CN105153544B - A kind of polypropylene/bacteria cellulose composite material and preparation method thereof - Google Patents

Abstract

The invention relates to a polypropylene/bacterial cellulose composite material and a preparation method thereof, which consists of the following components in terms of weight percentage: 97-99.5 wt% of polypropylene homopolymer and 0.5-99.5 wt% of esterified modified bacterial cellulose powder 3 wt%. The present invention also proposes a preparation method of the composite material, mixing the polypropylene homopolymer and the esterification-modified bacterial cellulose powder, and melt-blending the mixture with a twin-screw extruder at a temperature of 170-200°C Extrusion, casting, granulation and injection molding, the composite material is obtained. The invention blends the polypropylene homopolymer and the esterified modified bacterial cellulose powder through a twin-screw extruder, so that the bacterial cellulose powder can be uniformly dispersed in the polypropylene homopolymer matrix, and the tensile strength of the obtained composite material is The strength is about 13% higher than that of pure polypropylene, the impact strength is about 18% higher than that of pure polypropylene, and the tensile modulus is about 13% higher than that of pure polypropylene.

Description

A kind of polypropylene/bacterial cellulose composite material and preparation method thereof

technical field

The invention belongs to the technical field of polymer materials, and in particular relates to a polypropylene composite material, in particular to a polypropylene/bacterial cellulose composite material and a preparation method thereof.

Background technique

Due to its high melting point, high tensile strength, low relative density, corrosion resistance and other excellent properties, polypropylene (iPP) has become the resin with the fastest consumption growth rate among the five general-purpose resins, and is widely used in aerospace, electrical, automotive, etc. and other fields. Although polypropylene has excellent properties such as regular structure and high crystallinity, traditional polypropylene has disadvantages such as poor impact performance and high embrittlement temperature that cannot be ignored. So to some extent, its application scope is greatly limited.

Natural fiber reinforced polypropylene is the focus of research work in recent years. Although natural fibers have the advantages of light weight, low price, and easy availability of raw materials, and in most cases, the strength of the composite system can meet the general application requirements. However, the inhomogeneity of natural fibers and the incompatibility with matrix resin greatly limit their application in polypropylene.

Although bacterial cellulose (BC) has the same molecular structure unit as plant natural cellulose, it has many unique properties compared with natural cellulose. For example, the appearance structure is uniform and the surface is smooth; the crystallinity and polymerization degree are high; the tensile strength and elastic modulus are high; and it can be artificially adjusted during biosynthesis. Based on the above characteristics, the combination of bacterial cellulose and polypropylene can not only have the advantages of polypropylene/natural fiber composite materials, but also make up for the shortcomings of natural fibers, thereby endowing polypropylene with better mechanical properties.

In order to improve the compatibility of bacterial cellulose and polypropylene matrix, bacterial cellulose needs to be pretreated. Usually, the treatment methods include coupling agent treatment, esterification modification, etc. Through the pretreatment of bacterial cellulose, the mechanical properties and crystallization properties of composite materials can be significantly improved. There is no relevant report on this type of research.

Contents of the invention

The purpose of the present invention is to provide a polypropylene/bacterial cellulose composite material with high mechanical properties.

Another object of the present invention is to use octanoyl chloride as an esterification modifier to carry out esterification modification on bacterial cellulose at a specific temperature to prepare esterification-modified bacterial cellulose powder.

In order to realize the above-mentioned invention object, the technical scheme of the present invention is as follows: a kind of polypropylene/bacterial cellulose composite material, by weight percentage, is made up of following components: polypropylene homopolymer 97～99.5wt% and esterification modification 0.5-3wt% bacterial cellulose powder. The invention provides a polypropylene/bacterial cellulose composite material with high mechanical properties.

Preferably, the esterification-modified bacterial cellulose powder is obtained from esterification-modified bacterial cellulose with octanoyl chloride. Esterification modification of bacterial cellulose can enhance the lipophilicity of bacterial cellulose, and make bacterial cellulose form nano-dispersion in polypropylene matrix, thereby improving the performance of polypropylene/bacterial cellulose composite material.

