A dynamic crosslinking type POE / EVA copolymer compatibilizer and a preparation process thereof

Abstract

The application discloses a dynamic crosslinking type POE / EVA copolymer compatilizer and a preparation process thereof, and belongs to the technical field of plastics. The compatilizer comprises 30-40 parts of a copolymer of formula (I), 15-20 parts of a copolymer of formula (II) and 5-10 parts of a compound of formula (III) by weight. The copolymer of formula (I) and the copolymer of formula (II) are both covalently modified by a compound with a maleimide structure on an EVA or POE main chain, and the modified maleimide structure compound contains a polyether chain or a fatty chain, so that the compatibility of polar and non-polar copolymers can be enhanced. The compound of formula (III) is a crosslinking agent containing a double bond, and has a disulfide bond with a dynamic crosslinking effect.

Description

Technical Field

[0001] This invention relates to the field of plastics technology, specifically to a dynamic cross-linking POE / EVA copolymer compatibilizer and its preparation process. Background Technology

[0002] Copolymer compatibilizers are additives that promote compatibility between different polymers. In the blending or compounding of polymer materials, compatibility issues often arise due to differences in chemical structure, polarity, molecular weight, etc., leading to a decline in the performance of the blend. Copolymer compatibilizers, through their unique molecular structure, can act as a "bridge" between different polymers, improving their compatibility.

[0003] There are three main ways in which compatibilizers improve compatibility: 1) Promoting compatibility: Copolymer compatibilizers interact with two or more polymers through different segments of their molecules, such as hydrogen bonds and van der Waals forces, thereby forming an interfacial layer between different polymers. This interfacial layer can reduce the interfacial tension between different polymers, making them easier to mix and disperse. 2) Promoting dispersion: During the blending process, copolymer compatibilizers can adsorb onto the surface of dispersed phase particles, forming a protective film to prevent particle aggregation and precipitation. 3) Enhancing interfacial bonding: Copolymer compatibilizers can form chemical bonds or physical adsorption between different polymers, thereby enhancing the interfacial bonding between them. This enhanced interfacial bonding can improve the mechanical properties and thermal stability of the blend.

[0004] Existing technology CN118562061A discloses a preparation process for a compatibilizer for low-smoke halogen-free cable materials. First, high-density polyethylene is prepared. Then, using polyethylene as the main component, MAH as a grafting component, and BIBP as an initiator, the compatibilizer is obtained through melt extrusion using a twin-screw extruder. However, this method involves a complex high-density polyethylene preparation process, making it difficult to control product quality and resolve the compatibility issues between the two copolymers.

[0005] Existing technology CN113234498B discloses a plastic compatibilizer, which is prepared by polypropylene, norbornene adiene anhydride, and dicumyl peroxide using a twin-screw extruder. However, it is essentially similar to commercially available compatibilizers, as the compatibilizer's structure is still based on grafted adiene anhydride structures onto the main chain, and it does not provide good performance improvement.

[0006] It is evident that current technologies still lack high-performance compatibilizers. In industrial production, it is necessary to blend two or more copolymers to form new materials to obtain products with superior performance. However, different copolymers have different polarities, and the uniformity of mixing has a significant impact on product performance. Existing compatibilizers have many shortcomings, such as poor crosslinking performance and weak compatibility-promoting effects. Therefore, there is an urgent need to develop a novel copolymer compatibilizer that meets market demands. Summary of the Invention

[0007] To overcome the shortcomings of the existing technology, the present invention provides a dynamically cross-linked POE / EVA copolymer compatibilizer and its preparation process.

[0008] The technical solution for achieving the objective of this invention is as follows:

[0009] A dynamic crosslinking POE / EVA copolymer compatibilizer, by weight, comprises 30-40 parts of copolymer of formula (I), 15-20 parts of copolymer of formula (II), and 5-10 parts of compound of formula (III).

[0010] The copolymer structure of formula (I) is as follows:

[0011] The ratio of m to n is (10-30):(50-80), and z is less than m.

[0012] The structural formula of the copolymer of formula (II) is as follows:

[0013] The ratio of x to y is (10-30):(40-60), and p is less than x.

