CN105061818A - Blow-molding preparation method of starch/chitosan composite thin film - Google Patents
Blow-molding preparation method of starch/chitosan composite thin film Download PDFInfo
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- CN105061818A CN105061818A CN201510583672.4A CN201510583672A CN105061818A CN 105061818 A CN105061818 A CN 105061818A CN 201510583672 A CN201510583672 A CN 201510583672A CN 105061818 A CN105061818 A CN 105061818A
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Abstract
The invention discloses a blow-molding preparation method of a starch/chitosan composition thin film. The blow-molding preparation method is characterized in that the starch/chitosan composition thin film is prepared by adopting an efficient composite modifier and taking starch and chitosan as raw materials through a blow molding technology; the composite modifier comprises three main components: the component I is one or more of choline chloride and ammonium chloride, the component II is one or more of ferric nitrate and ferric chloride, and the component III is one or more of small organic molecule glycerinum, ethylene glycol, cholamine and formamide; the component I is mainly used for plastifying modified starch; the component II is mainly used for plastifying modified chitosan; the component III can be used for effectively cooperating the modifying action of the component I and the component II on starch and chitosan. By adopting the blow-molding preparation method disclosed by the invention, the problems of an existing starch/chitosan thin film preparation technology that the efficiency is low and the like can be solved, and the starch/chitosan composition thin film in excellent performance can be efficiently prepared.
Description
Technical field
The invention belongs to laminated film preparing technical field, be specifically related to the blow molding preparation method of a kind of starch/chitosan laminated film.
Background technology
Starch is the natural macromolecular material being considered to be hopeful most spread use at present.Starch can be divided into amylose starch (amylose) and amylopectin (amylopectin).The former is branchiess spirane structure; The latter is that 24 ~ 30 glucosyl residues join end to end form with α-Isosorbide-5-Nitrae-glycosidic link, is that α-1,6-glycosidic link connects at side chain place.In the seed that starch resource is present in each kind of plant in a large number and stem block, its abundance, cheap, have edibility, belong to renewable resources, it has good film-forming properties simultaneously, is therefore often used to the manufacture of film product.
Chitosan is the product prepared through part deacetylation by chitin, is a kind of common native biopolymer polymkeric substance, and chemistry [Isosorbide-5-Nitrae]-2-amino-2-deoxidation-β-D dextran by name is a kind of alkaline polysaccharide unique in organic sphere.Chitosan is a kind of water miscible natural polymer, there is excellent film-forming properties, nontoxicity and good degradability and biocompatibility, and the reactive group of chitosan (amino and hydroxyl) has very strong chelating, absorption and ion exchange to some electroactive substance, makes chitosan demonstrate very strong application prospect in fields such as film, fiber, hydrogels.Chitosan also has anti-microbial property, by chitosan-based film coated when foodstuff surface, effectively can stop the growth of foodstuff surface bacterium and fungi.
Although edible degradable biomass film will can be prepared after chitosan and starch compound, but due to starch and chitosan molecule chain all containing a large amount of oh groups, very easily hydrogen bond action is formed between oh group, make starch and chitosan be difficult to reach molten state, therefore starch and the chitosan mode that is difficult to be processed by the thermoplastic of routine is shaping.Therefore, research work existing more both at home and abroad in the thermoplastic of starch and chitosan is processing modified, and to add softening agent modification be the most frequently used approach improving polymer processing performance.Though thermoplastic processing and the blow molding of starch can be realized by the mode adding softening agent, not yet there is the report being prepared starch/chitosan film by thermoplastic processing blow molding at present.In order to prepare starch/chitosan laminated film efficiently, the invention provides the blow molding preparation method of a kind of starch/chitosan laminated film, first it adopt a kind of NEW TYPE OF COMPOSITE properties-correcting agent to carry out modification to starch and chitosan, and by after Single screw extrusion granulation again blow molding prepare starch/chitosan laminated film.
Summary of the invention
The object of the present invention is to provide the blow molding preparation method of a kind of starch/chitosan laminated film, it is for Problems existing in existing starch/chitosan laminated film preparation, adopt a kind of composite modifier starch and chitosan to highly plasticized modification efficiency to carry out modification to starch, chitosan, and utilize blow molding technique to prepare the starch/chitosan laminated film of excellent property.
For achieving the above object, the present invention adopts following technical scheme:
A blow molding preparation method for starch/chitosan laminated film is with starch, chitosan for raw material, adopts composite modifier, prepares described starch/chitosan laminated film through blow moulding process;
Three kinds of main ingredients are comprised in described composite modifier, component one is one or more in choline chloride 60, ammonium chloride, component two is one or more in iron nitrate, iron(ic) chloride, and component three is one or more in organic molecule glycerine, ethylene glycol, thanomin, methane amide.
