Dynamic covalent cross-linked material based on thermoplastic polymer and preparation method and application thereof

Abstract

The application relates to a thermoplastic polymer-based dynamic covalent cross-linking material and a preparation method and application thereof, and belongs to the technical field of polymer materials. The preparation method of the dynamic covalent cross-linking material comprises the following steps: S1. a mixture containing a thermoplastic polymer, an acid anhydride substance and an initiator is subjected to first melt blending to obtain a melt blend; S2. the melt blend, a cross-linking agent and a catalyst are uniformly mixed, and second melt blending is carried out to obtain the thermoplastic polymer-based dynamic covalent cross-linking material; the cross-linking agent is a bisglycidyl ether type epoxide. The preparation method of the dynamic covalent cross-linking material provided by the application is simple in process and short in preparation period, can be used for converting thermoplastic polymers and waste thermoplastic polymers into dynamic cross-linking materials with excellent mechanical properties, creep resistance, heat resistance and chemical solvent resistance, realizes high value of the dynamic cross-linking materials, and is suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular materials, in particular to a dynamic covalent cross-linked material based on thermoplastic high polymer and a preparation method and application thereof. BACKGROUND

[0002] Thermoplastic high polymer is a kind of polymer material that can soften when heated and re-solidify after cooling, has good processability and mechanical properties, and is widely used in electronic, electrical, automotive, medical and other fields. However, due to its linear molecular chain structure, the molecular chains mainly rely on physical forces such as chain entanglement or crystallization to maintain structural stability, so that the mechanical strength, creep resistance and thermal stability of thermoplastic high polymer are greatly limited compared with thermosetting high polymer. Under high temperature or long-term load, traditional thermoplastic high polymer is prone to deformation, creep and performance degradation, which limits its application. SUMMARY

[0003] In view of one or more technical problems existing in the prior art, the present application provides a dynamic covalent cross-linked material based on thermoplastic high polymer and a preparation method and application thereof. The preparation method of the dynamic covalent cross-linked material provided by the present application is simple in process and short in preparation period, and can be used to convert thermoplastic high polymer and waste thermoplastic high polymer into a dynamic cross-linked material with excellent mechanical, creep resistance, heat resistance and chemical solvent resistance, realizing its high value and being suitable for industrial production.

[0004] The present application provides a preparation method of a dynamic covalent cross-linked material based on thermoplastic high polymer, which comprises the following steps:

[0005] S1. First melt blending a mixture comprising thermoplastic high polymer, acid anhydride substance and initiator to obtain a melt blend;

[0006] S2. Mixing the melt blend, cross-linking agent and catalyst uniformly, and second melt blending to obtain a dynamic covalent cross-linked material based on thermoplastic high polymer; the cross-linking agent is a bisglycidyl ether type epoxide.

[0007] Preferably, the mass ratio of the acid anhydride substance to the thermoplastic high polymer is 0.1-15:100;

[0008] The mass ratio of the initiator to the thermoplastic high polymer is 0.01-1.5:100;

[0009] The mass ratio of the cross-linking agent to the thermoplastic high polymer is 0.5-120:100; and / or

[0010] The mass ratio of the catalyst to the thermoplastic high polymer is 0.02-5:100.

[0011] Preferably, the mixture further comprises an auxiliary agent; the auxiliary agent is one or more of α-methylstyrene, styrene, dimethylformamide, decene, ethyl benzoate, 2,2'-dipyridyl, stearyl amide, dimethylacetamide, N,N-diethylcinnamamide, N,N-dimethylacetamide, 3-(2-furyl)acrylic acid, ethyl cinnamate, dimethyl aniline, dilaurylthiopropionate, trimethylolpropane triacrylate, butyl 3-(2-furyl)acrylate, butyl 3-(2-thienyl)acrylate, 4,4'-diaminodiphenyl methane, cashew nut shell liquid, triallylisocyanurate, 1,2-polybutadiene.

[0012] Preferably, the mass ratio of the auxiliary agent to the thermoplastic polymer is 0.1-15:100.

[0013] Preferably, the thermoplastic polymer is one or more of acrylonitrile-butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, styrene-ethylene-butylene-styrene copolymer, styrene-isoprene-styrene copolymer, ethylene-vinyl acetate copolymer, polyolefin elastomer, polyethylene, polypropylene, and recycled materials thereof.

