the polymer.Example 7: preparation of oligomer 10

[0191] 50 g of Escorez 8400 (GPC: Mn 311, Mw 610, Mw / Mn 1.961, unsaturated olefin CH: 0.011 mol / g), 0.07 g of Rh(acac)(CO)2(CAS: 14874-82-9) and 0.3 g TDTBPP (CAS: 31570-04-4) were dissolved in 500 mL toluene. The solution was transferred to a hydroformylation reactor. The hydroformylation reaction was carried out at under CO / H2 (20 bar:20 bar) at 100°C for 24 hours. The resulting mixture was precipitated in methanol to yield 36 g light yellow solid as the product, 71% yield. 'H NMR spectra of the oligomer 10 were shown in Figure 7. GPC results were as follows: oligomer 10: Mn 505, Mw 955, Mw / Mn 1.893.

[0192] Figure 7 shows 'H NMR Spectrum for oligomer 10. Peaks from 9.0-10.0 ppm indicate the generated CHO after hydroformylation reaction. Peaks from 4.8 ppm - 6.2 ppm indicate the remaining unsaturated olefin bonds after hydroformylation. With the NMRinternal standard: methyl 3,5-dinitrobenzoate, the mol of -CHO per gram of oligomers was calculated to be 0.0030 mol / g and the unsaturated olefin-H was calculated to be 0.0020 mol / g. The amount of the carbon-carbon double bond carrying hydrogen atoms (unsaturated degree) in the oligomer 10 is half of the amount of olefin-H, i.e., 0.0010 mol / g.Example 8: preparation of comparative polymer 1

[0193] 10 g DCPD and 34.5 mg P(Ph)s were injected to a 20 mL vial at ambient conditions, and later transferred to mix with 9.6 mg 2ndgeneration Grubbs catalyst in ultrasonic, during which the process was operated without exposure to air and moisture. The ISO 37 type 3 specimen mold was placed on the polyimide (PI) film at the bottom and pre-heated at 50°C. After the catalyst was totally dissolved, the mixture was injected to the mold and then sealed by polyimide (PI) film on the top. Once witnessing the obvious curing phenomena of sample bar, the sample was held for 15 minutes. DMTA measurement was performed to identify if the polymer can flow at elevated temperature.Example 9: preparation of comparative polymer 2

[0194] 9 g DCPD and 1 g 2,2-diisopropyl-4,7-dihydro-l,3,2-dioxasilepine were injected to a 20 mL vial at ambient conditions, and later transferred to mix with 9.6 mg 2ndgeneration Grubbs catalyst in ultrasonic, during which the process was operated without exposure to air and moisture. The ISO 37 type 3 specimen mold was placed on the polyimide (PI) film at the bottom and pre-heated at 50°C. After the catalyst was totally dissolved, the mixture was injected to the mold and then sealed by polyimide (PI) film on the top. Once witnessing the obvious curing phenomena of sample bar, the sample was held at 120°C for 30 minutes. DMTA measurement was performed to identify if the polymer can flow at elevated temperature.Example 10: preparation of comparative polymer 3, and polymers 4, 5

[0195] According to Table 4, oligomer and boric acid were dissolved in 40 mL THF. The volatiles were removed under vacuum at 100°C for 24 hours and the resulting polymer was hot pressed at 150°C with The ISO 37 type 3 specimen mold to achieve sample bars for mechanical performance test. DMTA was measured to determine if the polymer is flowable at elevated temperatures. Boric acid is used in excess, the amount of the reversible moieties in the polymers (vitrimers) corresponds to the amount of OH in the oligomers used for the preparation of the polymers. The amount of the carbon-carbon double bond carrying hydrogen atoms (unsaturated degree) in the polymer is half of the amount of olefin-H. As mentioned in example 6, the unsaturated degree of the polymer (vitrimer) corresponds to the unsaturated degree of the oligomer used for the preparation of the polymer, since the amount of the carbon-carbon unsaturated double bond remains basically unchanged and the amount of linking compound(i.e., boric acid) is very low in the preparation of the polymer. Therefore, the unsaturated degree of the polymer corresponds to half of the amount of olefin-H of the oligomer used for preparing the polymer. The unsaturated degree of polymer 4 is 0.0045 mol / g and the unsaturated degree of polymer 5 is 0.000005 mol / g.Table 4. Amounts of oligomers and boric acid used in the reactions

[0196] Figure 8 shows pictures of hot-pressed polymer 3 (comparative), polymer 4 and oligomer 7. Polymer 3 (comparative) is non-flowable and not uniform and not reprocessable. Polymer 4 is flowable, uniform and reprocessable. For oligomer 7, cracked sample bars were obtained, which means a very poor mechanical performance.Example 11: preparation of polymer 6

[0197] 2.00 g oligomer 10 was mixed with 0.51 g hexamethylenediamine in THF. The volatiles were removed at 100°C for 24 hours and the resulting polymer was hot pressed at 180°C to synthesize polymer 6 for DMTA measurement. The amount of the reversible moi eties in the polymers (vitrimers) calculated based on the amount of -CHO in the oligomer 10 is about 2.39 mmol / g vitrimer, and the amount of the carbon-carbon double bond carrying hydrogen atoms (unsaturated degree) of polymer 6 calculated based on the amount of olefin -H in oligomer 10 is 0.0008 mol / g vitrimer.Example 12: preparation of polymers 7, 8, 9

