CN103172912A - Preparation method of modified microcrystalline cellulose enhanced starch plastic - Google Patents
Preparation method of modified microcrystalline cellulose enhanced starch plastic Download PDFInfo
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- CN103172912A CN103172912A CN2013100803903A CN201310080390A CN103172912A CN 103172912 A CN103172912 A CN 103172912A CN 2013100803903 A CN2013100803903 A CN 2013100803903A CN 201310080390 A CN201310080390 A CN 201310080390A CN 103172912 A CN103172912 A CN 103172912A
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Abstract
The invention relates to a preparation method of modified microcrystalline cellulose enhanced starch plastic, and belongs to the fields of highly value-added utilization of cellulose resources and starch plastics. The method comprises the following steps: firstly oxidizing microcrystalline cellulose, and further blending with the thermoplastic starch for extruding, thereby obtaining the modified microcrystalline cellulose enhanced starch plastic. The oxidized microcrystalline cellulose has an enhancement function, and the formyl group also has certain crosslinked action with the starch. The natural cellulose and starch are wide in source, low in price and entirely degradable, and the starch plastic is hopefully applied in the field of food packaging.
Description
Technical field
The invention belongs to the high value added utilization field of cellulose resource and starch plastic, relate to the preparation method that a kind of modified microcrystalline cellulose strengthens starch plastic.
Background technology
Mierocrystalline cellulose extensively is present in nature, and the whole world can produce hundreds billion of tons of Mierocrystalline celluloses every year, is the incomparable reproducible great resource of oil.Microcrystalline Cellulose (Microcrystalline cellulose, MCC) is a kind of direct type polysaccharide with β-Isosorbide-5-Nitrae glucoside bond combination, is prepared through dilute acid hydrolysis to the limit polymerization degree by natural cellulose, has good biocompatibility.Microcrystalline Cellulose mainly contains essential characteristic: the 1. mean polymerisation degree polymerization degree value that reaches capacity; 2. have cellulosic patterned features, degree of crystallinity is higher than the protofibril element; 3. has extremely strong water-absorbent.
Microcrystalline Cellulose is a kind of tasteless, imperceptible white corynebacterium vesicular particle, and its granular size is generally at the 20-80 micron, levelling-off DP at (LOOP) between 15-375; Do not have fibering and mobility is extremely strong; Water insoluble, diluted acid, organic solvent and grease are partly dissolved in dilute alkaline soln, swollen.Have higher reactivity worth in carboxymethylation, acetylize, esterification process, very favourable to the chemical modification utilization.
Starch is due to one of degradable, wide material sources, cheap, renewable biodegradable material that is considered to tool development prospect.Thermoplastic starch is starch under the condition that softening agent exists through the shear at high temperature effect, destroy its original crystalline texture and form full starch plastic, yet its relatively poor mechanical property and water resistance has affected its application.
Exploring and open up frontier that reproducible cellulose resource and derivative thereof use and to the enhancing research of thermoplastic starch, is all current and the hot subject of research both at home and abroad from now on.At present, strengthen starch plastic with Microcrystalline Cellulose and appear in the newspapers, and Mierocrystalline cellulose and derivative thereof are carried out chemical modification, modification, give and be used for again strengthening starch plastic after its new performance and yet there are no report.
Summary of the invention
At first the present invention carries out oxidation to Microcrystalline Cellulose, further with the thermoplastic starch blending extrusion, thereby obtains the starch plastic that strengthens based on modified microcrystalline cellulose.
For achieving the above object, the preparation method that the present invention adopts is:
1) preparation of oxidation Microcrystalline Cellulose
Adopt sodium periodate as oxygenant, make two secondary hydroxy oxidations of cellulose chain unit become aldehyde radical, obtain dialdehyde cellulose, reaction equation is as follows:
Step:
Get one of 250ml there-necked flask, rise to preset temp, regulating pH is 6, adds the sodium periodate solution of preset concentration, adds fast a certain amount of Microcrystalline Cellulose, after lucifuge isothermal reaction 6h, adds 10ml glycol reaction 1h to remove unreacted NaIO
4, suction filtration is used the distilled water repetitive scrubbing, and oven dry gets the oxidation Microcrystalline Cellulose.
2) oxidation Microcrystalline Cellulose and starch blending are extruded
Aldehyde radical on oxidation Microcrystalline Cellulose molecular chain and the hydroxyl reaction on starch molecule play certain crosslinked action.Reactional equation is as follows:
Step:
Get one of plastic tub, take 300g starch, add glycerine and a certain amount of oxidation Microcrystalline Cellulose of 100g, mix by extruding under twin screw extruder shear at high temperature condition, each is distinguished temperature and is respectively 109,115,119 and 115 ℃ (from spout to the ground).Pelletizing is injected into the dumbbell shaped batten, and injection moulding machine is respectively distinguished temperature and is respectively 123,125,130,125,123 ℃.
The invention has the advantages that:
1) Microcrystalline Cellulose that uses in the present invention is the natural reproducible material, environmental protection.
2) Microcrystalline Cellulose that uses in the present invention has good biocompatibility.
3) modified microcrystalline cellulose of the present invention's preparation strengthens the starch plastic mechanical property, thermal characteristics is improved.
4) the modified microcrystalline cellulose enhancing starch plastic of the present invention's preparation can be used for the food product pack industry.
5) synthetic route and technique are simple.
Embodiment
Embodiment 1: the oxidation Microcrystalline Cellulose can obtain according to following method:
1. get one of 250ml there-necked flask, rise to 35 ℃, regulating pH is 6, adds the sodium periodate solution of 0.015mol/L, adds fast the 2g Microcrystalline Cellulose, after lucifuge isothermal reaction 6h, adds 10ml glycol reaction 1h to remove unreacted NaIO
4, suction filtration is used the distilled water repetitive scrubbing, and oven dry gets the oxidation Microcrystalline Cellulose.
2. get one of 250ml there-necked flask, rise to 35 ℃, regulating pH is 6, adds the sodium periodate solution of 0.030mol/L, adds fast the 2g Microcrystalline Cellulose, after lucifuge isothermal reaction 6h, adds 10ml glycol reaction 1h to remove unreacted NaIO
4, suction filtration is used the distilled water repetitive scrubbing, and oven dry gets the oxidation Microcrystalline Cellulose.
3. get one of 250ml there-necked flask, rise to 35 ℃, regulating pH is 6, adds the sodium periodate solution of 0.045mol/L, adds fast the 2g Microcrystalline Cellulose, after lucifuge isothermal reaction 6h, adds 10ml glycol reaction 1h to remove unreacted NaIO
4, suction filtration is used the distilled water repetitive scrubbing, and oven dry gets the oxidation Microcrystalline Cellulose.
4. get one of 250ml there-necked flask, rise to 40 ℃, regulating pH is 6, adds the sodium periodate solution of 0.015mol/L, adds fast the 2g Microcrystalline Cellulose, after lucifuge isothermal reaction 6h, adds 10ml glycol reaction 1h to remove unreacted NaIO
4, suction filtration is used the distilled water repetitive scrubbing, and oven dry gets the oxidation Microcrystalline Cellulose.
5. get one of 250ml there-necked flask, rise to 40 ℃, regulating pH is 6, adds the sodium periodate solution of 0.030mol/L, adds fast the 2g Microcrystalline Cellulose, after lucifuge isothermal reaction 6h, adds 10ml glycol reaction 1h to remove unreacted NaIO
4, suction filtration is used the distilled water repetitive scrubbing, and oven dry gets the oxidation Microcrystalline Cellulose.
6. get one of 250ml there-necked flask, rise to 40 ℃, regulating pH is 6, adds the sodium periodate solution of 0.045mol/L, adds fast the 2g Microcrystalline Cellulose, after lucifuge isothermal reaction 6h, adds 10ml glycol reaction 1h to remove unreacted NaIO
4, suction filtration is used the distilled water repetitive scrubbing, and oven dry gets the oxidation Microcrystalline Cellulose.
7. get one of 250ml there-necked flask, rise to 45 ℃, regulating pH is 6, adds the sodium periodate solution of 0.015mol/L, adds fast the 2g Microcrystalline Cellulose, after lucifuge isothermal reaction 6h, adds 10ml glycol reaction 1h to remove unreacted NaIO
4, suction filtration is used the distilled water repetitive scrubbing, and oven dry gets the oxidation Microcrystalline Cellulose.
8. get one of 250ml there-necked flask, rise to 45 ℃, regulating pH is 6, adds the sodium periodate solution of 0.030mol/L, adds fast the 2g Microcrystalline Cellulose, after lucifuge isothermal reaction 6h, adds 10ml glycol reaction 1h to remove unreacted NaIO
4, suction filtration is used the distilled water repetitive scrubbing, and oven dry gets the oxidation Microcrystalline Cellulose.
9. get one of 250ml there-necked flask, rise to 45 ℃, regulating pH is 6, adds the sodium periodate solution of 0.045mol/L, adds fast the 2g Microcrystalline Cellulose, after lucifuge isothermal reaction 6h, adds 10ml glycol reaction 1h to remove unreacted NaIO
4, suction filtration is used the distilled water repetitive scrubbing, and oven dry gets the oxidation Microcrystalline Cellulose.
Embodiment 2: get one of plastic tub, take 300g starch, add glycerine and the 12g oxidation Microcrystalline Cellulose of 100g, mix by extruding under twin screw extruder shear at high temperature condition, each is distinguished temperature and is respectively 109,115,119 and 115 ℃ (from spout to the ground).Pelletizing is injected into the dumbbell shaped batten, and injection moulding machine is respectively distinguished temperature and is respectively 123,125,130,125,123 ℃.
Embodiment 3: get one of plastic tub, take 300g starch, add glycerine and the 24g oxidation Microcrystalline Cellulose of 100g, mix by extruding under twin screw extruder shear at high temperature condition, each is distinguished temperature and is respectively 109,115,119 and 115 ℃ (from spout to the ground).Pelletizing is injected into the dumbbell shaped batten, and injection moulding machine is respectively distinguished temperature and is respectively 123,125,130,125,123 ℃.
Embodiment 4: get one of plastic tub, take 300g starch, add glycerine and the 36g oxidation Microcrystalline Cellulose of 100g, mix by extruding under twin screw extruder shear at high temperature condition, each is distinguished temperature and is respectively 109,115,119 and 115 ℃ (from spout to the ground).Pelletizing is injected into the dumbbell shaped batten, and injection moulding machine is respectively distinguished temperature and is respectively 123,125,130,125,123 ℃.
Embodiment 5: get one of plastic tub, take 300g starch, add glycerine and the 48g oxidation Microcrystalline Cellulose of 100g, mix by extruding under twin screw extruder shear at high temperature condition, each is distinguished temperature and is respectively 109,115,119 and 115 ℃ (from spout to the ground).Pelletizing is injected into the dumbbell shaped batten, and injection moulding machine is respectively distinguished temperature and is respectively 123,125,130,125,123 ℃.
Embodiment 6: get one of plastic tub, take 300g starch, add glycerine and the 60g oxidation Microcrystalline Cellulose of 100g, mix by extruding under twin screw extruder shear at high temperature condition, each is distinguished temperature and is respectively 109,115,119 and 115 ℃ (from spout to the ground).Pelletizing is injected into the dumbbell shaped batten, and injection moulding machine is respectively distinguished temperature and is respectively 123,125,130,125,123 ℃.
Claims (7)
1. a modified microcrystalline cellulose strengthens the preparation method of starch plastic, it is characterized in that: modified microcrystalline cellulose strengthens starch plastic and obtains according to the following step:
1. get one of 250ml there-necked flask, rise to temperature of reaction (35,40,45 ℃), regulating pH is 6, add sodium periodate solution (0.015,0.03,0.045mol/L), add fast Microcrystalline Cellulose 2g, after lucifuge isothermal reaction 6h, add 10ml glycol reaction 1h to remove unreacted NaIO
4, suction filtration is used the distilled water repetitive scrubbing, oven dry.
2. get one of plastic tub, take 300g starch, add the glycerine of 100g and oxidation Microcrystalline Cellulose (12,24,36,48,60g), mix by extruding under twin screw extruder shear at high temperature condition, each is distinguished temperature and is respectively 109,115,119 and 115 ℃ (from spout to the ground).Pelletizing is injected into the dumbbell shaped batten, and injection moulding machine is respectively distinguished temperature and is respectively 123,125,130,125,123 ℃.
2. the preparation method who strengthens starch plastic based on modified microcrystalline cellulose according to claim 1, is characterized in that: oxygenant NaIO used
4Concentration be 0.015,0.03,0.045mol/L.
3. the preparation method who strengthens starch plastic based on modified microcrystalline cellulose according to claim 1, it is characterized in that: the temperature of oxidation Microcrystalline Cellulose reaction is 35,40,45 ℃.
4. the preparation method who strengthens starch plastic based on modified microcrystalline cellulose according to claim 1, is characterized in that: oxidation Microcrystalline Cellulose preparation feedback isothermal reaction 6h under lucifuge.
5. the preparation method who strengthens starch plastic based on modified microcrystalline cellulose according to claim 1 is characterized in that: the oxidation Microcrystalline Cellulose is 3,6,9,12 at the massfraction of starch plastic, 15%wt (in the total amount of starch and glycerine).
6. the preparation method who strengthens starch plastic based on modified microcrystalline cellulose according to claim 1, it is characterized in that: the temperature of respectively distinguishing of twin screw extruder is respectively 109,115,119 and 115 ℃ (from spout to the ground).
7. the preparation method who strengthens starch plastic based on modified microcrystalline cellulose according to claim 1, it is characterized in that: injection moulding machine is respectively distinguished temperature and is respectively 123,125,130,125,123 ℃.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277245A (en) * | 2013-07-04 | 2015-01-14 | 南京林业大学 | Method for preparation of crop straw enhanced starch plastic by C2 and 3-site oxidation |
| CN105400166A (en) * | 2015-12-11 | 2016-03-16 | 南京林业大学 | Composite material for 3D printing and production method therefor |
| CN107987233A (en) * | 2017-11-21 | 2018-05-04 | 安徽北马科技有限公司 | A kind of preparation method of styrene-grafted modified collagen albumen-sulfonated cellulose composite material |
| CN108048004A (en) * | 2017-11-21 | 2018-05-18 | 安徽北马科技有限公司 | A kind of preparation method of soybean protein base timber adhesive |
| CN110041567A (en) * | 2019-05-11 | 2019-07-23 | 王德秀 | A kind of lignocellulosic-starch degradable plastics and preparation method thereof |
| JP2020510711A (en) * | 2017-01-18 | 2020-04-09 | コーテーホー ホールディング アクチエボラグ | Melt-processed material with high cellulose fiber content |
| CN113831604A (en) * | 2020-06-24 | 2021-12-24 | 青岛周氏塑料包装有限公司 | High-strength high-toughness thermoplastic starch material and preparation method thereof |
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| CN101085850A (en) * | 2006-06-05 | 2007-12-12 | 许秀峰 | Degradable water soluble packaging film |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277245A (en) * | 2013-07-04 | 2015-01-14 | 南京林业大学 | Method for preparation of crop straw enhanced starch plastic by C2 and 3-site oxidation |
| CN105400166A (en) * | 2015-12-11 | 2016-03-16 | 南京林业大学 | Composite material for 3D printing and production method therefor |
| JP2020510711A (en) * | 2017-01-18 | 2020-04-09 | コーテーホー ホールディング アクチエボラグ | Melt-processed material with high cellulose fiber content |
| JP7106549B2 (en) | 2017-01-18 | 2022-07-26 | テトラ ラバル ホールディングス アンド ファイナンス エス エイ | Melt processed material with high cellulose fiber content |
| JP2022153464A (en) * | 2017-01-18 | 2022-10-12 | テトラ ラバル ホールディングス アンド ファイナンス エス エイ | Melt modified material having high cellulose fiber content |
| US11518821B2 (en) | 2017-01-18 | 2022-12-06 | Tetra Laval Holdings & Finance S.A. | Melt-processed material with high cellulose fiber content |
| JP7407876B2 (en) | 2017-01-18 | 2024-01-04 | テトラ ラバル ホールディングス アンド ファイナンス エス エイ | Melt processed materials with high cellulose fiber content |
| CN107987233A (en) * | 2017-11-21 | 2018-05-04 | 安徽北马科技有限公司 | A kind of preparation method of styrene-grafted modified collagen albumen-sulfonated cellulose composite material |
| CN108048004A (en) * | 2017-11-21 | 2018-05-18 | 安徽北马科技有限公司 | A kind of preparation method of soybean protein base timber adhesive |
| CN110041567A (en) * | 2019-05-11 | 2019-07-23 | 王德秀 | A kind of lignocellulosic-starch degradable plastics and preparation method thereof |
| CN113831604A (en) * | 2020-06-24 | 2021-12-24 | 青岛周氏塑料包装有限公司 | High-strength high-toughness thermoplastic starch material and preparation method thereof |
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Application publication date: 20130626 |