[0014] The anhydride is one or more of maleic anhydride, methyl isopropenyl anhydride, phthalic anhydride, tetrahydrophthalic anhydride, dimethyl maleic anhydride, methacrylic anhydride, itaconic anhydride, acrylic anhydride, trimellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, tetrachlorophthalic anhydride, acrylic anhydride, methyltetrahydrophthalic anhydride, benzoic anhydride, 4-bromo-1,8-naphthalic anhydride, 1,8-naphthalic anhydride, 3-nitrophthalic anhydride, tetrabromophthalic anhydride; and / or

[0015] The initiator is one or more of peroxide initiator, azo initiator, N,N-dimethyl amine; the peroxide initiator is preferably one or more of dicumyl peroxide, dibenzoyl peroxide, di-tert-butyl peroxide, dodecanoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, lauryl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate; the azo initiator is preferably azobis isobutyronitrile, azobis isohexylnitrile.

[0016] Preferably, the bisglycidyl ether epoxy is one or more of ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, resorcinol bisglycidyl ether; and / or

[0017] The catalyst is one or more of zinc acetylacetone, trisazo bicyclo decene, triphenyl phosphine.

[0018] Preferably, the temperature of the first melt blending is 110-230 DEG C, and the time is 7-15 min; and / or

[0019] The temperature of the second melt blending is 110-230 DEG C, and the time is 7-15 min.

[0020] The application provides in a second aspect a dynamic covalent cross-linked material based on thermoplastic polymer, which is characterized by being prepared by the preparation method in the first aspect.

[0021] The application provides in a third aspect an application of the dynamic covalent cross-linked material based on thermoplastic polymer in the second aspect, which is applied to preparation of a thermoplastic polymer composite material; and the preparation method of the thermoplastic polymer composite material comprises the following steps: mixing the dynamic covalent cross-linked material with the thermoplastic polymer, and performing third melt blending to obtain the thermoplastic polymer composite material.

[0022] Preferably, the temperature of the third melt blending is 110-230 DEG C, and the time is 7-15 min; and / or

[0023] The mass ratio of the dynamic covalent cross-linked material to the thermoplastic polymer is 5-70:30-95.

[0024] Compared with the prior art, the application has at least the following beneficial effects:

[0025] The application first melt blends the thermoplastic polymer, the acid anhydride and the initiator, improves the grafting amount of the acid anhydride on the thermoplastic polymer under the action of the initiator, and then makes the epoxy groups in the cross-linking agent react with the acid anhydride to generate ester groups and hydroxyl groups under the action of the catalyst, so that an ester exchange dynamic covalent cross-linked network is formed, the thermal stability and the mechanical strength of the thermoplastic polymer are effectively improved, and the repeatable processing performance of the thermoplastic polymer is not affected.

[0026] The preparation method of the dynamic covalent cross-linked material has the advantages of simple process and short preparation period, can be used for converting the thermoplastic polymer and the waste thermoplastic polymer into the dynamic cross-linked material with excellent mechanical properties, creep resistance, heat resistance and chemical solvent resistance, realizes high value of the thermoplastic polymer, and is suitable for industrial production.

[0027] The dynamic covalent cross-linking material provided by the application can endow the polymer material with higher thermal stability and mechanical strength without sacrificing the processability of the material, and also allows the material to realize the topological rearrangement of the polymer network through the reversible exchange reaction between different ester groups under the stimulation of light, heat or chemicals, so as to realize reshaping, repair and recycling, and meet the dual requirements of durability and processability, and significantly enhance the service life and stability of the material under extreme conditions.

[0028] The dynamic covalent cross-linking material is melt-blended with the thermoplastic polymer, so that a thermoplastic polymer composite material with excellent mechanical properties is obtained. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are some embodiments of the application, and other drawings can also be obtained by those skilled in the art without creative labor on the basis of these drawings.

[0030] Figure 1 is an infrared spectrum of the influence of the auxiliary agent of the application on the grafting amount of the reactive agent (acid anhydride substance);

[0031] Figure 2 is a storage modulus curve of the dynamic covalent cross-linking material based on ABS recycled material and ABS recycled material provided by the embodiment 4 of the application;

[0032] Figure 3 is a storage modulus curve of the dynamic covalent cross-linking material based on polypropylene material and polypropylene material provided by the embodiment 8 of the application;

[0033] Figure 4 is a stress-strain curve of the thermoplastic polymer composite material and ABS provided by the embodiment 12 of the application;

[0034] Figure 5 is a stress-strain curve of the thermoplastic polymer composite material and polypropylene material provided by the embodiment 13 of the application. DETAILED DESCRIPTION

[0035] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are some but not all of the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts should fall into the scope of the present application.