[0014] The structural formula of compound (Ⅲ) is as follows:

[0015]

[0016] The copolymer of formula (Ⅰ) is prepared by the following method:

[0017] S1:9-Octadecanol (C 18 OH) and 3-maleimide propionic acid (MPA) were dissolved in anhydrous dichloromethane, and N,N'-dicyclohexylcarbodiimide (DCC) as a dehydrating agent and 4-dimethylaminopyridine (DMAP) as an affinity catalyst were added. The mixture was stirred at room temperature for 5-10 hours under a nitrogen atmosphere. The precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure and purified by column chromatography to obtain octadecyl maleimide propionate (MPaC). 18 OH).

[0018] The molar ratio of 9-octadecyl alcohol, 3-maleimide propionic acid, N,N'-dicyclohexylcarbodiimide, and 4-dimethylaminopyridine is (1-1.2):1:(1-1.3):(0.1-0.5).

[0019] S2: Weigh out the vacuum-dried octadecyl maleimide propionate MPaC 18 OH and bis(tert-butylperoxide) cumene (BIBP) were added to a beaker, and an appropriate amount of acetone was added to dissolve them. The mixture was stirred until completely dissolved. Then, it was poured into a high-speed mixer containing ethylene-vinyl acetate copolymer (EVA) and stirred. Finally, the mixture was injected into a twin-screw extruder, granulated, and dried for later use to obtain copolymer (Ⅰ) EVA-g-MPaC. 18 OH.

[0020] The mass ratio of EVA, maleimide propionate octadecyl ester, and bis-tert-butyl peroxide is (80-100):(5-40):(0.1-2).

[0021] The preparation method of the copolymer of formula (II) is as follows:

[0022] Vacuum-dried N-maleimide-N-bis(diethylene glycol-amino) (MpaPEGNH2), bis(tert-butyl peroxide) cumene (BIBP), and ethylene-α-olefin random copolymer POE were stirred in a high-speed mixer. The mixture was then injected into a twin-screw extruder, granulated, and dried for later use to obtain copolymer (II) POE-g-MpaPEGNH2.

[0023] The mass ratio of POE, N-maleimide-N-bis(diethylene glycol-amino), and bis-tert-butyl peroxide is (80-100):(2-30):(0.1-2).

[0024] The preparation method of the compound of formula (III) is as follows:

[0025] Compound (III) is prepared by reacting compound 1 and compound 2 via a condensation reaction to form an amide bond. Compounds 1 and 2 have the following structures.

[0026]

[0027] On the other hand, the present invention provides the use of a dynamic crosslinking POE / EVA copolymer compatibilizer in the preparation of copolymer composite material additives, wherein the compatibilizer mass percentage in the copolymer composite material additive is 0.001-50% by weight.

[0028] The copolymer composite material is composed of at least two of the following: ASA resin, ABS resin, ethylene propylene rubber, styrene-butadiene rubber, nitrile rubber, SIS resin, ethylene / vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyoxyethylene, and polyolefin elastomer POE.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] This invention provides a dynamically crosslinked POE / EVA copolymer compatibilizer, comprising copolymer (I), copolymer (II), and compound (III). Copolymers (I) and (II) are covalently modified with maleimide compounds on the EVA or POE backbone. The amide structure (maleimide structure) enhances the mechanical stability of the copolymer material. Furthermore, both copolymers (I) and (II) are grafted with maleimide structures possessing long chains (aliphatic or polyether chains), improving the material's flexibility and tensile strength, resulting in better processing and performance. Simultaneously, compound (III) possesses a maleimide structure, enhancing the degree of crosslinking between the polymers to be mixed. The disulfide bonds in the molecule provide dynamic crosslinking, improving the reshaping ability and self-healing properties of the material formed by the mixed polymers.

[0031] The copolymer of formula (I) introduces non-polar branches, enhancing its bridging effect between polar and non-polar compounds. Similarly, after grafting polyether branches onto the copolymer of formula (II), it can also significantly improve its compatibility with polar and non-polar compounds. Experiments have shown that it has a better effect than similar commercially available products such as EVA-g-MAH and POE-g-MAH. Furthermore, the copolymers of formula (I) and formula (II) can promote each other through a certain dosage ratio, achieving a synergistic effect to improve the compatibility of copolymers with different polarities. Attached Figure Description

[0032] Figure 1 This is a flowchart of the synthesis process of copolymer (I).

[0033] Figure 2 This is a flowchart of the synthesis process of copolymer of formula (II).

