High-bio-based-content heat-resistant abs polymer modified material and preparation method thereof

Abstract

This invention relates to the field of polymer materials technology and discloses a high-bio-based heat-resistant ABS polymer modified material, which is prepared by emulsion polymerization of the following raw materials in parts by weight: 20-25 parts of bio-based acrylonitrile, 15-20 parts of petroleum-based butadiene, 40-50 parts of bio-based styrene, 5-10 parts of bio-based itaconic acid, and initiators, emulsifiers, and molecular weight regulators. This high-bio-based heat-resistant ABS polymer modified material and its preparation method have a total bio-based content of 50%-65%, and all bio-based monomers are derived from renewable glycerol, lignin, and biomass fermentation products. Its carbon footprint is reduced by more than 40% compared to traditional petrochemical-based ABS, meeting the standards for green and low-carbon materials.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a heat-resistant ABS polymer modified material with high bio-based content and its preparation method. Background Technology

[0002] As an acrylonitrile-butadiene-styrene terpolymer, ABS resin has become one of the most widely used general-purpose engineering plastics in the world due to its balanced rigidity, toughness, chemical corrosion resistance, easy processing and molding, and surface coating performance. It occupies a core application position in industries such as automobiles, electronics, home appliances, and light industry. The three monomers of traditional ABS resin are all derived from petroleum cracking products, which are completely dependent on non-renewable petrochemical resources. The production process has high energy consumption and large carbon emissions.

[0003] With the rapid development of bio-based polymer materials technology, bio-based ABS has become a core research direction to replace traditional petrochemical-based ABS. Currently, existing bio-based ABS technologies are mainly divided into two routes: one is the physical blending and filling route, which introduces bio-based components by directly adding natural bio-based fillers such as starch, bamboo powder, wood powder, and cellulose to ordinary ABS matrix. This method is simple and low-cost, but the bio-based fillers have extremely poor interfacial compatibility with the ABS matrix, which easily leads to phase separation and filler agglomeration, resulting in a significant decrease in the core mechanical and thermal properties of the material, such as impact strength, tensile strength, and heat resistance. Moreover, the bio-based content is limited by the filler addition ratio and is usually difficult to exceed 30%, which cannot meet the performance requirements of high-end application scenarios. The second route is the bio-based monomer polymerization route, which uses bio-based monomers to replace petrochemical monomers in copolymerization. However, existing technologies generally suffer from defects such as a single source of bio-based monomers, low substitution ratio, bio-based content of only 30%-40%, no significant improvement in heat resistance, and uncontrollable grafting structure. It is difficult to achieve synergistic optimization of high bio-based content, high heat resistance, and high mechanical strength at the same time. Summary of the Invention

[0004] (a) Technical problems to be solved To address the shortcomings of existing technologies, this invention provides a high-bio-based heat-resistant ABS polymer modified material and its preparation method, thus solving the aforementioned problems.

[0005] (II) Technical Solution To achieve the above objectives, the present invention provides the following technical solution: a high bio-based heat-resistant ABS polymer modified material, which, by weight, is made from the following raw materials through emulsion polymerization: 20-25 parts of bio-based acrylonitrile, 15-20 parts of petroleum-based butadiene, 40-50 parts of bio-based styrene, 5-10 parts of bio-based itaconic acid, as well as initiator, emulsifier, and molecular weight regulator; The bio-based acrylonitrile is obtained by converting glycerol, the bio-based styrene is obtained by depolymerizing lignin, and the bio-based itaconic acid is obtained by biomass fermentation.

[0006] Preferably, the total bio-based content of the material is ≥50%, and more preferably 50%-65%.

[0007] Preferably, the heat distortion temperature of the material is 95-105℃, which is 15-20℃ higher than that of ordinary petrochemical-based ABS.

[0008] Preferably, the notched impact strength of the material is 35-45 kJ / m. 2 Its tensile and flexural strengths are comparable to those of ordinary petrochemical-based ABS.

[0009] Preferably, the carbon footprint of the material is reduced by more than 40% compared to ordinary petrochemical-based ABS.

