Cross-linked polymer, polymer molded body and preparation method and application thereof

Abstract

The invention relates to a cross-linked polymer, a polymer molded body and a preparation method and application thereof. The cross-linked polymer disclosed by the invention has dynamic cross-linking performance brought by addition reaction of DHPMT and electron-deficient olefin, so that the cross-linked polymer has self-repairing capability, and meanwhile, the cross-linked polymer has blue light protection performance brought by DHPMT and carbazole groups. The cross-linked polymer disclosed by the invention has dynamic cross-linking property and ultraviolet and blue light protection performance, is good in machinability and reprocessability, can be processed and molded in modes such as melt molding and the like, and can be repeatedly processed and molded for multiple times. The polymer forming body provided by the invention has good self-repairing capability, excellent light transmission, excellent ultraviolet and blue light protection capability and good chemical corrosion resistance. The preparation method of the cross-linked polymer and the polymer forming body has the advantages of cheap and easily available raw materials, simple process and easiness in large-scale production.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, specifically relating to cross-linked polymers, polymer molded articles, their preparation methods and applications. Background Technology

[0002] With the widespread use of electronic devices, high-energy blue light (400–460 nm) has become an unavoidable source of radiation in daily life. Studies have shown that high-energy blue light is characterized by its high energy and strong penetrating power, posing a significant threat to human health, especially to the eyes and skin, potentially leading to eye oxidative stress, macular degeneration, and skin aging. Against this backdrop, the development of high-energy blue light protection materials is of great importance.

[0003] Patent document 1 discloses a blue light blocking polycarbonate-based resin composition for lenses, which uses a blue light blocking agent whose molecular structure contains a carbazole structure at one end, a benzophenone structure at the other end, and a long-chain alkane structure in the middle. This blue light blocking agent has excellent blue light blocking effect and UV resistance, and at the same time has high compatibility with the main resin, has a compatibilizing effect, and can reduce the amount of compatibilizer used.

[0004] References

[0005] Patent document 1: CN 116444972 A. Summary of the Invention

[0006] The problem the invention aims to solve

[0007] However, traditional blue light protection materials are easily damaged during use, and due to limitations in daily life, damaged materials are difficult to repair in a timely manner, thus significantly reducing their protective effect. Self-healing materials are those that can repair themselves under natural conditions without human intervention. Therefore, developing blue light protection materials with self-healing properties has significant research value.

[0008] Solution for solving the problem

[0009] While researching the above-mentioned problems, the inventors accidentally discovered that the addition reaction of 3,4-dihydropyrimidine-2-thione (DHPMT) with electron-deficient olefins has reversible properties. As a result, they proposed a crosslinking polymer that has dynamic crosslinking properties resulting from the addition reaction of DHPMT with electron-deficient olefins, thus possessing self-healing capabilities. It also has blue light protection properties resulting from the DHPMT and carbazole groups, thereby completing this invention.

[0010] Specifically, the present invention solves the problems of the present invention through the following solutions.

[0011] [1] A crosslinked polymer comprising the structure shown in Formula (I) and at least one structure selected from the structures shown in Formulas (II-1) to (II-3), wherein the * bonds in the structure shown in Formula (I) are connected to the # bonds in the structures shown in Formulas (II-1) to (II-3) to form a crosslinked network of the crosslinked polymer.

[0012] *-DAD-* (I)

[0013] In formula (I), A represents a divalent organic group, and D represents the group shown in formula (a) below.

[0014]

[0015] In formula (a), R2 and R3 independently represent halogens or alkyl groups having 1 to 40 carbon atoms, wherein one or more -CH2- groups in the alkyl group are optionally replaced by -O-, -CO-, or -COO- in such a way that the O atom is not directly connected; m represents an integer from 0 to 3, and z represents an integer from 0 to 4; R4 represents H, an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 15 carbon atoms; R5 represents hydrogen or an alkyl group having 1 to 10 carbon atoms; the bond marked with * is the bond marked with * in the structure shown in formula (I), and the bond marked with @ is the bond connected to A;

[0016]

[0017]

[0018] In formulas (II-1) to (II-3), n independently represents an integer greater than 3, E independently represents an n-valent organic group, F independently represents a divalent organic group or a single bond, and R1 independently represents H or a methyl group.

[0019] [2] According to the crosslinked polymer described in [1], wherein,

[0020] A represents an alkylene group having 2 to 40 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O-, -CO-, -COO- or -C=C- in such a way that the O atom is not directly attached;

[0021] n represents an integer from 3 to 6.

[0022] E independently represents a straight-chain, branched, or cyclic n-valent alkyl group having 1 to 20 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O-, -CO-, -COO-, or -C=C- in such a way that the O atom is not directly attached; or E represents an isocyanurate group;

[0023] F represents, independently, a single bond or an alkylene group having 1 to 20 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O-, -CO-, -COO-, or -C=C- in such a way that the O atom is not directly attached.

[0024] [3] According to the crosslinked polymer described in [2], wherein,

[0025] A represents an alkylene group with 2 to 20 carbon atoms, or the group -O-(CH2). t -O-, where t is an integer from 2 to 20;

[0026] E independently represents a straight-chain, branched, or cyclic n-valent alkyl group having 3 to 12 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O-, -CO-, -COO-, or -C=C- in such a way that the O atom is not directly connected;

[0027] F represents, independently, a single bond or an alkylene group having 1 to 6 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O- in such a way that the O atom is not directly attached;

[0028] R2 and R3 independently represent halogens or alkoxy groups having 1 to 6 carbon atoms;

[0029] m represents 0 or 1;

[0030] z represents 0 or 1;

[0031] R4 represents H;

[0032] R5 represents methyl, ethyl, propyl, or butyl.

