CN101864176A - Thermoplastic vegetable protein/starch blending material and preparation method thereof - Google Patents
Thermoplastic vegetable protein/starch blending material and preparation method thereof Download PDFInfo
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- CN101864176A CN101864176A CN200910058963A CN200910058963A CN101864176A CN 101864176 A CN101864176 A CN 101864176A CN 200910058963 A CN200910058963 A CN 200910058963A CN 200910058963 A CN200910058963 A CN 200910058963A CN 101864176 A CN101864176 A CN 101864176A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92923—Calibration, after-treatment or cooling zone
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a thermoplastic vegetable protein/starch blending material and a preparation method thereof. The thermoplastic vegetable protein/starch blending material comprises the following ingredients by weight parts: 1 to 99 of thermoplastic vegetable protein, 1 to 99 of thermoplastic starch, 0 to 10 of cross linking agents and 0 to 10 of plasticizing agents. The preparation method comprises the following steps: placing raw materials into a high-speed mixing machine to be stirred for 5 to 20 minutes; carrying out drying for 8 to 12 hours at a temperature between 30 and 60 DEG C; controlling the temperature between 100 and 140 DEG C; carrying out fused blending on blending materials in a double-screw plastic extruding machine for 5 to 10 min; and carrying out granulation at 110 to 150 DEG C and at 0.1 to 1 MPa to obtain products. The products of the invention have good processing performance, and have good thermoplastic processing characteristics and mechanical property in the plastic extrusion, plastic blowing, plastic injection molding and foaming processes. The products can be completely degraded after use, and in addition, the invention has the environment-friendly effect, and can be widely used in the production processing fields of chemical engineering, agricultural ground films, electromechanics, building materials, package, environment protection and the like.
Description
(1) technical field the present invention relates to a kind of thermoplastic vegetable protein/starch blending 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.
Vegetable-protein 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-protein.Thereby the plant protein resource utilization, development environment close friend's green product, the hot fields in having formed the green high-tech research of environment and having developed.Vegetable-protein 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-protein and material modified the discarding thereof.
Starch is that the source is abundant, low-cost natural high molecular substance, is a kind of inexhaustible renewable resources.Starch have can regenerate, cheap, the characteristics of easily preserving and being convenient to transport, can carry out various reactions under certain condition, derive numerous derivatives.Utilizability that starch is good and biological degradability make it become the good raw material of biodegradable material, the starch base derivant material can be by biological degradation under multiple environment, eventual degradation product C O2 and H2O can carry out recirculation by photosynthesis, can not produce any pollution to environment.Countries in the world are attached great importance to the research and development of starch base thermoplastic materials for many years, but the thermoplastic starch melt property is poor, exist difficulty in the processed and applied process, the viscosity of its material and intensity are all lower, cause in the molding process typing speed very slow, it is very big to implement processing mode difficulty such as blowing, calendering, injection moulding spinning, is difficult to process the product that meets service requirements by the working method of routine on the conventional polymer processing units.
The novel thermoplastic intermingling material processing characteristics that obtains after thermoplastic vegetable protein and the modification of thermoplastic starch 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 vegetable protein/starch blending material and preparation method thereof.Thermoplastic vegetable protein/starch blending can improve the processing characteristics of thermoplastic vegetable protein, simultaneously can play plastification preferably to thermoplastic starch, problems such as deficiency such as solution thermoplastic starch processing characteristics, toughness and tear resistance deficiency, elongation at break is low, film is more crisp, providing a kind of is raw material with the natural plant protein, the novel method of production environment close friend's vegetable-protein/starch thermoplastic materials is the service that large-scale develops and utilizes of renewable resources vegetable-protein.
2, technical scheme technical scheme of the present invention is:
A kind of thermoplastic vegetable protein/starch blending material, the weight part proportioning of its each component is: thermoplastic vegetable protein 1～99, thermoplastic starch 1～99, linking agent 0～10, softening agent 0～10.Described thermoplastic vegetable protein is that one or more plant protein materials in the soybean meal after the impurity elimination, peanut meal, the Semen Brassicae campestris dregs of rice, cottonseed meal, sunflower seed dregs, leached tea oil slag, rice bran, the wheat bran are pulverized, the NaOH solution that adds the pH8.0 of 10 times of vegetable-protein weight, handle 1h down at 50 ℃, filter, centrifugal, remove insoluble impurities, filtrate transfers pH to 4.5 to make the protein condenses precipitation, separate, wash, neutralize with sulfuric acid, promptly obtains the plant purifying protein; The urea buffered soln of 30 times of purifying vegetable-protein and purifying protein weight is added in the reactor, under the condition of logical nitrogen, stir 30min in 60 ℃, add the mercaptoethanol reaction 1h suitable then with purifying vegetable-protein weight, protein molecule fully stretches in solution, add initiator and grafted monomer more respectively, feed N2 stopped reaction behind reaction 3h under 60 ℃ simultaneously, fully precipitate with acetone, centrifugation gained solid obtains thermoplastic vegetable protein through being washed to neutral final vacuum drying; Described thermoplastic starch is to get 16 parts in 100 parts of starch, 15 parts of glycerine, 20 parts of maleic anhydrides, 0.035 part of tert-butyl peroxide, 3 parts of dioctyl maleates and water by weight, after high speed mixing roll mixing stirring, carry out the melt blending graft reaction at 140 ℃～160 ℃ by forcing machine, the extruding pelletization after reaction finishes obtains thermoplastic starch; Described 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; Described 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 vegetable protein of thermoplastic vegetable protein/starch blending material/starch blending material preparation method the steps include:
The first step, batching: by weight proportioning heat-obtaining plasticity vegetable-protein 1～99, thermoplastic starch 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 thermoplastic vegetable protein/starch blending material to the blend composition that drying is good in twin screw extruder.
3, the beneficial effect vegetable-protein is 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-protein is the thermoplastic vegetable protein/starch blending 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 thermoplastic vegetable protein/starch blending material is discarded.Thermoplastic vegetable protein and thermoplastic starch 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 vegetable protein and thermoplastic starch blending and modifying make its processing rheological characteristics similar to polyethylene, and conventional equipment easy to use carries out suitability for industrialized production.Thermoplastic vegetable protein and thermoplastic starch 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
Below in conjunction with embodiment the present invention is described in further details, wherein said raw material umber is parts by weight except that specified otherwise.
Embodiment 1: by weight 1 part of heat-obtaining plasticity vegetable-protein, 99 parts of thermoplastic starchs, 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 complete biodegradable thermoplastic vegetable protein/starch blending material under 110 ℃, 1MPa.
Embodiment 2: by weight 99 parts of heat-obtaining plasticity vegetable-proteins, 1 part of thermoplastic starch, 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 complete biodegradable thermoplastic vegetable protein/starch blending material under 150 ℃, 0.1MPa.
Embodiment 3: by weight 10 parts of heat-obtaining plasticity vegetable-proteins, 90 parts of thermoplastic starchs, 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 complete biodegradable thermoplastic vegetable protein/starch blending material under 120 ℃, 0.7MPa.
Embodiment 4: by weight 30 parts of heat-obtaining plasticity vegetable-proteins, 70 parts of thermoplastic starchs, 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 complete biodegradable thermoplastic vegetable protein/starch blending material under 130 ℃, 0.5MPa.
Embodiment 5: by weight 50 parts of heat-obtaining plasticity vegetable-proteins, 50 parts of thermoplastic starchs, 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 complete biodegradable thermoplastic vegetable protein/starch blending material under 140 ℃, 0.3MPa.
Embodiment 6: by weight 70 parts of heat-obtaining plasticity vegetable-proteins, 30 parts of thermoplastic starchs, 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 complete biodegradable thermoplastic vegetable protein/starch blending material under 150 ℃, 0.2MPa.
Claims (6)
1. a thermoplastic vegetable protein/starch blending material is characterized in that, the weight part proportioning of its each component is: thermoplastic vegetable protein 1～99, thermoplastic starch 1～99, linking agent 0～10, softening agent 0～10.
2. according to the described thermoplastic vegetable protein/starch blending material of claim 1, it is characterized in that, described thermoplastic vegetable protein is that one or more plant protein materials in the soybean meal after the impurity elimination, peanut meal, the Semen Brassicae campestris dregs of rice, cottonseed meal, sunflower seed dregs, leached tea oil slag, rice bran, the wheat bran are pulverized, the NaOH solution that adds the pH8.0 of 10 times of vegetable-protein weight, handle 1h down at 50 ℃, filter, centrifugal, remove insoluble impurities, filtrate transfers pH to 4.5 to make the protein condenses precipitation, separate, wash, neutralize with sulfuric acid, promptly obtains the plant purifying protein; The urea buffered soln of 30 times of purifying vegetable-protein and purifying protein weight is added in the reactor, under the condition of logical nitrogen, stir 30min in 60 ℃, add the mercaptoethanol reaction 1h suitable then with purifying vegetable-protein weight, protein molecule fully stretches in solution, add initiator and grafted monomer more respectively, feed N simultaneously
2Stopped reaction behind reaction 3h under 60 ℃ fully precipitates with acetone, and centrifugation gained solid obtains thermoplastic vegetable protein through being washed to neutral final vacuum drying.
3. thermoplastic vegetable protein/starch blending material according to claim 1, it is characterized in that, described thermoplastic starch is to get 16 parts in 100 parts of starch, 15 parts of glycerine, 20 parts of maleic anhydrides, 0.035 part of tert-butyl peroxide, 3 parts of dioctyl maleates and water by weight, after high speed mixing roll mixing stirring, carry out the melt blending graft reaction at 140 ℃～160 ℃ by forcing machine, the extruding pelletization after reaction finishes obtains thermoplastic starch.
4. thermoplastic vegetable protein/starch blending material according to claim 1 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. according to claim 1 described thermoplastic vegetable protein/starch blending material, it 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 vegetable protein/starch blending material of claim 1, the steps include:
The first step, batching: by weight proportioning heat-obtaining plasticity vegetable-protein 1～99, thermoplastic starch 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 thermoplastic vegetable protein/starch blending material to the blend composition that drying is good in twin screw extruder.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100589636A CN101864176B (en) | 2009-04-16 | 2009-04-16 | Thermoplastic vegetable protein/starch blending material and preparation method thereof |
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| CN2009100589636A CN101864176B (en) | 2009-04-16 | 2009-04-16 | Thermoplastic vegetable protein/starch blending material and preparation method thereof |
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| CN101864176A true CN101864176A (en) | 2010-10-20 |
| CN101864176B CN101864176B (en) | 2011-08-31 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665446A (en) * | 2013-11-29 | 2014-03-26 | 南宁市日建塑料包装有限责任公司 | Biodegradable plastic preparation method |
| CN109439332A (en) * | 2018-10-31 | 2019-03-08 | 曲靖促创科技有限公司 | A kind of anti-drought water-retaining agent and preparation method thereof |
| CN109679307A (en) * | 2018-12-27 | 2019-04-26 | 泸州天浩新材料研究所(普通合伙) | A kind of biodegradable pearl cotton and preparation method thereof |
| CN112659502A (en) * | 2020-12-27 | 2021-04-16 | 太仓奇晔塑料制品有限公司 | Environment-friendly injection molding process for preparing degradable plastic container product |
| CN113861635A (en) * | 2021-10-19 | 2021-12-31 | 上海复命新材料科技有限公司 | Starch modified PBAT/PLA biodegradable plastic film and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5922379A (en) * | 1998-05-05 | 1999-07-13 | Natural Polymer International Corporation | Biodegradable protein/starch-based thermoplastic composition |
| AU2003901311A0 (en) * | 2003-03-21 | 2003-04-03 | George Weston Foods Limited | Coating compositions |
| US8257775B2 (en) * | 2007-03-20 | 2012-09-04 | T.F.H. Publications, Inc. | Molded products based upon textured vegetable protein |
-
2009
- 2009-04-16 CN CN2009100589636A patent/CN101864176B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665446A (en) * | 2013-11-29 | 2014-03-26 | 南宁市日建塑料包装有限责任公司 | Biodegradable plastic preparation method |
| CN109439332A (en) * | 2018-10-31 | 2019-03-08 | 曲靖促创科技有限公司 | A kind of anti-drought water-retaining agent and preparation method thereof |
| CN109679307A (en) * | 2018-12-27 | 2019-04-26 | 泸州天浩新材料研究所(普通合伙) | A kind of biodegradable pearl cotton and preparation method thereof |
| CN112659502A (en) * | 2020-12-27 | 2021-04-16 | 太仓奇晔塑料制品有限公司 | Environment-friendly injection molding process for preparing degradable plastic container product |
| CN113861635A (en) * | 2021-10-19 | 2021-12-31 | 上海复命新材料科技有限公司 | Starch modified PBAT/PLA biodegradable plastic film and preparation method thereof |
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| CN101864176B (en) | 2011-08-31 |
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Granted publication date: 20110831 Termination date: 20120416 |