CN100436543C - Hydroxypropyl lignin modified soybean protein plastic and its preparation method - Google Patents
Hydroxypropyl lignin modified soybean protein plastic and its preparation method Download PDFInfo
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- CN100436543C CN100436543C CNB2006100181801A CN200610018180A CN100436543C CN 100436543 C CN100436543 C CN 100436543C CN B2006100181801 A CNB2006100181801 A CN B2006100181801A CN 200610018180 A CN200610018180 A CN 200610018180A CN 100436543 C CN100436543 C CN 100436543C
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- soybean protein
- lignin
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- protein isolate
- hydroxypropyl lignin
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Abstract
The present invention relates to soybean protein plastic with soybean isolated protein and a preparation method thereof. The modified soybean protein plastic of hydroxypropyl lignin of the present invention is characterized in that the plastic is prepared from 1 to 25 wt% of hydroxypropyl lignin, 75 to 99 wt % of soybean isolated protein and 20 to 50 wt% glycerol measured by the total weight of hydroxypropyl lignin, soybean isolated protein and glycerol. Tensile strength can be greatly improved without losing breaking elongation rate in the present invention; the soybean protein plastic has low cost, and is biodegradable.
Description
Technical field
The present invention relates to a kind of plastic of soybean protein that contains soybean protein isolate and preparation method thereof, belong to the high polymer material chemical field, also belong to the natural polymer field.
Background technology
Because the consumption day by day of petroleum resources and the environmental pollution that finished product cause thereof, the development and utilization of renewable resources---natural polymer is extremely paid attention to." industrial albumen plastics industry " based on soybean protein isolate and zein is in the ascendant, and its material is extruded by hot-forming, injection molding and screw rod usually and prepared.Plastic of soybean protein exist fragility greatly, not water-proof shortcoming, therefore must be by suitable poly-hydroxy softening agent (J.Macromol.Sci.:Pure Appl.Chem., 1996, A33,557-569), reactive plasticizer (J.Appl.Polym.Sci., 2001,81,166-175; 2000,78,1063-1070) and linking agent (Polymer, 2001,42,2569-2578) improve its processing characteristics, mechanical property and water repelling property.In addition, the method that adopts blend with soybean protein isolate respectively with polyester (Polymer, 2001,42,6961-6969; Polym.Int., 1999,48,1165-1172) and starch (United States Patent (USP): 1995,5397834; 1996,5523293; 1999,5922379) etc. the moulding of melt blending post-treatment obtains plastics sheet, thereby improves mechanical property effectively and improve water resistance.Utilize industrial lignin to fill plastic of soybean protein, can improve intensity and elongation simultaneously when the lignosulfonic acid calcium contents is suitable, and alkali lignin when improving intensity, make elongation at break descend (Chinese patent: 2004, ZL02115509.7; J.Appl.Polym.Sci., 2003,88,3284-3290; J.Appl.Polym.Sci., 2003,88,3291-3297).
Summary of the invention
The object of the present invention is to provide and a kind ofly can under the situation of not losing elongation at break, significantly improve tensile strength, with low cost, biodegradable hydroxypropyl lignin modified soybean protein plastic and preparation method thereof.
To achieve these goals, the technical solution adopted in the present invention is as follows: hydroxypropyl lignin modified soybean protein plastic, it is characterized in that it is made by hydroxypropyl lignin, soybean protein isolate and glycerine raw material, hydroxypropyl lignin, the shared hydroxypropyl lignin of each raw material of soybean protein isolate and soybean protein isolate weight percent are: hydroxypropyl lignin 1-25, soybean protein isolate 75-99; The add-on of glycerine is the 20-50% of hydroxypropyl lignin, soybean protein isolate and glycerine gross weight.