Preferably, the esterification-modified bacterial cellulose is prepared by the following method: 100 parts by weight of bacterial cellulose, 1000-3000 parts by weight of octanoyl chloride and 500-4000 parts by weight of pyridine are sequentially added to the reaction vessel, and the Under the condition of 60-100 DEG C, react for 4-8 hours, wash and dry the reaction product to obtain the esterification-modified bacterial cellulose.

Further, the esterified modified bacterial cellulose is washed to neutral with deionized water, dried, pulverized and sieved to obtain the esterified modified bacterial cellulose powder, the esterified modified bacterial cellulose powder is The bacterial cellulose powder has a particle size of 20-200nm.

Preferably, it consists of the following components in terms of weight percentage: 98% of polypropylene homopolymer and 2% of esterification-modified bacterial cellulose powder. When the weight percent of the esterification-modified bacterial cellulose powder in the polypropylene/bacterial cellulose composite material was 2%, the tensile strength and impact strength of the gained polypropylene/bacterial cellulose composite material were the highest, exceeding 2 %, the tensile strength and impact strength of the composite material decreased to a certain extent; when the content of the esterified modified bacterial cellulose powder in the polypropylene/bacterial cellulose composite material increased, the resulting polypropylene/bacterial cellulose The tensile modulus of the composite material is significantly improved.

Preferably, the particle diameter of the esterification-modified bacterial cellulose powder is 20-200 nm, and the weight-average molecular weight of the polypropylene homopolymer is 200,000-400,000.

The present invention also proposes a preparation method of polypropylene/bacterial cellulose composite material, which is composed of the following steps: 97-99.5wt% polypropylene homopolymer and 0.5-3wt% esterified modified bacterial cellulose Mix the powders to obtain a mixture, and then use a twin-screw extruder to carry out melt blending extrusion, belt casting, granulation and injection molding at a temperature of 170-200°C to obtain the polypropylene/bacteria fiber prime composite material. The invention blends the polypropylene homopolymer and the esterification-modified bacterial cellulose powder through a twin-screw extruder, so that the esterification-modified bacterial cellulose powder can be evenly dispersed in the polypropylene homopolymer matrix.

Preferably, the particle diameter of the esterification-modified bacterial cellulose powder is 20-200 nm, and the weight-average molecular weight of the polypropylene homopolymer is 200,000-400,000.

The beneficial effects of the present invention are: the present invention blends the polypropylene homopolymer and the esterification-modified bacterial cellulose powder through a twin-screw extruder, so that the bacterial cellulose powder can be uniformly dispersed in the polypropylene homopolymer matrix , the tensile strength of the obtained polypropylene/bacterial cellulose composite material is increased by about 13% relative to pure polypropylene, the impact strength is increased by about 18% compared with pure polypropylene, and the tensile modulus is also improved compared with pure polypropylene. About 13%.

Description of drawings

Accompanying drawing 1 is that the tensile strength of polypropylene homopolymer and the polypropylene/bacterial cellulose composite material of embodiment 1～4 of the present invention and comparative example 1 and comparative example 2 changes with the bacterial cellulose content of esterification modification change map;

Accompanying drawing 2 is the bacterial cellulose content of the tensile modulus of polypropylene homopolymer and the polypropylene/bacterial cellulose composite material of the present invention 1～4 and comparative example 1 and comparative example 2 with esterification modification change map;

Accompanying drawing 3 is the variation of the impact strength of polypropylene homopolymer and the polypropylene/bacterial cellulose composite material of embodiment 1～4 of the present invention and comparative example 1 and comparative example 2 along with the bacterial cellulose content of esterification modification picture.

detailed description

Below in conjunction with specific example, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention, not to limit the protection scope of the present invention. Improvements and adjustments made by skilled personnel according to the present invention in practical applications still belong to the protection scope of the present invention.

Unless otherwise specified, the raw materials, reagents and equipment used in the present invention are routinely commercially available in the technical field, and the methods used in the present invention are conventionally used methods in the technical field.