[0033] [4] A method for preparing a crosslinked polymer, comprising the following steps:

[0034] The compound represented by formula (III) is subjected to an addition reaction with at least one compound selected from formulas (IV-1) to (IV-3).

[0035] GAG (III)

[0036] In formula (III), A represents a divalent organic group, and G represents the group shown in formula (b) below.

[0037]

[0038] In formula (b), R2 and R3 independently represent halogens or alkyl groups having 1 to 40 carbon atoms, wherein one or more -CH2- groups in the alkyl group are optionally replaced by -O-, -CO-, or -COO- in such a way that the O atom is not directly connected; m represents an integer from 0 to 3, and z represents an integer from 0 to 4; R4 represents H, an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 15 carbon atoms; R5 represents hydrogen or an alkyl group having 1 to 10 carbon atoms; the bond marked with @ is a bond connected to A;

[0039]

[0040]

[0041] In formulas (IV-1) to (IV-3), n independently represents an integer greater than 3, E independently represents an n-valent organic group, F independently represents a divalent organic group or a single bond, and R1 independently represents H or a methyl group.

[0042] [5] The preparation method according to [4] further includes the following steps for preparing the compound represented by formula (III):

[0043] Reacting the compounds of formulas (1) to (3) yields the compound shown in formula (III).

[0044]

[0045] Among them, A, R2, R3, R4, R5, m and z have the meanings given in [4].

[0046] [6] According to the preparation method described in [4] or [5], wherein the compound shown in formula (III) is subjected to an addition reaction with the compound shown in formula (IV-1);

[0047] Preferably, the compound represented by formula (III) is the compound represented by formula (III-1):

[0048]

[0049] In equation (III-1), t1 represents an integer from 2 to 12;

[0050] Preferably, the compound represented by formula (IV-1) is selected from at least one of the following: trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane tetra(meth)acrylate, tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, tri(acryloyloxyethyl)isocyanurate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, and tripentaerythritol penta(meth)acrylate.

[0051] [7] The cross-linked polymer obtained by any one of [4] to [6].

[0052] [8] A polymer molded body containing a crosslinked polymer according to any one of [1] to [3] and [7].

[0053] [9] A method for preparing a polymer molded article, comprising the following steps:

[0054] The crosslinked polymer described in any one of [1] to [3] and [7] is melt-molded.

[0055]

[10] The crosslinked polymer according to any one of [1] to [3], [7] or the polymer molded body according to [8] is used for ultraviolet protection and / or blue light protection.

[0056] The effects of the invention

[0057] The crosslinked polymer of the present invention has dynamic crosslinking properties, UV and blue light protection properties, and good processability and reprocessability. It can be processed and shaped by means of melt molding and can be processed and shaped repeatedly.

[0058] The polymer molded body of the present invention has good self-healing ability, excellent light transmittance, excellent UV and blue light protection ability, and good chemical corrosion resistance.

[0059] The method for preparing the crosslinked polymer and polymer molded articles of the present invention uses inexpensive and readily available raw materials, has a simple process, and is easy to scale up. Attached Figure Description

[0060] Figure 1 This is the synthetic route for the dynamically crosslinked polymer P1 in Example 1.

[0061] Figure 2 Photos showing the experimental process and results of the chemical corrosion resistance test.

[0062] Figure 3 Photos showing the experimental process and results of the flexural strength test.

[0063] Figure 4 Photos showing the experimental process and results of the self-healing performance test.

[0064] Figure 5 a) is a photograph of the polymer film Cz film of Example 2.

[0065] Figure 5 b) is the UV-Vis transmission spectrum of the polymer film Cz film of Example 2.

[0066] Figure 6 Photos showing the experimental process and results of the blue light protection test. Detailed Implementation

[0067] The present invention will now be described in detail. The description of the technical features described below is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.

[0068] <Terminology and Definitions>

[0069] In this manual, "blue light protection" or similar terms refer to the performance of protecting an object from harmful blue light, where blue light refers to radiation in the electromagnetic spectrum with wavelengths of 400 to 460 nm.

[0070] In this specification, "ultraviolet protection," "ultraviolet protection," or similar terms refer to the property of protecting an object from ultraviolet radiation, where ultraviolet radiation refers to radiation in the electromagnetic spectrum with wavelengths below 400 nm (e.g., 10–400 nm, especially 280–400 nm).

[0071] In this specification, the term "alkyl" includes straight-chain, branched, or cyclic alkyl groups, unless otherwise expressly stated.

[0072] In this specification, the range of carbon atoms described for a group should be understood to encompass groups having carbon atoms at both ends of that range and any integer value between the two ends. For example, "alkyl groups having 1 to 40 carbon atoms" encompasses alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40 carbon atoms. Other groups should also be understood in this manner.

[0073] In this specification, the variable groups in the general formula shall be connected in a manner achievable in the art, for example, in a manner in which O and / or S atoms are not directly connected.

[0074] In this specification, the range of values ​​referred to as "value A to value B" refers to the range including the endpoint values ​​A and B.

[0075] In this specification, the numerical range indicated by "above" or "below" refers to the numerical range that includes the stated number.

[0076] In this specification, the word "may" has two meanings: to perform a certain process and not to perform a certain process.

