阅读说明：本技术 一种生物基材料phbv和聚酯改性抗菌消臭抗病毒母粒 (Biological-based material PHBV and polyester modified antibacterial, deodorizing and antiviral master batch ) 是由 周国敏 周缇娜 陈健 于 2021-07-28 设计创作，主要内容包括：本发明公开了一种生物基材料PHBV和聚酯改性抗菌消臭抗病毒母粒,包括按一定比例混合熔融的改性生物基颗粒和聚酯粒料,其中新型生物基由PHBV粒料经原位化学增熔扩链得到,具有更好的热稳定性,具体为将经真空干燥的PHBV粉料与适量的ADR扩链剂混合,再经双螺杆给料机充分共混并反应,挤出棒状固体样品,经切片得到相应颗粒。本发明针对PHB加工过程中的热降解问题,具体采用ADR 4468扩链剂参与进行扩链改性,其反应位阻作用可有效阻止六元环结构的形成,并加以双螺杆共混熔融挤出方法,改善PHBV加工过程中的热降解问题,提高PHBV的热稳定性,使得PHBV更加稳定、广泛地应用于生物基抗菌抗病毒纤维材料制备中,且能够起到更为持久长效的抗菌消臭抗病毒功能。(The invention discloses a bio-based material PHBV and polyester modified antibacterial, deodorizing and antiviral master batch, which comprises modified bio-based particles and polyester granules which are mixed and melted according to a certain proportion, wherein a novel bio-based material is obtained by carrying out in-situ chemical melting and chain extension on the PHBV granules, has better thermal stability, and specifically comprises the steps of mixing vacuum-dried PHBV powder with a proper amount of ADR chain extender, fully blending and reacting the mixture by a double-screw feeder, extruding a rod-shaped solid sample, and slicing the mixture to obtain corresponding particles. Aiming at the problem of thermal degradation in the PHB processing process, the invention specifically adopts ADR 4468 chain extender to participate in chain extension modification, the formation of a six-membered ring structure can be effectively prevented by the steric hindrance of the reaction, and a double-screw blending melt extrusion method is added to improve the problem of thermal degradation in the PHBV processing process and improve the thermal stability of the PHBV, so that the PHBV is more stable and widely applied to the preparation of bio-based antibacterial and antiviral fiber materials, and can play a role in more lasting and long-lasting antibacterial, deodorant and antiviral functions.)

1. A bio-based material PHBV and polyester modified antibacterial, deodorant and antiviral master batch is characterized in that: the modified PHBV granular material and the polyester granular material are mixed and melted according to the weight ratio of 1-10 percent and 90-99 percent, and the modified PHBV granular material and the polyester granular material have better processing thermal stability after being modified.

2. The bio-based material PHBV and polyester modified antibacterial, deodorant and antiviral master batch according to claim 1, characterized in that: the modified PHBV granules are obtained by carrying out in-situ chemical melting and chain extension on PHBV powder on a novel bio-base, and the preparation process of the modified PHBV granules is as follows: mixing vacuum-dried PHBV granules with a mass ratio of 1: 0.2% -1: 0.5% and an ADR chain extender in a solid form in a high-shear mixer for 20-40s, adopting cold mixing with 0.2% of acrylic acid plasticizer, and extruding and molding by a double-screw extruder at the temperature of 220-280 ℃.

3. The bio-based material PHBV and polyester modified antibacterial, deodorant and antiviral master batch according to claim 1, characterized in that: the modified polyester granules comprise 40-70 parts of PET, 15-45 parts of reinforcing agent, 0.3-2 parts of lubricant, 0.3-1 part of antioxidant and 0.2-0.5 part of ADR 4468 chain extender, and the modified polyester granules are obtained by uniformly mixing, melting, extruding and granulating the raw materials.

4. The bio-based material PHBV and polyester modified antibacterial, deodorant and antiviral master batch according to claim 3, characterized in that: the reinforcing agent is glass fiber subjected to surface treatment by using a silane coupling agent, the lubricant is any one of stearic acid amide, PE wax and oleamide, and the antioxidant is any one of P262, BHT, 1010 and 168.

5. The bio-based material PHBV and polyester modified antibacterial, deodorant and antiviral master batch according to claim 1, characterized in that: the preparation process of the modified antibacterial, deodorizing and antiviral master batch comprises the following steps: mixing and melting modified PHBV granules obtained by melting and chain extension with dried modified polyester granules, extruding the mixed and melted solution through a control screw extruder through a spray hole, cooling in water bath, and cutting into modified antibacterial, deodorizing and antiviral master batches with certain specifications through a granulator; and cutting the master batch into pieces by a granulator, and drying the master batch by a vacuum drum dryer.

