CN111808334B - Processing technology of biomass-based composite material for non-woven fabric with high degradability - Google Patents

Processing technology of biomass-based composite material for non-woven fabric with high degradability Download PDF

Info

Publication number
CN111808334B
CN111808334B CN202010454895.1A CN202010454895A CN111808334B CN 111808334 B CN111808334 B CN 111808334B CN 202010454895 A CN202010454895 A CN 202010454895A CN 111808334 B CN111808334 B CN 111808334B
Authority
CN
China
Prior art keywords
mixing
mass
sodium alginate
stirring
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010454895.1A
Other languages
Chinese (zh)
Other versions
CN111808334A (en
Inventor
卢定华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Baoding High Tech Zone Biobased New Materials Co ltd
Original Assignee
Baoding High Tech Zone Biobased New Materials Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Baoding High Tech Zone Biobased New Materials Co ltd filed Critical Baoding High Tech Zone Biobased New Materials Co ltd
Priority to CN202010454895.1A priority Critical patent/CN111808334B/en
Publication of CN111808334A publication Critical patent/CN111808334A/en
Application granted granted Critical
Publication of CN111808334B publication Critical patent/CN111808334B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C08L3/10—Oxidised starch
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/168—Zinc halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention discloses a processing technology of a biomass-based composite material for non-woven fabrics with high degradability, 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 better heat resistance, excellent flexibility and better degradability, and is suitable for manufacturing the non-woven fabric.