[0036] The present application provides a preparation method of a dynamic covalent cross-linked material based on thermoplastic polymer, comprising the following steps:

[0037] S1. First melt blending a mixture comprising thermoplastic polymer, acid anhydride substance and initiator to obtain a melt blend;

[0038] S2. Mixing the melt blend, cross-linking agent and catalyst uniformly, and second melt blending to obtain a dynamic covalent cross-linked material based on thermoplastic polymer; the cross-linking agent is a diglycidyl ether type epoxide.

[0039] The present application first melt blends thermoplastic polymer, acid anhydride substance and initiator, under the action of the initiator, the grafting amount of acid anhydride on the thermoplastic polymer is increased, then under the action of the catalyst, the epoxy groups in the cross-linking agent and the acid anhydride react to form ester groups and hydroxyl groups, forming a dynamic covalent cross-linked network of ester exchange, without affecting the repeatable processing performance of the thermoplastic polymer, while effectively improving the thermal stability and mechanical strength of the thermoplastic polymer.

[0040] The preparation method of the dynamic covalent cross-linked material provided by the present application has simple process and short preparation period, and can be used to convert thermoplastic polymer and waste thermoplastic polymer into dynamic cross-linked material with excellent mechanical, creep resistance, heat resistance and chemical solvent resistance, realizing its high value, and being suitable for industrial production.

[0041] According to some preferred embodiments, the mass ratio of the acid anhydride substance to the thermoplastic polymer is 0.1-15:100 (for example, it can be 0.1:100, 1:100, 2:100, 3:100, 4:100, 5:100, 6:100, 7:100, 8:100, 9:100, 10:100, 11:100, 12:100, 13:100, 14:100 or 15:100).

[0042] According to some preferred embodiments, the mass ratio of the initiator to the thermoplastic polymer is 0.01-1.5:100 (for example, it can be 0.01:100, 0.1:100, 0.2:100, 0.3:100, 0.4:100, 0.5:100, 0.6:100, 0.7:100, 0.8:100, 0.9:100, 1.0:100, 1.1:100, 1.2:100, 1.3:100, 1.4:100, or 1.5:100).

[0043] The present application ensures the grafting amount of the reactive agent (anhydride-based substance) by controlling the use amount of the thermoplastic polymer, the anhydride-based substance, and the initiator within the above range, and further forms an ester-exchanged dynamic covalent crosslinking system by using the reaction between the anhydride and the epoxy group in the crosslinking agent to generate ester groups and hydroxyl groups, and further obtains a high-strength dynamic covalent crosslinking material. The inventors have found that if the use amount of the initiator is too small, the grafting amount of the reactive agent (anhydride-based substance) decreases, resulting in a decrease in the strength of the finally obtained material; and if the use amount of the initiator is too large, the thermoplastic polymer degrades, resulting in a decrease in the Young's modulus of the obtained dynamic covalent crosslinking material, i.e., a decrease in the strength.

[0044] According to some preferred embodiments, the mass ratio of the crosslinking agent to the thermoplastic polymer is 0.5-120:100 (for example, it can be 0.5:100, 0.8:100, 10:100, 20:100, 30:100, 40:100, 50:100, 60:100, 70:100, 80:100, 90:100, 100:100, 110:100, or 120:100).

[0045] The mass ratio of the catalyst to the thermoplastic polymer is 0.02-5:100 (for example, it can be 0.02:100, 0.05:100, 0.1:100, 0.5:100, 1:100, 1.5:100, 2:100, 2.5:100, 3:100, 3.5:100, 4:100, 4.5:100, or 5:100).

[0046] According to some preferred embodiments, the mixture further comprises an auxiliary agent; the auxiliary agent is one or more of α-methylstyrene, styrene, dimethylformamide, decene, ethyl benzoate, 2,2'-dipyridyl, stearyl amide, dimethylacetamide, N,N-diethyl cinnamamide, N,N-dimethylacetamide, 3-(2-furyl)acrylic acid, ethyl cinnamate, dimethyl aniline, dilauryl thiodipropionate, trimethylolpropane triacrylate, butyl 3-(2-furyl)acrylate, butyl 3-(2-thienyl)acrylate, 4,4-diamine diphenyl methane, cashew nut shell liquid, triallyl isocyanurate, and 1,2-polybutadiene.

[0047] According to some preferred embodiments, the mass ratio of the auxiliary agent to the thermoplastic polymer is 0.1-15:100 (for example, it can be 0.1:100, 1:100, 2:100, 3:100, 4:100, 5:100, 6:100, 7:100, 8:100, 9:100, 10:100, 11:100, 12:100, 13:100, 14:100 or 15:100).