[0010] A method for preparing a heat-resistant ABS polymer modified material with high bio-based content, employing a semi-continuous emulsion polymerization method, specifically includes the following steps: (1) Pre-emulsification: Bio-based styrene, bio-based itaconic acid and a portion of emulsifier are mixed and pre-emulsified by stirring at a constant temperature to obtain a uniform and stable pre-emulsion. (2) Preparation of base material: Add deionized water and remaining emulsifier to the reactor, stir evenly and heat to the preset temperature to form a stable aqueous phase system; (3) Polymerization reaction: Initiator is added in batches, and bio-based acrylonitrile, petroleum-based butadiene and pre-emulsion are added in batches at the same time. Copolymerization reaction is carried out at a controlled temperature of 65-75℃. (4) Grafting control: Cool down the polymer in the later stage of polymerization and add molecular weight regulator to control the polymer grafting rate to 35%-45%; (5) Post-processing: The polymer product is subjected to coagulation, washing and drying in sequence to obtain the bio-based ABS graft copolymer product.

[0011] Preferably, the pre-emulsification temperature in step (1) is 25-35℃, the stirring speed is 300-500r / min, the pre-emulsification time is 30-60min, and the amount of emulsifier added is 60%-70% of the total amount.

[0012] Preferably, the initiator in step (3) is added in 2-3 batches with an interval of 20-30 minutes; Bio-based acrylonitrile, petroleum-based butadiene, and pre-emulsion are added in 3-5 batches, with an interval of 15-25 minutes between each batch.

[0013] Preferably, the polymerization reaction time in step (4) is 4-6 hours, and after the reaction, the temperature is lowered to 30-40°C, and after adding a molecular weight regulator, the mixture is stirred for 30-45 minutes.

[0014] Preferably, the washing in step (5) involves centrifugal washing with deionized water 3-5 times, and the drying is vacuum drying at a temperature of 70-80℃ for 8-12 hours.

[0015] (III) Beneficial Effects Compared with the prior art, the present invention provides a high-bio-based content heat-resistant ABS polymer modified material and its preparation method, which has the following beneficial effects: 1. This high bio-based heat-resistant ABS polymer modified material and its preparation method have a total bio-based content of 50%-65%, and all bio-based monomers are derived from renewable glycerol, lignin, and biomass fermentation products. The carbon footprint is reduced by more than 40% compared with traditional petrochemical-based ABS, which meets the standards for green and low-carbon materials.

[0016] 2. This high bio-based heat-resistant ABS polymer modified material and its preparation method: Bio-based itaconic acid copolymerization introduces polar side carboxyl groups, which enhances the hydrogen bonding force between molecular chains and restricts the movement of molecular chains. The material's heat distortion temperature (HDT) reaches 95-105℃, which is 15-20℃ higher than that of ordinary ABS, and can meet the requirements for use in high-temperature environments.

[0017] 3. This high-bio-based heat-resistant ABS polymer modified material and its preparation method, without the addition of inert fillers, achieves a perfect bond between the elastomer and the matrix through precise control of the grafting ratio, maintaining a notched impact strength of 35-45 kJ / m. 2 Its tensile strength, flexural strength and other properties are comparable to those of ordinary ABS, meeting the mechanical requirements of automotive interiors and electronic appliance housings.

[0018] 4. The high bio-based heat-resistant ABS polymer modified material and its preparation method are based on a semi-continuous emulsion polymerization process that is simple to operate, has adjustable parameters, produces products with uniform structure and high performance consistency, and can be directly scaled up on existing ABS emulsion polymerization production lines without the need for additional special equipment.

[0019] 5. This high bio-based heat-resistant ABS polymer modified material and its preparation method have the advantages of high bio-based content, high heat resistance and high toughness. It can fully replace traditional petrochemical-based ABS and expand to high-end application scenarios such as automotive engine peripheral parts, high-temperature housings of electronic appliances and heat-resistant accessories for smart homes. Detailed Implementation

[0020] 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.