Description

Processing technology of biomass-based composite material for non-woven fabric with high degradability
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 with high degradability for non-woven fabrics.
Background
With the progress of technology and the development of human civilization, polymer material products such as plastic bags, cutlery boxes, medical and a series of plastic products in daily life are continuously produced and become waste.
Since the beginning of the 20 th century, a great deal of application of synthetic polymer materials has caused serious environmental pollution, and the search and application of novel polymer materials friendly to the environment have received wide attention from all countries of the world. Under this situation, biodegradable polymer materials rapidly develop. The practice proves that the biodegradable polymer material is different from the common synthetic polymer material, has two characteristics of biological source and biodegradability, can reduce environmental pollution, save petroleum resources and reduce the global warming 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 through a chemical synthesis method, belongs to thermoplastic aliphatic polyester, is in a glass state at normal temperature, has a glass transition temperature and a melting point of about 60 ℃ and 170 ℃ respectively, and has similar performance to polystyrene. The polylactic acid can be extruded, injection molded, blow molded, thermoformed and other molding processing on general equipment like common polymers, and the produced films, sheets and fibers are subjected to thermoforming, spinning and other secondary processing 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 construction, medical and health products, living goods and the like.
However, the traditional polylactic acid product has the disadvantages that the polylactic acid cannot be popularized due to higher production cost of the 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 with high degradability for non-woven fabrics and a processing technology thereof, so as to solve the problems in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the biomass-based composite material for the non-woven fabric with high degradability 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 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 for the non-woven fabric with high degradability 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 addition of the polyallylamine hydrochloride can form a crosslinked network with oxidized starch in the product, so that the crosslinking density of the product is improved, and the flexibility and the tensile strength of the product are improved.
As optimization, the polylactic acid is polylactic acid with 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 filler, so that the tensile property of the product is improved.
As optimization, the oxidized starch is prepared by oxidizing starch with hydrogen peroxide, and the starch is any one of tapioca starch and corn starch.
As optimization, the modified sodium alginate is prepared by mixing sodium alginate and nano silicon dioxide and then treating the mixture by a silane coupling agent KH-550, and the addition of the modified sodium alginate can play a role in filling filler into the pore structure of a product, so that the heat resistance of the product is improved, and the crosslinking density of the product is further improved, so that the flexibility of the product is improved.
As optimization, the biomass-based composite material for the non-woven fabric with high degradability 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 for the non-woven fabric with high degradability 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 with polyallylamine hydrochloride, adding water and the substance obtained in the step (2), regulating 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 for the non-woven fabric with high degradability mainly comprises the following steps:
(1) Sodium alginate and water are mixed according to the mass ratio of 1: 50-1: 55, adding ethyl orthosilicate with the mass of 2-4 times of sodium alginate and absolute ethyl alcohol with the mass of 5-10 times of sodium alginate, stirring and mixing, adding ammonia water with the mass of 20-25 times of sodium alginate, stirring and reacting, and then vacuum defoaming;
(2) Mixing the substance obtained in the step (1) with a silane coupling agent KH-550 according to a mass ratio of 10:1 to 12:1, adding water with the mass of 2-3 times of that of a silane coupling agent KH-550, 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) Polylactic acid and epoxidized soybean oil are mixed according to the mass ratio of 1: 1-2: 1, adding zinc chloride with the mass of 0.1 to 0.3 times of that of the polylactic acid, and stirring and mixing;
(4) Oxidized starch and polyallylamine hydrochloride are mixed according to the mass ratio of 5:1 to 8:1 mixing in a beaker, adding a substance obtained in the step (2) with the mass of 0.5-0.6 times of that of oxidized starch and water with the mass of 4-8 times of that of oxidized starch into the beaker, stirring and mixing, adjusting the pH value of the material in the beaker to 9.8-10.0, stirring and reacting for 2-3 hours, adding a reducing agent with the mass of 0.1-0.2 times of that of oxidized starch into the beaker, stirring and reacting, filtering, and drying;
(5) Mixing the substance obtained in the step (3) with 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 or potassium borohydride.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, oxidized starch and polyallylamine hydrochloride are added into a product when the biomass-based composite material for the non-woven fabric with high degradability is prepared, and modified sodium alginate is added at the same time, firstly, the oxidized starch contains aldehyde groups and can react with amino groups in the polyallylamine hydrochloride to form crosslinking, so that after the oxidized starch is added into the product, the internal crosslinking network of the product can be enriched, the flexibility of the product is improved, and after the crosslinking network is enriched, the heat resistance of the product can be improved, namely the crystallization temperature of the product is improved; 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 of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing in detail the methods for testing various indexes of the biomass-based composite material for non-woven fabrics with high degradability, which are prepared in the following examples, as follows:
crystallization temperature: taking 5mg of the biomass-based composite material with high degradability for the non-woven fabric, which is obtained in each example, heating the composite material to 200 ℃ from room temperature at 5 ℃/min under nitrogen atmosphere on a differential scanning calorimeter calibrated by indium, tin and zinc, and preserving heat for 5min; then 5 ℃/min is used for reducing the temperature from 200 ℃ to 30 ℃, a DSC curve is recorded, and the peak temperature on the temperature reduction curve is taken as the crystallization temperature;
mechanical properties: the high-degradability biomass-based composite material for the non-woven fabric obtained in each embodiment is added into a miniature injection molding machine to be molded into test strips required by mechanical property test, wherein the injection molding temperature is 200 ℃, the mold temperature is 40 ℃, and the injection pressure is 0.5MPa. The microcomputer is used for controlling an electronic universal tester and a cantilever beam impact tester to test the mechanical properties of the test strip, and the tensile strength is measured 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 naturally for 30 days, and the degradation rate was measured.
Example 1:
the biomass-based composite material for the non-woven fabric with high degradability mainly comprises the following raw materials 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;
a processing technology of a biomass-based composite material for non-woven fabrics with high degradability, which mainly comprises the following steps:
(1) Sodium alginate and water are mixed according to the mass ratio of 1:55, adding ethyl orthosilicate with the mass of 4 times of sodium alginate and absolute ethyl alcohol with the mass of 10 times of sodium alginate into the 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 with the mass of 25 times 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) with a silane coupling agent KH-550 according to a mass ratio of 12:1, mixing, adding water 3 times the mass of the silane coupling agent KH-550 into the 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% by an extruder, standing for 3 hours, filtering, and drying to obtain modified sodium alginate;
(3) Polylactic acid and epoxidized soybean oil are mixed according to a mass ratio of 2:1, mixing, adding zinc chloride with the mass of 0.3 times of that of the polylactic acid into the mixture of the polylactic acid and the epoxidized soybean oil, and stirring and mixing;
(4) Oxidized starch and polyallylamine hydrochloride are mixed according to the mass ratio of 8:1 mixing in a beaker, adding a substance obtained in the step (2) with the mass of 0.6 times of that of oxidized starch and water with the mass of 8 times of that of the oxidized starch into the beaker, stirring and mixing for 1h at the temperature of 30 ℃ and the rotating speed of 350r/min, regulating the pH value of the material in the beaker to 10.0, continuing stirring and reacting for 3h at the temperature of 60 ℃ and the rotating speed of 300r/min, adding a reducing agent with the mass of 0.2 times of that of the oxidized starch into the beaker, stirring and reacting for 3h at the temperature of 60 ℃ and the rotating speed of 300r/min, filtering and drying;
(5) Mixing the substance obtained in the step (3) with 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) And (5) performing index analysis on the substance obtained in the step (5).
Preferably, the reducing agent in the step (4) is sodium borohydride.
Example 2:
the biomass-based composite material for the non-woven fabric with high degradability mainly comprises the following raw materials 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 and 8 parts of modified sodium alginate;
a processing technology of a biomass-based composite material for non-woven fabrics with high degradability, which mainly comprises the following steps:
(1) Sodium alginate and water are mixed according to the mass ratio of 1:55, adding ethyl orthosilicate with the mass of 4 times of sodium alginate and absolute ethyl alcohol with the mass of 10 times of sodium alginate into the 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 with the mass of 25 times 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) with a silane coupling agent KH-550 according to a mass ratio of 12:1, mixing, adding water 3 times the mass of the silane coupling agent KH-550 into the 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% by an extruder, standing for 3 hours, filtering, and drying to obtain modified sodium alginate;
(3) Polylactic acid and epoxidized soybean oil are mixed according to a mass ratio of 2:1, mixing, adding zinc chloride with the mass of 0.3 times of 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 obtained in the step (2) with the mass 0.6 times of that of the oxidized starch and water with the mass 8 times of that of the oxidized starch into the beaker, stirring and mixing for 1h at the temperature of 30 ℃ and the rotating speed of 350r/min, adjusting the pH value of the material in the beaker to 10.0, continuing stirring and reacting for 3h at the temperature of 60 ℃ and the rotating speed of 300r/min, adding a reducing agent with the mass 0.2 times of that of the oxidized starch into the beaker, stirring and reacting for 3h at the temperature of 60 ℃ and the rotating speed of 300r/min, filtering and drying;
(5) Mixing the substance obtained in the step (3) with 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) And (5) performing index analysis on the substance obtained in the step (5).
Preferably, the reducing agent in the step (4) is sodium borohydride.
Example 3:
the biomass-based composite material for the non-woven fabric with high degradability mainly comprises the following raw materials 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 sodium alginate;
a processing technology of a biomass-based composite material for non-woven fabrics with high degradability, which mainly comprises the following steps:
(1) Sodium alginate and a silane coupling agent KH-550 are mixed according to a mass ratio of 12:1, adding 3 times of water by mass of a silane coupling agent KH-550 and 1 time of calcium chloride by mass of the silane coupling agent KH-550 into a mixture of sodium alginate 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, filtering and drying;
(2) Polylactic acid and epoxidized soybean oil are mixed according to a mass ratio of 2:1, mixing, adding zinc chloride with the mass of 0.3 times of that of the polylactic acid into the mixture of the polylactic acid and the epoxidized soybean oil, and stirring and mixing;
(3) Oxidized starch and polyallylamine hydrochloride are mixed according to the mass ratio of 8:1 mixing in a beaker, adding a substance obtained in the step (1) with the mass of 0.6 times of the mass of oxidized starch and water with the mass of 8 times of the mass of oxidized starch into the beaker, stirring and mixing for 1h at the temperature of 30 ℃ and the rotating speed of 350r/min, adjusting the pH value of the material in the beaker to 10.0, continuing stirring and reacting for 3h at the temperature of 60 ℃ and the rotating speed of 300r/min, adding a reducing agent with the mass of 0.2 times of the mass of oxidized starch into the beaker, stirring and reacting for 3h at the temperature of 60 ℃ and the rotating speed of 300r/min, filtering and drying;
(4) Mixing the substance obtained in the step (2) with the substance obtained in the step (3) according to the mass ratio of 1.0:1.8, mixing under a closed condition, and granulating;
(5) And (3) performing index analysis on the substance obtained in the step (4).
Preferably, the reducing agent in the step (3) is sodium borohydride.
Example 4:
the biomass-based composite material for the non-woven fabric with high degradability mainly comprises the following raw materials in parts by weight: 8 parts of polylactic acid, 6 parts of epoxidized soybean oil, 16 parts of oxidized starch, 3 parts of polyallylamine hydrochloride and 8 parts of modified sodium alginate;
a processing technology of a biomass-based composite material for non-woven fabrics with high degradability, which mainly comprises the following steps:
(1) Sodium alginate and water are mixed according to the mass ratio of 1:55, adding ethyl orthosilicate with the mass of 4 times of sodium alginate and absolute ethyl alcohol with the mass of 10 times of sodium alginate into the 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 with the mass of 25 times 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) with a silane coupling agent KH-550 according to a mass ratio of 12:1, mixing, adding water 3 times the mass of the silane coupling agent KH-550 into the 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% by an extruder, standing for 3 hours, filtering, and drying to obtain modified sodium alginate;
(3) Polylactic acid and epoxidized soybean oil are mixed according to a mass ratio of 2:1, mixing, stirring and mixing;
(4) Oxidized starch and polyallylamine hydrochloride are mixed according to the mass ratio of 8:1 mixing in a beaker, adding a substance obtained in the step (2) with the mass of 0.6 times of that of oxidized starch and water with the mass of 8 times of that of the oxidized starch into the beaker, stirring and mixing for 1h at the temperature of 30 ℃ and the rotating speed of 350r/min, regulating the pH value of the material in the beaker to 10.0, continuing stirring and reacting for 3h at the temperature of 60 ℃ and the rotating speed of 300r/min, adding a reducing agent with the mass of 0.2 times of that of the oxidized starch into the beaker, stirring and reacting for 3h at the temperature of 60 ℃ and the rotating speed of 300r/min, filtering and drying;
(5) Mixing the substance obtained in the step (3) with 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) And (5) performing index analysis on the substance obtained in the step (5).
Preferably, the reducing agent in the step (4) is sodium borohydride.
Comparative example:
the biomass-based composite material for the non-woven fabric with high degradability mainly comprises the following raw materials in parts by weight: 8 parts of polylactic acid, 6 parts of epoxidized soybean oil, 16 parts of oxidized starch and 8 parts of sodium alginate;
a processing technology of a biomass-based composite material for non-woven fabrics with high degradability, which mainly comprises the following steps:
(1) Sodium alginate and a silane coupling agent KH-550 are mixed according to a mass ratio of 12:1, adding 3 times of water by mass of a silane coupling agent KH-550 and 1 time of calcium chloride by mass of the silane coupling agent KH-550 into a mixture of sodium alginate 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, filtering and drying;
(2) Polylactic acid and epoxidized soybean oil are mixed according to a mass ratio of 2:1, mixing, stirring and mixing;
(3) Adding oxidized starch into a beaker, adding a substance obtained in the step (1) with the mass 0.6 times of that of the oxidized starch and water with the mass 8 times of that of the oxidized starch into the beaker, stirring and mixing for 1h at the temperature of 30 ℃ and the rotating speed of 350r/min, adjusting the pH value of the material in the beaker to 10.0, continuing stirring and reacting for 3h at the temperature of 60 ℃ and the rotating speed of 300r/min, adding a reducing agent with the mass 0.2 times of that of the oxidized starch into the beaker, stirring and reacting for 3h at the temperature of 60 ℃ and the rotating speed of 300r/min, filtering and drying;
(4) Mixing the substance obtained in the step (2) with the substance obtained in the step (3) according to the mass ratio of 1.0:1.8, mixing under a closed condition, and granulating;
(5) And (3) performing index analysis on the substance obtained in the step (4).
Preferably, the reducing agent in the step (3) is sodium borohydride.
Effect example:
table 1 below gives the results of index analysis of the biomass-based composite materials having high degradability and the processing processes thereof using examples 1 to 4 and comparative examples of the present invention.
TABLE 1
Tensile strength (MPa) Flexural Strength (MPa) Crystallization temperature (. Degree. C.) Degradation rate (%)
Example 1 72.0 5000 145 68
Example 2 68.8 4763 132 69
Example 3 65.3 4338 112 70
Example 4 64.3 4225 118 69
Comparative example 33.4 2831 90.3 62
As can be seen from the experimental data in Table 1, compared with the comparative example, the product prepared by the invention has better heat resistance and flexibility, and the degradation performance is improved, and as can be seen from the comparison of the example 1 and the example 2, when the polyallylamine hydrochloride is not added into the product, the crosslinking density in the product is reduced, the hydrophilic group of oxidized starch is exposed, so that the mechanical property and heat resistance of the product are reduced, but the degradation performance of the product is improved; from comparison of example 1 and example 3, it can be found that when sodium alginate added into the product is not modified, pores of a crosslinked network in the product cannot be filled due to disappearance of nano silicon dioxide, so that degradation performance of the product is improved, and epoxy soybean oil only plays a role of a plasticizer in the product due to disappearance of silicon dioxide, and a new crosslinked network is not formed, so that heat resistance and flexibility of the product are reduced; as can be seen from a comparison of example 1 and example 4, when no catalyst was added to the product, the epoxidized soybean oil could not form a better crosslink with the modified sodium alginate, thereby reducing the heat resistance and flexibility of the product.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (1)