[0048] The present application further improves the grafting amount of the reactive agent (acid anhydride substance) by introducing an auxiliary agent into the reaction system, and further improves the strength of the material. The inventors have found that if the amount of the auxiliary agent is too much, the small molecules in the obtained dynamic covalent cross-linked material system will increase, which may overflow to the surface of the material in the subsequent use of the material, affecting the use effect of the material, and also causing the decrease of the strength of the dynamic covalent cross-linked material. Therefore, the amount of the auxiliary agent is controlled in the above range.

[0049] The present application takes styrene as an example to explore the influence of the auxiliary agent on the grafting amount of the reactive agent (acid anhydride substance), and the infrared spectrum is as shown in Figure 1 It should be noted that, Figure 1 rABS is ABS recycled material, rABS-MA is prepared without adding auxiliary agent, and rABS-MA-St is prepared by adding auxiliary agent; the wavelength of 1780 cm -1 is the infrared absorption peak of maleic anhydride, and the greater the peak value represents the more maleic anhydride grafted onto ABS. It can be seen from Figure 1 that the ABS recycled material has no absorption peak at 1780 cm -1 , and the carbonyl absorption peak of rABS-MA-St prepared by adding auxiliary agent is larger than that of rABS-MA prepared without adding auxiliary agent, which shows that adding auxiliary agent is beneficial to improve the grafting rate of acid anhydride.

[0050] According to some preferred embodiments, the thermoplastic polymer is one or more of acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene-styrene copolymer (SBS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-isoprene-styrene copolymer (SIS), ethylene-vinyl acetate copolymer, polyolefin elastomer, polyethylene (PE), polypropylene (PP) and their recycled materials. The thermoplastic polymer material is at least one of block and granular. Among them, the polyethylene (PE) includes at least one of high-density polyethylene, low-density polyethylene and linear low-density polyethylene.

[0051] According to some preferred embodiments, the anhydride is one or more of maleic anhydride, methyl isopropenyl anhydride, phthalic anhydride, tetrahydrophthalic anhydride, dimethyl maleic anhydride, methacrylic anhydride, itaconic anhydride, acrylic anhydride, trimellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, tetrachlorophthalic anhydride, acrylic anhydride, methyltetrahydrophthalic anhydride, benzoic anhydride, 4-bromo-1,8-naphthalic anhydride, 1,8-naphthalic anhydride, 3-nitrophthalic anhydride, and / or tetra-bromo phthalic anhydride.

[0052] According to some preferred embodiments, the initiator is one or more of a peroxide initiator, an azo initiator, and / or N,N-dimethyl amine; the peroxide initiator is preferably one or more of dicumyl peroxide, dibenzoyl peroxide, di-tert-butyl peroxide, dodecanoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, lauryl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, and / or dicyclohexyl peroxydicarbonate; the azo initiator is preferably azobisisobutyronitrile and / or azobisisoheptane nitrile.

[0053] According to some preferred embodiments, the bisglycidyl ether epoxy is one or more of ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, and / or resorcinol bisglycidyl ether. The present application selects bisglycidyl ether epoxy as the crosslinking agent, and utilizes the epoxy groups in the bisglycidyl ether epoxy and the anhydride to react to form ester groups and hydroxyl groups, forming a transesterified dynamic covalent crosslinking network, and thereby obtaining a dynamic covalent crosslinked material.

[0054] According to some preferred embodiments, the catalyst is one or more of zinc acetylacetonate (Zn(acac)2), trisazo bicyclo decene (TBD), and / or triphenylphosphine (PPh3).

[0055] According to some preferred embodiments, the temperature of the first melt blending is 110-230°C (for example, it can be 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, or 230°C), and the time is 7-15 min (for example, it can be 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, or 15 min).

[0056] According to some preferred embodiments, the temperature of the second melt blending is 110-230℃ (for example, it can be 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃ or 230℃), and the time is 7-15min (for example, it can be 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min).

[0057] The application provides, in a second aspect, a thermoplastic polymer-based dynamic covalent cross-linked material, which is prepared by the method of the first aspect.

[0058] The dynamic covalent cross-linked material provided by the application can endow the polymer material with higher thermal stability and mechanical strength without sacrificing its processability, and also allows the material to realize the topological rearrangement of the polymer network through the reversible exchange reaction between different ester groups under the stimulation of light, heat or chemicals, so as to realize reshaping, repair and recycling, and meet the dual requirements of durability and processability, and significantly enhance the service life and stability of the material under extreme conditions.