Among them, the polypropylene copolymer S1003 was purchased from Beijing Yanshan Petrochemical Co., Ltd., the polypropylene homopolymer was S1003, and the weight average molecular weight of the polypropylene homopolymer was 200,000 to 400,000; the bacterial cellulose was provided by Hainan Yide Food Co., Ltd. , Acetyl chloride, propionyl chloride, and octanoyl chloride were provided by Aladdin Reagent Co., Ltd., and pyridine was provided by Tianjin Damao Chemical Factory.

The test methods for tensile strength, tensile modulus and impact strength are based on GB/T1040.2-2006 Determination of plastic tensile properties.

Example 1

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 2000 parts by weight of octanoyl chloride, and 2000 parts by weight of pyridine were reacted at 80°C for 6 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CO) modified by octanoyl chloride esterification.

In percent by weight, uniformly mix 99.5% polypropylene homopolymer and 0.5% octanoyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder to heat the mixture at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CO composite material is obtained by injection molding with an injection molding machine.

Comparative example 1

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 2000 parts by weight of acetyl chloride, and 2000 parts by weight of pyridine were reacted at 80°C for 6 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CA) modified by acetyl chloride esterification.

In percent by weight, uniformly mix 99.5% polypropylene homopolymer and 0.5% acetyl chloride esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder to heat the mixture at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CA composite material is obtained by injection molding with an injection molding machine.

Comparative example 2

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 2000 parts by weight of propionyl chloride, and 2000 parts by weight of pyridine were reacted at 80°C for 6 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CP) modified by propionyl chloride esterification.

In percent by weight, uniformly mix 99.5% polypropylene homopolymer and 0.5% propionyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder to heat the mixture at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CP composite material is obtained by injection molding with an injection molding machine.

Example 2

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 2000 parts by weight of octanoyl chloride, and 2000 parts by weight of pyridine were reacted at 80°C for 6 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CO) modified by octanoyl chloride esterification.

In percent by weight, uniformly mix 99% polypropylene homopolymer and 1% octanoyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CO composite material is obtained by injection molding with an injection molding machine.

Comparative example 1

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 2000 parts by weight of acetyl chloride, and 2000 parts by weight of pyridine were reacted at 80°C for 6 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CA) modified by acetyl chloride esterification.

In weight percent, uniformly mix 99% polypropylene homopolymer and 1% acetyl chloride-esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CA composite material is obtained by injection molding with an injection molding machine.

Comparative example 2

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 2000 parts by weight of propionyl chloride, and 2000 parts by weight of pyridine were reacted at 80°C for 6 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CP) modified by propionyl chloride esterification.

In percent by weight, uniformly mix 99% polypropylene homopolymer and 1% propionyl chloride esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CP composite material is obtained by injection molding with an injection molding machine.

Example 3

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 2000 parts by weight of octanoyl chloride, and 2000 parts by weight of pyridine were reacted at 80°C for 6 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CO) modified by octanoyl chloride esterification.

In percent by weight, uniformly mix 98% polypropylene homopolymer and 2% octanoyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CO composite material is obtained by injection molding with an injection molding machine.

Comparative example 1

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 2000 parts by weight of acetyl chloride, and 2000 parts by weight of pyridine were reacted at 80°C for 6 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CA) modified by acetyl chloride esterification.

In percent by weight, uniformly mix 98% polypropylene homopolymer and 2% acetyl chloride-esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CA composite material is obtained by injection molding with an injection molding machine.

Comparative example 2

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 2000 parts by weight of propionyl chloride, and 2000 parts by weight of pyridine were reacted at 80°C for 6 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CP) modified by propionyl chloride esterification.

In percent by weight, uniformly mix 98% polypropylene homopolymer and 2% propionyl chloride esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CP composite material is obtained by injection molding with an injection molding machine.

Example 4

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 2000 parts by weight of octanoyl chloride, and 2000 parts by weight of pyridine were reacted at 80°C for 6 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CO) modified by octanoyl chloride esterification.

