CN102443269A - Radiation modified soybean isolated protein/starch plastic and preparation method thereof - Google Patents
Radiation modified soybean isolated protein/starch plastic and preparation method thereof Download PDFInfo
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- CN102443269A CN102443269A CN2011103163721A CN201110316372A CN102443269A CN 102443269 A CN102443269 A CN 102443269A CN 2011103163721 A CN2011103163721 A CN 2011103163721A CN 201110316372 A CN201110316372 A CN 201110316372A CN 102443269 A CN102443269 A CN 102443269A
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Abstract
The invention claims a radiation modified soybean isolated protein/starch biodegradable plastic and a preparation method thereof, wherein the radiation modified soybean isolated protein/starch plastic is prepared by taking soybean isolated protein and starch as main materials and modifying the materials by ray radiation; when the biodegradable plastic is prepared, each material is mixed according to the following parts by weight: 85-95 parts of modified soybean isolated protein, 5-15 parts of modified starch, 1-3 parts of caprolactam, 10-20 parts of water and 10-25 parts of glycerol. The invention has the following advantages: the soybean isolated protein is modified by proper methanol or ethanol, so hydrophilic group in the protein is reduced and water resistance of the plastic is improved. Proper starch is taken as the filler, so that flexibility of the plastic is enhanced and cost is reduced to be suitable for industrial production. Meanwhile, by regulating content of the starch and irradiation dose, materials with different mechanical properties can be obtained, thereby obtaining high technology content and innovation. The preparation technology adopts a common plastic device and a method thereof, so the process is simple, and easy to operate. Furthermore, the radiation modified soybean isolated protein/starch plastic is formed by the modified soybean isolated protein and a plasticiser by hot pressing, so that the radiation modified soybean isolated protein/starch plastic, after being discarded, is very easy to decompose into carbon dioxide and water by microbe without environmental pollution. The soybean protein is an inexhaustible renewable resource.
Description
Technical field
The present invention the invention belongs to the natural macromolecular material field, relates to plastic of soybean protein and radiation processing technology, is specifically related to Sunlover 10 and the crosslinked bio-degradable plastics of starch and preparation method thereof, also belongs to technical field of environmental science.
Background technology
After 20th century; The research of synthesized polymer material this respect is advanced by leaps and bounds, and material has promoted development of human society and human civilization advance as the basic substance of social development; Performance based on the excellence of petroleum base macromolecule polymer material has been widely used in fields of society.Yet, plastics bring life facility, the quality of making the life better to people when, also brought two more insoluble problems to the mankind: the one, environmental pollution is serious; The 2nd, petroleum resources are in short supply.Plastics pollution is the problem that the current whole world is paid close attention to seeking new eco-friendly non-petroleum base polymkeric substance, and the effective way that Biodegradable material takes stopgap measures just and effects a permanent cure becomes the needs of China's Sustainable development.
Irradiation has been widely used in chemical industry since rising from the sixties as a kind of processing technology and means, organic polymer material complete processing particularly, and its correlative study constantly heats up, and has formed the level of commercial production scale.Irradiation can cause that the chemical transformation of high molecular polymer wrapping material has crosslinking reaction, depolymerization reaction etc., and crosslinked and cracking usually takes place polymkeric substance simultaneously.The factor that influences chemical transformation mainly is irradiation dose, Material Characteristics, no oxygen existence etc. is arranged that the size of dose rate does not influence degree of crosslinking and degree of depolymerizaton.Because Plastic Packaging Materials is synthesized polymer material, be the polymkeric substance of organic monomer, so various materials are because molecule monomer, degree of crosslinking, compound method, other compositions of being added are not quite similar, its character also has bigger difference.Irradiation products has its original characteristics than the product of traditional chemical method production: suitable machining at low temperature, operate continuously property is strong, product purity is high, quality is good, less energy consumption, cost is low, technology is simple, and pollutes for a short time, meets the trend of following environmental protection.Therefore, estimate that the following relevant research and development of radiotechnology aspect polymer will obtain bigger development.
Source such as natural high molecular substance such as starch, Mierocrystalline cellulose, semicellulose, xylogen, pectin, chitin, protein is abundant, cheap; Particularly utilize the bioabsorbable polymer material of their preparations to degrade fully; Has excellent biological compatibility; And safety non-toxic, the product that forms thus have the double meaning with environmental improvement that makes full use of of natural renewable resource concurrently, thereby receive the attention of various countries.That natural macromolecular material has is cheap, plurality of advantages such as degraded fully, and for this reason, eye is all invested the research and development of renewable resources-natural polymer by world developed country.Exploitation and popularization renewable resources product not only help preserving the ecological environment, and help developing new farm crop and new chemical technology and the growth of promotion agricultural and the chance that creates more jobs, for developing country brings than the large economy benefit.