[0059] The application provides, in a third aspect, an application of the thermoplastic polymer-based dynamic covalent cross-linked material of the second aspect, which is applied to the preparation of a thermoplastic polymer composite material; and the preparation method of the thermoplastic polymer composite material comprises the following steps: mixing the dynamic covalent cross-linked material with a thermoplastic polymer, and performing third melt blending to obtain the thermoplastic polymer composite material.

[0060] The dynamic covalent cross-linked material is melt blended with the thermoplastic polymer, so that a thermoplastic polymer composite material with excellent mechanical properties is obtained, and the thermoplastic polymer composite material has more excellent mechanical properties and creep resistance than the thermoplastic polymer raw material and the dynamic covalent cross-linked material.

[0061] It should be noted that the thermoplastic polymer used in the process of mixing the dynamic covalent cross-linked material with the thermoplastic polymer can be the same or different from the thermoplastic polymer used in the preparation of the dynamic covalent cross-linked material.

[0062] According to some preferred embodiments, the temperature of the third melt blending is 110-230℃ (for example, it can be 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃ or 230℃), and the time is 7-15min (for example, it can be 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min); and / or

[0063] The mass ratio of the dynamic covalent cross-linked material to the thermoplastic polymer is 5-70:30-95 (for example, it can be 5:95, 10:90, 15:85, 20:80, 25:75, 30:70, 40:60, 50:50, 60:40 or 70:30), preferably 5-30:70-95.

[0064] In order to more clearly illustrate the technical solutions and advantages of the present application, the present application will be further described below in conjunction with examples. The sources of the reagents used in the examples and comparative examples of the present application are not specifically limited, and they can be directly purchased or synthesized by the present application.

[0065] It should be noted that the test method of the performance data of the dynamic covalent cross-linked material and the thermoplastic polymer composite provided in the examples and comparative examples of the present application is as follows:

[0066] Dumbbell-shaped samples were prepared on a hot press, and the mechanical properties of the prepared samples were tested using a universal material testing machine, i.e. the Young's modulus, yield strength and elongation at break of the prepared samples were obtained.

[0067] Preparation of a dynamic covalent cross-linked material based on a thermoplastic polymer

[0068] Example 1

[0069] The recycled ABS material, maleic anhydride and dicumyl peroxide were mixed uniformly at a mass ratio of 100:3:0.25, and then melt blended in an internal mixer at a temperature of 190°C and a speed of 60 rpm for 8 minutes. Then, ethylene glycol diglycidyl ether and zinc acetylacetonate were added to the internal mixer at a mass ratio of 10:0.5:100 with respect to the recycled ABS material, and the internal mixer was continued to blend at a temperature of 190°C and a speed of 60 rpm for 10 minutes, thereby preparing a dynamic covalent cross-linked material based on ABS recycled material.

[0070] Example 2

[0071] The polyethylene material, maleic anhydride, dicumyl peroxide and styrene were mixed uniformly at a mass ratio of 100:3:0.25, and then melt blended in an internal mixer at a temperature of 190°C and a speed of 60 rpm for 8 minutes. Then, ethylene glycol diglycidyl ether and zinc acetylacetonate were added to the internal mixer at a mass ratio of 10:0.5:100 with respect to the recycled ABS material, and the internal mixer was continued to blend at a temperature of 190°C and a speed of 60 rpm for 10 minutes, thereby preparing a dynamic covalent cross-linked material based on polyethylene material.

[0072] Example 3

[0073] The polypropylene material, maleic anhydride, dicumyl peroxide were mixed uniformly in a mass ratio of 100:3:0.25, and then melt blended in an internal mixer at a temperature of 190°C and a rotation speed of 60 rpm for 8 minutes. Then, the ethylene glycol diglycidyl ether and zinc acetylacetonate were added to the internal mixer in a mass ratio of 10:0.5:100 with respect to the recycled ABS material, and the internal mixer was continued to blend at a temperature of 190°C and a rotation speed of 60 rpm for 10 minutes, to obtain a dynamic covalent cross-linked material based on the polypropylene material.

[0074] Example 4

[0075] The recycled ABS material, maleic anhydride, dicumyl peroxide and styrene were mixed uniformly in a mass ratio of 100:3:0.25:3, and then melt blended in an internal mixer at a temperature of 190°C and a rotation speed of 60 rpm for 8 minutes. Then, the ethylene glycol diglycidyl ether and zinc acetylacetonate were added to the internal mixer in a mass ratio of 10:0.5:100 with respect to the recycled ABS material, and the internal mixer was continued to blend at a temperature of 190°C and a rotation speed of 60 rpm for 10 minutes, to obtain a dynamic covalent cross-linked material based on the ABS recycled material.

