阅读说明：本技术 无纺布用生物质基复合材料的加工工艺 (Processing technology of biomass-based composite material for non-woven fabric ) 是由 卢定华 于 2019-04-22 设计创作，主要内容包括：本发明公开了一种无纺布用生物质基复合材料的加工工艺,属于生物降解高分子复合材料技术领域,本发明先将海藻酸钠和纳米二氧化硅混合后,再经硅烷偶联剂KH-550处理后制得改性海藻酸钠,然后,将氧化淀粉与聚烯丙胺盐酸盐混合反应,并加入改性海藻酸钠,搅拌反应制得添加料,将聚乳酸与环氧大豆油混合,并加入催化剂和添加料,混合密炼,造粒,得具有高降解性的无纺布用生物质基复合材料。本发明制备的具有高降解性的无纺布用生物质基复合材料拥有较好的耐热性,且柔韧性极佳,降解性较好,适合于制造无纺布。(The invention discloses a processing technology of a biomass-based composite material for non-woven fabrics, which belongs to the technical field of biodegradable polymer composite materials. The biomass-based composite material for the non-woven fabric with high degradability, which is prepared by the invention, has the advantages of good heat resistance, excellent flexibility and good degradability, and is suitable for manufacturing the non-woven fabric.)

1. A processing technology of biomass-based composite material for non-woven fabric mainly comprises the following steps:

(1) mixing sodium alginate and water according to a mass ratio of 1: 55, adding tetraethoxysilane 4 times of the mass of sodium alginate and absolute ethyl alcohol 10 times of the mass of sodium alginate into a mixture of sodium alginate and water, stirring and mixing for 30min at the temperature of 30 ℃ and the rotating speed of 300r/min, adding ammonia water 25 times of the mass of sodium alginate into the mixture of sodium alginate and water, stirring and reacting for 3h at the temperature of 50 ℃ and the rotating speed of 350r/min, and then defoaming in vacuum;

(2) mixing the substance obtained in the step (1) and a silane coupling agent KH-550 in a mass ratio of 12: 1, adding water with the mass being 3 times that of the silane coupling agent KH-550 into a mixture of the substance obtained in the step (1) and the silane coupling agent KH-550, stirring and mixing for 2 hours at the temperature of 40 ℃ and the rotating speed of 250r/min to obtain a pre-modified sodium alginate mixture, extruding the pre-modified sodium alginate mixture into a calcium chloride solution with the mass fraction of 2% through an extruder, standing for 3 hours, filtering, and drying to obtain modified sodium alginate;

(3) mixing polylactic acid and epoxy soybean oil according to a mass ratio of 2: 1, adding zinc chloride with the mass of 0.3 time that of the polylactic acid into the mixture of the polylactic acid and the epoxidized soybean oil, and stirring and mixing;

(4) adding oxidized starch into a beaker, adding a substance which is 0.6 time of the mass of the oxidized starch and is obtained in the step (2) and water which is 8 times of the mass of the oxidized starch into the beaker, stirring and mixing for 1 hour under the conditions that the temperature is 30 ℃ and the rotating speed is 350r/min, adjusting the pH value of a material in the beaker to 10.0, continuously stirring and reacting for 3 hours under the conditions that the temperature is 60 ℃ and the rotating speed is 300r/min, then adding a reducing agent which is 0.2 time of the mass of the oxidized starch into the beaker, stirring and reacting for 3 hours under the conditions that the temperature is 60 ℃ and the rotating speed is 300r/min, filtering and drying;

(5) mixing the substance obtained in the step (3) and the substance obtained in the step (4) according to the mass ratio of 1.0:1.8, mixing under a closed condition, and granulating;

(6) performing index analysis on the substance obtained in the step (5);

and (4) the reducing agent is sodium borohydride.

Technical Field

The invention relates to the technical field of composite materials for non-woven fabrics, in particular to a processing technology of a biomass-based composite material for non-woven fabrics.

Background

With the progress of science and technology and the development of human civilization, high polymer material products, such as plastic bags, lunch boxes, medical products and a series of plastic products in daily life, are continuously produced and become waste.

