阅读说明：本技术 用于制备共价适应性网络的化学方法 (Chemical process for the preparation of covalent adaptive networks ) 是由 S.帕拉勒 K.萨加尔 于 2018-03-09 设计创作，主要内容包括：本公开提供了形成共价交联的大分子网络的方法,其包括使被定义为R<Sub>1</Sub>-L-X-R<Sub>3</Sub>的式(I)的化合物与被定义为HZ-R<Sub>2</Sub>的式(II)的化合物反应,以形成被定义为R<Sub>1</Sub>-L-Y的式(III)的大分子化合物,其中R<Sub>1</Sub>代表大分子聚合物主链,L代表芳基或芳基烷基,R<Sub>2</Sub>独立地代表任选取代的支化或直链C<Sub>1</Sub>-C<Sub>10</Sub>烷烃、C<Sub>2</Sub>-C<Sub>10</Sub>烯烃、C<Sub>2</Sub>-C<Sub>10</Sub>炔烃,其中任选取代基是第二HZ部分或羧酸酯部分,R<Sub>3</Sub>代表CF<Sub>3</Sub>、H或C<Sub>1</Sub>-C<Sub>10</Sub>烷烃,X代表-C(O)-、-C(O)-C(CH<Sub>2</Sub>)-或-C(CH<Sub>2</Sub>)-C(O)-,Y代表-C(OH)(R<Sub>3</Sub>)-Z-R<Sub>2</Sub>、-C(O)-CH(R<Sub>3</Sub>)-CH<Sub>2</Sub>-Z-R<Sub>2</Sub>或–CH(C(O)R<Sub>3</Sub>)-CH<Sub>2</Sub>-Z-R<Sub>2</Sub>；且Z代表S或NH。本公开另外提供通过如上文定义的方法形成的共价连接的适应性网络。(The present disclosure provides a method of forming a covalently crosslinked macromolecular network comprising reacting a compound defined as R 1 ‑L‑X‑R 3 A compound of formula (I) with a compound defined as HZ-R 2 To form a compound of formula (II) defined as R 1 -L-Y macromolecular compounds of formula (III) in which R 1 Represents a macromolecular polymer backbone, L represents an aryl or arylalkyl group, R 2 Independently represents optionally substituted branched or straight-chain C 1 ‑C 10 Alkane, C 2 ‑C 10 Olefin, C 2 ‑C 10 Alkyne of whichThe optional substituent being a second HZ moiety or a carboxylate moiety, R 3 Represents CF 3 H or C 1 ‑C 10 Alkane, X represents-C (O) -, -C (O) -C (CH) 2 ) -or-C (CH) 2 ) -C (O) -, Y represents-C (OH) (R) 3 )‑Z‑R 2 、‑C(O)‑CH(R 3 )‑CH 2 ‑Z‑R 2 or-CH (C (O) R 3 )‑CH 2 ‑Z‑R 2 (ii) a And Z represents S or NH. The present disclosure additionally provides covalently linked adaptive networks formed by the methods as defined above.)

1. A method of forming a covalently cross-linked macromolecular network comprising reacting a compound defined as R₁-L-X-R₃A compound of formula (I) with a compound defined as HZ-R₂To form a compound of formula (II) defined as R₁A macromolecular compound of formula (III) of-L-Y, wherein

R₁Represents the main chain of the macromolecular polymer,

l represents an aryl or arylalkyl group,

R₂independently represents optionally substituted branched or straight-chain C₁-C₁₀Alkane, C₂-C₁₀Olefins or C₂-C₁₀Alkyne, wherein the optional substituent is a second HZ moiety or a carboxylate moiety,

R₃represents CF₃H or C₁-C₁₀The alkane is selected from the group consisting of alkanes,

x represents-C (O) -, -C (O) -C (CH)₂) -or-C (CH)₂)-C(O)-，

Y represents-C (OH) (R)₃)-Z-R₂、-C(O)-CH(R₃)-CH₂-Z-R₂or-CH (C (O) R₃)-CH₂-Z-R₂(ii) a And is

Z represents S or NH.