The preparation method of hydroxypropyl lignin modified soybean protein plastic, it is characterized in that it comprises the steps: 1). the preparation of hydroxypropyl lignin: alkali lignin is dissolved in the 0.05-0.5M NaOH aqueous solution, (unit: ratio mL) is 1: 5-1: 20 for the quality of alkali lignin (unit: restrain) and the volume of the 0.05-0.5M NaOH aqueous solution, dropwise add propylene oxide then, the weight ratio of alkali lignin and propylene oxide is 1: 1-3 gets mixed liquor; Mixed liquor obtains sticky product in 30-50 ℃ of following mechanical stirring, backflow 8-12 hour; Sticky product uses the hydrochloric acid acidizing reaction product to pH=1-4, and centrifugation obtains the hydroxypropyl lignin precipitation then, and then with normal hexane washing three times, last vacuum-drying gets hydroxypropyl lignin; 2). by hydroxypropyl lignin, the shared hydroxypropyl lignin of each raw material of soybean protein isolate and soybean protein isolate weight percent be: hydroxypropyl lignin 1-25, soybean protein isolate 75-99, choose hydroxypropyl lignin and soybean protein isolate is standby; Add-on by glycerine is the 20-50% of hydroxypropyl lignin, soybean protein isolate and glycerine gross weight, and it is standby to choose glycerine; 3). with hydroxypropyl lignin and soybean protein isolate mechanically mixing, be dissolved in the 0.05-0.5M NaOH aqueous solution and form homogeneous solution, (unit: ratio mL) is 1: 5-1: 25 for the quality of soybean protein isolate and hydroxypropyl lignin (unit: restrain) and the volume of the 0.05-0.5M NaOH aqueous solution, get mixed solution, then mixed solution is adjusted the pH value to 3.0-4.0 with hydrochloric acid, obtain the mixture precipitation by centrifuging, and it is standby all over postlyophilization to give a baby a bath on the third day after its birth with dilute hydrochloric acid (pH=3.0-4.0), gets mixture; Add glycerine plasticising in the mixture, in Banbury mixer, under 120-170 ℃, 10-100rpm condition, carried out melt blending 3-15 minute then; Hot pressing obtains sheet material under 120-180 ℃, 10-30MPa then, promptly gets product.
The present invention adopts the introducing of hydroxypropyl lignin raw material to prepare hydroxypropyl lignin modified soybean protein plastic with soybean protein isolate and glycerine raw material, can significantly improve tensile strength under the situation of not losing elongation at break, this mainly is because the result of side chain that hydroxypropyl lignin stretches and the mutual effect of soybean protein matrix phase, chain entanglement.Method of the present invention is utilized hydroxypropyl lignin and these inexpensive renewable resource of soybean protein isolate, and is with low cost; Make hydroxypropyl lignin modified soybean protein plastic by simple process; And the raw materials used natural polymer that is, have biodegradable, help environmental protection.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
The preparation method of hydroxypropyl lignin modified soybean protein plastic, it comprises the steps: 1). the preparation of hydroxypropyl lignin: the 10g alkali lignin (is called for short AL, paper mill, Yanzhou, Shandong Province) is dissolved in the 150mL 0.1M NaOH aqueous solution, dropwise add 15g propylene oxide (being called for short PO) (weight ratio of AL and PO is 2: 3) then, get mixed liquor.Mixed liquor obtains sticky product 35 ℃ of following mechanical stirring, backflow 10 hours.To pH=2, centrifugation obtains the hydroxypropyl lignin precipitation then with 1M hydrochloric acid acidizing reaction product, and then with normal hexane washing three times, it is standby that last vacuum-drying obtains hydroxypropyl lignin (HL) sample.
2). soybean protein isolate (is called for short SPI, by Yunmeng-protein company limited of Du Pont) and HL by weight 98: 2 mechanically mixing, be dissolved in form in the 0.01M NaOH aqueous solution homogeneous solution (quality of soybean protein isolate and hydroxypropyl lignin is 1g with the ratio of the volume of the 0.01M NaOH aqueous solution: 20mL), mixed solution; Then mixed solution is adjusted pH value to 3.8 with hydrochloric acid, obtain SPI/HL mixture precipitation, and it is standby all over postlyophilization to give a baby a bath on the third day after its birth with dilute hydrochloric acid (pH=3.8), gets the SPI/HL mixture by centrifuging.The SPI/HL mixture of 70 weight parts mixed 15 minutes under 140 ℃ of temperature, shearing rate 75rpm in Banbury mixer earlier with the glycerine of 30 weight parts, then at 140 ℃ of temperature, pressure 20MPa compacted under 10 minutes, follow air-cooled 30 minutes to 50 ℃, last relief pressure obtains the SPI/HL sheet material (SL) of moulding.Test piece is labeled as SL-2 by the weight fraction of HL in the solid composite.The mechanical property of test piece is newly thought carefully in Shenzhen with reference to ISO6239-1986 (E) standard on the CMT6503 instrument of testing tool company and is recorded, and lists in table 1.
Embodiment 2:
Prepare hydroxypropyl lignin with example 1.Soybean protein isolate and hydroxypropyl lignin mixed by weight 94: 6,90: 10,86: 14,82: 18 and 78: 22 respectively, film-making process and condition are with embodiment 1, and test piece is labeled as SL-6, SL-10, SL-14, SL-18 and SL-22 respectively by the weight fraction of HL in the solid composite.The mechanical property of test piece is newly thought carefully in Shenzhen with reference to ISO6239-1986 (E) standard on the CMT6503 instrument of testing tool company and is recorded, and lists in table 1.