[0077] In this specification, the terms "optionally" or "optionally" are used to indicate the use or non-use of certain substances, components, procedures, application conditions, etc.

[0078] All unit names used in this manual are international standard unit names, and unless otherwise stated, the "%" used refers to weight or mass percentage content.

[0079] In this specification, references to "preferred embodiments," "implementation methods," etc., mean that a specific element (e.g., feature, structure, property, and / or characteristic) related to that embodiment is included in at least one of the embodiments described herein, and may or may not be present in other embodiments. Furthermore, it should be understood that the elements may be combined in any suitable manner in various embodiments.

[0080] Crosslinked polymers

[0081] One object of the present invention is to provide a crosslinked polymer comprising the structure shown in formula (I) and at least one structure selected from the structures shown in formulas (II-1) to (II-3), wherein the bonds with * in the structure shown in formula (I) are connected to the bonds with # in the structures shown in formulas (II-1) to (II-3) to form a crosslinked network of the crosslinked polymer.

[0082] *-DAD-* (I)

[0083] In formula (I), A represents a divalent organic group, and D represents the group shown in formula (a) below.

[0084]

[0085] In formula (a), R2 and R3 independently represent halogens or alkyl groups having 1 to 40 carbon atoms, wherein one or more -CH2- groups in the alkyl group are optionally replaced by -O-, -CO-, or -COO- in such a way that the O atom is not directly connected; m represents an integer from 0 to 3, and z represents an integer from 0 to 4; R4 represents H, an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 15 carbon atoms; R5 represents hydrogen or an alkyl group having 1 to 10 carbon atoms; the bond marked with * is the bond marked with * in the structure shown in formula (I), and the bond marked with @ is the bond connected to A;

[0086]

[0087] In formulas (II-1) to (II-3), n independently represents an integer greater than 3, E independently represents an n-valent organic group, F independently represents a divalent organic group or a single bond, and R1 independently represents H or a methyl group.

[0088] In the crosslinked polymer of the present invention, the divalent structure shown in formula (I) is interconnected with the n-valent structures shown in formulas (II-1) to (II-3) to form a crosslinked network.

[0089] In the structure shown in formula (I), D represents a structure having a 3,4-dihydropyrimidine-2-thione moiety and a carbazole moiety, and A represents a linking group between the two groups represented by D.

[0090] In this invention, there are no particular restrictions on A as the linking group; it can be any suitable divalent group.

[0091] In some embodiments, A represents an alkylene group having 2 to 40 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O-, -CO-, -COO-, or -C=C- in such a way that the O atom is not directly attached.

[0092] In this specification, the group in which the -CH2- group in the alkylene group is replaced by -O- can be, for example, an oxyalkylene group (-O-(CH2)). k -), alkyleneoxy group (-O-(CH2) l -O-), alkyleneoxyalkylene (-(CH2)) p -O-(CH2)q -), etc., where k is an integer from 2 to 39, and l, q, and q are independently integers from 2 to 38, for example, they can be independently 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.; the group in the alkylene group whose -CH2- group is replaced by -CO- and -COO- can be, for example, -CO-(CH2). k -、-CO-(CH2) l -CO-, -(CH2) p -CO-(CH2) q -、-COO-(CH2) k -、-COO-(CH2) l -COO-, -(CH2) p -COO-(CH2) q -; The group in an alkylene group that has been replaced by a -C=C- group can be, for example, -(CH2). p -C=C-(CH2) q -

[0093] Preferably, A represents an alkylene group having 2 to 20 carbon atoms. Specifically, examples of groups represented by A include ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene.

[0094] D represents the group shown in formula (a), which is a DHPMT structure with a carbazole substituent, wherein the benzene ring of the carbazole group optionally has substituents R2 and R3, the N of the carbazole group optionally has substituent R5, the bond marked with @ is the bond connected to A, and the bond marked with * is the bond forming a cross-linked network.

[0095] In some embodiments, R2 and R3 independently represent a halogen (e.g., fluorine, chlorine, bromine, iodine) or an alkyl group having 1 to 40 (preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10) carbon atoms, wherein one or more -CH2- groups in the alkyl group are optionally replaced by -O-, -CO-, -COO-, or -C=C- in such a way that the O atom is not directly connected.

[0096] In this specification, the group in which the -CH2- group in an alkyl group is replaced by -O-, -CO-, -COO-, or -C=C- can be, for example, -O-(CH2). r1 -CH3, -(CH2) r2 -O-(CH2) r3 -CH3, -CO-(CH2) r1 -CH3, -(CH2) r2 -CO-(CH2) r3-CH3, -COO-(CH2) r1 -CH3, -(CH2) r2 -COO-(CH2) r3 -CH3, -(CH2) r2 -C=C-(CH2) r3 -CH3, where r1, r2 and r3 are independent integers of 0 or 1 to 20, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0097] Preferably, R2 and R3 independently represent halogens (fluorine, chlorine, bromine, iodine) or alkoxy groups having 1 to 6 carbon atoms.

[0098] m and z respectively represent the number of substituents R2 and R3, where m is an integer from 0 to 3, for example 0, 1, 2, 3; and z is an integer from 0 to 4, for example 0, 1, 2, 3, 4. Preferably, m and z represent 0.

[0099] In some embodiments, R4 represents H, an alkyl group having 1 to 20 (preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6) carbon atoms, or an aromatic group having 6 to 15 (preferably 6 to 10) carbon atoms. The aromatic group is more preferably phenyl, alkylphenyl (e.g., benzyl), phenylalkyl (e.g., benzyl, phenethyl, etc.). Preferably, R4 represents H.

