阅读说明：本技术 一种低蛋白吸附防污防水塑料颗粒的制备方法 (Preparation method of low-protein adsorption antifouling waterproof plastic particles ) 是由 蒋娜 于 2020-06-24 设计创作，主要内容包括：本发明公开了一种低蛋白吸附防污防水塑料颗粒的制备方法,本发明属于高分子材料技术领域,本发明通过共混改性和低蛋白吸附处理,使制备的塑料颗粒具有较低的低蛋白吸附性能,本发明所生产出来的塑料颗粒既具备原先的机械性能,同时表面还有良好的防水和防油的特性,具有很好的防油污、耐脏污功能,被油污、酸性碱性食物等沾污后,仅需抹布擦拭或清水冲洗,即可很轻易地清洁,无需洗涤剂,从而保持环境清洁,减少清洁成本,而且,有很强的市场竞争力。(The invention discloses a preparation method of low-protein adsorption antifouling waterproof plastic particles, which belongs to the technical field of high polymer materials, and the prepared plastic particles have lower low-protein adsorption performance through blending modification and low-protein adsorption treatment.)

1. A preparation method of low-protein adsorption antifouling waterproof plastic particles is characterized by comprising the following steps:

weighing 20-24 parts of polytetramethylene ether glycol, adding into a reaction kettle, carrying out vacuum dehydration for 2 hours at 110 ℃, cooling to 60 ℃, adding 8-12 parts of diethylbenzene isocyanate, adding 130-140 parts of dimethylacetamide, introducing nitrogen for protection, mechanically stirring, reacting for 30 minutes at 60 ℃, cooling the reaction mixture to 30 ℃, adding 4.5-5 parts of benzopinacol, uniformly stirring, adding 0.001-0.01 part of di-n-butyltin oxide, stirring and reacting for 12-24 hours at 30 ℃, adding 5.0-6.5 parts of methanol to continuously react for 15 minutes before the reaction is finished, precipitating and demulsifying for 1-3 minutes, precipitating the reaction product in water for 2 times, and carrying out suction filtration to obtain a macroinitiator; (2) weighing 40-45 parts of polytetramethylene ether glycol subjected to azeotropic distillation by anhydrous toluene, weighing 13-15 parts of triethanolamine and 150-160 parts of dichloromethane, adding into another reaction kettle, slowly dripping 15.4-17 parts of methacryloyl chloride into the reaction kettle in an ice water bath through a dropping funnel, removing the ice water bath after dripping is finished, reacting at room temperature for 24 hours, carrying out suction filtration on a reaction product, and precipitating in cold diethyl ether to obtain a prepolymer; (3) preparing a 5 mass percent potassium persulfate solution, adding deionized water and 0.1-0.4 part of sodium dioctyl sulfosuccinate as an emulsifier into a reaction kettle, fully stirring, gradually adding 6.0-8 parts of polyvinyl alcohol 1788, stirring for 10min, heating, raising the temperature, keeping the temperature at 80-90 ℃ for 1-2 h until the polyvinyl alcohol is completely dissolved, adding 10-20 parts of vinyl acetate and 4-5 parts of the macromolecular initiator obtained in the step (1) into the reaction kettle, stirring until the mixture is fully emulsified, heating in a water bath, keeping the temperature at 65-75 ℃, keeping the reaction temperature until the reflux basically disappears, controlling the reaction temperature at 70-80 ℃, slowly adding the prepolymer obtained in the step (2) by using a dropping funnel within 2h without stopping stirring, dropping 1 part of a 5 mass percent potassium persulfate solution and 10-15 parts of vinyl acetate, then slowly heating to 90 ℃ until no reflux exists, cooling the reaction system to 50 ℃, adding 3-6 parts of 5% sodium bicarbonate water solution, adjusting the pH to 7-8, then slowly adding 10-15 parts of dioctyl sebacate and 15-16 parts of vinyl chloride-vinyl acetate copolymer emulsion, stirring and cooling for 1h to obtain pre-plasticizing emulsion; (4) adjusting the pH value of the pre-plastic emulsion to 7-7.5 by using edible alkali, filtering to obtain polymer emulsion, and drying for 24-48 h at 70-80 ℃ to obtain resin powder; (5) weighing and mixing the resin powder obtained in the step (4) and the plant alkali according to the weight ratio of 10-12: 1, pouring the mixed material into a feed inlet of a double-screw extruder, and setting the extrusion temperature at 100-120 ℃ and the screw rotation speed at 30-35 Hz; the extruded materials are subjected to tabletting and coarse crushing, then are subjected to fine crushing and grinding by a high-speed crusher, and are sieved by a screen with 180-240 meshes according to requirements to obtain preplasticized powder; (6) and (3) granulating, namely mixing the preplasticized powder obtained in the step (5) with water to prepare suspension, setting the air inlet temperature of a boiling dryer to be 100-110 ℃ and the air outlet temperature to be 80-90 ℃ for warm boiling granulation, uniformly mixing the suspension in a high-speed mixer, atomizing the dispersing agent by using a peristaltic pump, spraying the atomized dispersing agent into the boiling dryer to obtain uniform waxy solid particles, spraying the uniformly mixed suspension into the boiling dryer by using the peristaltic pump at the rotating speed of 15-25 rpm to form plastic particles, and drying at the temperature of 100-110 ℃ for 24-30 hours to obtain the plastic particles.