[0198] According to Table 5, 10 g of oligomers were loaded to Xplore micro compounders at 210°C at the speed of 100 rpm. Boric acid solution was prepared by dissolving the amount of boric acid according to table 5 to 2 mL distilled water and added to the micro compounder dropwise. After mixing for 5 minutes, the polymers were extruded as pellets and injection molded as the sample bars (ISO 37 type 3 specimen) for mechanical performance measurement. Boric acid is used in excess, the amount of the reversible moieties in the polymers (vitrimers) corresponds to the amount of OH in the oligomers used for the preparation of the polymers.The amount of the carbon-carbon double bond carrying hydrogen atoms (unsaturated degree) of the polymer corresponds to half of the amount of olefin-H of the oligomer used for preparing the polymer. The unsaturated degree of polymer 7 is 0.0020 mol / g. The unsaturated degree of polymer 8 is 0.008 mol / g. The unsaturated degree of polymer 9 is 0.0014 mol / g.Table 5. Amounts of oligomers and boric acid used in the reactionsExample 13: preparation of composite 1

[0199] 8 g of polymer 9 pellets and 2 g of short cut glass fiber (OWENS CORNING SE4849 Type 30™, diameter 17 pm) were loaded to Xplore micro compounders at 210°C. After mixing for 2 minutes, the composite 1 was injection molded as the sample bars (ISO 37 type 3 specimen) for mechanical performance measurement.DMTA tests

[0200] Figure 9 shows DMTA curves of polymer 2 (comparative), polymer 3 (comparative), and polymer 4. For polymer 2 (comparative) and polymer 3 (comparative), storage modulus is always higher than loss modulus at elevated temperature, which indicate that polymers 2 and 3 (comparative) are not flowable, which means not reprocessable. For polymer 4, it starts to flow at 167°C, which indicates that polymer 4 is reprocessable.

[0201] Figure 10 shows DMTA curves of polymer 6. For polymer 6, it starts to flow at 178°C, which indicates that polymer 6 is reprocessable.

[0202] Tg and Tf of polymers tested by DMTA are summarized in the following Table 6. Reprocessability of polymers are also summarized in Table 6.Table 6

[0203] Polymer 5 was hot-pressed for 3 times, Tg and Tf of the first hot-pressed, the second hot-pressed and the third hot-pressed polymer were tested by DMTA and summarized in Table 6, showing that the polymer was still flowable after been reprocessed.Tensile Tests

[0204] The results of tensile tests of polymers and composite were summarized in Table 7.Table 7

[0205] The tensile results shows that the vitrimers (such as polymers 4, 7, 8, 9 and 15) and composite of this disclosure have good mechanical properties.OTHER EMBODIMENTS

[0206] It is to be understood that while the present application has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the present application, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims.

Claims

1. ClaimsWhat is claimed is:

1. A vitrimer comprising cyclic structure units and reversible moieties, wherein the vitrimer has an unsaturation degree of no more than 0.01 mol / g, wherein the unsaturation degree is calculated by mol of carbon-carbon unsaturated double bond carrying at least one hydrogen atom per gram of vitrimer.

2. The vitrimer according to claim 1, wherein the vitrimer has an unsaturation degree of from 0 mol / g to 0.009 mol / g or from 0 mol / g to 0.008 mol / g or from 0 mol / g to 0.006 mol / g or from 0 mol / g to 0.004 mol / g, wherein the unsaturation degree is calculated by mol of carboncarbon unsaturated double bond carrying at least one hydrogen atom per gram of vitrimer.

3. The vitrimer according to claim 1 or 2, wherein the ring system of the cyclic structure units has 4 to 20 ring members, for example 5 to 15 ring members, and / or the ring system of the cyclic structure units has 1, 2 or more rings, such as hydrocarbon ring, optionally the ring system of the cyclic structure units carries one or more substituents selected from the group consisting of OH, halogen, anhydride group, Ci-Ce alkyl, Ci-Ce alkoxy, Ci-Ce alkylthio, C3-C6 cycloalkyl, and C6-C12 aryl, the aforementioned Ci-Ce alkyl, Ci-Ce alkoxy, Ci-Ce alkylthio, C3-C6 cycloalkyl, and C6-C12 aryl can be further substituted by one or more OH.

4. The vitrimer according to any of claims 1 to 3, wherein the cyclic structure units are derived from:(x) an oligomer formed from cyclic olefin by ring-opening metathesis polymerization (ROMP) involving a chain transfer agent and then at least partial hydrogenation;(y) an oligomer formed by degrading a cleavable polymer and then at least partially hydrogenating, wherein the cleavable polymer is formed from cyclic olefin and cleavable comonomer; and(z) a functionalized oligomer comprising the cyclic structure units;wherein the oligomer (x), oligomer (y) and oligomer (z) have an unsaturation degree of no more than 0.01 mol / g, wherein the unsaturation degree is calculated by mol of carboncarbon unsaturated double bond carrying at least one hydrogen atom per gram of oligomer, for example, the weight average molecular weight of the oligomer (x), oligomer (y) and oligomer (z) is in the range from 300 to 60,000 g / mol, such as from 400 to 50,000 g / mol.

5. The vitrimer according to claim 4, wherein the cyclic olefin contains one or more endocyclic double bond and has one or two or more rings, optionally the ring system of the cyclic olefin can carry one or more hetero atoms selected from N, O and S as ring member, optionally the ring system of the cyclic olefin carries one or more substituents selected from the group consisting of OH, halogen, anhydride group, Ci-Ce alkyl, Ci-Ce alkoxy, Ci-Ce alkylthio, C3-C6 cycloalkyl, and C6-C12 aryl, the aforementioned Ci-Ce alkyl, Ci-Ce alkoxy, Ci-Ce alkylthio, C3-C6 cycloalkyl, and C6-C12 aryl can be further substituted by one or more OH.

6. The vitrimer according to claim 4 or 5, wherein the ring system of the cyclic olefin has 4 to 20 ring members, such as 5 to 15 ring members, and the cyclic olefin has one, two or more rings, such as hydrocarbon ring.

7. The vitrimer according to any of claims 4 to 6, wherein the cyclic olefin is selected from single ring olefins, multi-ring olefins, multi-ring fused ring olefins, and multi-ring fused and bridged ring olefins, or selected from multi-ring olefins, multi-ring fused ring olefins, and multi-ring fused and bridged ring olefins.

8. The vitrimer according to any of claims 4 to 7, wherein the chain transfer agent is a mono-olefin carrying at least one functional group (a), for example hydroxyl group, carboxylic group and amino group.

9. The vitrimer according to any of claims 4 to 8, wherein the cleavable comonomer is an olefin metathesis active comonomers containing cleavable bond, for example selected from Si-containing monomer, a monomer having a bicyclic oxazinone structure containing an endocyclic double bond, substituted or unsubstituted 2, 3 -dihydrofuran, a substituted or unsubstituted 2,3 -dihydropyran.

10. The vitrimer according to claim 4, wherein the oligomer (z) is a functionalized petroleum resin, or a functionalized oligomer derived from ROMP.

11. The vitrimer according to any of claims 1 to 10, wherein the reversible moi eties are selected from dissociative and associative reversible moieties, for example the reversible structure moieties are selected from ester bond, boronic ester bond, amine, imine, disulfide, carbamate, vinylogous urethane, and bond formed from furan and anhydride.

12. The vitrimer according to any of claims 1 to 11, wherein the reversible structure moieties comprise a moiety selected from boronic ester bond and imine.

13. The vitrimer according to any of claims 1 to 12, wherein the amount of cyclic structure units is in the range from 55% to 99% by weight, for example 65% to 98.8% by weight, or 75% to 98.6% by weight, or 85% to 98.5% by weight, based on the total weight of the vitrimer.

14. The vitrimer according to any of claims 1 to 13, wherein the amount of the reversible moieties is in the range from 0.1 to 5 mmol / g vitrimer, such as 0.15 to 3 mmol / g vitrimer.

15. The vitrimer according to any of claims 1 to 14, wherein there are or are not connecting groups between the cyclic structure units and the reversible structure moieties, for example, the connecting groups have 1 to 20 or 2 to 10 or 3 to 10 carbon atoms.

16. The vitrimer according to claim 15, wherein the connecting groups are derived from a compound having one or more hydroxyl groups (e.g. 1 or 2 hydroxyl groups) and a carboncarbon double bond.

17. The vitrimer according to any of claims 1 to 16, wherein the flow temperature of the vitrimer is 90°C to 250°C, such as 95°C to 220°C, 100°C to 200°C, or 100°C to 180°C.

18. A method for preparing the vitrimer according to any of claims 1 to 17, comprising reacting an oligomer having a functional group (a) and cyclic structure units with a linking compound capable of forming the reversible structure moieties with the functional group (a).

19. The method according to claim 18, wherein the oligomer is the oligomer defined in claim 4.

20. An oligomer selected from:(x) an oligomer formed from cyclic olefin by ring-opening metathesis polymerization (ROMP) involving a chain transfer agent and then at least partial hydrogenation;(y) an oligomer formed by degrading a cleavable polymer and then at least partially hydrogenating, wherein the cleavable polymer is formed from cyclic olefin and cleavable comonomer; and(z) a functionalized oligomer comprising the cyclic structure units;wherein the oligomer (x), oligomer (y) and oligomer (z) have an unsaturation degree of nomore than 0.01 mol / g, wherein the unsaturation degree is calculated by mol of carbon-carbon unsaturated double bond carrying at least one hydrogen atom per gram of oligomer,for example, the weight average molecular weight of the oligomer (x), oligomer (y) and oligomer (z) is in the range from 300 to 60,000 g / mol, such as from 400 to 50,000 g / mol.

21. A composite material comprising a substrate and the vitrimer as defined in any of claims 1 to 17.

Images