Described preparation method specifically comprises the steps:
1) starch and chitosan are mixed with the component one in composite modifier and component two respectively in high-speed mixer, obtain treated starch and modified chitosan respectively;
2) by step 1) gained treated starch and modified chitosan mixing, and after adding the component three in composite modifier, mix in high-speed mixer, obtain composite modified starch/chitosan;
3) by step 2) the composite modified starch/chitosan of gained is placed in single screw extrusion machine extruding pelletization;
4) step 3) gained pellet is joined extrusion-blown modling film forming in single screw extrusion machine, obtain described starch/chitosan laminated film.
In raw material, the weight ratio of starch and chitosan is 1:0.3 ~ 0.5.
The weight ratio that in step 1), starch mixes with component one is 1:0.1-0.3.The weight ratio that chitosan mixes with component two is 1:0.1-0.2; Step 2) in the consumption of component three be the 10wt% ~ 20wt% of starch and chitosan gross weight.
Described mixing mixes 10-15min in 60 DEG C of high-speed mixers.
Prepared starch/chitosan laminated film is suitable for the use in the field such as article packing, agricultural mulching.
remarkable advantage of the present invention is:
(1) the invention provides a kind of NEW TYPE OF COMPOSITE properties-correcting agent and carry out modification to starch and chitosan, this composite modifier comprises three kinds of main ingredients, and its component one is mainly used in treated starch, has very high plasticization and modification efficiency to starch; Component two is mainly used in modified chitosan, has very high plasticization and modification efficiency to chitosan; And component three effectively can work in coordination with the modification efficiency improving component one and component two pairs of starch and chitosan.
(2) according to starch and chitosan constructional feature separately, the present invention adopts different components to carry out modification respectively to starch and chitosan, avoid starch in traditional method and use the shortcoming of single softening agent together with chitosan, make the plasticising performance etc. of modified starch, chitosan obtain larger raising.
(3) component one in the composite modifier used in the present invention and component two work to starch and chitosan separately, and component three can play synergy, finally effectively improves the thermal characteristics of starch and chitosan, expands the hot processing window of starch/chitosan.
(4) adopt composite modifier modified, the crystalline texture of starch and chitosan is all destroyed, and the consistency of starch and chitosan is mentioned greatly, has finally prepared complete compatible homogeneous phase starch/Chitosan Composites.
(5) preparation method of the present invention is adopted can to solve the problems such as existing starch/chitosan film preparation technology efficiency is low, break through existing starch/chitosan film solution and be difficult to shaping restriction, by the blow molding method of thermoplastic shaping, efficiently prepare the starch/chitosan laminated film of excellent property.
Embodiment
A blow molding preparation method for starch/chitosan laminated film is with starch, chitosan for raw material, adopts composite modifier, prepares described starch/chitosan laminated film through blow moulding process;
Three kinds of main ingredients are comprised in described composite modifier, component one is one or more in choline chloride 60, ammonium chloride, component two is one or more in iron nitrate, iron(ic) chloride, and component three is one or more in organic molecule glycerine, ethylene glycol, thanomin, methane amide.
Described preparation method specifically comprises the steps:
1) coordinated by weight 1:0.1-0.3 with the component one in composite modifier by starch, in high-speed mixer, 60 DEG C of mixing 10-15min, obtain treated starch;
2) coordinated by weight 1:0.1-0.2 with the component two in composite modifier by chitosan, in high-speed mixer, 60 DEG C of mixing 10-15min, obtain modified chitosan;
3) by step 1), step 2) gained treated starch and modified chitosan mixing, and after adding the component three in composite modifier in high-speed mixer 60 DEG C mixing 10-15min, obtain composite modified starch/chitosan; The consumption of component three is the 10wt% ~ 20wt% of starch and chitosan gross weight;
4) starch/chitosan composite modified for step 3) gained is placed in single screw extrusion machine extruding pelletization;
5) step 4) gained pellet is joined extrusion-blown modling film forming in single screw extrusion machine, obtain described starch/chitosan laminated film.
In raw material, the weight ratio of starch and chitosan is 1:0.3 ~ 0.5.
More being convenient to make content of the present invention understand, below in conjunction with embodiment, technical solutions according to the invention are described further, but the present invention being not limited only to this.In embodiment, involved number is weight part.