Since beginning particularly the eighties, countries in the world are dropped into the research and development that a large amount of human and material resources are devoted to the degradable polymer material one after another seventies, and the progress that obtains in many aspects so far is encouraging.But protein material also has some technical barriers that need to be resolved hurrily in research and application process, these difficult problems mainly concentrate on the following aspects:
(1) soybean protein isolate Biodegradable material rigidity is strong, snappiness is poor, water resisting property is poor, is difficult to satisfy suitability for industrialized production processing needs.
(2) soybean protein isolate Biodegradable material cost is higher, in view of present form, is difficult to the market operation.
(3) use partially filled raw material to improve product performance in the soybean protein isolate Biodegradable material, but builder and Sunlover 10 are difficult to perfect adaptation, cause that material surface is rough, color and luster is not attractive in appearance.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of be easy to after discarded by microbiological degradation become carbonic acid gas and water, have favorable biological degradability, environmentally safe, the protection that helps ecotope, material surface compactness and tensile strength is high, material is more smoothly glossy, water resisting property and transmittance height, cost are lower, the simple radiation modification soybean protein isolate/starch plastic of production technique and preparation method thereof.
For solving its technical problem, the present invention realizes through following technical scheme:
According to an aspect of the present invention, a kind of radiation modification soybean protein isolate/starch bio-degradable plastics being provided, is main raw material with soybean protein isolate and starch; Be prepared from through the ray modified feedstock, when the said bio-degradable plastics of preparation, each feed composition mixes according to following weight part and forms: modified soybean protein isolate 85-95 part; Treated starch 5-15 part; Hexanolactam 1-3 part, water 10-20 part, glycerine 10-25 part.
According to a further aspect in the invention; The preparation method of a kind of radiation modification soybean protein isolate/starch bio-degradable plastics is provided; Comprise following process step: (1) is scattered in the methyl alcohol or ethanol of 3 times of weight after soybean protein isolate (SPI) and starch are processed mixture according to the ratio of 85-95 weight part/5-15 weight part; Mechanical stirring was uniformly dispersed mixture in 30 minutes, during every concentration of adding 1L at a distance from 10 minutes be the hydrochloric acid of 0.05-0.15mol/L, react finish after with sample suction filtration 5-10 minute; Naturally dry, obtain the blocking modification raw material with subsequent use; (2) 1-3 part hexanolactam is dissolved in 10-20 part zero(ppm) water; In step 1, add the zero(ppm) water that 10-20 part is contained hexanolactam in the sample of preparation; Machinery is stirred to moisture distribution when even fast, pours in the aluminium foil sack, vacuumizes encapsulation process with Vacuum Packaging Machine; (3) adopt the dosage of 10～50kGy to carry out radiation treatment the SPI/ starch mixture in the aluminium foil sack, impel crosslinking reaction and oxidizing reaction take place between the material molecule; (4) SPI/ starch mixture and the glycerine machinery radiation treatment in the step 3 crossed are stirred to the even fluffy nothing bulk of protein powder fast; Mixture is placed mould; Take out after putting into the vulcanizing press heating and pressurizing, under the 95-150 ℃ of mold temperature and under the forming pressure of 10-25Mpa, hot pressing 10-20 minute; The hot goods that take out are the room temperature cooling forming under same pressure, promptly gets Sunlover 10/starch bio-degradable plastics goods.
What need special instruction is; In radiation modification soybean protein isolate of the present invention/starch bio-degradable plastics and preparation method thereof; For making prepared bio-degradable plastics have higher material mechanical performance and transmittance, in raw material, added an amount of hexanolactam, in the water dissolution hexanolactam process as initiator; Make the polar group grafting, crosslinked of hexanolactam open loop and protein molecule molecule; Thereby increase proteinic molecular chain, interaction force between protein molecule is strengthened and the protein surface group is reduced, reduced the absorption of surface group light.
In the present invention, said starch can be any one of W-Gum, wheat starch, tapioca(flour), potato starch, sweet potato starch; The ray that irradiation adopts can be
60Co or
137Electron beam or X ray that the gamma-rays that Cs produces, rumbatron produce.
Above-mentioned plastic of soybean protein can be used for biodegradable green material such as disposable tableware, food product pack, industrial matrix material etc.