[0076] From Figure 2 It can be seen that the dynamic covalent cross-linked material based on the ABS recycled material (rABS-v) prepared in Example 4 has a rubber platform compared with the ABS recycled material (rABS), which shows that the prepared rABS-v forms cross-linking.

[0077] Example 5

[0078] The recycled ABS material, maleic anhydride, dicumyl peroxide and styrene were mixed uniformly in a mass ratio of 100:0.1:0.01:0.1, and then melt blended in an internal mixer at a temperature of 190°C and a rotation speed of 60 rpm for 8 minutes. Then, the ethylene glycol diglycidyl ether and zinc acetylacetonate were added to the internal mixer in a mass ratio of 0.8:0.02:100 with respect to the recycled ABS material, and the internal mixer was continued to blend at a temperature of 190°C and a rotation speed of 60 rpm for 10 minutes, to obtain a dynamic covalent cross-linked material based on the ABS recycled material.

[0079] Example 6

[0080] The recycled ABS material, maleic anhydride, dicumyl peroxide and styrene were mixed uniformly in a mass ratio of 100:15:1.5:15, and then melt blended in an internal mixer at a temperature of 190°C and a rotation speed of 60 rpm for 8 minutes. Then, the ethylene glycol diglycidyl ether and zinc acetylacetonate were added to the internal mixer in a mass ratio of 120:3:100 with respect to the recycled ABS material, and the internal mixer was continued to blend at a temperature of 190°C and a rotation speed of 60 rpm for 10 minutes, to obtain a dynamic covalent cross-linked material based on the ABS recycled material.

[0081] Example 7

[0082] The polyethylene material, maleic anhydride, dicumyl peroxide and styrene were mixed uniformly in a mass ratio of 100:3:0.25:3, and then melt blended in an internal mixer at a temperature of 190 °C and a rotation speed of 60 rpm for 8 minutes. Then, the ethylene glycol diglycidyl ether and zinc acetylacetonate were added into the internal mixer in a mass ratio of 10:0.5:100 with the recycled ABS material, and the mixture was further blended in the internal mixer at a temperature of 190 °C and a rotation speed of 60 rpm for 10 minutes, to obtain a dynamic covalent crosslinked material based on the polyethylene material.

[0083] Example 8

[0084] The polypropylene material, maleic anhydride, dicumyl peroxide and styrene were mixed uniformly in a mass ratio of 100:3:0.25:3, and then melt blended in an internal mixer at a temperature of 190 °C and a rotation speed of 60 rpm for 8 minutes. Then, the ethylene glycol diglycidyl ether and zinc acetylacetonate were added into the internal mixer in a mass ratio of 10:0.5:100 with the recycled ABS material, and the mixture was further blended in the internal mixer at a temperature of 190 °C and a rotation speed of 60 rpm for 10 minutes, to obtain a dynamic covalent crosslinked material based on the polypropylene material.

[0085] From Figure 3 It can be seen that the dynamic covalent crosslinked material based on the polypropylene material (PP-v) prepared in Example 8 has a rubber platform compared with the polypropylene material (PP), which shows that the prepared PP-v forms crosslinking.

[0086] Comparative Example 1

[0087] The same as Example 4, except that the mass ratio of the recycled ABS material, maleic anhydride, dicumyl peroxide and styrene was 100:3:0.005:3.

[0088] Comparative Example 2

[0089] The same as Example 4, except that the mass ratio of the recycled ABS material, maleic anhydride, dicumyl peroxide and styrene was 100:3:6:3.

[0090] Comparative Example 3

[0091] The same as Example 4, except that the mass ratio of the recycled ABS material, maleic anhydride, dicumyl peroxide and styrene was 100:3:0.25:30.

[0092] Comparative Example 4

[0093] The same as example 4, the only difference is that the mass ratio of recycled ABS material, maleic anhydride, dicumyl peroxide and styrene is 100:3:0:0.

[0094] Comparative example 5

[0095] The same as example 4, the only difference is that the mass ratio of recycled ABS material, maleic anhydride, dicumyl peroxide and styrene is 100:3:0:0.

[0096] Comparative example 6

[0097] The recycled ABS material is melt blended in an internal mixer at a temperature of 190℃ and a rotating speed of 60rpm for 18 minutes.

