CN102140220A - Thermoplastic animal protein/polylactic acid blend material and preparation method thereof - Google Patents
Thermoplastic animal protein/polylactic acid blend material and preparation method thereof Download PDFInfo
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- CN102140220A CN102140220A CN 201110110962 CN201110110962A CN102140220A CN 102140220 A CN102140220 A CN 102140220A CN 201110110962 CN201110110962 CN 201110110962 CN 201110110962 A CN201110110962 A CN 201110110962A CN 102140220 A CN102140220 A CN 102140220A
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Abstract
The invention discloses a thermoplastic animal protein/polylactic acid blend material and a preparation method thereof. The thermoplastic animal protein/polylactic acid blend material comprises the following components in part by weight: 1 to 99 parts of thermoplastic animal protein, 1 to 99 parts of polylactic acid, 0 to 10 parts of cross-linking agent and 0 to 10 parts of plasticizer. The preparation method comprises the steps of preparing materials, drying and granulating. The product has high processability and has high thermoplastic processability and excellent mechanical properties in the processes of plastic extrusion, plastic blowing, plastic injection and foaming. The product, after being used, can be degraded completely and therefore is environmentally friendly. The product can be widely used in the production and processing fields, such as chemical, agricultural mulching film, electromechanical, building material, packaging and environment protection fields and other fields.
Description
Technical field
The present invention relates to thermoplastic animal albumen/polylactic acid blend material and preparation method thereof.
Background technology
The 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.
Animal proteinum 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 animal proteinum.Thereby the animal 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.Animal proteinum 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 animal proteinum and material modified the discarding thereof.
Poly(lactic acid) (PLA) is by artificial semisynthetic thermoplasticity aliphatic polyester, it is a kind of important lactic acid derivatives, be with lactic acid be monomer through the family macromolecule material that chemosynthesis obtains, be a kind of real biological plastics, its nontoxic, nonirritant, has excellent biological compatibility, plasticity-is good, biodegradable absorption, and its degraded product is water and carbonic acid gas, its physical properties is between PET and PA-6, and purposes is very extensive.But, poly(lactic acid) is as a kind of biolytic aliphatic polyester series material, different with the polyolefins material, the melt property of this class material is poor, the viscosity of material and intensity are all lower in the processed and applied process, 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; The decomposition of very easy generating material under melt state simultaneously makes the molecular weight and molecular weight of polymkeric substance surpass 50%, causes the mechanical strength of forming process goods seriously to descend.Therefore the processing characteristics of poly(lactic acid) is relatively poor, 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 animal albumen and the modification of poly(lactic acid) 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.
Summary of the invention
The purpose of this invention is to provide a kind of eco-friendly thermoplastic animal albumen/polylactic acid blend material and preparation method thereof.Thermoplastic animal albumen/polylactic acid blend can improve the processing characteristics of thermoplastic animal albumen, simultaneously can play plastification preferably to poly(lactic acid), problems such as deficiency such as solution poly(lactic acid) 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 animal albumen, the novel method of production environment close friend's animal proteinum/poly(lactic acid) thermoplastic materials is the service that large-scale develops and utilizes of renewable resources animal proteinum.
Technical scheme of the present invention is: with 1～99 part in thermoplastic animal albumen, 1～99 part of poly(lactic acid), 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 animal albumen/polylactic acid blend material under 110～150 ℃, 0.1～1MPa.
Above-mentioned thermoplastic animal albumen is that the animal wool behind the removal impurity is expanded, add raw material and weigh 2 times prozyme liquid, prozyme liquid is formulated by every kg water lipase 0.7g, neutral protease 2.0g and sanitas Sodium Silicofluoride 3.5g, raw material is with after prozyme liquid mixes, about adjust pH to 7.0,40 ℃ are interrupted stirring reaction 10 h down, the removal of impurities of enzymolysis after-filtration, add deionized water colloidal sol, collosol temperature is 70 ℃ → 80 ℃ → 90 ℃, initial pH value is 5, again through concentrated, dry, pulverizing, promptly obtains the purifying animal proteinum after the separation and purification of gained glue; Get 20 parts of purifying animal proteinums by weight, 600 parts of 50% liquor zinci chloridis are in reactor, and transferring the PH value with hydrochloric acid is 2, make its sour sex change, be warming up to 95 ℃ after 30 minutes, be incubated 30 minutes, make protein heat denaturation, add 20 parts of hydrogen peroxide after the sex change, 60 ℃ down reaction 60 minutes the gal4 amino acid side chain is modified, reaction finishes to add 20 parts of reactions of sodium bisulfite 30 minutes, removes unnecessary oxygen, add 60 parts in 0.2 part of ammonium persulphate and vinylformic acid more respectively, feed N simultaneously
2Stopped reaction behind reaction 2h under 60 ℃, reaction fully precipitates with acetone after finishing, and centrifugation gained solid obtains thermoplastic animal albumen through being washed to neutral final vacuum drying.