Since the beginning of the 20 th century, the application of synthetic polymer materials in large quantities has caused serious environmental pollution, and the search and application of novel polymer materials which are friendly to the environment have been widely regarded by various countries in the world. Under this situation, biodegradable polymer materials are rapidly developing. Practice proves that the biodegradable high molecular material is different from common synthetic high molecular materials, has the characteristics of biogenesis and biodegradability, can reduce environmental pollution, save petroleum resources and reduce global greenhouse effect, and is widely applied to industry. Taking polylactic acid as an example, the monomer of the polylactic acid is lactic acid, is a biodegradable polymer prepared from renewable plant resources such as corn, beet and the like by a chemical synthesis method, belongs to thermoplastic aliphatic polyester, is in a glass state at normal temperature, has the glass transition temperature and the melting point of about 60 ℃ and 170 ℃ respectively, and has the performance similar to polystyrene. Polylactic acid can be subjected to extrusion, injection molding, blow molding, thermoforming and other forming processing on general equipment like common polymers, and the produced films, sheets and fibers are subjected to secondary processing such as thermoforming, spinning and the like to obtain products, so that the polylactic acid can be widely applied to the fields of textiles, clothing, non-woven fabrics, packaging, agriculture, forestry, civil engineering and construction, medical and health products, living goods and the like.

However, the traditional polylactic acid product cannot be popularized due to high production cost of polylactic acid, and the polylactic acid product has poor heat resistance and crisp texture, so that research and development of a biomass-based composite material for non-woven fabrics, which has low cost and good heat resistance, flexibility and degradability, are urgently needed.

Disclosure of Invention

The invention aims to provide a biomass-based composite material for non-woven fabric with high degradability and a processing technology thereof, so as to solve the problems in the prior art.

In order to achieve the purpose, the invention provides the following technical scheme:

the biomass-based composite material for the non-woven fabric is characterized by mainly comprising the following raw material components in parts by weight: 8-12 parts of polylactic acid, 5-8 parts of epoxidized soybean oil, 1-2 parts of a catalyst and 15-18 parts of oxidized starch; the epoxidized soybean oil can play a role of a plasticizer after being added into the product, thereby improving the flexibility of the product.

The biomass-based composite material with high degradability for the non-woven fabric is characterized by further comprising the following raw material components in parts by weight: 3-6 parts of polyallylamine hydrochloride and 8-10 parts of modified sodium alginate, wherein the polyallylamine hydrochloride and the oxidized starch can form a cross-linked network in the product, so that the cross-linking density of the product is improved, and the flexibility and the tensile strength of the product are improved.

The polylactic acid is polylactic acid with the molecular weight of 80000-120000, the catalyst is any one of zinc chloride or magnesium chloride, and the added catalyst can play a role of a filler and improve the tensile property of the product.

Preferably, the oxidized starch is prepared by oxidizing starch with hydrogen peroxide, and the starch is any one of tapioca starch or corn starch.

The modified sodium alginate is prepared by mixing sodium alginate and nano-silica and then treating the mixture with a silane coupling agent KH-550, and the addition of the modified sodium alginate can play a role of filling filler in the pore structure of the product to improve the heat resistance of the product, and can further improve the crosslinking density of the product and improve the flexibility of the product.

As optimization, the biomass-based composite material with high degradability for the non-woven fabric mainly comprises the following raw material components in parts by weight: 8 parts of polylactic acid, 6 parts of epoxidized soybean oil, 2 parts of zinc chloride, 16 parts of oxidized starch, 3 parts of polyallylamine hydrochloride and 8 parts of modified sodium alginate.

As optimization, the processing technology of the biomass-based composite material with high degradability for the non-woven fabric mainly comprises the following steps:

(1) mixing sodium alginate and ethyl orthosilicate for reaction, and then defoaming in vacuum;

(2) mixing the substance obtained in the step (1) with a silane coupling agent KH-550, extruding, filtering and drying to obtain modified sodium alginate;

(3) mixing polylactic acid and epoxidized soybean oil, adding a catalyst, and stirring and mixing;

(4) mixing oxidized starch and polyallylamine hydrochloride, adding water and the substance obtained in the step (2), adjusting the pH value, stirring for reaction, adding a reducing agent, continuing the reaction, filtering and drying;

(5) mixing the substance obtained in the step (3) with the substance obtained in the step (4), mixing and granulating;

(6) and (5) performing index analysis on the substance obtained in the step (5).