1. A processing technology of a biomass-based composite material for non-woven fabrics with high degradability mainly comprises the following steps:
(1) Sodium alginate and water are mixed according to the mass ratio of 1:55, adding ethyl orthosilicate with the mass of 4 times of sodium alginate and absolute ethyl alcohol with the mass of 10 times of sodium alginate into the 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 with the mass of 25 times 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) with a silane coupling agent KH-550 according to a mass ratio of 12:1, mixing, adding water 3 times the mass of the silane coupling agent KH-550 into the 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% by an extruder, standing for 3 hours, filtering, and drying to obtain modified sodium alginate;
(3) Polylactic acid and epoxidized soybean oil are mixed according to a mass ratio of 2:1, mixing, adding zinc chloride with the mass of 0.3 times of that of the polylactic acid into the mixture of the polylactic acid and the epoxidized soybean oil, and stirring and mixing;
(4) Oxidized starch and polyallylamine hydrochloride are mixed according to the mass ratio of 8:1 mixing in a beaker, adding a substance obtained in the step (2) with the mass of 0.6 times of that of oxidized starch and water with the mass of 8 times of that of the oxidized starch into the beaker, stirring and mixing for 1h at the temperature of 30 ℃ and the rotating speed of 350r/min, regulating the pH value of the material in the beaker to 10.0, continuing stirring and reacting for 3h at the temperature of 60 ℃ and the rotating speed of 300r/min, adding a reducing agent with the mass of 0.2 times of that of the oxidized starch into the beaker, stirring and reacting for 3h at the temperature of 60 ℃ and the rotating speed of 300r/min, filtering and drying;
(5) Mixing the substance obtained in the step (3) with 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);
the reducing agent in the step (4) is sodium borohydride;
the oxidized starch in the step (4) is prepared by oxidizing starch with hydrogen peroxide, wherein the starch is any one of tapioca starch and corn starch.
CN202010454895.1A 2019-04-22 2019-04-22 Processing technology of biomass-based composite material for non-woven fabric with high degradability Active CN111808334B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010454895.1A CN111808334B (en) 2019-04-22 2019-04-22 Processing technology of biomass-based composite material for non-woven fabric with high degradability