Poly(lactic acid) is selected poly-DL-lactic acid, poly (l-lactic acid), poly-DL-lactic acid copolymer or poly (l-lactic acid) multipolymer for use.
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 adipic acid dibutylester.
Thermoplastic animal albumen/polylactic acid blend material and preparation method thereof, its preparation process is:
The first step, batching: by weight proportioning heat-obtaining plasticity animal proteinum 1～99, poly(lactic acid) 1～99, linking agent 0～10, softening agent 0～10, stirring and evenly mixing 5～20 min 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 animal albumen/polylactic acid blend material to the blend composition that drying is good in twin screw extruder.
Useful technique effect of the present invention:
Animal proteinum 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 animal proteinum is the thermoplastic animal albumen/polylactic acid blend 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 animal albumen/polylactic acid blend material is discarded.Thermoplastic animal albumen and polylactic acid blend modification, 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 animal albumen and polylactic acid blend modification make its processing rheological characteristics similar to polyethylene, and conventional equipment easy to use carries out suitability for industrialized production.Thermoplastic animal albumen and polylactic acid blend modified 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.
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 done into-goes on foot detailed description.
Embodiment 1:By weight 1 part of heat-obtaining plasticity animal proteinum, 99 parts of poly-DL-lactic acid, 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 animal albumen/polylactic acid blend material under 110 ℃, 1MPa.
Embodiment 2:By weight 99 parts of heat-obtaining plasticity animal proteinums, 1 part of poly (l-lactic acid), 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 animal albumen/polylactic acid blend material under 150 ℃, 0.1MPa.
Embodiment 3:By weight 10 parts of heat-obtaining plasticity animal proteinums, 90 parts of poly-DL-lactic acid copolymers, 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 animal albumen/polylactic acid blend material under 120 ℃, 0.7MPa.
Embodiment 4:By weight 30 parts of heat-obtaining plasticity animal proteinums, 70 parts of poly (l-lactic acid) multipolymers, 5 parts of ethylene bis stearic acid amides and adipic acid dibutylester 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 animal albumen/polylactic acid blend material under 130 ℃, 0.5MPa.
Embodiment 5:By weight 50 parts of heat-obtaining plasticity animal proteinums, 50 parts of poly (l-lactic acid)s, 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 animal albumen/polylactic acid blend material under 140 ℃, 0.3MPa.
Embodiment 6:By weight 70 parts of heat-obtaining plasticity animal proteinums, 30 parts of poly (l-lactic acid) multipolymers, 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 animal albumen/polylactic acid blend material under 150 ℃, 0.2MPa.
Claims (6)
1. a thermoplastic animal albumen/polylactic acid blend material is characterized in that, the weight part proportioning of its each component is: thermoplastic animal albumen 1～99, poly(lactic acid) 1～99, linking agent 0～10, softening agent 0～10.
2. according to the described thermoplastic animal albumen/polylactic acid blend material of claim 1, it is characterized in that, described thermoplastic animal albumen is that the animal wool behind the removal impurity is expanded, add raw material and weigh 2 times prozyme liquid, prozyme liquid is by every kg water lipase 0.7g, neutral protease 2.0g and sanitas Sodium Silicofluoride 3.5g are formulated, raw material is with after prozyme liquid mixes, about adjust pH to 7.0,40 ℃ are interrupted stirring reaction 10 h down, and the removal of impurities of enzymolysis after-filtration adds deionized water colloidal sol, collosol temperature is 70 ℃ → 80 ℃ → 90 ℃, initial pH value is 5, and warp is concentrated again after the separation and purification of gained glue, dry, pulverize, promptly obtain the purifying animal proteinum; Get 20 parts of purifying animal proteinums by weight, 600 parts of 50% liquor zinci chloridis are in reactor, and transferring the PH value with hydrochloric acid is 2, make its sour sex change, be warming up to 95 ℃ after 30 minutes, be incubated 30 minutes, make protein heat denaturation, add 20 parts of hydrogen peroxide after the sex change, 60 ℃ down reaction 60 minutes the gal4 amino acid side chain is modified, reaction finishes to add 20 parts of reactions of sodium bisulfite 30 minutes, removes unnecessary oxygen, add 60 parts in 0.2 part of ammonium persulphate and vinylformic acid more respectively, feed N simultaneously
2Stopped reaction behind reaction 2h under 60 ℃, reaction fully precipitates with acetone after finishing, and centrifugation gained solid obtains thermoplastic animal albumen through being washed to neutral final vacuum drying.
3. thermoplastic animal albumen/polylactic acid blend material according to claim 1 is characterized in that, described poly(lactic acid) is poly-DL-lactic acid, poly (l-lactic acid), poly-DL-lactic acid copolymer or poly (l-lactic acid) multipolymer.
4. thermoplastic animal albumen/polylactic acid blend material according to claim 1 is characterized in that, described linking agent is a MALEIC ANHYDRIDE, the combination of one or more in tributyl citrate, ethylene bis stearic acid amide, the hexagonal boron nitride.
5. thermoplastic animal albumen/polylactic acid blend material according to claim 1 is characterized in that, described softening agent is a glycerol, polyoxyethylene glycol, dibutyl phthalate, the combination of one or more in the adipic acid dibutylester.
6. the method for preparing the described thermoplastic animal albumen/polylactic acid blend material of claim 1, its preparation process is:
The first step, batching: by weight proportioning heat-obtaining plasticity animal proteinum 1～99, poly(lactic acid) 1～99, linking agent 0～10, softening agent 0～10, stirring and evenly mixing 5～20 min 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 promptly gets product to the blend composition that drying is good under 110～150 ℃, 0.1～1MPa in twin screw extruder.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725070A (en) * | 2015-03-19 | 2015-06-24 | 烟台大学 | Method for preparing hair cement foaming agent |
| CN113912879A (en) * | 2021-08-20 | 2022-01-11 | 山东亿隆薄膜材料有限责任公司 | Environment-friendly heat shrinkable film |
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| CN101824229A (en) * | 2009-03-06 | 2010-09-08 | 西南科技大学 | Thermoplastic plant fiber/polylactic acid blending material and preparation method thereof |
| CN101851424A (en) * | 2009-03-31 | 2010-10-06 | 西南科技大学 | Thermoplastic plant protein/polylactic acid blend material and preparation method thereof |
| CN101864175A (en) * | 2009-04-16 | 2010-10-20 | 西南科技大学 | Thermoplastic animal protein/starch blending material and preparation method thereof |
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2011
- 2011-04-29 CN CN 201110110962 patent/CN102140220A/en active Pending
Patent Citations (3)
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| CN101824229A (en) * | 2009-03-06 | 2010-09-08 | 西南科技大学 | Thermoplastic plant fiber/polylactic acid blending material and preparation method thereof |
| CN101851424A (en) * | 2009-03-31 | 2010-10-06 | 西南科技大学 | Thermoplastic plant protein/polylactic acid blend material and preparation method thereof |
| CN101864175A (en) * | 2009-04-16 | 2010-10-20 | 西南科技大学 | Thermoplastic animal protein/starch blending material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725070A (en) * | 2015-03-19 | 2015-06-24 | 烟台大学 | Method for preparing hair cement foaming agent |
| CN104725070B (en) * | 2015-03-19 | 2016-08-24 | 烟台大学 | A kind of preparation method of hair cement blowing agent |
| CN113912879A (en) * | 2021-08-20 | 2022-01-11 | 山东亿隆薄膜材料有限责任公司 | Environment-friendly heat shrinkable film |
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Application publication date: 20110803 |