As optimization, the processing technology of the biomass-based composite material with high degradability for the non-woven fabric mainly comprises the following steps:

(1) mixing sodium alginate and water according to a mass ratio of 1: 50-1: 55, adding ethyl orthosilicate with the mass 2-4 times that of sodium alginate and absolute ethyl alcohol with the mass 5-10 times that of sodium alginate, stirring and mixing, adding ammonia water with the mass 20-25 times that of sodium alginate, stirring and reacting, and performing vacuum defoaming;

(2) mixing the substance obtained in the step (1) and a silane coupling agent KH-550 in a mass ratio of 10: 1-12: 1, mixing, adding water with the mass of 2-3 times that of KH-550 of silane coupling agent, stirring and mixing to obtain a pre-modified sodium alginate mixture, extruding the pre-modified sodium alginate mixture into a calcium chloride solution with the mass fraction of 2% through an extruder, filtering, and drying to obtain modified sodium alginate;

(3) mixing polylactic acid and epoxy soybean oil according to a mass ratio of 1: 1-2: 1, mixing, adding zinc chloride with the mass of 0.1-0.3 time that of the polylactic acid, and stirring and mixing;

(4) mixing oxidized starch and polyallylamine hydrochloride according to a mass ratio of 5: 1-8: 1, mixing the materials obtained in the step (2) and water, wherein the mass of the materials is 0.5-0.6 time that of the oxidized starch, and the mass of the materials and the water is 4-8 times that of the oxidized starch, adding a reducing agent, wherein the mass of the reducing agent is 0.1-0.2 time that of the oxidized starch, into the beaker after stirring and mixing, adjusting the pH of the materials in the beaker to 9.8-10.0, stirring and reacting for 2-3 hours, filtering and drying after stirring and reacting;

(5) mixing the substance obtained in the step (3) and the substance obtained in the step (4) according to the mass ratio of 1.0: 1.8-1.0: 2.0, mixing under a closed condition, and granulating;

(6) and (5) performing index analysis on the substance obtained in the step (5).

Preferably, the reducing agent in the step (4) is any one of sodium borohydride and potassium borohydride.

Compared with the prior art, the invention has the beneficial effects that: the invention adds oxidized starch and polyallylamine hydrochloride into the product when preparing the biomass-based composite material with high degradability, and adds modified sodium alginate, firstly, the oxidized starch contains aldehyde group which can react with the amine group in the polyallylamine hydrochloride and form cross-linking, thereby enriching the cross-linking network in the product after being added into the product, improving the flexibility of the product, and after the cross-linking network is enriched, improving the heat resistance of the product, namely improving the crystallization temperature of the product, secondly, the modified sodium alginate is prepared after being mixed by the sodium alginate and the nano-silica and then being treated by silane coupling agent KH-550, because the modified sodium alginate contains silicon dioxide, after being added into the product, the modified sodium alginate can be used as filler to be filled in the pores of the cross-linking network in the product, thereby improving the density of the product, the heat resistance and tensile strength of the product are further improved, and because the surface of the silicon dioxide contains primary amino groups after the treatment of the silane coupling agent KH-550, after the silicon dioxide is mixed with the epoxidized soybean oil, a richer crosslinking network can be formed in the product in the preparation process of the product, so that the heat resistance and flexibility of the product are further improved, and the product is suitable for manufacturing non-woven fabrics; in addition, the addition of polylactic acid is reduced in the preparation process of the product, so that the cost of the product is greatly reduced, and the popularization of the product is improved.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In order to more clearly illustrate the method provided by the present invention, the following examples are given, and the method for testing each index of the biomass-based composite material for nonwoven fabric having high degradability prepared in the following examples is as follows:

crystallization temperature: taking 5mg of the biomass-based composite material for the non-woven fabric with high degradability obtained in each example, heating the biomass-based composite material to 200 ℃ from room temperature at the speed of 5 ℃/min under the nitrogen atmosphere on a differential scanning calorimeter calibrated by indium, tin and zinc, and keeping the temperature for 5 min; then reducing the temperature from 200 ℃ to 30 ℃ at the speed of 5 ℃/min, recording a DSC curve, and taking the peak temperature on the temperature reduction curve as the crystallization temperature;

mechanical properties: the biomass-based composite material for the non-woven fabric with high degradability obtained in each embodiment is added into a micro injection molding machine, and is subjected to injection molding to form a test strip required by mechanical property test, wherein the injection molding temperature is 200 ℃, the mold temperature is 40 ℃, and the injection pressure is 0.5 MPa. Testing the mechanical property of the test strip by utilizing a microcomputer controlled electronic universal testing machine and a cantilever beam impact testing machine, and measuring the tensile strength according to GB/T1040.1; flexural modulus was measured according to GB/T9341.

Degradability: the biomass-based composite material for nonwoven fabric having high degradability obtained in each example was left to stand for 30 days, and the degradation rate was measured.