6. The bio-based material PHBV and polyester modified antibacterial, deodorant and antiviral master batch according to claim 5, characterized in that: screw rotation speed of extruder: 100-: 20-40r/min, powder side feeding speed: 3-15r/min, side feeding speed: 5-40 r/min. The temperature of the extruder was 220 ℃ and 255 ℃.

Technical Field

The invention relates to the technical field of antibacterial and bacteriostatic materials, in particular to a bio-based material PHBV and polyester modified antibacterial, deodorizing and antiviral master batch.

Background

PHBV (polyhydroxybutyrate-hydroxyvalerate) copolymer, namely a novel biopolymer 3-hydroxybutyrate and 3-hydroxyvalerate copolymer, is thermoplastic aliphatic polyester synthesized by bacterial fermentation, mainly takes starch as a raw material, and is a biological material prepared by a fermentation engineering technology, so that the biological material has excellent biodegradability, biocompatibility, optical activity and other excellent characteristics, but the hydroxybutanoic acid valerate (PHBV) has poor thermal stability and serious degradation in a processing process, starts to degrade at a temperature higher than a melting point, and is difficult to apply to fabric production, the molecular mass of the PHBV is continuously reduced, the physical processing performance of the PHBV is reduced, and the market popularization and application progress of the PHBV is influenced.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a bio-based material PHBV and polyester modified antibacterial, deodorant and antiviral master batch, which solves the problems in the background technology.

(II) technical scheme

In order to achieve the purpose, the invention is realized by the following technical scheme: the biological base material PHBV and polyester modified antibiotic, deodorizing and antiviral mother grain has modified PHBV granule in 1-10 wt% and modified polyester granule in 90-99 wt% mixed and molten, and the modified PHBV granule and polyester granule have high processing heat stability.

Preferably, the modified PHBV granules are obtained by carrying out in-situ chemical melting and chain extension on PHBV powder based on a novel bio-base, and the preparation process of the modified PHBV granules is as follows: mixing vacuum-dried PHBV granules with a mass ratio of 1: 0.2% -1: 0.5% and an ADR chain extender in a solid form in a high-shear mixer for 20-40s, adopting cold mixing with 0.2% of acrylic acid plasticizer, and extruding and molding by a double-screw extruder at the temperature of 220-280 ℃.

Wherein the screw assembly prior to the vacuum vent is a dispersive mixing of ADR chain extender and PHBV pellets, without the desire to react and without local overheating due to shear heat; and the ADR chain extender and the PHBV granules are required to fully react between the natural exhaust port and the die of the machine head so as to achieve the chain extension effect.

In order to make the chain extension effect of the ADR chain extender uniform, it is suggested to add a screen at the die to increase the reflux.

Preferably, the preparation process of the antibacterial, deodorant and antiviral master batch is as follows: mixing and melting PHBV granules obtained by melting and chain extension with dried polyester chips, extruding the mixed and melted solution through a control screw extruder by a spray orifice, cooling in water bath, and cutting into modified antibacterial, deodorant and antiviral master batches with certain specifications by a granulator; and cutting into pieces by a granulator, and drying the antibacterial polyester master batches by a vacuum drum dryer.

Preferably, the modified polyester granules comprise 40-70 parts of PET, 15-45 parts of reinforcing agent, 0.3-2 parts of lubricant, 0.3-1 part of antioxidant and 0.2-0.5 part of ADR 4468 chain extender, and the modified polyester granules are obtained by uniformly mixing, melting, extruding and granulating the raw materials.

The reinforcing agent is glass fiber subjected to surface treatment by using a silane coupling agent, the lubricant is any one of stearic acid amide, PE wax and oleamide, and the antioxidant is any one of P262, BHT, 1010 and 168.

The preparation process of the modified antibacterial, deodorizing and antiviral master batch comprises the following steps: mixing and melting modified PHBV granules obtained by melting and chain extension with dried modified polyester granules, extruding the mixed and melted solution through a control screw extruder through a spray hole, cooling in water bath, and cutting into modified antibacterial, deodorizing and antiviral master batches with certain specifications through a granulator; and cutting the master batch into pieces by a granulator, and drying the master batch by a vacuum drum dryer.

Screw rotation speed of extruder: 100-: 20-40r/min, powder side feeding speed: 3-15r/min, side feeding speed: 5-40 r/min. The temperature of the extruder was 220 ℃ and 255 ℃.

The PHBV can be generated by A, eutrophus and other strains under the nitrogen environment (pH value is 7.O), is of an isotactic structure, and is chemically synthesized with a syndiotactic body. The PHBV melting temperature decreases with increasing HV content, reaching a minimum of 84 ℃ at 28% (r.p.1), and then increases again with increasing HV content. Therefore, in the process of preparing the PHBV, the content of HV is increased by adopting a mode of extending the PHBV chain, and further the thermal stability of the PHBV is improved.

Polyester (PET) belongs to a high molecular compound. Polyethylene terephthalate (PET) is produced by Polycondensation of Terephthalic Acid (PTA) and Ethylene Glycol (EG).

The principle shows that the PHBV is a heat-sensitive material, the PHBV starts to degrade at a temperature higher than the melting point, the molecular mass is continuously reduced along with the time, the melt torque is continuously reduced, the ester group part of a PHBV molecular chain is easy to form a six-membered ring structure at a high temperature, and then the chain is broken to obtain the macromonomer containing double bonds and carboxyl terminal groups. Therefore, the ADR 4468 chain extender used in the scheme participates in the chain extension reaction, and the steric hindrance effect of the reaction can effectively prevent the formation of a six-membered ring structure, so that the thermal stability of the PHBV is improved.

(III) advantageous effects

After adopting the technical scheme, compared with the prior art, the invention has the following advantages: aiming at the thermal degradation of PHB in the processing process, the biological base material PHBV and polyester modified antibacterial, deodorant and antiviral master batch provided by the invention adopts a reactive processing technology to carry out in-situ chemical chain extension on the PHB so as to improve the molecular weight of the product, further improve the thermal degradation problem in the PHBV processing process, increase the thermal stability of the product, improve the processing performance of the product, ensure that the PHBV is more stably and widely applied to the preparation of a biological base antibacterial and antiviral fiber material, and can play a role in more lasting and long-acting antibacterial, deodorant and antiviral functions.

Detailed Description

The present invention is further illustrated by the following examples.

The biological base material PHBV and polyester modified antibiotic, deodorizing and antiviral mother grain has modified PHBV granule in 1-10 wt% and modified polyester granule in 90-99 wt% mixed and molten, and the modified PHBV granule and polyester granule have high processing heat stability.

The method comprises the steps of modifying PHBV granules to obtain novel bio-based particles, specifically, carrying out in-situ chemical melting and chain extension on the PHBV granules to obtain the novel bio-based particles with better thermal stability, specifically, mixing PHBV powder subjected to vacuum drying for 24 hours with a proper amount of ADR 4468 chain extender, fully blending and reacting the mixture by a double-screw feeder, extruding a rod-shaped solid sample, and slicing to obtain corresponding particles.

The melt torque reaches the highest point when the two are melted and mixed for about 20-40s, and the high-temperature-resistant high-strength high-toughness high-strength high-toughness high. Then, the molecular mass is continuously reduced and the melt torque is continuously reduced along with the time.

The adding amount of the ADR chain extender is 0.2-1.5% of the mass of the PHBV granules participating in the reaction.

Adopting a screw length-diameter ratio L/D of 37, L/D of 48: 1, to ensure that the best chain extension effect is obtained at lower temperature and higher output (higher screw rotation speed).

The PHBV material particles modified by the melt-increasing chain extension can improve the problem of easy thermal degradation in the processing process, thereby increasing the thermal stability of the PHBV material particles and further playing a role in more lasting and long-lasting antibacterial and antiviral functions.

Nine active epoxy groups on each ADR 4468 molecule react with the polymer chemically, chain-broken molecular chains are re-linked in the processes of synthesis, processing and recovery, the molecular weight and viscosity of the polymer are recovered or improved, the head pressure is increased, the extrusion stability is improved, the melt strength and the molecular weight of the polymer are improved, the degradation of the polymer in the processing process is improved, and the processing performance is improved.

The ADR chain extender is Bassfur ADR 4468. It is noted that the solid basf ADR 4468 is fed into the first zone of the extruder or injection molding machine, suggesting operation at a temperature 20 ℃ to 40 ℃ lower than normal to prevent premature melting and caking of the additives. Basf ADR 4468 reacts rapidly, it can stay at 200 ℃ for at least 120 seconds, and the reaction will be more than 99% complete. Alternatively, a 30 second dwell at 280 ℃ will achieve 99% completion.

Mixing and melting modified PHBV granules obtained by melting and chain extension with dried modified polyester granules, extruding the mixed and melted solution through a control screw extruder through a spray hole, cooling in water bath, and cutting into modified antibacterial, deodorizing and antiviral master batches with certain specifications through a granulator; and cutting the master batch into pieces by a granulator, and drying the master batch by a vacuum drum dryer. The use parameters of the extruder, the screw rotation speed of 200r/min, the main feeding rotation speed: 30r/min, powder side feeding speed: 7r/min, side feeding speed: 30 r/min. The temperature of the extruder was 230 ℃.

The PHBV modified granules subjected to melting and chain extension are not easy to degrade in the processing process, have more stable hot processing performance, and the prepared antibacterial, deodorant and antiviral master batch can be widely applied to preparation of bio-based antibacterial and antiviral fiber materials, can play a more lasting and long-acting antibacterial, deodorant and antiviral function,

In light of the foregoing, it will be apparent to those skilled in the art from this disclosure that various changes and modifications can be made without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and the protection scope must be determined by the scope of the claims.