Embodiment 1
A blow molding preparation method for starch/chitosan laminated film, specifically comprises the steps:
1) extracting corn starch 100 parts, choline chloride 60 15 parts, in high-speed mixer, 60 DEG C of mixing 10min, obtain treated starch;
2) chitosan 30 parts, nitric acid is got
iron6 parts, in high-speed mixer, 60 DEG C of mixing 10min, obtain modified chitosan;
3) by step 1) and step 2) gained treated starch and modified chitosan mixing, after adding 20 parts of glycerine in high-speed mixer 60 DEG C mixing 15min obtain composite modified starch/chitosan;
4) starch/chitosan composite modified for step 3) gained is placed in single screw extrusion machine extruding pelletization; From opening for feed to discharge port, the temperature of forcing machine is set to 150 DEG C, 155 DEG C, 150 DEG C, 145 DEG C respectively, and forcing machine rotating speed is 30rpm/min;
5) step 4) gained pellet is joined extrusion-blown modling film forming in single screw extrusion machine, obtain described starch/chitosan laminated film.
Embodiment 2
A blow molding preparation method for starch/chitosan laminated film, specifically comprises the steps:
1) get wheat starch 100 parts, ammonium chloride 30 parts, in high-speed mixer, 60 DEG C of mixing 15min, obtain treated starch;
2) get chitosan 40 parts, 4 parts, iron(ic) chloride, in high-speed mixer, 60 DEG C of mixing 15min, obtain modified chitosan;
3) by step 1) and step 2) gained treated starch and modified chitosan mixing, after adding 14 parts of ethylene glycol in high-speed mixer 60 DEG C mixing 15min obtain composite modified starch/chitosan;
4) starch/chitosan composite modified for step 3) gained is placed in single screw extrusion machine extruding pelletization; From opening for feed to discharge port, the temperature of forcing machine is set to 140 DEG C, 145 DEG C, 140 DEG C, 135 DEG C respectively, and forcing machine rotating speed is 30rpm/min;
5) step 4) gained pellet is joined extrusion-blown modling film forming in single screw extrusion machine, obtain described starch/chitosan laminated film.
Embodiment 3
A blow molding preparation method for starch/chitosan laminated film, specifically comprises the steps:
1) get wheat starch 100 parts, choline chloride 60 10 parts and ammonium chloride 10 parts, in high-speed mixer, 60 DEG C of mixing 12min, obtain treated starch;
2) get chitosan 50 parts, iron nitrate 8 parts, in high-speed mixer, 60 DEG C of mixing 10min, obtain modified chitosan;
3) by step 1) and step 2) gained treated starch and modified chitosan mixing, after adding 30 parts of thanomins in high-speed mixer 60 DEG C mixing 12min obtain composite modified starch/chitosan;
4) starch/chitosan composite modified for step 3) gained is placed in single screw extrusion machine extruding pelletization; From opening for feed to discharge port, the temperature of forcing machine is set to 130 DEG C, 135 DEG C, 130 DEG C, 125 DEG C respectively, and forcing machine rotating speed is 30rpm/min;
5) step 4) gained pellet is joined extrusion-blown modling film forming in single screw extrusion machine, obtain described starch/chitosan laminated film.
Embodiment 4
A blow molding preparation method for starch/chitosan laminated film, specifically comprises the steps:
1) get potato starch 100 parts, ammonium chloride 20 parts, in high-speed mixer, 60 DEG C of mixing 15min, obtain treated starch;
2) get chitosan 30 parts, iron nitrate 6 parts, in high-speed mixer, 60 DEG C of mixing 10min, obtain modified chitosan;
3) by step 1) and step 2) gained treated starch and modified chitosan mixing, after adding 10 parts of methane amides, 6 parts of ethylene glycol in high-speed mixer 60 DEG C mixing 15min obtain composite modified starch/chitosan;
4) starch/chitosan composite modified for step 3) gained is placed in single screw extrusion machine extruding pelletization; From opening for feed to discharge port, the temperature of forcing machine is set to 140 DEG C, 145 DEG C, 140 DEG C, 135 DEG C respectively, and forcing machine rotating speed is 30rpm/min;
5) step 4) gained pellet is joined extrusion-blown modling film forming in single screw extrusion machine, obtain described starch/chitosan laminated film.