Advantage of the present invention is:
(1) the plasticizing soy protein matter tableware of the present invention's development; Be by soybean protein isolate, starch, water, glycerine preparation, be easy to become carbonic acid gas and water after it is discarded to have favorable biological degradability by microbiological degradation; Environmentally safe helps the protection of ecotope;
(2) the plasticizing soy protein matter tableware of the present invention's development, after composite elasticizer was modified, the tensile strength of tableware and light transmission have obtained raising to a certain degree, and be high in technological content, has novelty;
(3) the present invention adopts irradiation technique, and is safe and effective, improves material surface compactness and tensile strength, makes material more smoothly glossy, and then water resisting property and transmittance raising;
(4) the present invention adopts starch as weighting agent, because of starch is the raw material more cheap than albumen, so practice thrift cost, helps bio-degradable plastics and puts goods on the market as early as possible;
(5) the modified soybean protein tableware of the present invention's development, its production technique is simple, is easy to industrial operation;
(6) Sunlover 10 is a kind of reproducible natural polymer child resource, and comparing with the petroleum base tableware has inexhaustible advantage;
Embodiment
For a better understanding of the present invention, further illustrate content of the present invention, but content of the present invention is not limited to following embodiment below in conjunction with embodiment.
Embodiment 1
(1) soybean protein isolate of 100kg and starch are (88: 12; W/W) mixture is scattered in the methyl alcohol or ethanol of 300kg; After mechanical stirring is uniformly dispersed SPI, after stirring, divide three times each (10 minutes at interval) to add 1L hydrochloric acid (0.1mol/L); Stirred altogether 30 minutes, and reacted the back suction filtration that finishes, dry, obtain the blocking modification raw material for standby naturally;
(2) in 15kg water, add the 1kg hexanolactam, in the 100kg raw material, add 15kg water, mechanical stirring is block to fluffy nothing, vacuum-sealing, and the dosage of employing 10kGy carries out cross-linking radiation to be handled;
(3) take by weighing 100kg soybean protein isolate and the starch mixture that radiation treatment is crossed; Add 20kg glycerine, with these raw material thorough mixing evenly after, pour in the flat plate mold of vulcanizing press; Under 120 ℃ of mold temperatures and under the forming pressure of 15Mpa; Hot pressing 15 minutes, hot goods are the room temperature cooling forming under 15Mpa pressure, obtains product (sheet material).The mechanical property of the sheet material that makes, water repelling property and optical property are seen table 1.
Embodiment 2
(1) soybean protein isolate of 100kg and starch are (88: 12; W/W) mixture is scattered in the methyl alcohol or ethanol of 300kg; After mechanical stirring is uniformly dispersed SPI, after stirring, divide three times each (10 minutes at interval) to add 1L hydrochloric acid (0.1mol/L); Stirred altogether 30 minutes, and reacted the back suction filtration that finishes, dry, obtain the blocking modification raw material for standby naturally;
(2) in 15kg water, add the 1kg hexanolactam, in the 100kg raw material, add 15kg water, mechanical stirring is block to fluffy nothing, vacuum-sealing, and the dosage of employing 30kGy carries out cross-linking radiation to be handled;
(3) take by weighing 100kg soybean protein isolate and the starch mixture that radiation treatment is crossed; Add 20kg glycerine, with these raw material thorough mixing evenly after, pour in the flat plate mold of vulcanizing press; Under 120 ℃ of mold temperatures and under the forming pressure of 15Mpa; Hot pressing 15 minutes, hot goods are the room temperature cooling forming under 15Mpa pressure, obtains product (sheet material).The mechanical property of the sheet material that makes, water repelling property and optical property are seen table 1.
Comparative example 1
(1) soybean protein isolate of 100kg and starch are (88: 12; W/W) mixture is scattered in the methyl alcohol or ethanol of 300kg; After mechanical stirring is uniformly dispersed SPI, after stirring, divide three times each (10 minutes at interval) to add 1L hydrochloric acid (0.1mol/L); Stirred altogether 30 minutes, and reacted the back suction filtration that finishes, dry, obtain the blocking modification raw material for standby naturally;
(2) in 15kg water, add the 1kg hexanolactam, in the 100kg raw material, add 15kg water, mechanical stirring is block to fluffy nothing, and vacuum-sealing was sealed up for safekeeping 3 days;
(3) take by weighing 100kg soybean protein isolate and the starch mixture that radiation treatment is crossed; Add 20kg glycerine, with these raw material thorough mixing evenly after, pour in the flat plate mold of vulcanizing press; Under 120 ℃ of mold temperatures and under the forming pressure of 15Mpa; Hot pressing 15 minutes, hot goods are the room temperature cooling forming under 15Mpa pressure, obtains product (sheet material).The mechanical property of the sheet material that makes, water repelling property and optical property are seen table 1.
Comparative example 2
(1) soybean protein isolate of 100kg and starch are (85: 15; W/W) mixture is scattered in the methyl alcohol or ethanol of 300kg; After mechanical stirring is uniformly dispersed SPI, after stirring, divide three times each (10 minutes at interval) to add 1L hydrochloric acid (0.1mol/L); Stirred altogether 30 minutes, and reacted the back suction filtration that finishes, dry, obtain the blocking modification raw material for standby naturally;
(2) in 15kg water, add the 1kg hexanolactam, in the 100kg raw material, add 15kg water, mechanical stirring is block to fluffy nothing, vacuum-sealing, and the dosage of employing 30kGy carries out cross-linking radiation to be handled;
(3) take by weighing 100kg soybean protein isolate and the starch mixture that radiation treatment is crossed; Add 20kg glycerine, with these raw material thorough mixing evenly after, pour in the flat plate mold of vulcanizing press; Under 120 ℃ of mold temperatures and under the forming pressure of 15Mpa; Hot pressing 15 minutes, hot goods are the room temperature cooling forming under 15Mpa pressure, obtains product (sheet material).The mechanical property of the sheet material that makes, water repelling property and optical property are seen table 1.
Comparative example 3
(1) soybean protein isolate of 100kg and starch are (91: 9; W/W) mixture is scattered in the methyl alcohol or ethanol of 300kg; After mechanical stirring is uniformly dispersed SPI, after stirring, divide three times each (10 minutes at interval) to add 1L hydrochloric acid (0.1mol/L); Stirred altogether 30 minutes, and reacted the back suction filtration that finishes, dry, obtain the blocking modification raw material for standby naturally;
(2) in 15kg water, add the 1kg hexanolactam, in the 100kg raw material, add 15kg water, mechanical stirring is block to fluffy nothing, vacuum-sealing, and the dosage of employing 30kGy carries out cross-linking radiation to be handled;
(3) take by weighing 100kg soybean protein isolate and the starch mixture that radiation treatment is crossed; Add 20kg glycerine, with these raw material thorough mixing evenly after, pour in the flat plate mold of vulcanizing press; Under 120 ℃ of mold temperatures and under the forming pressure of 15Mpa; Hot pressing 15 minutes, hot goods are the room temperature cooling forming under 15Mpa pressure, obtains product (sheet material).The mechanical property of the sheet material that makes, water repelling property and optical property are seen table 1.
Embodiment 3
(1) soybean protein isolate of 100kg and starch are (85: 15; W/W) mixture is scattered in the methyl alcohol or ethanol of 300kg; After mechanical stirring is uniformly dispersed SPI, after stirring, divide three times each (10 minutes at interval) to add 1L hydrochloric acid (0.1mol/L); Stirred altogether 30 minutes, and reacted the back suction filtration that finishes, dry, obtain the blocking modification raw material for standby naturally;
(2) in 15kg water, add the 1kg hexanolactam, in the 100kg raw material, add 15kg water, mechanical stirring is block to fluffy nothing, vacuum-sealing, and the dosage of employing 50kGy carries out cross-linking radiation to be handled;
(3) take by weighing 100kg soybean protein isolate and the starch mixture that radiation treatment is crossed; Add 20kg glycerine, with these raw material thorough mixing evenly after, pour in the flat plate mold of vulcanizing press; Under 120 ℃ of mold temperatures and under the forming pressure of 15Mpa; Hot pressing 15 minutes, hot goods are the room temperature cooling forming under 15Mpa pressure, obtains product (sheet material).The mechanical property of the sheet material that makes, water repelling property and optical property are seen table 1.
Soybean protein isolate in the foregoing description is the commercially available prod, and water is tap water, and starch and glycerine are analytical pure.
The performance comparison of table 1 soybean protein isolate/starch degradable plastics
The testing method of plastic of soybean protein properties of sample in the table 1: mechanical property newly thinks carefully in Shenzhen that according to GB/T 1040-92 the CMT-0104 type microcomputer control electronics universal testing machine of measurement technology ltd measures, and draw speed is 50mm/min; Water repelling property is measured (water repelling property representes that with water-intake rate the low more water repelling property of water-intake rate is good more) according to GB/T 1034-1998 method 2; Light transmission is used the WGT-S transmittance/mist degree determinator of Ltd of Nereid section and is measured.
Can know that by table 1 it is fine and close more that the rising of irradiation dose helps the material internal structure, thereby improve tensile strength, water repelling property and the transmittance of plastic of soybean protein.The rising of starch content impels the raising of the elongation at break of product, and snappiness strengthens.Regulate irradiation dose, the variation of contents of starch and increase and decrease on each performance, all the increasing of softening agent than soybean protein.
Above-described specific embodiment has carried out further explain to the object of the invention, technical scheme and beneficial effect.Institute it should be understood that the above is merely specific embodiment of the present invention, is not limited to the present invention, and is all within spirit of the present invention and principle, any modification of being made, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. radiation modification soybean protein isolate/starch bio-degradable plastics is a main raw material with soybean protein isolate and starch, and auxiliary material comprises hexanolactam, water and glycerine; Said soybean protein isolate and starch are through the x radiation x modification; It is characterized in that: each feed composition mixes according to following weight part and forms: soybean protein isolate 85-95 part, starch 5-15 part, hexanolactam 1-3 part; Water 10-20 part, glycerine 10-25 part; When the said bio-degradable plastics of preparation, soybean protein isolate carries out blocking modification to reduce the hydrophilic radical in the albumen, the water repelling property of raising plastics through methyl alcohol or ethanol, and starch serves as the snappiness of the weighting agent of soybean protein isolate with reinforced plastics.
2. radiation modification soybean protein isolate according to claim 1/starch bio-degradable plastics, it is characterized in that: said ray can be
60Co or
137Electron beam or X ray that the gamma-rays that Cs produces, rumbatron produce.
3. radiation modification soybean protein isolate according to claim 1/starch bio-degradable plastics is characterized in that: said starch can be any one of W-Gum, wheat starch, tapioca(flour), potato starch, sweet potato starch.
4. preparation method like each described radiation modification soybean protein isolate/starch bio-degradable plastics of claim 1 to 3, it is characterized in that: said preparation method comprises following process step:
(11) after being processed mixture according to the ratio of 85-95 weight part/5-15 weight part, soybean protein isolate (SPI) and starch is scattered in the methyl alcohol or ethanol of 3 times of weight; Mechanical stirring was uniformly dispersed mixture in 30 minutes; Whenever adding 1L concentration at a distance from 10 minutes during this time is the hydrochloric acid of 0.05-0.15mol/L; With sample suction filtration 5-10 minute, dry naturally after reaction finishes, the sample that obtains blocking modification is with subsequent use;
(2) 1-3 weight part hexanolactam is dissolved in the 10-20 weight part zero(ppm) water; In step 1, add the zero(ppm) water that contains hexanolactam in the sample of preparation; Machinery is stirred to moisture distribution when even fast, pours in the aluminium foil sack, vacuumizes encapsulation process with Vacuum Packaging Machine;
(3) adopt the dosage of 10～50kGy to carry out radiation treatment the SPI/ starch mixture in the aluminium foil sack, impel crosslinking reaction and oxidizing reaction take place between the material molecule;
(4) SPI/ starch mixture and the glycerine machinery radiation treatment in the step 3 crossed are stirred to the even fluffy nothing bulk of protein powder fast; Mixture is placed mould; Take out after putting into the vulcanizing press heating and pressurizing, under the 95-150 ℃ of mold temperature and under the forming pressure of 10-25Mpa, hot pressing 10-20 minute; The hot goods that take out are the room temperature cooling forming under same pressure, promptly gets Sunlover 10/starch bio-degradable plastics goods.
5. preparation method according to claim 3 is characterized in that: methyl alcohol in the step 1 or ethanol reusable edible.
6. according to claim 3 or 4 described preparing methods, it is characterized in that: the irradiation in the step 3 by
60Co or
137Electron beam or X ray that the gamma-rays that Cs produces, rumbatron produce provide.
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| CN102816439A (en) * | 2012-06-28 | 2012-12-12 | 河南工业大学 | Composite modified soybean protein plastic and its preparation method |
| CN112322003A (en) * | 2020-09-25 | 2021-02-05 | 黄友耐 | Sweet potato starch-based degradable straw and preparation method thereof |
| CN115584133A (en) * | 2021-07-06 | 2023-01-10 | 宋悠洋 | Thermoplastic composition based on degradable biopolymer and preparation method and application thereof |
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| CN112322003A (en) * | 2020-09-25 | 2021-02-05 | 黄友耐 | Sweet potato starch-based degradable straw and preparation method thereof |
| CN115584133A (en) * | 2021-07-06 | 2023-01-10 | 宋悠洋 | Thermoplastic composition based on degradable biopolymer and preparation method and application thereof |
| CN115584133B (en) * | 2021-07-06 | 2023-12-15 | 深圳市朴飞生物科技有限公司 | Thermoplastic composition based on degradable biopolymer, preparation method and application thereof |
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