In percent by weight, uniformly mix 97% polypropylene homopolymer and 3% octanoyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder to heat the mixture at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CO composite material is obtained by injection molding with an injection molding machine.

Comparative example 1

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 2000 parts by weight of acetyl chloride, and 2000 parts by weight of pyridine were reacted at 80°C for 6 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CA) modified by acetyl chloride esterification.

In percent by weight, uniformly mix 97% polypropylene homopolymer and 3% acetyl chloride-esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CA composite material is obtained by injection molding with an injection molding machine.

Comparative example 2

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 2000 parts by weight of propionyl chloride, and 2000 parts by weight of pyridine were reacted at 80°C for 6 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CP) modified by propionyl chloride esterification.

In percent by weight, uniformly mix 97% polypropylene homopolymer and 3% propionyl chloride esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CP composite material is obtained by injection molding with an injection molding machine.

Comparative example 3

In terms of weight percentage, 100% polypropylene homopolymer is melt-blended with a twin-screw extruder at a temperature of 170-200° C., and then injected by an injection molding machine to obtain a polypropylene material.

Examples 1 to 4 and their comparative examples 1 and 2 prepared respectively the bacterial cellulose composite material (iPP/CO) modified by the esterification of polypropylene and octanoyl chloride, and the bacteria modified by esterification of polypropylene and acetyl chloride. The mechanical properties of the cellulose composite material (iPP/CA) and the bacterial cellulose composite material (iPP/CP) modified by esterification of polypropylene and propionyl chloride were compared with Comparative Example 3. The specific mechanical properties are shown in Figure 1 , 2, 3 shown.

It can be seen from Fig. 1, Fig. 2 and Fig. 3 that the mechanical properties of the obtained polypropylene/bacterial cellulose composite are in the order of adding acetyl chloride, propionyl chloride and octanoyl chloride to modify the bacterial cellulose, and the tensile strength of the composite material is Compared with pure polypropylene homopolymer, the tensile modulus is increased by about 1%, 11%, and 13%, respectively, and the tensile modulus is increased by about 14%, 16%, and 18% compared with pure polypropylene homopolymer. Compared with the polymer, it is about 6%, 15%, 18%.

Therefore, when the content of the esterification-modified bacterial cellulose powder in the polypropylene/bacterial cellulose composite increases, the tensile modulus of the obtained polypropylene/bacterial cellulose composite increases significantly. The mechanical properties of the composite material of modified bacterial cellulose and polypropylene also have a great increase.

Example 5

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 1000 parts by weight of octanoyl chloride, and 500 parts by weight of pyridine were reacted at 60°C for 4 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CO) modified by octanoyl chloride esterification.

In percent by weight, uniformly mix 99.5% polypropylene homopolymer and 0.5% octanoyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder to heat the mixture at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CO composite material is obtained by injection molding with an injection molding machine.

Comparative example 1

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 1000 parts by weight of acetyl chloride, and 500 parts by weight of pyridine were reacted at 60°C for 4 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CA) modified by acetyl chloride esterification.

In percent by weight, uniformly mix 99.5% polypropylene homopolymer and 0.5% acetyl chloride esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder to heat the mixture at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CA composite material is obtained by injection molding with an injection molding machine.

Comparative example 2

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 1000 parts by weight of propionyl chloride, and 500 parts by weight of pyridine were reacted at 60°C for 4 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CP) modified by propionyl chloride esterification.

In percent by weight, uniformly mix 99.5% polypropylene homopolymer and 0.5% propionyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder to heat the mixture at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CP composite material is obtained by injection molding with an injection molding machine.

Example 6

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 1000 parts by weight of octanoyl chloride, and 500 parts by weight of pyridine were reacted at 60°C for 4 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CO) modified by octanoyl chloride esterification.

In percent by weight, uniformly mix 99% polypropylene homopolymer and 1% octanoyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CO composite material is obtained by injection molding with an injection molding machine.

Comparative example 1

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 1000 parts by weight of acetyl chloride, and 500 parts by weight of pyridine were reacted at 60°C for 4 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CA) modified by acetyl chloride esterification.