Embodiment 5
A blow molding preparation method for starch/chitosan laminated film, specifically comprises the steps:
1) extracting corn starch 100 parts, choline chloride 60 30 parts, in high-speed mixer, 60 DEG C of mixing 12min, obtain treated starch;
2) get chitosan 35 parts, iron nitrate 3 parts and 3 parts, iron(ic) chloride, in high-speed mixer, 60 DEG C of mixing 10min, obtain modified chitosan;
3) by step 1) and step 2) gained treated starch and modified chitosan mixing, after adding 8 parts of ethylene glycol, 6 parts of glycerine in high-speed mixer 60 DEG C mixing 15min obtain composite modified starch/chitosan;
4) starch/chitosan composite modified for step 3) gained is placed in single screw extrusion machine extruding pelletization; From opening for feed to discharge port, the temperature of forcing machine is set to 140 DEG C, 145 DEG C, 140 DEG C, 135 DEG C respectively, and forcing machine rotating speed is 30rpm/min;
5) step 4) gained pellet is joined extrusion-blown modling film forming in single screw extrusion machine, obtain described starch/chitosan laminated film.
Embodiment 6
A blow molding preparation method for starch/chitosan laminated film, specifically comprises the steps:
1) extracting corn starch 100 parts, ammonium chloride 10 parts, in high-speed mixer, 60 DEG C of mixing 10min, obtain treated starch;
2) get chitosan 45 parts, iron nitrate 9 parts, in high-speed mixer, 60 DEG C of mixing 10min, obtain modified chitosan;
3) by step 1) and step 2) gained treated starch and modified chitosan mixing, after adding 10 parts of ethylene glycol, 7 parts of glycerine, 5 parts of thanomins in high-speed mixer 60 DEG C mixing 15min obtain composite modified starch/chitosan;
4) starch/chitosan composite modified for step 3) gained is placed in single screw extrusion machine extruding pelletization; From opening for feed to discharge port, the temperature of forcing machine is set to 140 DEG C, 145 DEG C, 140 DEG C, 135 DEG C respectively, and forcing machine rotating speed is 30rpm/min;
5) step 4) gained pellet is joined extrusion-blown modling film forming in single screw extrusion machine, obtain described starch/chitosan laminated film.
Comparative example 1: the starch/chitosan film jointly prepared with chitosan after the independent treated starch of component one
Its preparation procedure is as follows:
1) extracting corn starch 100 parts and ammonium chloride 41 parts 60 DEG C of mixing 10min in high-speed mixer, obtain treated starch; Add chitosan 45 parts again, 60 DEG C of mixing 10min in high-speed mixer;
2) step 1) gained treated starch/chitosan is placed in single screw extrusion machine extruding pelletization; From opening for feed to discharge port, the temperature of forcing machine is set to 140 DEG C, 145 DEG C, 140 DEG C, 135 DEG C respectively, and forcing machine rotating speed is 30rpm/min;
3) by step 2) gained pellet joins extrusion-blown modling film forming in single screw extrusion machine, obtains starch/chitosan laminated film.
Comparative example 2: the starch/chitosan film jointly prepared with starch after the independent modified chitosan of component two
Its preparation procedure is as follows:
1) get chitosan 45 parts and iron nitrate 41 parts 60 DEG C of mixing 10min in high-speed mixer, obtain modified chitosan; Add W-Gum 100 parts again, 60 DEG C of mixing 10min in high-speed mixer;
2) step 1) gained starch/modified chitosan is placed in single screw extrusion machine extruding pelletization; From opening for feed to discharge port, the temperature of forcing machine is set to 138 DEG C, 142 DEG C, 138 DEG C, 132 DEG C respectively, and forcing machine rotating speed is 30rpm/min;
3) by step 2) gained pellet joins extrusion-blown modling film forming in single screw extrusion machine, obtains starch/chitosan laminated film.
Comparative example 3: starch/chitosan film that component three modification prepares
Its preparation procedure is as follows:
1) extracting corn starch 100 parts, chitosan 45 parts and glycerine 41 parts 60 DEG C of mixing 10min in high-speed mixer, obtain treated starch/chitosan;
2) starch/chitosan composite modified for step 1) gained is placed in single screw extrusion machine extruding pelletization; From opening for feed to discharge port, the temperature of forcing machine is set to 144 DEG C, 147 DEG C, 142 DEG C, 137 DEG C respectively, and forcing machine rotating speed is 30rpm/min;
3) by step 2) gained pellet joins extrusion-blown modling film forming in single screw extrusion machine, obtains starch/chitosan laminated film.
Starch/chitosan the laminated film of preparation in embodiment 6 and comparative example 1,2,3 gained starch/chitosan laminated film are carried out the mensuration of crystal property, thermal characteristics and mechanical property, the results are shown in Table 1.
