CN101824166A - Thermoplastic glucomannan/plant fiber blending material and preparation method thereof - Google Patents

Abstract

The invention discloses a thermoplastic glucomannan/plant fiber blending material and a preparation method thereof. The material comprises the following components in parts by weight: 1-99 parts of thermoplastic glucomannan, 1-99 parts of thermoplastic plant fiber, 0-10 parts of cross-linking agent and 0-10 parts of plasticizer. The preparation method comprises the following steps: stirring the raw materials in a high-speed mixer for 5-20 minutes; drying the materials at the temperature of 30-60 DEG C for 8-12 hours; controlling the temperature to 100-140 DEG C, and then melt-mixing the mixture in a double-screw extruder for 5-10 minutes; and finally granulating at the temperature of 110-150 DEG C and under the pressure of 0.1-1MPa to obtain the completely biodegradable thermoplastic glucomannan/plant fiber blending material. The obtained thermoplastic glucomannan/plant fiber blending material has good processability, excellent thermoplastic processing characteristics and excellent mechanical properties in the process of extrusion molding, blow molding, injection molding and foaming; and the obtained finished product can be completely degradable after being used and is environment-friendly, and can be widely applied to the production and processing fields of chemical industry, mulch, electromechanical industry, building materials, package, environmental protection and the like.

Description

Thermoplastic glucomannan material and preparation method thereof

(1) technical field the present invention relates to thermoplastic glucomannan material and preparation method thereof.

(2) the background technology whole world has limited petrochemical industry resources such as 1.5 hundred million tons of oil, Sweet natural gas to be used for chemosynthesis " synthetic macromolecule " every year, in order to reduce discarded synthesized polymer material product to the influence of environment and the utilization of limited resources, the human society of constructing Sustainable development has again become the common recognition of countries in the world.Realize the Sustainable development of world economy, one of correlative study both domestic and external forward position is to utilize clearer production technology, with reproducible biomass resource, modification, the synthetic environmental friendliness polymer novel material that satisfies service requirements, reduction is to the consumption of limited resources, reduce material and use the pollution of back to environment, correlative study both domestic and external for this reason more pays attention to seeking new natural polymer plastic material.

Konjac glucomanna is a kind of from plant konjaku, jerusalem artichoke, any of several broadleaf plants lotus root; the natural macromolecule amylose that extracts in the microbial bacterial; comprise glucose and seminose in its molecule; with β-1; the 4-glycosidic link connects; simultaneously also have the short-chain branch structure on seminose C-3 position, and also have acetyl group (having an ethanoyl on per approximately 19 saccharide residues) on the C-6 position, the size of macromolecule water-solubility has been controlled in the existence of these ethanoyl.Multifrequency natures such as konjac glucomanna possess hydrophilic property, gelation, film-forming properties, germ resistance, edibility, low heat value and the physiological function that some are special can be widely used in environmental protection, food, medicine, chemical industry and biological field.Sufficient, biodegradable as a kind of renewable natural resource source, have chemical modifiable functional group, and have certain complexing of metal ion ability.Thermoplastic remodeling back konjac glucomanna, be that a kind of process is by Rhizoma amorphophalli glucomannan and various organic monomer radical polymerization, grafting, but the thermoplastic materials of a kind of fully biodegradable that chemical process such as crosslinked obtains, has very strong hydrophobicity, have vast market prospect, provide new thinking for substituting the petrochemical complex plastic prod future, but the processing characteristics of thermoplastic glucomannan glycan is not good, its rheological characteristics is not suitable for processing the product that meets service requirements on the conventional polymer processing units, and comprehensive mechanical property is difficult to satisfy service requirements.

Vegetable fibre is a reproducibility biopolymer resource huge on the earth.From Sustainable utilization of resources, protection environment and biocompatible and Biodegradable characteristics, people have entrusted to the care of very big expectation for the utilization of energy regenerated vegetable fibre.Thereby the vegetable fibre recycling, development environment close friend's green product, the hot fields in having formed the green high-tech research of environment and having developed.Vegetable fibre is as renewable resources, its modification and utilization can be saved the bulk petroleum resource on the one hand, the environmental pollution that a large amount of non-degraded synthesized polymer material wastes cause can be alleviated on the other hand, the circulation of biomass can be in physical environment, realized after vegetable fibre and material modified the discarding thereof.

The novel thermoplastic intermingling material processing characteristics that obtains after thermoplastic glucomannan and the modification of thermoplastic plant fiber melt blending is good, in extrusion molding, blowing, injection moulding and foaming process, have good thermoplastic processing characteristics and mechanical property, degrade fully and environmental friendliness after its goods use, can be widely used in process for processing fields such as chemical industry, farmland film, electromechanics, material of construction, packing and environmental protection.

(3) summary of the invention

1, goal of the invention the purpose of this invention is to provide a kind of eco-friendly thermoplastic glucomannan material and preparation method thereof.Thermoplastic glucomannan can be improved the processing characteristics of thermoplastic plant fiber, simultaneously can play plastification preferably to thermoplastic glucomannan, problems such as deficiency such as solution thermoplastic glucomannan processing characteristics, toughness and tear resistance deficiency, elongation at break is low, film is more crisp, providing a kind of is raw material with natural konjac glucomanna and vegetable fibre, the novel method of thermoplastic glucomannan/sponge of production environment close friend is the service that large-scale develops and utilizes of renewable resources konjac glucomanna and vegetable fibre.

2, technical scheme technical scheme of the present invention is: a kind of thermoplastic glucomannan material, the weight part of its each component is: thermoplastic glucomannan 1～99, thermoplastic plant fiber 1～99, linking agent 0～10, softening agent 0～10.Its preparation method is: with 1～99 part of thermoplastic glucomannan, 1～99 part of thermoplastic plant fiber, 0～10 part of linking agent and softening agent stirred in high-speed mixer 5～20 minutes for 0～10 part, 30～60 ℃ of dryings of temperature 8～12 hours, temperature control in 100～140 ℃ with blend composition melt blending 5～10min in Bitruder, granulation obtains complete biodegradable thermoplastic glucomannan material under 110～150 ℃, 0.1～1MPa.

Thermoplastic glucomannan is by weight ratio with 100 parts of purifying konjac glucomannas, swells in 500 parts of 50% the konjac glucomanna aqueous ethanolic solutions of pH10; temperature control carried out deacetylation 10 hours for 50 ℃; filter, washing is to neutral, 50 ℃ of dryings 12 hours, swell in again in 500 parts of water; 50 ℃ of temperature controls; add 2 parts of Potassium Persulphates and 100 parts of monomers of methyl acrylate 1～5 initiator, graft copolymerization 4 hours filters and cleans; drying 12 under 50 ℃～hour, thermoplastic glucomannan promptly obtained.

Thermoplastic plant fiber is that the plant fiber material after the impurity elimination is pulverized, the 1%H2SO4 solution expanded, that adding vegetable fibre weight is 2 times is handled 1h down at 120 ℃, filter, clean, dry, pulverized 40 mesh sieves, obtain removing the pure plant fiber powder of lignin and pentosan; The 18%NaOH solution that in pure plant fiber powder, adds 3 times, at 30 ℃ of dipping 2h down, squeezing is squeezed and is removed unnecessary alkali lye, makes to contain alkali lye in the vegetable fibre and be controlled at 50%, promptly obtains the alkalization vegetable fibre; Get 200 parts of alkalization 100 parts on vegetable fibre, 2 parts of Potassium Persulphates, methyl acrylates by weight in reactor, feed N2 simultaneously, 30 ℃ of following stirring reaction 10h are neutralized to pH7.0 to the acetum that adds 10% after material is pulpous state; Reaction solution is removed solution by centrifugation, and the gained solid is drying to obtain thermoplastic plant fiber through being washed to neutral final vacuum; Linking agent is selected MALEIC ANHYDRIDE for use, the arbitrary combination of one or more in tributyl citrate, ethylene bis stearic acid amide, the hexagonal boron nitride; Softening agent is selected glycerol for use, polyoxyethylene glycol, dibutyl phthalate, the arbitrary combination of one or more in the Polycizer W 260.

The thermoplastic glucomannan preparation methods, its preparation process is:

The first step, batching: by weight proportioning heat-obtaining plasticity konjac glucomanna 1～99, thermoplastic plant fiber 1～99, linking agent 0～10, softening agent 0～10, stirring and evenly mixing 5～20min in high-speed mixer.

Second step, drying: with the blend that mixes 30～60 ℃ of dryings of temperature 8～12 hours.

In the 3rd step, the blend granulation: in 100～140 ℃ of melt blending 5～10min, extruding pelletization under 110～150 ℃, 0.1～1MPa is prepared into the thermoplastic glucomannan material to the blend composition that drying is good in twin screw extruder.

3, beneficial effect konjac glucomanna and vegetable fibre are as a kind of renewable natural resource, and the source is sufficient and biodegradable.It is carried out blending and modifying, and can obtain with the vegetable fibre is the thermoplastic glucomannan novel material of skeleton.As renewable resources, its blending and modifying and utilization can be saved the bulk petroleum resource on the one hand, the environmental pollution that a large amount of non-degraded synthesized polymer material wastes cause can be alleviated on the other hand, the circulation of biomass can be in physical environment, realized after the thermoplastic glucomannan material is discarded.Thermoplastic glucomannan and thermoplastic plant fiber blending and modifying, both consistencies are fine, can reach the thermodynamic compatibility state, avoid the phenomenon of phase separation of product, improved the stability of modified product performance.Thermoplastic glucomannan and thermoplastic plant fiber blending and modifying make its processing rheological characteristics similar to polyethylene, and conventional equipment easy to use carries out suitability for industrialized production.Thermoplastic glucomannan and thermoplastic plant fiber blending and modifying product, comprehensive mechanical property is good, degrades fully and environmental friendliness after its goods use, and can be widely used in process for processing fields such as chemical industry, farmland film, electromechanics, material of construction, packing and environmental protection.

(4) embodiment the present invention realizes that by following concrete implementing measure wherein said raw material umber is parts by weight except that specified otherwise.Below in conjunction with embodiment the present invention is described in further details.

Embodiment 1: by weight 1 part of heat-obtaining plasticity konjac glucomanna, 99 parts of thermoplastic plant fibers, MALEIC ANHYDRIDE stirred 5 minutes in high-speed mixer for 1 part, 30 ℃ of dryings of temperature 12 hours, temperature control in 100 ℃ with blend composition melt blending 5min in Bitruder, granulation obtains product of the present invention under 110 ℃, 1MPa.

Embodiment 2: by weight 99 parts of heat-obtaining plasticity konjac glucomannas, 1 part of thermoplastic plant fiber, dibutyl phthalate stirred 20 minutes in high-speed mixer for 10 parts, 60 ℃ of dryings of temperature 8 hours, temperature control in 140 ℃ with blend composition melt blending 10min in Bitruder, granulation obtains product of the present invention under 150 ℃, 0.1MPa.

Embodiment 3: by weight 10 parts of heat-obtaining plasticity konjac glucomannas, 90 parts of thermoplastic plant fibers, 3 parts of tributyl citrates and 3 parts of glycerol, polyoxyethylene glycol stirred 8 minutes in high-speed mixer for 7 parts, 40 ℃ of dryings of temperature 10 hours, temperature control in 110 ℃ with melt blending material blend 6min in Bitruder, granulation obtains product of the present invention under 120 ℃, 0.7MPa.

Embodiment 4: by weight 30 parts of heat-obtaining plasticity konjac glucomannas, 70 parts of thermoplastic plant fibers, 5 parts of ethylene bis stearic acid amides and Polycizer W 260 stirred 10 minutes in high-speed mixer for 3 parts, 45 ℃ of dryings of temperature 12 hours, temperature control in 120 ℃ with blend composition melt blending 7min in Bitruder, granulation obtains product of the present invention under 130 ℃, 0.5MPa.。

Embodiment 5: by weight 50 parts of heat-obtaining plasticity konjac glucomannas, 50 parts of thermoplastic plant fibers, 7 parts of hexagonal boron nitrides and polyoxyethylene glycol stirred 15 minutes in high-speed mixer for 5 parts, 35 ℃ of dryings of temperature 12 hours, temperature control in 130 ℃ with blend composition melt blending 8min in Bitruder, granulation obtains product of the present invention under 140 ℃, 0.3MPa.

Embodiment 6: by weight 70 parts of heat-obtaining plasticity konjac glucomannas, 30 parts of thermoplastic plant fibers, 5 parts of tributyl citrates, 5 parts of ethylene bis stearic acid amides and glycerol stirred 12 minutes in high-speed mixer for 7 parts, 50 ℃ of dryings of temperature 8 hours, temperature control in 140 ℃ with blend composition melt blending 9min in Bitruder, granulation obtains product of the present invention under 150 ℃, 0.2MPa.

Claims (6)

1. a thermoplastic glucomannan material is characterized in that, the weight part of its each component is: thermoplastic glucomannan 1～99, thermoplastic plant fiber 1～99, linking agent 0～10, softening agent 0～10.

2. according to the described thermoplastic glucomannan material of claim 1; it is characterized in that; described thermoplastic glucomannan; be by weight ratio with 100 parts of purifying konjac glucomannas; swell in 500 parts of 50% the konjac glucomanna aqueous ethanolic solutions of pH10; temperature control carried out deacetylation 10 hours for 50 ℃; filter; washing is to neutral, 50 ℃ of dryings 12 hours, swells in 500 parts of water again; 50 ℃ of temperature controls; add 2 parts of Potassium Persulphates and 100 parts of monomers of methyl acrylate 1～5 initiator, graft copolymerization 4 hours filters and cleans; drying 12 under 50 ℃～hour, thermoplastic glucomannan promptly obtained.

3. according to the described thermoplastic glucomannan material of claim 1, it is characterized in that, described thermoplastic plant fiber, be that the plant fiber material after the impurity elimination is pulverized, the 1%H2SO4 solution expanded, that adding vegetable fibre weight is 2 times is handled 1h down at 120 ℃, filter, clean, dry, pulverized 40 mesh sieves, obtain removing the pure plant fiber powder of lignin and pentosan; The 18%NaOH solution that in pure plant fiber powder, adds 3 times, at 30 ℃ of dipping 2h down, squeezing is squeezed and is removed unnecessary alkali lye, makes to contain alkali lye in the vegetable fibre and be controlled at 50%, promptly obtains the alkalization vegetable fibre; Get 200 parts of alkalization 100 parts on vegetable fibre, 2 parts of Potassium Persulphates, methyl acrylates by weight in reactor, feed N2 simultaneously, 30 ℃ of following stirring reaction 10h are neutralized to pH7.0 to the acetum that adds 10% after material is pulpous state; Reaction solution is removed solution by centrifugation, and the gained solid is drying to obtain thermoplastic plant fiber through being washed to neutral final vacuum.

4. thermoplastic glucomannan material according to claim 1, it is characterized in that, described linking agent is a MALEIC ANHYDRIDE, the arbitrary combination of one or more in tributyl citrate, ethylene bis stearic acid amide, the hexagonal boron nitride.

5. thermoplastic glucomannan material according to claim 1 is characterized in that, described softening agent is a glycerol, polyoxyethylene glycol, dibutyl phthalate, the arbitrary combination of one or more in the Polycizer W 260.

6. prepare the method for the described thermoplastic glucomannan material of claim 1, the steps include:

The first step, batching: by weight proportioning heat-obtaining plasticity konjac glucomanna 1～99, thermoplastic plant fiber 1～99, linking agent 0～10, softening agent 0～10, stirring and evenly mixing 5～20min in high-speed mixer;

Second step, drying: with the blend that mixes 30～60 ℃ of dryings of temperature 8～12 hours;

In the 3rd step, the blend granulation: in 100～140 ℃ of melt blending 5～10min, extruding pelletization under 110～150 ℃, 0.1～1MPa is prepared into the thermoplastic glucomannan material to the blend composition that drying is good in twin screw extruder.