[0100] In some embodiments, R5 represents an alkyl group having 1 to 6 carbon atoms, preferably methyl, ethyl, propyl, or butyl.

[0101] In some embodiments, the structure shown in formula (I) is derived from the compound shown in formula (III) below (or a preferred embodiment thereof).

[0102] The structures shown in formulas (II-1) to (II-3) are derived from polyfunctional electron-deficient olefins, which are connected to the structure shown in formula (I) through # bonds to form a cross-linked network.

[0103] The present invention does not impose any particular limitation on E in formulas (II-1) to (II-3), which can be any suitable n-valent organic group.

[0104] In some embodiments, E independently represents a straight-chain, branched, or cyclic n-valent alkyl group having 1 to 20 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O-, -CO-, -COO-, or -C=C- in such a way that the O atom is not directly connected, or E represents an isocyanurate group.

[0105] Preferably, E independently represents a straight-chain, branched, or cyclic n-valent alkyl group having 3 to 12 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O- and -COO- in such a way that the O atoms are not directly connected.

[0106] n represents the number of groups within “[]”, which are independent integers of 3 or more, such as 3, 4, 5, 6, 7, 8, 9, 10, etc.

[0107] F is a linking group. This invention does not impose any particular limitation on F; it can be any suitable divalent organic group or single bond. In some embodiments, F independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O-, -CO-, -COO-, or -C=C- in such a way that the O atom is not directly connected.

[0108] Preferably, F represents an alkylene group having 2 to 20 carbon atoms, or represents the group -O-(CH2). t -O-, where t is an integer from 1 to 20. Specifically, groups represented by F include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, -O-(CH2)2-O-, -O-(CH2)3-O-, -O-(CH2)4-O-, -O-(CH2)5-O-, -O-(CH2)6-O-, -O-(CH2)7-O-, -O-(CH2)8-O-, -O-(CH2)9-O-, and -O-(CH2) 10 -O- etc.

[0109] Preferably, F represents a single bond or an alkylene group having 1 to 6 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O- in such a way that the O atom is not directly attached.

[0110] In this specification, the term "independently" used in the definition of each letter means that when the letter appears multiple times in one general formula or multiple times in different general formulas, it may have the same or different meanings.

[0111] In some embodiments, the structures shown in formulas (II-1) to (II-3) are derived from compounds of formulas (IV-1) to (IV-3) below.

[0112] <Preparation Methods of Crosslinked Polymers>

[0113] One objective of this invention is to provide a method for preparing a crosslinked polymer, comprising the following steps:

[0114] The compound represented by formula (III) is subjected to an addition reaction with at least one compound selected from formulas (IV-1) to (IV-3).

[0115] GAG (III)

[0116] In formula (III), G represents the group shown in formula (b) below.

[0117]

[0118] In equations (III), (b), (IV-1) to (IV-3), A, E, F, R1, R2, R3, R4, R5, m, n, and z have one of the meanings given in the context; the key with @ is the key connected to A.

[0119] The preparation method of the present invention involves subjecting a compound of formula (III) having two 3,4-dihydropyrimidine-2-thione structures to an aza-Michael addition reaction with at least one of the polyfunctional electron-deficient olefins shown in formulas (IV-1) to (IV-3) to obtain the crosslinked polymer of the present invention.

[0120] In this specification, "polyfunctional electron-deficient olefins" refers to compounds having three or more electron-deficient vinyl groups.

[0121] In this specification, when describing the reaction in this step, "addition reaction" and "polymerization reaction" have the same meaning.

[0122] In some embodiments, the addition reaction is carried out in the presence of a catalyst. Preferably, the catalyst is a base, more preferably a moderately strong base, specifically a monobasic organic moderately strong base, and more specifically at least one of 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) and 4-dimethylaminopyridine (DMAP).

[0123] In some embodiments, the monomer feed molar ratio (the total of compounds represented by formula (III) : compounds represented by formulas (IV-1), (IV-2) and (IV-3)) can be (n' to 1.5n'): (1 to 3), preferably (1.1n' to 1.3n'): (1.5 to 2.5), for example, 1.2n': 2. Wherein n' is the molar weighted average of n in the compounds represented by formulas (IV-1), (IV-2) and (IV-3).

[0124] The monomer molar ratio affects the crosslinking density of the resulting crosslinked polymer, and thus its mechanical properties. Theoretically, the closer the monomer molar ratio is to n':2, the greater the crosslinking density of the resulting polymer and the stronger its mechanical strength. In some embodiments, considering the flexibility of the material, the compound shown in formula (III) can be used in excess, for example, in a ratio of (1.1n' to 1.3n'):2. Those skilled in the art can select a suitable monomer molar ratio according to actual needs.

[0125] In some embodiments, the total molar ratio of the compounds represented by formulas (IV-1), (IV-2) and (IV-3) to the catalyst can be (1-3):(0.04n'-0.4n'), preferably (1.5-2.5):(0.1n'-0.2n'), for example 2:0.15n'.

[0126] In some embodiments, the total of the compounds shown in formula (III) : (IV-1), (IV-2) and (IV-3) : catalyst in the feed molar ratio can be (n'~1.5n'): (1~3): (0.04n'~0.4n'), preferably (1.1n'~1.3n'): (1.5~2.5): (0.1n'~0.2n'), for example 1.2n': 2: 0.15n'. Wherein n' is the molar weighted average of n in the compounds shown in formulas (IV-1), (IV-2) and (IV-3).

[0127] In the specific implementation plan, the addition reaction includes the following three steps:

[0128] (i) Monomer melting: The compound shown in formula (III) and at least one of the compounds shown in formula (IV-1), (IV-2) and (IV-3) are mixed and heated to melt the mixture;

[0129] (ii) Pre-crosslinking reaction: Stop heating, then add the catalyst to the mixture obtained in (i), and optionally apply stirring to carry out the pre-crosslinking reaction to obtain the prepolymer;

[0130] (iii) Crosslinking reaction: The prepolymer is heated to carry out a crosslinking reaction.

[0131] In step (i), the melting temperature of the mixture is preferably higher than the melting point of the compound represented by formula (III) and at least one of the compounds represented by formulas (IV-1), (IV-2) and (IV-3), and lower than the decomposition temperature of these compounds and the catalyst. For example, the melting temperature can be 100–180°C, preferably 120–160°C.

[0132] In step (ii), the pre-crosslinking reaction can take 10–60 seconds, preferably 20–50 seconds. The pre-crosslinking reaction is preferably carried out under stirring. During the pre-crosslinking reaction, an increase in system viscosity can be observed until the system solidifies, at which point the pre-crosslinking reaction ends.

[0133] In step (iii), the temperature of the crosslinking reaction is 20 to 160°C, preferably 100 to 160°C, and more preferably 120 to 140°C.

[0134] In step (iii), the crosslinking reaction takes 2 to 40 minutes, preferably 3 to 30 minutes, and more preferably 5 to 20 minutes. By carrying out the crosslinking reaction in step (iii), the crosslinking reaction tends to be complete.

[0135] In some embodiments, the compound represented by formula (III) is the compound represented by formula (III-1).

[0136]

[0137] In equation (III-1), t1 represents an integer from 2 to 12, preferably from 4 to 10, such as 5, 6, 7, 8, 9, etc.

[0138] Preferably, the compound represented by formula (III) is one of the following compounds:

[0139]

[0140] In some embodiments, the crosslinked polymer of the present invention is obtained by reacting the compound of formula (III) with the compound of formula (IV-1) in an addition reaction.

[0141] Preferably, the polyfunctional (meth)acrylate represented by formula (IV-1) is selected from trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane tetra(meth)acrylate, tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, tri(acryloyloxyethyl)isocyanurate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, and tripentaerythritol penta(meth)acrylate.

[0142] In some embodiments, the preparation method of the present invention further includes the step of preparing the compound represented by formula (III).

[0143] Specifically, the compounds of formulas (1) to (3) are reacted to obtain the compound shown in formula (III).

[0144]

[0145] Among them, A, R2, R3, R4, R5, m, and z have one of the meanings given by the context.

[0146] The reactions that the compounds shown in formulas (1) to (3) undergo are Biginelli reactions.

[0147] Preferably, the Biginelli reaction temperature is 25–150°C, more preferably 50–130°C, and even more preferably 80–120°C. A reaction temperature within this range is beneficial for the efficient and rapid conduction of the Biginelli reaction.

[0148] Preferably, the Biginelli reaction time is 2–24 hours, more preferably 3–20 hours, and even more preferably 4–10 hours. A reaction time within this range is beneficial for the complete execution of the Biginelli reaction, ensuring the aldehyde component is fully converted to facilitate subsequent purification.

[0149] Preferably, the Biginelli reaction is carried out in the presence of a catalyst, which is preferably at least one selected from magnesium chloride, p-toluenesulfonic acid, hydrochloric acid, zinc chloride, cerium ammonium nitrate, ytterbium trifluoromethanesulfonate, and trimethylchlorosilane.

[0150] Preferably, the Biginelli reaction is carried out in a solvent, which is preferably selected from acetic acid, N,N-dimethylformamide, methanol, ethanol, and acetonitrile.

[0151] The molar ratio of the compound shown in formula (1), the compound shown in formula (3), and the compound shown in formula (2) is 1:(1.5~2.5):(2.5~3.5), specifically 1:(1.8~2.2):(2.8~3.2), for example 1:2:3.

[0152] In one aspect of these embodiments, the preparation method of the present invention further includes the step of preparing the compound shown in formula (1), which includes: subjecting tert-butyl acetoacetate to a substitution reaction with a diol compound to obtain the compound shown in formula (1).

[0153] Preferably, the diol compound can be an alkyl diol (preferably with 2 to 40 carbon atoms, more preferably 3 to 20), specifically 1,4-dibutanol, 1,5-dipentanol, 1,6-dihexanol, 1,8-dioctanol, etc. Different diols have different alkyl chain lengths and substitution positions, thus affecting the crosslinking density and mechanical properties of the final crosslinked polymer.

[0154] Preferably, the temperature of the substitution reaction is 80°C to 120°C.

[0155] Preferably, the substitution reaction takes 12 to 24 hours.

[0156] Preferably, the substitution reaction is carried out in a solvent, which is preferably a high-boiling-point aprotic solvent, more preferably at least one selected from xylene, toluene, acetonitrile, N,N-dimethylformamide, dioxane, and dimethyl sulfoxide.

[0157] Preferably, the molar ratio of tert-butyl acetoacetate to the diol compound is 2:(1 to 1.1), for example, 2:1.05.

[0158] After the substitution reaction is complete, a colorless and transparent liquid product can be collected by rapid column chromatography, which is the compound of formula (1) containing two β-keto ester end groups.