Table 1 compound plastic uptake film performance test result
From table 1, compared with comparative example 1,2,3, starch/chitosan film performance prepared by embodiment 6 is better, shows that, after three kinds of main ingredient process in composite modifier of the present invention, its modified synergic effect is better.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (7)
1. a blow molding preparation method for starch/chitosan laminated film, is characterized in that: with starch, chitosan for raw material, adopts composite modifier, prepares described starch/chitosan laminated film through blow moulding process;
Described composite modifier comprises three kinds of main ingredients, component one is one or more in choline chloride 60, ammonium chloride, component two is one or more in iron nitrate, iron(ic) chloride, and component three is one or more in organic molecule glycerine, ethylene glycol, thanomin, methane amide.
2. the blow molding preparation method of starch according to claim 1/chitosan laminated film, is characterized in that: it specifically comprises the steps:
1) starch and chitosan are mixed with the component one in composite modifier and component two respectively, obtain treated starch and modified chitosan respectively;
2) by step 1) gained treated starch and modified chitosan mixing, mix after adding the component three in composite modifier, obtain composite modified starch/chitosan;
3) by step 2) the composite modified starch/chitosan extruding pelletization of gained;
4) by step 3) gained pellet extrusion-blown modling film forming, described starch/chitosan laminated film is obtained.
3. the blow molding preparation method of starch according to claim 2/chitosan laminated film, is characterized in that: in raw material, the weight ratio of starch and chitosan is 1:0.3 ~ 0.5.
4. the blow molding preparation method of starch according to claim 2/chitosan laminated film, is characterized in that: the weight ratio that in step 1), starch mixes with component one is 1:0.1-0.3; The weight ratio that chitosan mixes with component two is 1:0.1-0.2.
5. the blow molding preparation method of starch according to claim 2/chitosan laminated film, is characterized in that: step 2) in the consumption of component three be the 10wt% ~ 20wt% of starch and chitosan gross weight.
6. the blow molding preparation method of starch according to claim 2/chitosan laminated film, is characterized in that: described mixing mixes 10-15min in 60 DEG C of high-speed mixers.
7. as starch/chitosan laminated film that claim 1 preparation method obtains, it is characterized in that: described starch/chitosan laminated film is suitable for the use in article packing, agricultural mulching field.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105461968A (en) * | 2015-12-08 | 2016-04-06 | 福州大学 | Preparation method of starch/chitosan solid electrolyte film |
| CN108795029A (en) * | 2018-06-28 | 2018-11-13 | 宁波工程学院 | A kind of method preparing polyamide/chitosan mixed film and application |
| CN109111628A (en) * | 2018-07-31 | 2019-01-01 | 展恒凯文科技(深圳)有限责任公司 | Carbohydrate-based biodegradable thermoplastic starch material and preparation method and application |
| CN112194870A (en) * | 2020-10-09 | 2021-01-08 | 骆家宽 | Process for preparing blown film |
| CN115785534A (en) * | 2022-11-15 | 2023-03-14 | 湖北第二师范学院 | Preparation method of formamide plasticized thermoplastic chitosan |
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2015
- 2015-09-15 CN CN201510583672.4A patent/CN105061818B/en not_active Expired - Fee Related
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461968A (en) * | 2015-12-08 | 2016-04-06 | 福州大学 | Preparation method of starch/chitosan solid electrolyte film |
| CN105461968B (en) * | 2015-12-08 | 2018-01-12 | 福州大学 | A kind of preparation method of starch/chitosan solid electrolytic thin-membrane |
| CN108795029A (en) * | 2018-06-28 | 2018-11-13 | 宁波工程学院 | A kind of method preparing polyamide/chitosan mixed film and application |
| CN108795029B (en) * | 2018-06-28 | 2020-09-04 | 宁波工程学院 | Method for preparing polyamide/chitosan blend membrane and application |
| CN109111628A (en) * | 2018-07-31 | 2019-01-01 | 展恒凯文科技(深圳)有限责任公司 | Carbohydrate-based biodegradable thermoplastic starch material and preparation method and application |
| CN112194870A (en) * | 2020-10-09 | 2021-01-08 | 骆家宽 | Process for preparing blown film |
| CN115785534A (en) * | 2022-11-15 | 2023-03-14 | 湖北第二师范学院 | Preparation method of formamide plasticized thermoplastic chitosan |
| CN115785534B (en) * | 2022-11-15 | 2024-04-02 | 湖北第二师范学院 | Preparation method of formamide plasticized thermoplastic chitosan |
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