In weight percent, uniformly mix 99% polypropylene homopolymer and 1% acetyl chloride-esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CA composite material is obtained by injection molding with an injection molding machine.

Comparative example 2

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 1000 parts by weight of propionyl chloride, and 500 parts by weight of pyridine were reacted at 60°C for 4 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CP) modified by propionyl chloride esterification.

In percent by weight, uniformly mix 99% polypropylene homopolymer and 1% propionyl chloride esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CP composite material is obtained by injection molding with an injection molding machine.

Example 7

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 1000 parts by weight of octanoyl chloride, and 500 parts by weight of pyridine were reacted at 60°C for 4 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CO) modified by octanoyl chloride esterification.

In percent by weight, uniformly mix 98% polypropylene homopolymer and 2% octanoyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CO composite material is obtained by injection molding with an injection molding machine.

Comparative example 1

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 1000 parts by weight of acetyl chloride, and 500 parts by weight of pyridine were reacted at 60°C for 4 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CA) modified by acetyl chloride esterification.

In percent by weight, uniformly mix 98% polypropylene homopolymer and 2% acetyl chloride-esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CA composite material is obtained by injection molding with an injection molding machine.

Comparative example 2

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 1000 parts by weight of propionyl chloride, and 500 parts by weight of pyridine were reacted at 60°C for 4 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CP) modified by propionyl chloride esterification.

In percent by weight, uniformly mix 98% polypropylene homopolymer and 2% propionyl chloride esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CP composite material is obtained by injection molding with an injection molding machine.

Example 8

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 1000 parts by weight of octanoyl chloride, and 500 parts by weight of pyridine were reacted at 60°C for 4 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CO) modified by octanoyl chloride esterification.

In percent by weight, uniformly mix 97% polypropylene homopolymer and 3% octanoyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder to heat the mixture at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CO composite material is obtained by injection molding with an injection molding machine.

Comparative example 1

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 1000 parts by weight of acetyl chloride, and 500 parts by weight of pyridine were reacted at 60°C for 4 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CA) modified by acetyl chloride esterification.

In percent by weight, uniformly mix 97% polypropylene homopolymer and 3% acetyl chloride-esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CA composite material is obtained by injection molding with an injection molding machine.

Comparative example 2

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 1000 parts by weight of propionyl chloride, and 500 parts by weight of pyridine were reacted at 60°C for 4 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CP) modified by propionyl chloride esterification.

In percent by weight, uniformly mix 97% polypropylene homopolymer and 3% propionyl chloride esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CP composite material is obtained by injection molding with an injection molding machine.

Comparative example 3

In terms of weight percentage, 100% polypropylene homopolymer is melt-blended with a twin-screw extruder at a temperature of 170-200° C., and then injected by an injection molding machine to obtain a polypropylene material.

Examples 5-8 and their comparative example 1 and comparative example 2, respectively prepare the bacterial cellulose composite material (iPP/CO) modified by the esterification of gained polypropylene and octanoyl chloride, and the bacteria modified by esterification of polypropylene and acetyl chloride The cellulose composite (iPP/CA) and the bacterial cellulose composite (iPP/CP) modified by the esterification of polypropylene and propionyl chloride, compared with Comparative Example 3, compared their mechanical properties, and the resulting polypropylene/bacteria The mechanical properties of cellulose composites are modified in the order of adding acetyl chloride, propionyl chloride, and octanoyl chloride to the modified bacterial cellulose. With the growth of the carbon chain of the acid chloride molecule, the mechanical properties of the modified bacterial cellulose and polypropylene composites are very different. With a large increase, the tensile strength, tensile modulus and impact strength are all improved.

Example 9

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 3000 parts by weight of octanoyl chloride, and 4000 parts by weight of pyridine were reacted at 100°C for 8 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CO) modified by octanoyl chloride esterification.

In percent by weight, uniformly mix 99.5% polypropylene homopolymer and 0.5% octanoyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder to heat the mixture at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CO composite material is obtained by injection molding with an injection molding machine.