[0098] Table 1. Performance data of the dynamic covalent cross-linked material provided by the inventive examples and comparative examples

[0099] Young's modulus (MPa) Yield strength (MPa) Elongation at break (%) Example 1 1000.4±9.3 42.1±0.9 11.1±0.6 Example 2 734.8±7.1 25.2±0.7 732.8±9.9 Example 3 942.9±5.3 39.9±0.8 14.6±2.5 Example 4 1010.2±9.4 43.9±0.9 13.1±0.5 Example 5 941.9±9.3 37.1±0.8 10.0±0.6 Example 6 991.6±5.6 41.1±0.8 9.8±2.5 Example 7 751.8±7.2 26.6±0.9 767.8±9.8 Example 8 957.9±6.2 40.9±0.7 15.6±2.4 Comparative Example 1 890.3±9.2 31.2±1.2 6.5±2.5 Comparative Example 2 850.5±6.4 28.8±1.1 5.6±0.8 Comparative Example 3 783.6±8.2 27.1±0.5 7.2±1.2 Comparative Example 4 854.6±9.6 26.4±0.5 5.2±1.5 Comparative Example 5 803.6±8.0 29.1±0.6 8.2±0.8 Comparative Example 6 910.3±8.2 34.2±2.5 8.8±1.0

[0100] As can be seen from Table 1, compared with example 4, the amount of initiator in comparative example 1 is too small, which causes the grafting amount of maleic anhydride to decrease, so that the Young's modulus, yield strength and elongation at break of the finally obtained material all decrease; the amount of initiator in comparative example 2 is too much, which will cause the degradation of thermoplastic polymer, so that the Young's modulus, yield strength and elongation at break of the finally obtained dynamic covalent cross-linked material all decrease. The amount of auxiliary agent in comparative example 3 is too much, which will increase the small molecules in the system of the dynamic covalent cross-linked material, resulting in the decrease of the Young's modulus, yield strength and elongation at break of the dynamic covalent cross-linked material. Comparative example 4 does not add initiator and auxiliary agent, so the grafting amount of maleic anhydride is small, which causes the Young's modulus, yield strength and elongation at break of the finally obtained material all decrease. Comparative example 5 uses too much cross-linking agent, so the cross-linking density is too high, which makes the material brittle, so that the Young's modulus, yield strength and elongation at break of the finally obtained material all decrease.

[0101] Compared with comparative example 6 (pure ABS recycled material), the Young's modulus, yield strength and elongation at break of the dynamic covalent cross-linked material based on ABS recycled material in inventive example 1 and examples 4-6 are all significantly improved, wherein the Young's modulus of example 4 is improved by 11%, the yield strength is improved by 28%, and the elongation at break is improved by 49%.

[0102] Application of the dynamic covalent cross-linked material based on thermoplastic polymer

[0103] Example 9

[0104] The dynamic covalent cross-linked material based on ABS recyclate prepared in Example 4 was blended with ABS at a ratio of 5:95 in an internal mixer at a temperature of 190°C and a rotating speed of 60 rpm for 10 minutes to obtain a thermoplastic polymer composite material (ABS / recyclate ABS dynamic cross-linked composite material).

[0105] Example 10

[0106] The dynamic covalent cross-linked material based on ABS recyclate prepared in Example 4 was blended with ABS at a ratio of 10:90 in an internal mixer at a temperature of 190°C and a rotating speed of 60 rpm for 10 minutes to obtain a thermoplastic polymer composite material (ABS / recyclate ABS dynamic cross-linked composite material).

[0107] Example 11

[0108] The dynamic covalent cross-linked material based on ABS recyclate prepared in Example 4 was blended with ABS at a ratio of 20:80 in an internal mixer at a temperature of 190°C and a rotating speed of 60 rpm for 10 minutes to obtain a thermoplastic polymer composite material (ABS / recyclate ABS dynamic cross-linked composite material).

[0109] Example 12

[0110] The dynamic covalent cross-linked material based on ABS recyclate prepared in Example 4 was blended with ABS at a ratio of 30:70 in an internal mixer at a temperature of 190°C and a rotating speed of 60 rpm for 10 minutes to obtain a thermoplastic polymer composite material (ABS / recyclate ABS dynamic cross-linked composite material).

[0111] From Figure 4 It can be seen that the elongation at break of the thermoplastic polymer composite material prepared by blending the dynamic covalent cross-linked material based on ABS recyclate with ABS is significantly improved compared with ABS.

[0112] Example 13

[0113] The dynamic covalent cross-linked material of polypropylene material prepared in Example 8 was blended with polypropylene at a ratio of 30:70 in an internal mixer at a temperature of 190°C and a rotating speed of 60 rpm for 10 minutes to obtain a thermoplastic polymer composite material (PP / PP material dynamic cross-linked composite material).

[0114] From Figure 5 It can be seen that the elongation at break of the thermoplastic polymer composite material prepared by blending the dynamic covalent cross-linked material based on ABS recyclate with ABS is significantly improved compared with ABS.

[0115] Comparative Example 7

[0116] ABS was added into the mixer at 190℃ and 60rpm for 10 minutes.

[0117] Table 2. Performance data of thermoplastic polymer composite provided by the inventive examples and comparative examples

[0118]

[0119] It should be noted that the mass ratio of the raw materials in Table 2 is the mass ratio of the thermoplastic polymer and the dynamic covalent cross-linked material based on the thermoplastic polymer. As can be seen from Table 2, compared with ABS (comparative example 7) and the dynamic covalent cross-linked material based on ABS recycled material (example 4), the dynamic covalent cross-linked composite prepared by using the dynamic covalent cross-linked material based on ABS recycled material (examples 9-12) has a significantly increased elongation at break, and the highest elongation at break can be 1.78 times that of ABS and 2.1 times that of the dynamic covalent cross-linked material based on ABS recycled material.

[0120] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can still be modified, or some technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for producing a dynamic covalent crosslinked material based on a thermoplastic high polymer, characterized by, The preparation method comprises the following steps: S1. A mixture comprising a thermoplastic polymer, an anhydride substance, and an initiator is subjected to first melt blending to obtain a melt blend; the mass ratio of the anhydride substance to the thermoplastic polymer is 0.1-15:100; the mass ratio of the initiator to the thermoplastic polymer is 0.01-1.5:100; the thermoplastic polymer is acrylonitrile-butadiene-styrene copolymer; the mixture further comprises an auxiliary agent, the auxiliary agent is styrene; the mass ratio of the auxiliary agent to the thermoplastic polymer is 0.1-15:100; the temperature of the first melt blending is 110-230 DEG C, and the time is 7-15 min; the anhydride substance is one or more of maleic anhydride, methyl isopropenyl anhydride, tetrahydrophthalic anhydride, dimethyl maleic anhydride, methyl acrylate anhydride, itaconic anhydride, acrylic anhydride, and methyl tetrahydrophthalic anhydride; S2. The melt blend, a crosslinking agent, and a catalyst are uniformly mixed to be subjected to second melt blending to obtain a thermoplastic polymer-based dynamic covalent crosslinked material; the crosslinking agent is a bisglycidyl ether type epoxide; the mass ratio of the crosslinking agent to the thermoplastic polymer is 0.5-120:100; the temperature of the second melt blending is 110-230 DEG C, and the time is 7-15 min.

2. The production method according to claim 1, characterized by, The mass ratio of the catalyst to the thermoplastic polymer is 0.02-5:

100.

3. The preparation method according to claim 1, characterized in that, The initiator is one or more of a peroxide initiator and an azo initiator.

4. The production method according to claim 3, characterized by, The peroxide initiator is one or more of dicumyl peroxide, dibenzoyl peroxide, di-tert-butyl peroxide, dilauryl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, lauryl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.

5. The preparation method according to claim 3, characterized in that, The azo initiator is azobis isobutyronitrile or azobis isohexylnitrile.

6. The method of claim 1, wherein, The bisglycidyl ether type epoxide is one or more of ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, and resorcinol diglycidyl ether; and / or The catalyst is one or more of zinc acetylacetonate, trisazo bicyclo decene, and triphenylphosphine.

7. A dynamic covalent cross-linked material based on thermoplastic high polymers, characterized in that The preparation method is prepared by any one of claims 1-6.

8. Use of a thermoplastic polymer-based dynamic covalent crosslinked material according to claim 7, characterized in that, The application is applied to the preparation of a thermoplastic polymer composite material; the preparation method of the thermoplastic polymer composite material comprises: a dynamic covalent crosslinked material is mixed with a thermoplastic polymer to be subjected to third melt blending to obtain a thermoplastic polymer composite material.

9. Use according to claim 8, characterized in that, The temperature of the third melt blending is 110-230 DEG C, and the time is 7-15 min; and / or The mass ratio of the dynamic covalent crosslinked material to the thermoplastic polymer is 5-70:30-95.

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