Comparative example 1:
Soybean protein isolate makes test piece according to film-making process and the condition of embodiment 1, and label is SL-0.The mechanical property of test piece is newly thought carefully in Shenzhen with reference to ISO6239-1986 (E) standard on the CMT6503 instrument of testing tool company and is recorded, and lists in table 1.
The mechanical property of the hydroxypropyl lignin modified soybean protein isolate plastics of table 1
As known from Table 1, after adding hydroxypropyl lignin, the tensile strength of composite modification material all is improved, and increases with the increase of hydroxypropyl lignin content; Simultaneously, after the 2wt% hydroxypropyl lignin adds, not only make intensity increase by 2.3 times, and elongation at break keep substantially.Reduce elongation at break with alkali lignin when improving tensile strength of material and compare, have advantage, hydroxypropyl lignin enhancing ability is more obvious simultaneously.
Embodiment 3:
The preparation method of hydroxypropyl lignin modified soybean protein plastic, it comprises the steps: 1). the preparation of hydroxypropyl lignin: alkali lignin is dissolved in the 0.05M NaOH aqueous solution, (unit: ratio mL) is 1: 5 for the quality of alkali lignin (unit: restrain) and the volume of the 0.05M NaOH aqueous solution, dropwise add propylene oxide then, the weight ratio of alkali lignin and propylene oxide is 1: 1, gets mixed liquor; Mixed liquor obtains sticky product 30 ℃ of following mechanical stirring, backflow 8 hours; Sticky product uses the hydrochloric acid acidizing reaction product to pH=1, and centrifugation obtains the hydroxypropyl lignin precipitation then, and then with normal hexane washing three times, last vacuum-drying gets hydroxypropyl lignin; 2). by the shared weight percent of each raw material be: hydroxypropyl lignin 1, soybean protein isolate 99, choose hydroxypropyl lignin and soybean protein isolate is standby; Add-on by glycerine is 20% of hydroxypropyl lignin, soybean protein isolate and a glycerine gross weight, and it is standby to choose glycerine; 3). with hydroxypropyl lignin and soybean protein isolate mechanically mixing, be dissolved in the 0.05M NaOH aqueous solution and form homogeneous solution, (unit: ratio mL) is 1: 5 for the quality of soybean protein isolate and hydroxypropyl lignin (unit: restrain) and the volume of the 0.05M NaOH aqueous solution, get mixed solution, then mixed solution is adjusted pH value to 3.0 with hydrochloric acid, obtain the mixture precipitation by centrifuging, and it is standby all over postlyophilization to give a baby a bath on the third day after its birth with dilute hydrochloric acid (pH=3.0), gets mixture; Add glycerine plasticising in the mixture, in Banbury mixer, under 120 ℃, 10rpm condition, carried out melt blending 3 minutes then; Hot pressing obtains sheet material under 120 ℃, 10MPa then, promptly gets product.
Embodiment 4:
The preparation method of hydroxypropyl lignin modified soybean protein plastic, it comprises the steps: 1). the preparation of hydroxypropyl lignin: alkali lignin is dissolved in the 0.5M NaOH aqueous solution, (unit: ratio mL) is 1: 20 for the quality of alkali lignin (unit: restrain) and the volume of the 0.5M NaOH aqueous solution, dropwise add propylene oxide then, the weight ratio of alkali lignin and propylene oxide is 1: 3, gets mixed liquor; Mixed liquor obtains sticky product 50 ℃ of following mechanical stirring, backflow 12 hours; Sticky product uses the hydrochloric acid acidizing reaction product to pH=4, and centrifugation obtains the hydroxypropyl lignin precipitation then, and then with normal hexane washing three times, last vacuum-drying gets hydroxypropyl lignin; 2). by the shared weight percent of each raw material be: hydroxypropyl lignin 25, soybean protein isolate 75, choose hydroxypropyl lignin and soybean protein isolate is standby; Add-on by glycerine is 50% of hydroxypropyl lignin, soybean protein isolate and a glycerine gross weight, and it is standby to choose glycerine; 3). with hydroxypropyl lignin and soybean protein isolate mechanically mixing, be dissolved in the 0.5M NaOH aqueous solution and form homogeneous solution, (unit: ratio mL) is 1: 25 for the quality of soybean protein isolate and hydroxypropyl lignin (unit: restrain) and the volume of the 0.5M NaOH aqueous solution, get mixed solution, then mixed solution is adjusted pH value to 4.0 with hydrochloric acid, obtain the mixture precipitation by centrifuging, and it is standby all over postlyophilization to give a baby a bath on the third day after its birth with dilute hydrochloric acid (pH=4.0), gets mixture; Add glycerine plasticising in the mixture, in Banbury mixer, under 170 ℃, 100rpm condition, carried out melt blending 15 minutes then; Hot pressing obtains sheet material under 180 ℃, 30MPa then, promptly gets product.
Claims (2)
1. hydroxypropyl lignin modified soybean protein plastic, it is characterized in that it is made by hydroxypropyl lignin, soybean protein isolate and glycerine raw material, hydroxypropyl lignin, the shared hydroxypropyl lignin of each raw material of soybean protein isolate and soybean protein isolate weight percent are: hydroxypropyl lignin 1-25, soybean protein isolate 75-99; The add-on of glycerine is the 20-50% of hydroxypropyl lignin, soybean protein isolate and glycerine gross weight.
2. the preparation method of hydroxypropyl lignin modified soybean protein plastic according to claim 1, it is characterized in that it comprises the steps: 1). the preparation of hydroxypropyl lignin: alkali lignin is dissolved in the 0.05-0.5M NaOH aqueous solution, the quality of alkali lignin is 1g: 5mL-1g: 20mL with the ratio of the volume of the 0.05-0.5M NaOH aqueous solution, dropwise add propylene oxide then, the weight ratio of alkali lignin and propylene oxide is 1: 1-3 gets mixed liquor; Mixed liquor obtains sticky product in 30-50 ℃ of following mechanical stirring, backflow 8-12 hour; Sticky product uses the hydrochloric acid acidizing reaction product to pH=1-4, and centrifugation obtains the hydroxypropyl lignin precipitation then, and then with normal hexane washing three times, last vacuum-drying gets hydroxypropyl lignin; 2). by hydroxypropyl lignin, the shared hydroxypropyl lignin of each raw material of soybean protein isolate and soybean protein isolate weight percent be: hydroxypropyl lignin 1-25, soybean protein isolate 75-99, choose hydroxypropyl lignin and soybean protein isolate is standby; Add-on by glycerine is the 20-50% of hydroxypropyl lignin, soybean protein isolate and glycerine gross weight, and it is standby to choose glycerine; 3). with hydroxypropyl lignin and soybean protein isolate mechanically mixing, be dissolved in the 0.05-0.5M NaOH aqueous solution and form homogeneous solution, the quality of soybean protein isolate and hydroxypropyl lignin is 1g: 5mL-1g: 25mL with the ratio of the volume of the 0.05-0.5M NaOH aqueous solution, get mixed solution, then mixed solution is adjusted the pH value to 3.0-4.0 with hydrochloric acid, obtain the mixture precipitation by centrifuging, and it is standby all over postlyophilization to give a baby a bath on the third day after its birth with dilute hydrochloric acid, gets mixture; Add glycerine plasticising in the mixture, in Banbury mixer, under 120-170 ℃, 10-100rpm condition, carried out melt blending 3-15 minute then; Hot pressing obtains sheet material under 120-180 ℃, 10-30MPa then, promptly gets product.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1362451A (en) * | 2002-02-01 | 2002-08-07 | 武汉大学 | Modified soybean protein plastic and its prepn. and use |
| CN1417261A (en) * | 2002-12-18 | 2003-05-14 | 中国农业大学 | Prepn of biodegradable material |
| US6632925B1 (en) * | 1999-05-04 | 2003-10-14 | Iowa State University Research Foundation, Inc. | Biodegradable plant protein composites and related methods |
| CN1583884A (en) * | 2004-05-24 | 2005-02-23 | 武汉大学 | Soya protein plastic with water polyurethane modification and preparing method thereof |
| CN1594434A (en) * | 2004-07-16 | 2005-03-16 | 武汉大学 | Modified soybean protein plastic and method for preparing same |
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- 2006-01-17 CN CNB2006100181801A patent/CN100436543C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6632925B1 (en) * | 1999-05-04 | 2003-10-14 | Iowa State University Research Foundation, Inc. | Biodegradable plant protein composites and related methods |
| CN1362451A (en) * | 2002-02-01 | 2002-08-07 | 武汉大学 | Modified soybean protein plastic and its prepn. and use |
| CN1417261A (en) * | 2002-12-18 | 2003-05-14 | 中国农业大学 | Prepn of biodegradable material |
| CN1583884A (en) * | 2004-05-24 | 2005-02-23 | 武汉大学 | Soya protein plastic with water polyurethane modification and preparing method thereof |
| CN1594434A (en) * | 2004-07-16 | 2005-03-16 | 武汉大学 | Modified soybean protein plastic and method for preparing same |
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