2. The preparation method of the low-protein adsorption antifouling waterproof plastic particles as claimed in claim 1, wherein the vinyl acetate-vinyl acetate emulsion is 50% -53% in solid content and 10% -13% in vinyl acetate content with viscosity of 500-3000 mpa.s at 25 ℃.

3. The method for preparing low-protein adsorption antifouling waterproof plastic particles as claimed in claim 1, wherein the dispersant in step (6) is one of insect wax, morpholine fatty acid salt and ethylene bis-stearoyl.

4. The method for preparing low-protein adsorption antifouling waterproof plastic granules as claimed in claim 1, wherein the plant alkaloid in step (5) is radix Sophorae Flavescentis extract, and the extraction method comprises adding 2000 parts of water into 500 parts of dried radix Sophorae Flavescentis, soaking for 1-2 hours, sterilizing at 100 deg.C for 60 minutes under hot pressure, filtering to remove residues, concentrating the filtrate to 500 parts, adding 1000 parts of 95% ethanol to dilute and precipitate for 2 hours, filtering, and drying for 5 hours.

5. The preparation method of the low-protein adsorption antifouling waterproof plastic particles as claimed in claim 1, wherein in the step (6), the rotation speed of the peristaltic pump is 110-130 rpm, the mass ratio of the preplasticized powder to water is 1: 3-1: 2, the mass ratio of the dispersing agent to the preplasticized powder is 1: 11-12, the air inlet temperature of the boiling dryer is set to be 50-70 ℃, and the air outlet temperature is set to be 40-50 ℃.

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of low-protein adsorption antifouling waterproof plastic particles.

Background

The traditional antifouling plastic kills marine organisms by utilizing toxic materials such as copper, tin, mercury, lead and the like released from the material. The first use is of highly toxic materials containing mercury, lead, etc. In the 70 s, people found that organotin can achieve broad-spectrum and high-efficiency antifouling effect under low concentration, so that organotin compounds quickly replace antifouling agents with high toxicity such as mercury, arsenic and the like, however, later, people found that tin can be accumulated in fish, shellfish and marine plants to cause genetic variation and enter a food chain to cause an immeasurable ecological problem. Such materials rely on the release of anti-fouling agents to inhibit the formation and growth of fouling and microbial fouling. However, its static antifouling ability is weak. In addition, since the polymer main chain cannot be degraded, they exist in the environment for a long time, causing environmental pollution problems. The low-surface-energy additive still has the toxicity problem, does not contain a biocide and is outstanding in environmental friendliness, but the performance of the low-surface-energy additive is influenced by factors such as the surface energy, the thickness, the elastic modulus and the surface finish of a coating. Although the materials are applied at present, the application range of the materials is limited to some special occasions. Particularly, the antifouling paint needs to be added with a heavy metal antifouling agent such as cuprous oxide, and although the antifouling paint is allowed to be used at present, the long-term use of the antifouling paint has great influence on marine ecology. Especially in the field of high-end laboratory consumable application, the pursuit of high efficiency and high-precision test results are the goals pursued by each user, and particularly, the loss rate of a protein sample is up to 50 percent without using special materials or specially treated plastic consumables. And the adsorption of the nutrient sources of the microorganisms such as protein and the like causes that the plastic is not resistant to pollution, even in medical instrument high-molecular plastic, aiming at the application requirement, the low-protein adsorption plastic resin is applied to the production of storage containers and laboratory consumables for proteomics and protein research, provides an innovative solution for high-end laboratory biochemical consumable manufacturers, and provides guarantee for researchers to obtain more accurate experimental data. Experimental data show that the adsorptivity of the low-protein adsorption plastic resin to bovine serum albumin is far lower than that of common plastic and even better than that of glass. The technical personnel in the field need to develop a novel preparation method of antifouling and waterproof plastic particles to meet higher performance requirements and use requirements.

Disclosure of Invention

The invention aims to provide a preparation method of low-protein adsorption antifouling waterproof plastic particles aiming at the existing problems.

A preparation method of low-protein adsorption antifouling waterproof plastic particles comprises the following steps:

(1) weighing 20-24 parts of polytetramethylene ether glycol, adding into a reaction kettle, carrying out vacuum dehydration for 2 hours at 110 ℃, cooling to 60 ℃, adding 8-12 parts of diethylbenzene isocyanate, adding 130-140 parts of dimethylacetamide, introducing nitrogen for protection, mechanically stirring, reacting for 30 minutes at 60 ℃, cooling the reaction mixture to 30 ℃, adding 4.5-5 parts of benzopinacol, uniformly stirring, adding 0.001-0.01 part of di-n-butyltin oxide, stirring and reacting for 12-24 hours at 30 ℃, adding 5.0-6.5 parts of methanol to continuously react for 15 minutes before the reaction is finished, precipitating and demulsifying for 1-3 minutes, precipitating the reaction product in water for 2 times, and carrying out suction filtration to obtain a macroinitiator; (2) weighing 40-45 parts of polytetramethylene ether glycol subjected to azeotropic distillation by anhydrous toluene, weighing 13-15 parts of triethanolamine and 150-160 parts of dichloromethane, adding into another reaction kettle, slowly dripping 15.4-17 parts of methacryloyl chloride into the reaction kettle in an ice water bath through a dropping funnel, removing the ice water bath after dripping is finished, reacting at room temperature for 24 hours, carrying out suction filtration on a reaction product, and precipitating in cold diethyl ether to obtain a prepolymer; (3) preparing a 5 mass percent potassium persulfate solution, adding deionized water and 0.1-0.4 part of sodium dioctyl sulfosuccinate as an emulsifier into a reaction kettle, fully stirring, gradually adding 6.0-8 parts of polyvinyl alcohol 1788, stirring for 10min, heating, raising the temperature, keeping the temperature at 80-90 ℃ for 1-2 h until the polyvinyl alcohol is completely dissolved, adding 10-20 parts of vinyl acetate and 4-5 parts of the macromolecular initiator obtained in the step (1) into the reaction kettle, stirring until the mixture is fully emulsified, heating in a water bath, keeping the temperature at 65-75 ℃, keeping the reaction temperature until the reflux basically disappears, controlling the reaction temperature at 70-80 ℃, slowly adding the prepolymer obtained in the step (2) by using a dropping funnel within 2h without stopping stirring, dropping 1 part of 5 mass percent potassium persulfate solution and 10-15 parts of vinyl acetate every time, then slowly heating to 90 ℃ until no reflux exists, cooling the reaction system to 50 ℃, adding 3-6 parts of 5% sodium bicarbonate water solution, adjusting the pH to 7-8, then slowly adding 10-15 parts of dioctyl sebacate and 15-16 parts of vinyl chloride-vinyl acetate copolymer emulsion, stirring and cooling for 1h to obtain pre-plasticizing emulsion; (4) adjusting the pH value of the pre-plastic emulsion to 7-7.5 by using edible alkali, filtering to obtain polymer emulsion, and drying for 24-48 h at 70-80 ℃ to obtain resin powder; (5) weighing and mixing the resin powder obtained in the step (4) and the plant alkali according to the weight ratio of 10-12: 1, pouring the mixed material into a feed inlet of a double-screw extruder, and setting the extrusion temperature at 100-120 ℃ and the screw rotation speed at 30-35 Hz; the extruded materials are subjected to tabletting and coarse crushing, then are subjected to fine crushing and grinding by a high-speed crusher, and are sieved by a screen with 180-240 meshes according to requirements to obtain preplasticized powder; (6) granulating, namely mixing the preplasticized powder obtained in the step (5) with water to prepare suspension, setting the air inlet temperature of a boiling dryer to be 100-110 ℃ and the air outlet temperature to be 80-90 ℃ for warm boiling granulation, and after the suspension is uniformly mixed in a high-speed mixer, atomizing the dispersing agent by using a peristaltic pump, and spraying the atomized dispersing agent into a fluidized bed dryer to obtain uniform waxy solid particles, wherein the rotating speed of the peristaltic pump is 110-130 rpm, and the preplasticizing powder is as follows: the mass ratio of water is 1: 3-1: 2, and the dispersant: the mass ratio of the preplasticizing powder is 1: 11-12, the air inlet temperature of the boiling dryer is set to be 50-70 ℃, the air outlet temperature is set to be 40-50 ℃, and then spraying the uniformly mixed suspension into a boiling dryer through a peristaltic pump, wherein the rotating speed of the peristaltic pump is 15-25 rpm, forming plastic particles, and drying for 24-30 hours at the temperature of 100-110 ℃ to obtain the plastic particles.

In a further scheme, the vinyl acetate-vinyl acetate copolymer emulsion has a solid content of 50-53% and a viscosity of 500-3000 mpa.s at 25 ℃ and has a vinyl acetate content of 10-13%.

In a further embodiment, the dispersant in step (6) is one of insect wax, morpholine fatty acid salt and ethylene bis-stearoyl.

In a further scheme, the plant alkaloid is a sophora flavescens extract, and the extraction method comprises the steps of adding 2000 parts of water into 500 parts of dried sophora flavescens, soaking for 1-2 hours, carrying out hot-pressing sterilization at 100 ℃ for 60 minutes, filtering to remove residues, concentrating the filtrate to 500 parts, adding 1000 parts of 95% ethanol, diluting and precipitating for 2 hours, filtering, and drying for 5 hours.

The invention has the beneficial effects that:

the plastic particles prepared by the preparation method do not contain components such as a biocide, an antibacterial agent and the like, and have outstanding environmental friendliness, and the performance of the plastic containing the additives can influence the thickness, the elastic modulus, the surface smoothness and other factors. The low-protein adsorption material is developed mainly based on the principle that marine biofouling is adsorption of proteins, glycoproteins and the like on the surface of a substrate. The plastic particles prepared by the invention contain polyethylene glycol, and can effectively inhibit the attachment of bacteria, spores and other microorganisms. The surface of the micro-nano structure is formed for antifouling by coating a dispersing agent for granulation through a fluidized bed dryer based on a bionic principle, and the granulation preparation process is simple and convenient and is different from the traditional extrusion granulation process, and can be kept stable for a long time. And the granules generate main chain fracture through hydrolysis and enzymolysis of ester bonds of the granules per se to form a dynamic surface, so that fouling organisms are inhibited from landing, adhering and growing on the surface of the granules. Has excellent antifouling capacity. The dispersant and the plant alkali are combined to form a multifunctional antifouling plastic particle, a dispersing and lubricating surface formed by the moistening dispersant is coated in the plastic particle with the nano microstructure, and the active ingredient of the plant alkali sophora flavescens is added to imitate the natural defense mechanism of plants existing in the nature and form an oxygen consuming surface, so that the adhesion of fouling microorganisms or proteins is not facilitated. The natural product of the sophora flavescens extract with antifouling activity is used as an antifouling agent, is nontoxic, has a simple extraction process, cannot be accumulated in organisms, is nontoxic and pollution-free in plastic particles, can be used as low-protein adsorption plastic and can also be used as antifouling plastic, and the two materials supplement each other.

Compared with the prior art, the invention has the following advantages:

the prepared plastic particles have lower low-protein adsorption performance through blending modification and low-protein adsorption treatment, the plastic particles produced by the invention have original mechanical performance, and simultaneously have good water-proof and oil-proof characteristics on the surface, have good oil-proof and dirt-proof functions, can be easily cleaned by wiping with rags or washing with clean water after being stained by oil stains, acidic and alkaline foods and the like, do not need detergents, thereby keeping the environment clean, reducing the cleaning cost and having strong market competitiveness.

Detailed Description

The invention is illustrated by the following specific examples, which are not intended to be limiting.