Comparative example 1

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 3000 parts by weight of acetyl chloride, and 4000 parts by weight of pyridine were reacted at 100°C for 8 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CA) modified by acetyl chloride esterification.

In percent by weight, uniformly mix 99.5% polypropylene homopolymer and 0.5% acetyl chloride esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder to heat the mixture at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CA composite material is obtained by injection molding with an injection molding machine.

Comparative example 2

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 3000 parts by weight of propionyl chloride, and 4000 parts by weight of pyridine were reacted at 100°C for 8 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CP) modified by propionyl chloride esterification.

In percent by weight, uniformly mix 99.5% polypropylene homopolymer and 0.5% propionyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder to heat the mixture at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CP composite material is obtained by injection molding with an injection molding machine.

Example 10

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 3000 parts by weight of octanoyl chloride, and 4000 parts by weight of pyridine were reacted at 100°C for 8 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CO) modified by octanoyl chloride esterification.

In percent by weight, uniformly mix 99% polypropylene homopolymer and 1% octanoyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CO composite material is obtained by injection molding with an injection molding machine.

Comparative example 1

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 3000 parts by weight of acetyl chloride, and 4000 parts by weight of pyridine were reacted at 100°C for 8 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CA) modified by acetyl chloride esterification.

In weight percent, uniformly mix 99% polypropylene homopolymer and 1% acetyl chloride-esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CA composite material is obtained by injection molding with an injection molding machine.

Comparative example 2

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 3000 parts by weight of propionyl chloride, and 4000 parts by weight of pyridine were reacted at 100°C for 8 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CP) modified by propionyl chloride esterification.

In percent by weight, uniformly mix 99% polypropylene homopolymer and 1% propionyl chloride esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CP composite material is obtained by injection molding with an injection molding machine.

Example 11

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 3000 parts by weight of octanoyl chloride, and 4000 parts by weight of pyridine were reacted at 100°C for 8 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CO) modified by octanoyl chloride esterification.

In percent by weight, uniformly mix 98% polypropylene homopolymer and 2% octanoyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CO composite material is obtained by injection molding with an injection molding machine.

Comparative example 1

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 3000 parts by weight of acetyl chloride, and 4000 parts by weight of pyridine were reacted at 100°C for 8 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CA) modified by acetyl chloride esterification.

In percent by weight, uniformly mix 98% polypropylene homopolymer and 2% acetyl chloride-esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CA composite material is obtained by injection molding with an injection molding machine.

Comparative example 2

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 3000 parts by weight of propionyl chloride, and 4000 parts by weight of pyridine were reacted at 100°C for 8 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CP) modified by propionyl chloride esterification.

In percent by weight, uniformly mix 98% polypropylene homopolymer and 2% propionyl chloride esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CP composite material is obtained by injection molding with an injection molding machine.

Example 12

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 3000 parts by weight of octanoyl chloride, and 4000 parts by weight of pyridine were reacted at 100°C for 8 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CO) modified by octanoyl chloride esterification.

In percent by weight, uniformly mix 97% polypropylene homopolymer and 3% octanoyl chloride esterified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder to heat the mixture at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CO composite material is obtained by injection molding with an injection molding machine.

Comparative example 1

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 3000 parts by weight of acetyl chloride, and 4000 parts by weight of pyridine were reacted at 100°C for 8 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CA) modified by acetyl chloride esterification.

In percent by weight, uniformly mix 97% polypropylene homopolymer and 3% acetyl chloride-esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CA composite material is obtained by injection molding with an injection molding machine.

Comparative example 2

Wash the film-like bacterial cellulose with a large amount of deionized water until it becomes neutral, dry it in a freeze dryer for 24 hours, pulverize it with a ball mill, and then pass the bacterial cellulose powder through a mesh sieve to obtain bacterial fibers with a particle size of 20-200nm Vegetarian powder.