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010454895.1A CN111808334B (en) 2019-04-22 2019-04-22 Processing technology of biomass-based composite material for non-woven fabric with high degradability
CN201910321068.2A CN110129918B (en) 2019-04-22 2019-04-22 Biomass-based composite material with high degradability for non-woven fabric and processing technology thereof

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201910321068.2A Division CN110129918B (en) 2019-04-22 2019-04-22 Biomass-based composite material with high degradability for non-woven fabric and processing technology thereof

Publications (2)

Publication Number Publication Date
CN111808334A CN111808334A (en) 2020-10-23
CN111808334B true CN111808334B (en) 2023-08-04

Family

ID=67570482

Family Applications (3)

Application Number Title Priority Date Filing Date
CN202010454906.6A Withdrawn CN111793252A (en) 2019-04-22 2019-04-22 Processing technology of biomass-based composite material for non-woven fabric
CN202010454895.1A Active CN111808334B (en) 2019-04-22 2019-04-22 Processing technology of biomass-based composite material for non-woven fabric with high degradability
CN201910321068.2A Active CN110129918B (en) 2019-04-22 2019-04-22 Biomass-based composite material with high degradability for non-woven fabric and processing technology thereof

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN202010454906.6A Withdrawn CN111793252A (en) 2019-04-22 2019-04-22 Processing technology of biomass-based composite material for non-woven fabric

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201910321068.2A Active CN110129918B (en) 2019-04-22 2019-04-22 Biomass-based composite material with high degradability for non-woven fabric and processing technology thereof

Country Status (1)