[0021] A high-bio-based, heat-resistant modified ABS polymer material, by weight, is produced from the following raw materials via a semi-continuous emulsion polymerization reaction: Bio-based acrylonitrile: 20-25 parts, produced by catalytic dehydration and ammonia oxidation of renewable glycerol, replacing traditional petrochemical-based acrylonitrile, providing material rigidity and chemical resistance; Petroleum-based butadiene: 15-20 parts, as an elastomer component, providing the material with basic toughness and impact resistance; Bio-based styrene: 40-50 parts, produced from agricultural and forestry waste lignin through depolymerization and catalytic reforming, replacing traditional petrochemical-based styrene and ensuring material processing fluidity and strength; Bio-based itaconic acid: 5-10 parts, derived from renewable biomass fermentation, as a heat-resistant modified comonomer, introduces polar side carboxyl groups to enhance intermolecular chain forces and heat resistance; Initiators, emulsifiers, and molecular weight regulators: in appropriate amounts, used to regulate the polymerization reaction rate, emulsion stability, and polymer molecular weight distribution.

[0022] All bio-based components of this invention are derived from renewable biomass resources, without the addition of inert fillers such as starch and bamboo powder. The bio-based components are covalently bonded to the polymer chains through in-situ copolymerization, thus avoiding the performance degradation problem caused by blending and filling from the source.

[0023] A method for preparing a heat-resistant ABS polymer modified material with high bio-based content, employing a semi-continuous emulsion polymerization method, is described below: (1) Pre-emulsification treatment: Add the formulated amount of bio-based styrene, bio-based itaconic acid and 60%-70% of the total emulsifier to the pre-emulsification kettle, and pre-emulsify at a stirring speed of 300-500r / min for 30-60min under constant temperature of 25-35℃ until a uniform, stable, non-layered and particle-free pre-emulsified liquid is formed to ensure that the heat-resistant monomer and styrene monomer are fully dispersed and to improve the uniformity of subsequent copolymerization. (2) Preparation and heating of the base material: Add deionized water and the remaining 30%-40% emulsifier to the polymerization reactor, turn on the stirring and heat to 60-65℃ at a rate of 1-2℃ / min, keep the temperature for 10-15min, so that the emulsifier is completely dissolved and a stable aqueous reaction system is formed. (3) Polymerization initiation and stepwise feeding: Add the initiator to the reactor in 2-3 batches, with an interval of 20-30 minutes between each batch, to ensure that the initiator is evenly dispersed; Simultaneously, bio-based acrylonitrile, petroleum-based butadiene, and pre-emulsion are slowly added in 3-5 batches, with an interval of 15-25 minutes between each batch. The polymerization reaction temperature is strictly controlled to be stable at 65-75℃ to avoid uneven monomer copolymerization and excessively wide molecular weight distribution caused by temperature fluctuations. (4) Precise control of grafting rate: After the polymerization reaction lasts for 4-6 hours, the reaction system is cooled to 30-40℃, and the molecular weight regulator is slowly added. The mixture is stirred for 30-45 minutes to precisely control the polymer grafting rate to be stable at 35%-45%, ensuring the bonding strength between the elastomer phase and the continuous phase, and improving the toughness and heat resistance of the material. (5) Post-processing purification: After the polymerization reaction is complete, an electrolyte coagulant is added to the system to coagulate and demulsify, and crude ABS resin is obtained. The crude product is centrifuged and washed 3-5 times with deionized water to remove residual emulsifier, unreacted monomer and inorganic salt. Finally, the washed resin is placed in a vacuum drying oven and dried at a constant temperature of 70-80℃ for 8-12 hours to completely remove moisture, thus obtaining a heat-resistant ABS graft copolymer product with high bio-based content.

[0024] Example 1: A high bio-based heat-resistant ABS polymer modified material, by weight, comprises: 20 parts bio-based acrylonitrile, 15 parts petroleum-based butadiene, 40 parts bio-based styrene, 5 parts bio-based itaconic acid, and appropriate amounts of potassium persulfate initiator, sodium dodecylbenzene sulfonate emulsifier, and tert-dodecyl mercaptan molecular weight regulator. A method for preparing a heat-resistant ABS polymer modified material with high bio-based content: Pre-emulsification: Bio-based styrene, itaconic acid and 70% emulsifier were pre-emulsified at 30℃ and 400r / min for 40min to obtain a stable pre-emulsion. For the preparation of the base material, add deionized water and the remaining 30% emulsifier to the reactor, stir and heat to 62°C, and keep warm for 12 minutes. The polymerization reaction was carried out by adding the initiator in two batches with an interval of 25 min; the monomer and pre-emulsion were added in four batches with an interval of 20 min, and the polymerization was carried out at 70℃ for 5 h. Grafting control: Cool to 35℃, add molecular weight regulator, stir for 40 minutes, and control the grafting rate to 40%. Post-treatment involved electrolyte coagulation, washing with deionized water four times, and vacuum drying at 75°C for 10 hours to obtain the finished product.

[0025] Performance testing (according to GB / T standard): Bio-based content 52%, heat distortion temperature 98℃, notched impact strength 38kJ / m 2 The carbon footprint was reduced by 42%.

[0026] Example 2: A high bio-based heat-resistant ABS polymer modified material, by weight, comprises: 23 parts bio-based acrylonitrile, 18 parts petroleum-based butadiene, 45 parts bio-based styrene, 8 parts bio-based itaconic acid, and appropriate amounts of initiator, emulsifier, and molecular weight regulator. A method for preparing a heat-resistant ABS polymer modified material with high bio-based content: Pre-emulsification: Pre-emulsify at 30℃ and 450r / min for 50min; Heat the base material to 63℃ and keep it at that temperature for 10 minutes. The initiator was added in 3 batches, with an interval of 20 min; the monomer and pre-emulsion were added in 5 batches, with an interval of 18 min, and polymerization was carried out at 72℃ for 4.5 h. Cool to 38℃, add molecular weight regulator, and control the grafting rate to 42%; Wash five times with deionized water and dry at 78°C for 9 hours to obtain the finished product.

[0027] Performance testing: Bio-based content 58%, heat distortion temperature 102℃, notched impact strength 42kJ / m 2 The carbon footprint was reduced by 45%.

[0028] Example 3: A high bio-based heat-resistant ABS polymer modified material, by weight, comprises: 25 parts bio-based acrylonitrile, 20 parts petroleum-based butadiene, 50 parts bio-based styrene, 10 parts bio-based itaconic acid, and appropriate amounts of initiator, emulsifier, and molecular weight regulator.

[0029] A method for preparing a heat-resistant ABS polymer modified material with high bio-based content: Pre-emulsification: Pre-emulsify at 35℃ and 500r / min for 60min; Heat the base material to 65℃ and keep it at that temperature for 15 minutes. Add the initiator in 3 batches, 30 min apart; add the monomer and pre-emulsion in 5 batches, 25 min apart, and polymerize at 75℃ for 6 h. Cool to 40℃, add molecular weight regulator, and control the grafting rate to 45%; Wash five times with deionized water and dry at 80℃ for 12 hours to obtain the finished product.

[0030] Performance testing: Bio-based content 65%, heat distortion temperature 105℃, notched impact strength 45kJ / m 2 The carbon footprint was reduced by 48%.

[0031] Comparative Example 1 (Common Petrochemical-Based ABS) It is prepared by traditional petrochemical-based acrylonitrile, styrene, and butadiene emulsion polymerization, without the addition of bio-based monomers and itaconic acid.

[0032] Performance testing: Bio-based content 0%, heat distortion temperature 83℃, notched impact strength 32kJ / m 2 The carbon footprint has not decreased.

[0033] Comparative Example 2 (Blended Filler Bio-based ABS) It was prepared by adding 25% bamboo powder to a regular ABS matrix.

[0034] Performance testing: Bio-based content 25%, heat distortion temperature 78℃, notched impact strength 18kJ / m 2 The mechanical properties are significantly reduced.

[0035]

[0036] Comparative data shows that the bio-based ABS material prepared by this invention is far superior to traditional petrochemical-based ABS and blended-filled bio-based ABS in terms of bio-based content, heat resistance, and impact strength, achieving a perfect balance between environmental protection and high performance.

[0037] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A heat-resistant ABS polymer modified material with high bio-based content, characterized in that: Based on the following raw materials, the product is prepared by emulsion polymerization in parts by weight: 20-25 parts of bio-based acrylonitrile, 15-20 parts of petroleum-based butadiene, 40-50 parts of bio-based styrene, 5-10 parts of bio-based itaconic acid, as well as initiators, emulsifiers, and molecular weight regulators. The bio-based acrylonitrile is obtained by converting glycerol, the bio-based styrene is obtained by depolymerizing lignin, and the bio-based itaconic acid is obtained by biomass fermentation.

2. The high bio-based content heat-resistant ABS polymer modified material according to claim 1, characterized in that: The total bio-based content of the material is ≥50%, preferably 50%-65%.

3. The high bio-based content heat-resistant ABS polymer modified material according to claim 1, characterized in that: The heat distortion temperature of the material is 95-105℃, which is 15-20℃ higher than that of ordinary petrochemical-based ABS.

4. The high bio-based content heat-resistant ABS polymer modified material according to claim 1, characterized in that: The notched impact strength of the material is 35-45 kJ / m. 2 Its tensile and flexural strengths are comparable to those of ordinary petrochemical-based ABS.

5. The high bio-based content heat-resistant ABS polymer modified material according to claim 1, characterized in that: The carbon footprint of the material is reduced by more than 40% compared to ordinary petrochemical-based ABS.

6. A method for preparing a high-bio-based content heat-resistant ABS polymer modified material according to any one of claims 1-5, characterized in that: The semi-continuous emulsion polymerization method includes the following steps: (1) Pre-emulsification: Bio-based styrene, bio-based itaconic acid and a portion of emulsifier are mixed and pre-emulsified by stirring at a constant temperature to obtain a uniform and stable pre-emulsion. (2) Preparation of base material: Add deionized water and remaining emulsifier to the reactor, stir evenly and heat to the preset temperature to form a stable aqueous phase system; (3) Polymerization reaction: Initiator is added in batches, and bio-based acrylonitrile, petroleum-based butadiene and pre-emulsion are added in batches at the same time. Copolymerization reaction is carried out at a controlled temperature of 65-75℃. (4) Grafting control: Cool down the polymer in the later stage of polymerization and add molecular weight regulator to control the polymer grafting rate to 35%-45%; (5) Post-processing: The polymer product is subjected to coagulation, washing and drying in sequence to obtain the bio-based ABS graft copolymer product.

7. The method for preparing a high-bio-based heat-resistant ABS polymer modified material according to claim 6, characterized in that: The pre-emulsification temperature in step (1) is 25-35℃, the stirring speed is 300-500r / min, the pre-emulsification time is 30-60min, and the amount of emulsifier added is 60%-70% of the total amount.

8. The method for preparing a high-bio-based heat-resistant ABS polymer modified material according to claim 6, characterized in that: The initiator mentioned in step (3) is added in 2-3 batches with an interval of 20-30 minutes; Bio-based acrylonitrile, petroleum-based butadiene, and pre-emulsion are added in 3-5 batches, with an interval of 15-25 minutes between each batch.

9. The method for preparing a high-bio-based heat-resistant ABS polymer modified material according to claim 6, characterized in that: The polymerization reaction time in step (4) is 4-6 hours. After the reaction, the temperature is lowered to 30-40°C, and the molecular weight regulator is added and the mixture is stirred for 30-45 minutes.

10. The method for preparing a high-bio-based heat-resistant ABS polymer modified material according to claim 6, characterized in that: The washing process in step (5) involves centrifugation with deionized water 3-5 times, followed by vacuum drying at 70-80℃ for 8-12 hours.

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