2. The method of claim 1, wherein the method is reversible.

3. The method of claim 1 or 2, wherein the method further comprises an energy source.

4. The method of claim 3, wherein the crosslinking is thermally induced by exposing the compounds of formula (I) and (II) to a temperature of 40 ℃ to 200 ℃.

5. The method of claim 3, wherein the crosslinking is activated by photoactivation by exposing the compounds of formula (I) and (II) to a light source of 200 nm to 500 nm.

6. The method of any one of claims 1-5, wherein the crosslinking reaction is an addition reaction.

7. The method of any one of claims 1-6, wherein R₃Represents CF₃X represents-C (O) -, Z represents NH and Y represents-C (OH) (CF)₃)-NH-R₂。

8. The method of any one of claims 1-6, wherein R₃Represents H, X represents-C (O) -, Z represents S and Y represents-CH (OH) -S-R₂。

9. The method of any one of claims 1-6, wherein R₃represents-C₁-C₁₀Alkane, X represents-C (O) -C (CH)₂) -, Z represents S and Y represents-C (O) -CH (-C)₁-C₁₀Alkane) -CH₂-Z-R₂。

10. A covalently linked adaptive network formed by the method of any one of claims 1-9.

Technical Field

The present disclosure relates to a method of reversibly forming an adaptive (adaptive) network in a thermoset polymer.

Background

Polymeric materials are generally classified by their behavior upon heating: thermoplastics deform and flow at temperatures above their melting point, while thermosets remain difficult to process until temperatures are reached at which destructive decomposition occurs. Such a classification system is suitable for polymers formed by essentially irreversible high energy release reactions; however, polymers containing readily reversible covalent bonds capable of undergoing rearrangement can be used to create materials that fall completely out of either class and have the beneficial attributes of both. Furthermore, the living nature of such polymerizations (living nature) leads to unique post-polymerization behaviors.

Thermoreversible, adaptive polymers are materials that are capable of undergoing reversible transformations because they contain thermoreversible bonds. These thermally reversible covalent bonds are an order of magnitude stronger than hydrogen bonds, but they still allow the material to be thermally reversibly transformed from a crosslinked solid to an oligomeric state. Therefore, the material has high mechanical strength and can easily cure cracks and other defects. Unfortunately, thermoreversible healing mechanisms are often limited by irreversible side reactions that occur at elevated temperatures. In addition, strategies for selectively heating materials that are spatially confined or surrounded by other heat sensitive materials have their own set of challenges.

In principle, most crosslinking reactions are reversible. However, achieving de-crosslinking generally results in complete and irreversible degradation of the polymer. Certain polymers, including those made by free radical polymerization and ionic polymerization, often depolymerize upon heating above the usually fairly high upper temperature limit. At such temperatures, irreversible degradation of other molecular structures typically occurs. A few polymers, including poly- (R-methylstyrene) and poly (isobutylene), exhibit more moderate upper temperatures (61 ℃ C. and 50 ℃ C., respectively). In the polycondensation, the condensate removal promotes the forward reaction, and therefore the reverse reaction is achieved only when the condensate is present in a large amount.

The current state of the art for covalently adaptable networks of organic polymers is the utilization of Diels-Alder (DA) reactions and thiol-ene chemistry. For example, U.S. patent No. 6,933,361 describes a thermally-repairable (thermally re-polymerizable) polymeric material made from a polyvalent furan monomer and a polyvalent maleimide monomer by a diels-alder (DA) reaction. The furan monomer is described as requiring at least three furan moieties and the maleimide monomer is described as requiring at least three maleimide monomers.

In organic chemistry, there are other synthetic routes available for forming reversible covalent bonds.

Thus, there is a need for a method of reversibly forming a crosslinked polymer network that does not face the above-mentioned disadvantages.

SUMMARY

In a first aspect, there is provided a method of forming a covalently cross-linked macromolecular network comprising reacting a compound defined as R₁-L-X-R₃A compound of formula (I) with a compound defined as HZ-R₂To form a compound of formula (II) defined as R₁A macromolecular compound of formula (III) of-L-Y, wherein

R₁Represents the main chain of the macromolecular polymer,

l represents an aryl or arylalkyl group,

R₂independently represents optionally substituted branched or straight-chain C₁-C₁₀Alkane, C₂-C₁₀OlefinsOr C₂-C₁₀Alkyne, wherein the optional substituent is a second HZ moiety or a carboxylate moiety,

R₃represents CF₃H or C₁-C₁₀The alkane is selected from the group consisting of alkanes,

x represents-C (O) -, -C (O) -C (CH)₂) -or-C (CH)₂)-C(O)-，

Y represents-C (OH) (R)₃)-Z-R₂、-C(O)-CH(R₃)-CH₂-Z-R₂or-CH (C (O) R₃)-CH₂-Z-R₂(ii) a And is

Z represents S or NH.

The reaction used in the process is an addition reaction. This provides enhanced reaction control and ease of inversion, as the inversion reaction is a well-known elimination reaction. Addition reactions offer improvements over other crosslinking reactions, such as condensation reactions, because condensation reactions may require constant equilibrium stoichiometry to ensure reversibility of the reaction. The addition reaction can be promoted by using trifluoromethyl moieties in the macromolecular polymer of formula (I), which brings about an electron-withdrawing effect and thus promotes the addition of an electron-donating, i.e. nucleophilic, addition partner (addition partner). The addition reaction can be carried out under moderate conditions, i.e., temperature, solvent, etc., that generally avoid degradation of the polymer or chemical alteration of the structural units. The functional groups required to carry out the above reaction can be easily attached to the macromonomer backbone, and physical and chemical properties from reversible thermosetting materials can be achieved similar to those in the case of conventional thermosetting polymers.

In a second aspect, there is provided a covalently linked adaptive network formed by a method as defined above.

Brief Description of Drawings

Figure 1 shows a schematic of a reversible covalent network. 2 represents a macromolecular polymer of a compound according to formula (I), 4 represents a crosslinker of a compound according to formula (II), a) shows a thermosetting polymer with functional groups, b) shows crosslinker molecules with matching terminal functional groups. More than 2 functional groups may be present, which may result in a higher crosslink density of the network polymer. c) Represents a covalently cross-linked macromolecular network following reaction between these two functional groups.

Detailed description of the invention

The above-mentioned problems of polymer degradation or difficulties in reversibility of the crosslinking reaction can be solved by the methods disclosed herein. Therefore, by carrying out the addition reaction, the above-mentioned problems can be avoided.

Accordingly, in a first aspect, there is provided a method of forming a covalently cross-linked macromolecular network comprising reacting a compound defined as R₁-L-X-R₃A compound of formula (I) with a compound defined as HZ-R₂To form a compound of formula (II) defined as R₁A macromolecular compound of formula (III) of-L-Y, wherein

R₁Represents the main chain of the macromolecular polymer,

l represents an aryl or arylalkyl group,

R₂independently represents optionally substituted branched or straight-chain C₁-C₁₀Alkane, C₂-C₁₀Olefins or C₂-C₁₀Alkyne, wherein the optional substituent is a second HZ moiety or a carboxylate moiety,

R₃represents CF₃H or C₁-C₁₀The alkane is selected from the group consisting of alkanes,

x represents-C (O) -, -C (O) -C (CH)₂) -or-C (CH)₂)-C(O)，

Y represents-C (OH) (R)₃)-Z-R₂、-C(O)-CH(R₃)-CH₂-Z-R₂or-CH (C (O) R₃)-CH₂-Z-R₂(ii) a And is

Z represents S or NH.

The reaction may comprise as a first starting material a compound of formula (I), which may be a macromolecular polymer comprising additional functional groups, wherein the compound of formula (I) may be defined as R₁-L-X-R₃。R₁Represents a macromolecular backbone. Suitable macromolecular backbones for the addition reaction may be derived from polyesters, epoxy polymers, polyacrylates, polystyrenes, and combinations thereof. The macromolecular compound according to formula (I) may optionally comprise a trifluoromethyl group, or a trifluoroacetyl group when taken together with X as carbonyl group, which mayBringing about an electron-withdrawing effect, thereby promoting the addition of an electron-donating, i.e. nucleophilic, addition partner. Trifluoroacetyl groups can be grafted onto the vinyl backbone of the macromolecular backbone. Suitable macromolecular chains comprising a trifluoroacetyl function are selected from the group consisting of poly (p-vinyltrifluoroacetylphenyl), poly (trifluoroacetyl-p-xylene) and poly (trifluoroacetyl-L-lysine). The macromolecule may also be described as a thermoset polymer, for example it may be a thermoset polymer selected from epoxy, polyester and polyurethane. The linking group L may be bonded to the macromolecular backbone and may be an aryl or arylalkyl group. The aryl or arylalkyl component of the linker may link the macromolecular backbone to functional group X. Thus, the aryl component may be disubstituted. The disubstituted may be ortho, meta or para to each other. Preferably, the disubstituted are in the para position relative to each other. The optional alkyl component may be C₁-C₁₀Alkyl moieties, preferably ethyl moieties. "aryl" may refer to an optionally substituted phenyl moiety. The functional group X may be divalent, i.e. it is linked to R on both sides thereof₁And R₃. X may be selected from the group consisting of carbonyl, i.e., -C (O) -, and carbonyl adjacent to the double bond, i.e., - (C (O) -C (CH)₂) -or-C (CH)₂) -C (O) -. If the functional group X contains a double bond, this double bond may be geminally substituted, i.e. two substituents, R₁and-C (O) -, or-C (O) -and R₃May be bonded to the same carbon atom. The functional group X may be unsaturated, i.e. it contains sp capable of undergoing an addition reaction²A hybrid atom. Thus, the functional group X may change during the above process. As mentioned above, the functional group may be appended with a moiety R₃And (4) substitution. This moiety R₃May be a trifluoroalkyl group, e.g. CF₃. Alternatively, it may be hydrogen, thereby forming an aldehyde with X in the case where X is-C (O) -. Alternatively, it may be C₁-C₁₀Alkanes, such as ethyl. R₃The parts may remain unchanged during the process. However, the functional group R₃The addition reaction can be facilitated by decreasing the electron density of the unsaturated functional group X, and thus the addition reaction of the reaction partner (reaction partner) that feeds electrons is promoted.

The reaction may comprise the formula(II) As a second starting material, a compound which can be defined as HZ-R₂And wherein Z represents S or NH. The functional group Z may be electron rich, i.e. it may have a free electron pair. The free electron pair may have the effect of donating electrons to the functional group X, thereby resulting in the formation of a covalent bond. The Z functionality may be altered in the addition reaction by forming a covalent bond with the unsaturated moiety X and supplying the hydrogen atom bonded thereto to an atom adjacent to the atom forming a covalent bond with Z. Z may be divalent. Examples of divalent Z are thiol moieties and primary amines. Z may be substituted by at least one moiety R₂And (4) substitution. R₂May independently be optionally substituted branched or straight chain C₁-C₁₀Alkane, C₂-C₁₀Olefins or C₂-C₁₀Alkyne, wherein the optional substituent is a second HZ moiety or a carboxylate moiety. Where the optional substituent is an ester moiety, the HZ moiety may be on a fragment of the carbonyl component of the ester. Or, R₂May independently be branched or straight C₁-C₈Alkanes, branched or straight-chain C₂-C₈Olefins or C₂-C₈Alkynes, branched or straight-chain C₃-C₈Alkanes, branched or straight-chain C₄-C₈Olefins or C₄-C₈Alkynes, branched or straight-chain C₁-C₆Alkane, C₂-C₆Olefins or C₂-C₆Alkynes, branched or straight-chain C₁-C₄Alkane, C₂-C₄Olefins or C₂-C₄Alkynes, branched or straight-chain C₁-C₂Alkane, C₂-C₃Olefins or C₂-C₃Alkynes, branched or straight-chain C₄-C₁₀Alkane, C₄-C₁₀Olefins or C₄-C₁₀An alkyne. As mentioned above, R₂The compound which may have two Z functions, for example of formula (II), may be a diamine, such as diethylene diamine. In the case where the compound of formula (II) has more than one Z function, multiple Z functions may participate in the addition reaction with the compound of formula (I).

The reaction may comprise as reaction product a compound of formula (III), which may be defined as R₁-L-Y。R₁、R₂、R₃And the nature of Z may remain unchanged before and after the reaction. The unsaturation in X can become a saturated moiety in Y. Depending on the moiety X, such saturated moieties in Y may be hydroxyl groups C (OH) (when X is a carbonyl group) or ethyl moieties CHCH with a carbonyl moiety adjacent thereto₂(when X is a double bond adjacent to a carbonyl group).

As mentioned above, the crosslinking reaction may be an addition reaction. Thus, the reaction can be characterized as an organic reaction in which two or more molecules combine to form a larger molecule (adduct). The addition reaction is limited to chemical compounds with multiple bonds, such as molecules with carbon-carbon double bonds (olefins). Molecules containing carbon-heterodouble bonds, such as carbonyl groups (C = O), can undergo addition because they also have double bond character.

The addition reaction is the reverse of the elimination reaction. There are two main types of polar addition reactions: electrophilic addition and nucleophilic addition. Addition reactions are also encountered in polymerization and are known as polyaddition. In the present case, since the unsaturated component X has a low electron density, the present addition reaction is classified as a nucleophilic addition reaction.

As mentioned above, the process described above is reversible. Thus, after formation of the macromolecular network described by formula (III), the reaction can be reversed. An exemplary reversible reaction is shown below in scheme 1:

scheme 1

The reverse reaction type would be an elimination reaction. The starting material for the elimination reaction will be according to the network defined as the compound of formula (III). The reaction product of such an elimination reaction will be a compound described as formula (I) and formula (II).

The reaction to form the compound of formula (III) from the compounds of formulae (I) and (II) may further comprise an energy source. Such energy source may be selected from a light source, e.g. photo-activated, or from a thermal energy source, e.g. heat. If the crosslinking reaction is thermally induced, the compounds of formula (I) and (II) may be exposed to a temperature of from about 40 ℃ to about 200 ℃, or from about 50 ℃ to about 150 ℃, or from about 50 ℃ to about 120 ℃. Alternatively, the reaction may be carried out at room temperature, i.e., without a source of thermal energy. If the crosslinking reaction is activated by light, the compounds of formula (I) and (II) may be exposed to a light source of from about 200 nm to about 500 nm, optionally from about 200 nm to about 450 nm, optionally from about 220 nm to about 400 nm. In this case, the reaction may further comprise a photoinitiator, which may be a peroxide. The peroxide is selected from dicumyl peroxide, lauroyl peroxide, and t-butyl peroxide. They may be azo-based thermal initiators, such as azobisisobutyronitrile or azobiscyclohexanecarbonitrile. Alternatively, they may be benzophenones, such as acetophenone, benzophenone or dimethoxyphenylacetophenone. The photoinitiator may be added in substoichiometric amounts. In various embodiments, the photoinitiator may be added in an amount of about 0.1 to 0.5 equivalents, or about 0.2 to 0.4 equivalents, or about 0.3 equivalents. Alternatively, the reaction may be carried out in the absence of a photoinitiator.

The reaction time may be from about 1 minute to about 10 hours, or from about 5 minutes to about 2 hours, or from about 10 minutes or about 1 hour.

If a photoinitiator is used to form the compound of formula (III), the reverse reaction may be carried out using a light source as defined above, which may result in de-crosslinking of the polymer network.

The formation of the compound of formula (III) from the compounds of formulae (I) and (II) may be further carried out in the presence of a reagent (locking agent) which locks the compound of formula (III), which means that reverse reactions will be prevented. The locking agent may be added in sub-stoichiometric amounts. In various embodiments, the locking agent may be added in an amount of about 0.1 to 0.5 equivalents, or about 0.15 to 0.3 equivalents, or about 0.3 equivalents. The locking agent may be such that it forms a strong bond with the newly formed functional group of the compound of formula (III). In the embodiment as depicted in scheme 1, the reagent that locks the compound of formula (III) may be a silyl containing reagent. In this embodiment, the silyl group forms a strong interaction with the-OH group of the hemiaminal, which shifts the equilibrium of the reaction towards the compound of formula (III). In one example, the silyl containing agent may be N-trimethylsilylimidazole. In this case the reverse reaction can be carried out by subjecting the compound of formula (III) to the same reaction conditions but without the use of a locking agent. An elimination reaction may thus occur such that the polymer network is de-crosslinked.

The formation of the compound of formula (III) from the compounds of formulae (I) and (II) may further be carried out in the presence of a solvent. Alternatively, no solvent may be used. Suitable solvents for this reaction may be selected from non-polar solvents such as cyclopentane, hexane, cyclohexane, benzene, toluene, 1, 4-dioxane, chloroform, diethyl ether or dichloromethane. Alternatively, the solvent may be selected from polar aprotic solvents such as tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, nitromethane or propylene carbonate.

The formation of the compound of formula (III) from the compounds of formulae (I) and (II) may further be carried out in the presence of a base. Suitable bases used may be nitrogen bases such as pyridine, trimethylamine, triethylamine or DIPEA.

In a preferred embodiment, the trifluoroacetyl functional group can form a reversible covalent bond with an amine. In particular, R₃May represent CF₃X may represent-C (O) -, Z may represent NH and Y may represent-C (OH) (CF)₃)-NH-R₂. Accordingly, the reaction sequence of the preferred embodiment can be represented by the following reaction scheme:

in another preferred embodiment, the thiol-functional group can form a reversible covalent bond with an aldehyde group. In particular, R₃May represent H, X may represent-C (O) -, Z may represent S and Y may represent-CH (OH) -S-R₂. Accordingly, the reaction sequence of this preferred embodiment can be represented by the following reaction scheme:

in still another preferred embodimentIn one embodiment, the thiol-functional group can form a reversible covalent bond with an enone (α - β -unsaturated carbonyl) group, wherein the double bond is adjacent to the linker. In particular, X may represent-C (CH)₂) -C (O) -, Z may represent S and Y may represent-CH (C (O) R₃)-CH₂-Z-R₂. Accordingly, the reaction sequence of this preferred embodiment can be represented by the following reaction scheme:

in yet another preferred embodiment, the thiol-functional group can form a reversible covalent bond with an enone (α - β -unsaturated carbonyl) group, wherein the carbonyl group is adjacent to the linker. In particular, X may represent-C (O) -C (CH)₂) -, Z may represent S and Y may represent-C (O) -CH (R)₃)-CH₂-Z-R₂. Accordingly, the reaction sequence of this preferred embodiment can be represented by the following reaction scheme:

all of the above chemical routes can be used to form a covalently adaptable network in thermosetting polymers by adding one of the substituted functional groups on the polymer chain. Using another substituent as a crosslinking agent (functionality < 2), a reversible polymer network can be formed according to common crosslinking techniques using heat, light, or any other energy source.

In a second aspect, there is provided a covalently linked adaptive network formed by the method as described above.

The chemical routes disclosed above for forming reversible networks can provide greater flexibility in designing reversible polymer networks. This feature can be exploited to design a variety of reversible polymer networks according to their applicability, without being limited to a few known chemical routes.

Examples