100 parts by weight of dried bacterial cellulose powder, 3000 parts by weight of propionyl chloride, and 4000 parts by weight of pyridine were reacted at 100°C for 8 hours. After the reaction, the product was rinsed with deionized water and ethanol and dried to obtain Bacterial cellulose (CP) modified by propionyl chloride esterification.

In percent by weight, uniformly mix 97% polypropylene homopolymer and 3% propionyl chloride esterified modified bacterial cellulose powder to obtain a mixture, and then use a twin-screw extruder at a temperature of 170 to 200 Melt blending is carried out at ℃, and then the iPP/CP composite material is obtained by injection molding with an injection molding machine.

Comparative example 3

In terms of weight percentage, 100% polypropylene homopolymer is melt-blended with a twin-screw extruder at a temperature of 170-200° C., and then injected by an injection molding machine to obtain a polypropylene material.

Examples 9-12 and their comparative example 1 and comparative example 2, respectively prepare the bacterial cellulose composite material (iPP/CO) modified by esterification of gained polypropylene and octanoyl chloride, and the bacteria modified by esterification of polypropylene and acetyl chloride The cellulose composite (iPP/CA) and the bacterial cellulose composite (iPP/CP) modified by the esterification of polypropylene and propionyl chloride, compared with Comparative Example 3, compared their mechanical properties, and the resulting polypropylene/bacteria The mechanical properties of cellulose composites are modified in the order of adding acetyl chloride, propionyl chloride, and octanoyl chloride to the modified bacterial cellulose. With the growth of the carbon chain of the acid chloride molecule, the mechanical properties of the modified bacterial cellulose and polypropylene composites are very different. With a large increase, the tensile strength, tensile modulus and impact strength are all improved.

Claims (9)

1. a kind of polypropylene/bacteria cellulose composite material, it is characterised in that by weight percentage, composed of the following components： 97~99.5wt% of polypropylene homopolymer and esterification modification 0.5~3wt% of bacteria cellulose powder, the esterification modification it is thin Fungin powder is obtained by caprylyl chloride esterification modification bacteria cellulose.

2. polypropylene/bacteria cellulose composite material according to claim 1, it is characterised in that the esterification modification Bacteria cellulose is prepared by the following method：By the bacteria cellulose of 100 parts by weight, 1000~3000 parts by weight caprylyl chlorides and 500~4000 parts by weight pyridines, are added sequentially in reaction vessel, under the conditions of 60~100 DEG C, react 4~8 hours, will be anti- Answer product to rinse and dry, obtain the bacteria cellulose of esterification modification.

3. polypropylene/bacteria cellulose composite material according to claim 2, it is characterised in that：By the esterification modification Bacteria cellulose be washed with deionized to neutrality, through drying, crush and sieve, obtain the bacterial fibers of the esterification modification Plain powder.

4. polypropylene/bacteria cellulose composite material according to claim 3, it is characterised in that：The esterification modification The particle diameter of bacteria cellulose powder is 20~200nm.

5. polypropylene/bacteria cellulose composite material according to claim 1, it is characterised in that by weight percentage, It is composed of the following components：The bacteria cellulose powder 2% of polypropylene homopolymer 98% and esterification modification.

6. polypropylene/bacteria cellulose composite material according to claim 1, it is characterised in that：The polypropylene homo The weight average molecular weight of thing is 20~400,000.

7. a kind of preparation method of polypropylene/bacteria cellulose composite material described in claim 1, it is characterised in that by with Lower step composition：By 97~99.5wt% polypropylene homopolymer and the bacteria cellulose powder of 0.5~3wt% esterification modification Progress is mixed to get mixture, is then melted the mixture in the case where temperature is 170~200 DEG C with double screw extruder Blending extrusion, Cast Strip, granulation and injection, that is, be made the polypropylene/bacteria cellulose composite material.

8. the preparation method of polypropylene/bacteria cellulose composite material according to claim 7, it is characterised in that described The particle diameter of the bacteria cellulose powder of esterification modification is 20~200nm.

9. the preparation method of polypropylene/bacteria cellulose composite material according to claim 7, it is characterised in that described The weight average molecular weight of polypropylene homopolymer is 20~400,000.