[0034] Figure 3 This is a flowchart of the synthesis of compound (Ⅲ). Detailed Implementation

[0035] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0036] Unless otherwise specified, the experimental methods used in the embodiments are conventional methods, and the materials and reagents used are commercially available unless otherwise specified.

[0037] The raw materials used in the examples and comparative examples are described below:

[0038] Ethylene-vinyl acetate copolymer (EVA): purchased from Nantong Runfeng Petroleum Co., Ltd. (VA content 28%);

[0039] Ethylene-octene copolymer (POE): purchased from DuPont Dow Elastomers Ltd., octene mass fraction 17%;

[0040] Di-tert-butyl peroxide (BIBP): Purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd.;

[0041] N-maleimide-N-bis(diethylene glycol-amino): purchased from Jilin Zhongke Science & Technology Co., Ltd.;

[0042] 3-Maleimide propionic acid: purchased from Nanjing New Anjie Chemical Technology Co., Ltd.;

[0043] Maleimide-diethylene glycol-amine (compound 2): purchased from Hangzhou Jieheng Chemical Co., Ltd.

[0044] Mal-NH-ethyl-SS-propionicacid (compound 1): purchased from Zhengzhou Huiju Chemical Co., Ltd.

[0045] Unless otherwise specified, the raw materials used in the embodiments and comparative examples of this invention are all commercially available raw materials, and the raw materials used in each parallel experiment are the same.

[0046] The preparation method of copolymer (I) is as follows:

[0047] S1:9-Octadecanol (C 18 OH) and 3-maleimide propionic acid (MPA) were dissolved in anhydrous dichloromethane, and N,N'-dicyclohexylcarbodiimide (DCC) as a dehydrating agent and 4-dimethylaminopyridine (DMAP) as an affinity catalyst were added. The mixture was stirred at room temperature for 8 hours under a nitrogen atmosphere. The precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure and purified by column chromatography to obtain octadecyl maleimide propionate MpaC. 18 OH.

[0048] The molar ratio of 9-octadecyl alcohol, 3-maleimide propionic acid, N,N'-dicyclohexylcarbodiimide, and 4-dimethylaminopyridine is 1.1:1:1.1:0.3.

[0049] S2: Weigh out the vacuum-dried octadecyl maleimide propionate MPaC 18 OH and bis(tert-butylperoxy)-bis(trimeth ... 18 OH.

[0050] The mass ratio of EVA, maleimide propionate octadecyl ester, and bis-tert-butyl peroxide is 90:25:1.

[0051] The self-preparation method of copolymer (II) is as follows:

[0052] Vacuum-dried N-maleimide-N-bis(diethylene glycol-amino) (MpaPEGNH2), bis(tert-butyl peroxide) cumene (BIBP), and the random copolymer of ethylene and α-olefins POE were stirred in a high-speed mixer for 10 min. The mixture was then injected into a twin-screw extruder, where the extruder barrel temperatures were 170, 180, 190, 190, 190, 190, 190, and 180°C (die head temperature), the main extruder speed was 300 r / min, the feed speed was 30 r / min, and the vacuum level was 0.04-0.08 MPa. Granulation and drying were then performed to obtain copolymer (II) POE-g-MpaPEGNH2.

[0053] The mass ratio of POE, N-maleimide-N-bis(diethylene glycol-amino), and bis-tert-butyl peroxide is 90:16:1.

[0054] The preparation method of compound (III) is as follows:

[0055] Under a nitrogen atmosphere, compound 1 was dissolved in DMSO, DCC and NHS were added, and the mixture was stirred for 1 hour. Then, compound 2 was added and stirred for 2 hours. The mixture was purified to obtain compound (III). The molar ratio of compound 1, DCC, NHS and compound 2 was 1:1:1.2:1.

[0056] Example 1

[0057] A dynamic crosslinking POE / EVA copolymer compatibilizer, by weight, comprises 30 parts of copolymer of formula (I), 15 parts of copolymer of formula (II), and 5 parts of compound of formula (III).

[0058] Example 2

[0059] A dynamic crosslinking POE / EVA copolymer compatibilizer, by weight, comprises 35 parts of copolymer of formula (I), 18 parts of copolymer of formula (II), and 6 parts of compound of formula (III).

[0060] Example 3

[0061] A dynamic crosslinking POE / EVA copolymer compatibilizer, by weight, comprises 38 parts of copolymer of formula (I), 16 parts of copolymer of formula (II), and 6 parts of compound of formula (III).

[0062] Example 4

[0063] A dynamic crosslinking POE / EVA copolymer compatibilizer, by weight, comprises 40 parts of copolymer of formula (I), 20 parts of copolymer of formula (II), and 7 parts of compound of formula (III).

[0064] Comparative Example 1

[0065] A copolymer compatibilizer, by weight, comprises 45 parts of copolymer of formula (I) and 5 parts of compound of formula (III).

[0066] Comparative Example 2

[0067] A copolymer compatibilizer, by weight, comprises 45 parts of copolymer of formula (II) and 5 parts of compound of formula (III).

[0068] Comparative Example 3

[0069] A copolymer compatibilizer, by weight, comprises 30 parts of copolymer of type (I) and 15 parts of copolymer of type (II).

[0070] Comparative Example 4

[0071] A copolymer compatibilizer, by weight, contains 45 parts of EVA-g-MAH (EVA-g-MAH is a commercially available product).

[0072] Comparative Example 5

[0073] A copolymer compatibilizer, by weight, contains 45 parts of POE-g-MAH (POE-g-MAH is a commercially available product).

[0074] Comparative Example 6

[0075] A copolymer compatibilizer, by weight, contains 30 parts of EVA-g-MAH and 15 parts of POE-g-MAH (EVA-g-MAH (SK General Chemicals 18211) and POE-g-MAH (Dow GR21) are commercially available products).

[0076] Table 1. Composition and number of parts (by weight) of the Examples and Comparative Examples

[0077]

[0078]

[0079] The copolymers of formula (I), (II), and (III) were mixed in a high-speed mixer and stirred for 10 minutes. The mixture was then fed into a twin-screw extruder and melt-blended, extruded, and granulated at 180–220°C. The temperatures of each zone of the extruder barrel were 180, 180, 190, 190, 190, 190, 190, and 180°C (die head temperature). The main extruder speed was 300 r / min, the feed speed was 20 r / min, and the vacuum level in the vacuum section was 0.04–0.08 MPa. Granulation was then performed to obtain the compatibilizer.

[0080] Application Examples 1-9

[0081] 70 parts ASA, 30 parts POE, and 5 parts compatibilizer (using the compatibilizers prepared in Examples 1-4 and Comparative Examples 1-6 respectively) were vacuum dried for 5 hours. The dried ASA, POE, and compatibilizer were then added to a high-speed mixer. 0.1 parts BIBP were added, and the mixture was mixed at 800 rpm for 10 minutes, followed by a mixing time of 1600 rpm for 5 minutes. The resulting mixture was fed into a twin-screw extruder with the following barrel temperatures: 160, 170, 180, 180, 180, 180, 180 (die head temperature); main extruder speed: 300 rpm; feed speed: 30 rpm; vacuum level: 0.04-0.08 MPa. The extruded material was used for performance testing.

[0082] Application Example 11

[0083] The only difference between Application Example 11 and Application Examples 1-10 is that no compatibilizer is added.

[0084] Table 2. Dosage of each component in Application Examples 1-11 (parts by weight)

[0085]

[0086]

[0087] The elongation at break was tested according to GB / T 1040-2006, the tensile strength was tested according to GB / T1040-2006, the flexural strength was tested according to GB / T9341-2008, and the notched impact strength was tested according to GB / T1043.1-2008. The performance test results are shown in Table 3.

[0088] Table 3 Performance test results

[0089]

[0090]

[0091] According to the data in the table above, Application Examples 1-4 show superior mechanical properties compared to Application Examples 4-11. (1) Application Examples 1-10 use the compatibilizers described in Examples 1-4 and Comparative Examples 1-6, respectively. Comparing Application Examples 1-4 with Application Examples 5-6, it can be seen that the compatibilizers used in Examples 1-4, which combine copolymers of formula (I) and formula (II), can more significantly promote the compatibility and mixing of ASA and POE than compatibilizers composed of only formula (I) or formula (II). This results in Application Examples 1-4 significantly improving the relevant mechanical properties compared to Application Examples 5-6, indicating that the (I) copolymer and the (II) copolymer have a synergistic effect. (2) Compared to Application Example 7, Application Examples 1-4 do not contain compound (III) in the compatibilizer used in Application Example 7. Compound (III) has a dynamic crosslinking effect, which can enhance tensile strength and notched impact strength. (3) Compared with Application Examples 8, 9 and 10, Application Examples 5, 6 and 7 show that the compatibilizers composed of copolymers of formula (I) and formula (II) of the present invention have a stronger ability to promote ASA / POE compatibility than commercially available EVA-g-MAH, POE-g-MAH or a combination of the two.

[0092] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A dynamically crosslinked POE / EVA copolymer compatibilizer, characterized in that, By weight, it contains 30-40 parts of copolymer of formula (I), 15-20 parts of copolymer of formula (II), and 5-10 parts of compound of formula (III); The copolymer of formula (Ⅰ) has the following structural formula: The ratio of m to n is (10-30):(50-80), and z is less than m; The structural formula of the copolymer of formula (II) is as follows: The ratio of x to y is (10-30):(40-60), and p is less than x; The structural formula of compound (Ⅲ) is as follows:

2. The dynamically crosslinked POE / EVA copolymer compatibilizer as described in claim 1, characterized in that, The preparation method of the copolymer of formula (I) is as follows: S1: 9-Octadecanol and 3-maleimide propionate MPA were dissolved in anhydrous dichloromethane, and dehydrating agent N,N'-dicyclohexylcarbodiimide DCC and affinity reaction catalyst 4-dimethylaminopyridine DMAP were added; under nitrogen atmosphere, the mixture was stirred at room temperature for 5-10 h, and then filtered and purified to obtain octadecyl maleimide propionate. S2: Weigh out vacuum-dried octadecyl maleimide propionate and bis(tert-butyl)-peroxide (BIBP), add them to a beaker, pour in an appropriate amount of acetone to dissolve them, and stir until completely dissolved; then add them to a high-speed mixer containing ethylene-vinyl acetate copolymer (EVA) and stir; finally, inject the mixture into a twin-screw extruder, granulate, and dry for later use to obtain copolymer (Ⅰ) EVA-g-MPaC. 18 OH.

3. The dynamically crosslinked POE / EVA copolymer compatibilizer as described in claim 2, characterized in that, In step S1 of the preparation method of copolymer (I), the molar ratio of 9-octadecyl alcohol, 3-maleimide propionic acid, N,N'-dicyclohexylcarbodiimide and 4-dimethylaminopyridine is (1-1.2):1:(1-1.3):(0.1-0.5).

4. The dynamically crosslinked POE / EVA copolymer compatibilizer as described in claim 2, characterized in that, In step S2 of the preparation method of copolymer of formula (I), the mass ratio of EVA, octadecyl maleimide propionate and bis-tert-butyl peroxide is (80-100):(5-40):(0.1-2).

5. The dynamically crosslinked POE / EVA copolymer compatibilizer as described in claim 1, characterized in that, The preparation method of copolymer (II) is as follows: The vacuum-dried N-maleimide-N-bis(diethylene glycol-amino), bis(tert-butyl peroxide) bis(trimethylammonium ...

6. The dynamically crosslinked POE / EVA copolymer compatibilizer as described in claim 5, characterized in that, The mass ratio of POE, N-maleimide-N-bis(diethylene glycol-amino), and bis-tert-butyl peroxide is (80-100):(2-30):(0.1-2).

7. The dynamically crosslinked POE / EVA copolymer compatibilizer as described in claim 1, characterized in that, Compound (III) is prepared by condensation reaction of compound 1 and compound 2 to form an amide bond. Compounds 1 and 2 have the following structures:

8. The method for preparing the dynamically crosslinked POE / EVA copolymer compatibilizer according to any one of claims 1-7, characterized in that, Includes the following steps: After mixing the copolymer of formula (I), the copolymer of formula (II), and the compound of formula (III), the mixture is added to a twin-screw extruder and melt-blended extrusion granulation is carried out at 180-220°C.

9. The use of the dynamically crosslinked POE / EVA copolymer compatibilizer according to any one of claims 1-7 in the preparation of copolymer composite material additives, characterized in that, The compatibilizer content in copolymer composite additives ranges from 0.001% to 50% by weight.

10. The use as described in claim 9, characterized in that, The copolymer composite material is composed of at least two of the following: ASA resin, ABS resin, ethylene propylene rubber, styrene-butadiene rubber, nitrile rubber, SIS resin, ethylene / vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyoxyethylene, and polyolefin elastomer POE.

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