[0159] The compound shown in formula (2) is preferably N-alkylthiourea, specifically thiourea, N-methylthiourea, N-ethylthiourea, N-allylthiourea, etc. Since different thiourea compounds have different substituents, the side chain substituents of the crosslinked polymer can be adjusted as needed, and the properties and functions of the crosslinked polymer can be adjusted accordingly.

[0160] The compound shown in formula (3) is an aldehyde compound with a carbazole group, preferably N-methylcarbazole-3-carbazole, N-ethylcarbazole-3-carbazole, N-propylcarbazole-3-carbazole, N-methylcarbazole-2-carbazole, N-ethylcarbazole-2-carbazole, etc.

[0161] The present invention also relates to crosslinked polymers prepared by the preparation method of the present invention described above.

[0162] <Polymer Molded Articles and Their Preparation Methods>

[0163] One object of the present invention is to provide a polymer molded article comprising the crosslinked polymer of the present invention.

[0164] The polymer molded articles of this invention exhibit excellent light transmittance and blue light protection properties. Based on the dynamic cross-linking properties of the cross-linked polymer of this invention, the polymer molded articles can be processed and molded multiple times, thus enabling easy recycling and reuse, and demonstrating significant environmental friendliness.

[0165] In one embodiment, the polymer molded body of the present invention can be a material having various shapes, such as a film, sheet, plate, pipe or profile.

[0166] In a preferred embodiment, the content of the crosslinked polymer in the polymer molded article of the present invention is 90 wt% or more, preferably 95 wt% or more, and more preferably 97 wt% or more.

[0167] As needed, the polymer molded articles of the present invention may also contain other additives, such as one or more additives selected from pigments, dyes, antioxidants, ultraviolet absorbers, processing aids, fillers, etc.

[0168] In a preferred embodiment, the polymer molded body of the present invention is a polymer film. Preferably, the thickness of the polymer film is 0.05 to 10 mm, more preferably 0.1 to 1 mm, for example 0.15 to 0.5 mm.

[0169] Preferably, the polymer film of the present invention has a shielding rate of 90% or more for blue light with a wavelength of 400-460nm when the film thickness is 0.2mm, more preferably 93% or more, more preferably 95% or more, for example 96% or more.

[0170] Preferably, the polymer film of the present invention has a shielding rate of 90% or more for ultraviolet light with a wavelength of 250 to 400 nm when the film thickness is 0.2 mm, more preferably 93% or more, more preferably 95% or more, for example 96% or more.

[0171] Preferably, the polymer film of the present invention has a transmittance of 70% or more, preferably 75% or more, and for example 76% or more, to visible light with a wavelength of 460 to 760 nm when the film thickness is 0.2 mm.

[0172] Based on the dynamic crosslinking properties of the crosslinked polymer of the present invention, the polymer molded body of the present invention can be prepared by melt molding. Therefore, the present invention also provides a method for preparing the polymer molded body of the present invention, which includes the step of melt molding the crosslinked polymer of the present invention.

[0173] Preferably, the melt molding can be hot pressing, extrusion molding, injection molding, molding, etc., and those skilled in the art can select the appropriate method based on the type of molded body.

[0174] In a preferred embodiment, melt forming is hot pressing.

[0175] Preferably, the hot pressing temperature is 140–180°C, more preferably 150–170°C, for example 160°C.

[0176] Preferably, the hot pressing pressure is 2 to 6 MPa, more preferably 3 to 5 MPa, for example 4 MPa.

[0177] Preferably, the hot pressing time is 5 minutes to 1 hour, more preferably 7 to 30 minutes, for example 10 minutes.

[0178] <Applications>

[0179] This invention also relates to the use of the crosslinked polymers and polymer molded articles of this invention for ultraviolet and / or blue light protection. Specifically, they can be used in building exteriors, window films, transparent shop windows, eyeglass coatings, blue light shields, packaging materials, etc.

[0180] Example

[0181] The present invention will be described in more detail below through specific embodiments. These embodiments are merely illustrative and do not constitute a limitation thereof. The practical application examples of these embodiments are easily grasped and verified by those skilled in the art. Any modifications made to this invention do not depart from its scope.

[0182] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0183] Example 1: Preparation of dynamically crosslinked polymer P1 with carbazole substituents

[0184] According to such Figure 1 The route shown is used to synthesize the dynamically crosslinked polymer P1.

[0185] Preparation of the precursor di-keto

[0186] tert-butyl acetoacetate and 1,8-dioctyl alcohol were dissolved in toluene at a molar ratio of 2:1.05 to achieve a tert-butyl acetoacetate concentration of 2 mol / L. The resulting reaction mixture was then refluxed at 110 °C for 16 hours. After the reaction was complete, the reaction solvent was removed by rotary evaporation, and the product was purified by rapid column chromatography using petroleum ether as the eluent to obtain the precursor di-keto, a colorless and transparent liquid containing two β-keto ester end groups, in approximately 95% yield.

[0187] Preparation of B2 monomers with carbazole substituents (Cz-B2 monomers)

[0188] The precursor di-keto, N-ethylcarbazole-3-carboxaldehyde, and thiourea were dissolved in N,N-dimethylformamide at a molar ratio of 1:2:3, with the concentration of N-ethylcarbazole-3-carboxaldehyde being 2 mol / L. Trimethylchlorosilane (200 mol% relative to N-ethylcarbazole-3-carboxaldehyde) was added as a Lewis acid, and the reaction was heated to 80°C for 6 hours. After the reaction, the reaction solution was dropped into cold water to precipitate the solid precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by precipitation with ten times the volume of petroleum ether to obtain the Cz-B2 monomer as an orange-yellow solid powder, with a yield of approximately 88%.

[0189] Preparation of dynamically crosslinked polymer P1

[0190] Cz-B2 monomer and ethoxylated trimethylolpropane triacrylate (hereinafter referred to as A3 monomer, molecular weight 692) were placed in a heat-conducting silicone container at a molar ratio of 1.8:1. The container was placed on a hot plate and the heating temperature was set to 160°C. When the monomer was almost completely melted, the mixture was stirred to ensure homogeneity. The container was removed from the heat source, and DBU was added in batches as a catalyst (molar ratio of A3 monomer to DBU was 1:0.225) before the system solidified, while stirring to ensure homogeneity of the catalyst. The system was observed to be exothermic and the viscosity gradually increased, indicating that the crosslinking reaction was proceeding smoothly. Stirring was continued for about 30 seconds until the system reached a high viscosity. The container was returned to the hot plate and the heating temperature was set to 160°C. The reaction was continued for 10 minutes to ensure that the crosslinking reaction was nearing completion, yielding a dynamically crosslinked polymer P1 with carbazole substituents.

[0191] Example 2: Preparation of blue light blocking polymer film Cz film

[0192] The dynamically crosslinked polymer P1 obtained in Example 1 was placed in a square mold and hot-pressed using a tablet press at a temperature of 160°C and a pressure of 4 MPa. After hot pressing for 10 minutes, the mold was removed and the sample was separated, successfully preparing a uniform polymer film Cz film with dimensions of 25 mm × 25 mm × 0.2 mm.

[0193] <Tests and Evaluations>

[0194] Chemical corrosion resistance test

[0195] The polymer film Cz film obtained in Example 2 was cut into rectangles (25mm × 10mm × 0.2mm) as test samples, and a polycarbonate (PC) film of the same size (purchased from Huiying Plastic Materials Factory), a commonly used protective film material for electronic devices, was used as a control group. Tetrahydrofuran liquid was dropped onto the central area of ​​the surface of both films using a dropper, and allowed to stand for a period of time to allow the tetrahydrofuran to evaporate. The state of the two films was then observed, and the results are as follows: Figure 2 As shown. By Figure 2 It can be seen that the PC film is significantly corroded by organic solvents, while the polymer film (Cz film) is resistant to corrosion by organic solvents. This experiment demonstrates that the polymer film (Cz film) has excellent chemical corrosion resistance.

[0196] Bending resistance test

[0197] The polymer film Cz film obtained in Example 2 was cut into rectangles (25mm × 10mm × 0.2mm) as test samples, and a commonly used electronic device protective film material, polycarbonate (PC) film of the same size, was used as a control group. After fixing the positions of both films, they were folded in half 100 times consecutively, and the state of the two films was then observed. The results are as follows: Figure 3 As shown. By Figure 3 As can be seen, a noticeable crease appeared in the middle of the PC film, while no crease appeared in the middle of the Cz film. This experiment demonstrates that the polymer film Cz film has excellent bending resistance.

[0198] Self-repair performance test

[0199] The polymer film Cz film obtained in Example 2 was cut into square samples (10mm × 10mm × 0.2mm), and then cut in half to simulate damage during use (e.g., Figure 4 (As shown on the left); Gently bring the two sides of the scratch together and allow it to self-heal at room temperature. After 2 hours, hold both sides of the polymer film and stretch it outwards. No cracks appeared at the scratch, indicating that the polymer film was successfully repaired (as shown on the left). Figure 4 (As shown on the right). This experiment demonstrates that the polymer film Cz film has excellent self-healing capabilities at room temperature.

[0200] Blue light protection capability and light transmittance test

[0201] (1) The polymer film Cz film obtained in Example 2 was cut (10mm × 10mm × 0.2mm) and placed on paper printed with the Tsinghua University emblem. Its light transmittance was visually observed. Figure 5 As shown in a), the school emblem is still clearly visible after being covered by the polymer film, which preliminarily indicates that the polymer film Cz film has good light transmittance.

[0202] (2) The blue light blocking ability and light transmittance of the polymer film were further characterized using ultraviolet-visible transmission spectroscopy, and the results are as follows: Figure 5As shown in b). Based on the integral calculation of the spectral data, the polymer film Cz film has good protection capabilities for the ultraviolet light band (250nm~400nm) and the high-energy blue light band (400nm~460nm) (protection rate greater than 97%), while it has good light transmittance for other visible light bands (460nm~760nm) (transmittance of about 79%). This indicates that the polymer film Cz film is a highly transparent material with excellent blue light protection capabilities.

[0203] (3) The blue light blocking performance of the polymer film Cz film was tested by comparing it with opaque white paper using a blue light lamp and blue light test paper. Figure 6 As shown on the left, a single sheet of white paper (1cm x 1cm, 100μm thick), two sheets of white paper (200μm thick), and a polymer film (Cz film) were placed sequentially from left to right on a commercially available blue light test strip. A 420nm blue light lamp (8W) was used to illuminate the test strip from 5cm directly above it for 1 minute. Then, the white paper and the polymer film (Cz film) were removed. The results are as follows. Figure 6 As shown on the right. (By...) Figure 6 As shown on the right, the uncovered areas of the blue light test strip all changed color, indicating that the test strip responds to 420nm blue light. The areas covered by a single sheet of white paper also changed color, but the color was lighter than the uncovered areas. The areas covered by two sheets of white paper and the polymer film (Cz film) did not change color. These results demonstrate that under these test conditions, the polymer film (Cz film) provides significantly better protection against blue light than a single opaque sheet of white paper, and its effect is comparable to that of two sheets of white paper.

[0204] Industrial availability

[0205] The polymers and polymer molded articles of the present invention can be widely used for blue light protection.

Claims

1. A crosslinked polymer, characterized in that, The crosslinked polymer comprises the structure shown in formula (I) and at least one structure selected from the structures shown in formulas (II-1) to (II-3), wherein the bonds with * in the structure shown in formula (I) are connected to the bonds with # in the structures shown in formulas (II-1) to (II-3) to form a crosslinked network of the crosslinked polymer. *-DAD-* (I) In formula (I), A represents a divalent organic group, and D represents the group shown in formula (a) below. In formula (a), R2 and R3 independently represent halogens or alkyl groups having 1 to 40 carbon atoms, wherein one or more -CH2- groups in the alkyl group are optionally replaced by -O-, -CO-, or -COO- in such a way that the O atom is not directly connected; m represents an integer from 0 to 3, and z represents an integer from 0 to 4; R4 represents H, an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 15 carbon atoms; R5 represents hydrogen or an alkyl group having 1 to 10 carbon atoms; the bond marked with * is the bond marked with * in the structure shown in formula (I), and the bond marked with @ is the bond connected to A; In formulas (II-1) to (II-3), n independently represents an integer greater than 3, E independently represents an n-valent organic group, F independently represents a divalent organic group or a single bond, and R1 independently represents H or a methyl group.

2. The crosslinked polymer according to claim 1, characterized in that, A represents an alkylene group having 2 to 40 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O-, -CO-, -COO- or -C=C- in such a way that the O atom is not directly attached; n represents an integer from 3 to 6. E independently represents a straight-chain, branched, or cyclic n-valent alkyl group having 1 to 20 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O-, -CO-, -COO-, or -C=C- in such a way that the O atom is not directly attached; or E represents an isocyanurate group; F represents, independently, a single bond or an alkylene group having 1 to 20 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O-, -CO-, -COO-, or -C=C- in such a way that the O atom is not directly attached.

3. The crosslinked polymer according to claim 2, characterized in that, A represents an alkylene group with 2 to 20 carbon atoms, or the group -O-(CH2). t -O-, where t is an integer from 2 to 20; E independently represents a straight-chain, branched, or cyclic n-valent alkyl group having 3 to 12 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O-, -CO-, -COO-, or -C=C- in such a way that the O atom is not directly connected; F represents, independently, a single bond or an alkylene group having 1 to 6 carbon atoms, wherein one or more -CH2- groups are optionally replaced by -O- in such a way that the O atom is not directly attached; R2 and R3 independently represent halogens or alkoxy groups having 1 to 6 carbon atoms; m represents 0 or 1; z represents 0 or 1; R4 represents H; R5 represents methyl, ethyl, propyl, or butyl.

4. A method for preparing a cross-linked polymer, characterized in that, Includes the following steps: The compound represented by formula (III) is subjected to an addition reaction with at least one compound selected from formulas (IV-1) to (IV-3). GAG (III) In formula (III), A represents a divalent organic group, and G represents the group shown in formula (b) below. In formula (b), R2 and R3 independently represent halogens or alkyl groups having 1 to 40 carbon atoms, wherein one or more -CH2- groups in the alkyl group are optionally replaced by -O-, -CO-, or -COO- in such a way that the O atom is not directly connected; m represents an integer from 0 to 3, and z represents an integer from 0 to 4; R4 represents H, an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 15 carbon atoms; R5 represents hydrogen or an alkyl group having 1 to 10 carbon atoms; the bond marked with @ is a bond connected to A; In formulas (IV-1) to (IV-3), n independently represents an integer greater than 3, E independently represents an n-valent organic group, F independently represents a divalent organic group or a single bond, and R1 independently represents H or a methyl group.

5. The preparation method according to claim 4, characterized in that, It also includes the following steps for preparing the compound shown in formula (III): Reacting the compounds of formulas (1) to (3) yields the compound shown in formula (III). Wherein, A, R2, R3, R4, R5, m, and z have the meanings given in claim 4.

6. The preparation method according to claim 4 or 5, characterized in that, The compound represented by formula (III) undergoes an addition reaction with the compound represented by formula (IV-1); Preferably, the compound represented by formula (III) is the compound represented by formula (III-1): In equation (III-1), t1 represents an integer from 2 to 12; Preferably, the compound represented by formula (IV-1) is selected from at least one of the following: trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane tetra(meth)acrylate, tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, tri(acryloyloxyethyl)isocyanurate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, and tripentaerythritol penta(meth)acrylate.

7. The crosslinked polymer obtained by the preparation method according to any one of claims 4 to 6.

8. A polymer molded article, characterized in that, It contains a crosslinked polymer according to any one of claims 1 to 3 and 7.

9. A method for preparing a polymer molded article, characterized in that, Includes the following steps: The crosslinked polymer according to any one of claims 1 to 3 and 7 is melt-molded.

10. Use of the crosslinked polymer according to any one of claims 1 to 3 and 7, or the polymer molded article according to claim 8, for ultraviolet protection and / or blue light protection.

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