A polymer material and a method for producing the same

Abstract

The application provides a polymer material and a preparation method thereof. The special molecular structure of the modified plant phenol can play multiple key roles in the polymer material. The rigid groups of POSS in the molecular chain and the dense crosslinking network can effectively disperse external stress, avoid material damage caused by stress concentration, and significantly improve the tensile strength and elongation at break of the material. The crosslinking network structure also has excellent thermal stability and is not prone to chain segment rupture or structure collapse in a long-term thermal oxygen aging environment, thereby maintaining the stability of the mechanical properties of the material and greatly reducing the performance attenuation amplitude. Meanwhile, the flexible ester bond in the modified plant phenol molecule can improve the compatibility of the modified plant phenol with the first polymer, reduce interface defects, further ensure the improvement of the comprehensive performance of the material, and effectively solve the defects of poor compatibility, insufficient mechanical properties, poor weather resistance and the like of traditional modified materials.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a polymer material and its preparation method. Background Technology

[0002] Polymer materials, with their numerous advantages such as lightweight, ease of processing, and controllable cost, have been widely used in many fields, including construction, automobiles, and electronics. As various industries continue to raise their requirements for materials, polymer materials that combine excellent mechanical properties with long-term weather resistance are gradually becoming a research focus. At the same time, the development of new materials based on renewable resources also aligns with the current green and environmentally friendly development concept.

[0003] In the study of performance optimization of polymer materials, researchers often use the method of modifying natural polymers by introducing specific active groups to promote grafting, cross-linking and other reactions with other components, thereby improving the overall performance of the materials. Related technical routes have become common research directions in this field.

[0004] However, existing modification technologies still have obvious limitations. Some technologies fail to fully improve the compatibility between the modified components and the polymer matrix due to unreasonable modification process design. As a result, the materials produced not only have mechanical strength and toughness that are difficult to meet the needs of practical applications, but also experience rapid performance degradation under long-term thermo-oxidative aging environment, making them unsuitable for the stringent requirements of many application scenarios.

[0005] In conclusion, a new technical solution is urgently needed to address the problems existing in the current technology. Summary of the Invention

[0006] Based on this, the present invention provides a polymer material and its preparation method. The special molecular structure of the modified plant phenol of the present invention can play multiple key roles in the polymer material. The POSS rigid groups and dense cross-linked network in its molecular chain can effectively disperse external stress, avoid material damage caused by stress concentration, and significantly improve the tensile strength and elongation at break of the material. This cross-linked network structure also has excellent thermal stability, and is not prone to chain segment breakage or structural collapse under long-term thermo-oxidative aging environment, maintaining the stability of the material's mechanical properties and greatly reducing the performance degradation. At the same time, the flexible ester bonds in the modified plant phenol molecule can improve its compatibility with the first polymer, reduce interface defects, further ensure the improvement of the material's comprehensive performance, and effectively solve the defects of traditional modified materials such as poor compatibility, insufficient mechanical properties, and poor weather resistance.

[0007] One object of the present invention is to provide a polymer material comprising a first polymer and a second polymer; in, The first polymer is a natural polymer or a synthetic polymer; The second polymer is a modified plant phenol; The modified plant phenol is obtained by reacting epoxidized plant phenol with POSS containing double bonds and then polymerizing it with acrylate.

[0008] Furthermore, the plant phenols of the present invention are a general term for a class of plant secondary metabolites containing one or more phenolic hydroxyl groups, with diverse structures, including simple phenols, phenolic acids, flavonoids, tannins, and lignin.

[0009] Furthermore, the amount of the first polymer used is 5-90 wt%.

[0010] Furthermore, the first polymer includes chemical plastics (including recycled plastics) and biodegradable plastics.

[0011] Furthermore, the amount of the second polymer used is 5-90 wt%.

[0012] Further, the first polymer is selected from one or more of polyisoprene, polyolefin, polyester, polyamide, polyvinyl chloride, polystyrene, synthetic rubber, polyurethane, epoxy resin, polyacrylic acid, polyacrylate or polyacrylate.

[0013] Furthermore, the polymer material also includes compatibilizers and additives.

[0014] Furthermore, the amount of the compatibilizer is 1-15 wt%.

[0015] Furthermore, the compatibilizer is a maleic anhydride-grafted ethylene-octene copolymer.

[0016] Furthermore, the additive is selected from one or more of coupling agents, antioxidants, impact modifiers, or lubricants.

[0017] Further, the amount of the coupling agent is 0.2-10 wt%; the amount of the antioxidant is 0.2-2 wt%; the amount of the impact modifier is 1-10 wt%; and the amount of the lubricant is 1-10 wt%.

[0018] Furthermore, the method for preparing the polymer material includes the following steps: S1. Polyamino POSS, triethylamine and acryloyl chloride are mixed and reacted under inert gas and low temperature conditions to obtain polyamino POSS containing double bonds; S2. Epoxidized plant phenols are mixed with POSS containing double bonds and heated to react, yielding an intermediate product. S3. The intermediate product and acrylate are blended together, an initiator is added, and the mixture is heated to react, thereby obtaining modified plant phenols. S4. Mix all components thoroughly to obtain a polymer material.

[0019] Further, in step S1, the mass ratio of the polyamino POSS, triethylamine and acryloyl chloride is 1:(0.1-0.5):(0.1-0.9); the low temperature condition is an ice bath.

[0020] Further, in step S2, the mass ratio of the epoxidized plant phenol to the double-bonded polyamino POSS is 1:(0.1-0.9).

[0021] Further, in step S3, the mass ratio of the intermediate product to the acrylate is 1:(1-3); the heating temperature is 70-90℃.

[0022] The present invention has the following beneficial effects: This invention provides a polymer material and its preparation method. First, a double bond is introduced into the polyamino POSS structure by reacting polyamino POSS with acryloyl chloride, while retaining some amino groups, thus providing a basis for subsequent polymerization reactions. Then, through the reaction of amino groups with epoxy groups, the double-bonded polyamino POSS is grafted with epoxidized phytosterols to form an intermediate product, which is then polymerized with acrylates to obtain the modified phytosterol.

[0023] The unique molecular structure of modified phytophenols plays multiple crucial roles in polymer materials. On one hand, the rigid POSS groups and dense cross-linked network within their molecular chains effectively disperse external stress, preventing material breakage caused by stress concentration, thereby significantly improving the tensile strength and elongation at break of the polymer material. On the other hand, this cross-linked network structure also possesses excellent thermal stability, resisting chain segment breakage or structural collapse under long-term thermo-oxidative aging conditions, maintaining stable mechanical properties and significantly reducing performance degradation. Simultaneously, the flexible ester bonds in the modified phytophenol molecules improve compatibility with the primary polymer, reducing interfacial defects between components and further ensuring improved overall material performance, effectively addressing the shortcomings of traditional modified materials such as poor compatibility, insufficient mechanical properties, and poor weather resistance. Detailed Implementation

[0024] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0025] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0026] It should be understood that, except in any operational instance or otherwise indicated, the amounts or all figures representing ingredients used, for example, in the specification and claims, should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximate values ​​varying according to the desired performance to be obtained according to the invention.

[0027] The following raw materials are used in the embodiments of the present invention: Polypropylene: Grade TV00555, purchased from Yingxin Laboratory.

[0028] Polyethylene terephthalate: Grade P697813, purchased from Maclean's Reagents.

[0029] Polybutylene terephthalate: grade P909269, purchased from Maclean's Reagents.

[0030] Polylactic acid: grade S25341, purchased from Shanghai Yuanye.

[0031] Polyvinyl chloride: purchased from Qianyan Chemical.

[0032] Polymethyl methacrylate: Grade 200336, purchased from Merck.

[0033] Compatibilizer: Maleic anhydride-grafted ethylene-octene copolymer, brand name W1L, purchased from Xiamen Keaisi.

[0034] Coupling agent: (3-aminopropyl)triethoxysilane, brand name A3648, purchased from Merck.

[0035] Antioxidant: Pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxycinnamate), brand name Irgnox1010, purchased from Merck.

[0036] Impact modifier: methyl methacrylate-butadiene-styrene copolymer, brand name MBS E-920, purchased from Arkema.

[0037] Lubricant: Zinc stearate, brand name BS-2818, purchased from Gaomi Xinwei.

[0038] Plant phenols: alkaline lignin, purchased from Hubei Shishun Biotechnology Co., Ltd.

[0039] OctaaminoPOSS: Octaammonium cage-like silsesquioxane, brand name Q-0247616, purchased from Xi'an Qiyue Biotechnology Co., Ltd.

[0040] The preparation method of epoxidized plant phenols includes the following steps: 250 g of epichlorohydrin and 50 g of basic lignin were thoroughly stirred and mixed. Then 0.5 g of tetrabutylammonium bromide was added, and the mixture was reacted at 100 °C for 4 h. The temperature was then lowered to 50 °C, and 11.5 g of sodium hydroxide was added. The mixture was reacted at 60 °C for 4 h. The reaction solution was washed with deionized water until neutral and then dried under vacuum to obtain epoxidized phytophenol.

[0041] Unless otherwise specified, the water used in the embodiments of this invention is deionized water.

[0042] Example 1 A polymer material comprising the following raw materials in parts by weight: 60 parts of polypropylene 19 parts of modified plant phenols 10 parts compatibilizer 5 parts of coupling agent 1 part antioxidant 3 parts impact modifier Two parts lubricant.

[0043] The method for preparing the polymer material includes the following steps: S1. Under ice bath conditions, 12 g of octaaminoPOSS and 3 g of triethylamine were dissolved in 300 mL of tetrahydrofuran to obtain solution 1. The solution was stirred and protected with nitrogen. 5 g of acryloyl chloride was dissolved in 200 mL of tetrahydrofuran to obtain solution 2. Solution 2 was added to solution 1, and the mixture was reacted under ice bath conditions for 12 h. The mixture was then filtered, rotary evaporated, and dried to obtain polyaminoPOSS containing double bonds. S2. Using an ethanol-water mixture (ethanol:water = 1:100, V / V) as a solvent, epoxidized plant phenol and POSS containing double bonds (mass ratio of epoxidized plant phenol to POSS containing double bonds is 1:0.5) were mixed, heated under reflux for 1.5 h, washed, filtered, and dried to obtain the intermediate product. S3. Using DMF as solvent, the intermediate product and methyl acrylate are blended (the mass ratio of intermediate product to methyl acrylate is 1:1), and the initiator azobisisobutyronitrile (1% of the mass of the reactants) is added. The mixture is reacted at 70°C for 8 h, and the solvent is removed to obtain the modified plant phenol. S4. Mix all components evenly according to the above mass proportions to obtain a polymer material.

[0044] Example 2 A polymer material comprising the following raw materials in parts by weight: 50 parts of polypropylene 32 parts of modified plant phenols 8 parts compatibilizer 4 parts of coupling agent 1 part antioxidant 3 parts impact modifier Two parts lubricant.

[0045] The preparation method of the polymer material is the same as in Example 1.

[0046] Example 3 A polymer material comprising the following raw materials in parts by weight: 70 parts of polypropylene 14 parts of modified plant phenols 7 parts compatibilizer 5 parts of coupling agent 1 part antioxidant 2 parts impact modifier 1 part lubricant.

[0047] The preparation method of the polymer material is the same as in Example 1.

[0048] Example 4 A polymer material comprising the following raw materials in parts by weight: 75 parts of polyethylene terephthalate 12 parts of modified plant phenols 5 parts compatibilizer 2 parts coupling agent 1 part antioxidant 2 parts impact modifier 3 parts lubricant.

[0049] The preparation method of the polymer material is the same as in Example 1.

[0050] Example 5 A polymer material comprising the following raw materials in parts by weight: 45 parts of polybutylene terephthalate 40 parts of modified plant phenols 8 parts compatibilizer 1 part coupling agent 2 portions of antioxidants 2 parts impact modifier Two parts lubricant.

[0051] The preparation method of the polymer material is the same as in Example 1.

[0052] Example 6 A polymer material comprising the following raw materials in parts by weight: 85 parts of polylactic acid 5 parts of modified plant phenols 5 parts compatibilizer 1 part coupling agent 1 part antioxidant 2 parts impact modifier 1 part lubricant.

[0053] The preparation method of the polymer material is the same as in Example 1.

[0054] Example 7 A polymer material comprising the following raw materials in parts by weight: 40 parts of polyvinyl chloride 40 parts of modified plant phenols 10 parts compatibilizer 3 parts coupling agent 1 part antioxidant 3 parts impact modifier 3 parts lubricant.

[0055] The preparation method of the polymer material is the same as in Example 1.

[0056] Example 8 A polymer material comprising the following raw materials in parts by weight: 60 parts of polymethyl methacrylate 15 parts of modified plant phenols 13 parts compatibilizer 5 parts of coupling agent 2 portions of antioxidants 3 parts impact modifier Two parts lubricant.

[0057] The preparation method of the polymer material is the same as in Example 1.

[0058] Comparative Example 1 A polymer material, the difference between this comparative example and Example 1 is that step S1 is omitted, and in step S2, the mass of the double-bonded polyamino POSS is replaced with polyamino POSS, while the other steps and amounts are the same as in Example 1.

[0059] Comparative Example 2 A polymer material, the difference between this comparative example and Example 1 is that in step S3, the methyl acrylate and other quantities are replaced with intermediate products, while the other steps and amounts are the same as in Example 1.

[0060] Test case The performance of Examples 1-3 and Comparative Examples 1-2 was tested.

[0061] Sample processing: The polymer materials from Examples 1-3 and Comparative Examples 1-2 were extruded and granulated using a twin-screw extruder. The temperatures of each zone were set as follows: die head temperature 165°C, zone 1 temperature 170°C, zone 2 temperature 175°C, zone 3 temperature 180°C, and zone 4 temperature 175°C. The particle length was 3.5 mm, and plastic granules were obtained. The plastic granules were then hot-pressed using a hot press at a temperature of 150°C for 6 minutes and a pressure of 4 MPa. They were then cold-pressed at room temperature for 6 minutes while maintaining the pressure, to obtain samples for performance testing.

[0062] Test method: Mechanical property testing: Refer to GB / T 1040.2-2006 and GB / T 1040.3-2006 to test the tensile strength and elongation at break of the samples.

[0063] Weather resistance test: Referring to GB / T 3512-2014, the prepared standard sample was placed in a DHG-9245A electric heating drying oven for a 30-day indoor thermo-oxidative aging test at a temperature of 100℃. Then, the tensile strength and elongation at break of the sample after 30 days of aging were tested using the above mechanical test method, and the tensile strength retention rate and elongation at break retention rate were calculated.

[0064] The calculation formula is as follows: ; .

[0065] The test results are shown in Table 1.

[0066] Table 1 Performance Test Results As can be seen from the above test results, the present invention has good mechanical properties and weather resistance.

[0067] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0068] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A polymer material, characterized in that, The polymer material includes a first polymer and a second polymer; in, The first polymer is a natural polymer or a synthetic polymer; The second polymer is a modified plant phenol; The modified plant phenol is obtained by reacting epoxidized plant phenol with POSS containing double bonds and then polymerizing it with acrylate.

2. The polymer material according to claim 1, characterized in that, The amount of the first polymer used is 5-90 wt.

3. The polymer material according to claim 1, characterized in that, The amount of the second polymer used is 5-90 wt%.

4. The polymer material according to claim 1, characterized in that, The first polymer is selected from one or more of polyisoprene, polyolefin, polyester, polyamide, polyvinyl chloride, polystyrene, synthetic rubber, polyurethane, epoxy resin, polyacrylic acid, polyacrylate, or polyacrylate.

5. The polymer material according to claim 1, characterized in that, The polymer material also includes compatibilizers and additives.

6. The polymer material according to claim 5, characterized in that, The compatibilizer is a maleic anhydride-grafted ethylene-octene copolymer; the additive is selected from one or more of coupling agents, antioxidants, impact modifiers, or lubricants.

7. A method for preparing the polymer material according to any one of claims 1-6, characterized in that, Includes the following steps: S1. Polyamino POSS, triethylamine and acryloyl chloride are mixed and reacted under inert gas and low temperature conditions to obtain polyamino POSS containing double bonds; S2. Epoxidized plant phenols are mixed with POSS containing double bonds and heated to react, yielding an intermediate product. S3. The intermediate product and acrylate are blended together, an initiator is added, and the mixture is heated to react, thereby obtaining modified plant phenols. S4. Mix all components thoroughly to obtain a polymer material.

8. The method for preparing the polymer material according to claim 7, characterized in that, In step S1, the mass ratio of the polyamino POSS, triethylamine, and acryloyl chloride is 1:(0.1-0.5):(0.1-0.9); the low-temperature condition is an ice bath.

9. The method for preparing the polymer material according to claim 7, characterized in that, In step S2, the mass ratio of the epoxidized plant phenol to the double-bonded polyamino POSS is 1:(0.1-0.9).

10. The method for preparing the polymer material according to claim 7, characterized in that, In step S3, the mass ratio of the intermediate product to acrylate is 1:(1-3); the heating temperature is 70-90℃.

Images