Country Link
CN (3) CN111793252A (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111979587B (en) * 2019-09-25 2022-10-25 昱天(上海)新材料有限公司 Manufacturing method of composite conductive fabric
CN112175366A (en) * 2020-10-09 2021-01-05 卢定华 Biodegradable plastic and preparation method thereof
CN113813930B (en) * 2021-10-22 2023-10-27 福州大学 Modified biomass-based composite adsorption material for treating radioactive pollutants
CN115746493A (en) * 2022-10-19 2023-03-07 深圳市富恒新材料股份有限公司 Foaming reinforced ABS composite material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102839443A (en) * 2012-08-20 2012-12-26 太原理工大学 Preparation method for heat-resisting polylactic acid fiber
CN103223302A (en) * 2013-05-21 2013-07-31 中国海洋大学 Preparation method of self-assembly covalent cross-linked sodium filter membrane
CN104894865A (en) * 2015-06-24 2015-09-09 安徽皖翎羽绒制品有限公司 Deodorant and breathable feather-down composite heat-insulating material and making method thereof
CN106192217A (en) * 2016-07-22 2016-12-07 丁少忠 Plant base biodegradable non-woven fabrics and manufacture method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5656543B2 (en) * 2010-10-06 2015-01-21 昭和電工株式会社 Multi-layer film with biodegradability
CN105440606A (en) * 2014-09-02 2016-03-30 允友成(宿迁)复合新材料有限公司 Preparation method of fully biodegradable starch/polylactic acid base resin
CN107298835A (en) * 2017-07-27 2017-10-27 东莞铭丰包装股份有限公司 One kind can degradable biomass-based composite material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102839443A (en) * 2012-08-20 2012-12-26 太原理工大学 Preparation method for heat-resisting polylactic acid fiber
CN103223302A (en) * 2013-05-21 2013-07-31 中国海洋大学 Preparation method of self-assembly covalent cross-linked sodium filter membrane
CN104894865A (en) * 2015-06-24 2015-09-09 安徽皖翎羽绒制品有限公司 Deodorant and breathable feather-down composite heat-insulating material and making method thereof
CN106192217A (en) * 2016-07-22 2016-12-07 丁少忠 Plant base biodegradable non-woven fabrics and manufacture method thereof

Also Published As

Publication number Publication date
CN110129918B (en) 2020-07-07
CN111793252A (en) 2020-10-20
CN111808334A (en) 2020-10-23
CN110129918A (en) 2019-08-16

Similar Documents

Publication Publication Date Title
CN111808334B (en) Processing technology of biomass-based composite material for non-woven fabric with high degradability
CN110091564A (en) A kind of complete biological 100% degradable composite membrane and its processing technology and application
CN111040400A (en) Full-biodegradable sheet and preparation method thereof
CN103205021A (en) Thermoplastic and PBAT blend and preparation method thereof
CN109111710B (en) Heat-resistant PLA-based degradable plastic bottle and preparation method thereof
CN104387732A (en) Transparent, tear-resistant and biodegradable polylactic acid thin film and preparation method thereof
CN101875764A (en) Formable polylactic resin composition and preparation method for plastic strip thereof
CN111349253B (en) Modified lignin/PBS (Poly Butylene succinate) bioplastic film and preparation method thereof
CN109608701A (en) A kind of thermoplastic starch based foam material and preparation method
CN109504042A (en) PHA modified TPS/PBAT biodegradable resin and preparation method thereof
CN105368017A (en) High-fluidity PLA bioplastic
CN114031914A (en) Bio-based plastic uptake material and preparation method thereof
CN102617969B (en) Preparation method of thermoplastic konjac glucomannan/poly butylenes succinate blending material
CN113930065B (en) High-strength degradable packaging bag and preparation method thereof
CN101381509A (en) Polylactic acid/colophonium compound material and preparation method thereof
CN105176022A (en) Polylactic acid toughening modification plastic and preparation method thereof
CN114907680A (en) Recyclable water-soluble degradable foam material and preparation method thereof
CN111849177A (en) Full-biodegradable material
CN114605798A (en) Production process of degradable high polymer material film
CN113652067A (en) Method for preparing carbon fiber polylactic acid composite material
CN112321999A (en) Preparation method of hyperbranched polybutylene adipate terephthalate material
CN107266760A (en) A kind of degradable stalk polyethylene film and preparation method thereof
CN111534062A (en) High-performance PLA/fibrilia composite material and preparation method thereof
CN111944288A (en) Modified PLA material for biodegradable mulching film and preparation method thereof
CN112375354A (en) Carbon fiber polylactic acid filling master batch and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20230627

Address after: Room 101, Unit 1, Building 6, No. 6077 North Third Ring Road, High tech Zone, Baoding City, Hebei Province, 071000

Applicant after: Baoding High tech Zone Biobased New Materials Co.,Ltd.

Address before: Room 501, Building 18, Donggang Jiayuan, Beibaixiang Town, Leqing City, Wenzhou City, Zhejiang Province 325600

Applicant before: Lu Dinghua

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant