CN109467752A - A kind of starch/lignin full-degradation paper imitation material and preparation method thereof - Google Patents
A kind of starch/lignin full-degradation paper imitation material and preparation method thereof Download PDFInfo
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- CN109467752A CN109467752A CN201811263120.5A CN201811263120A CN109467752A CN 109467752 A CN109467752 A CN 109467752A CN 201811263120 A CN201811263120 A CN 201811263120A CN 109467752 A CN109467752 A CN 109467752A
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- lignin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/10—Oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention belongs to the preparations and application technology of the new functional macromolecule material of high molecular material in new material, are related to modified plastics technical field, specifically a kind of starch/lignin full-degradation paper imitation material preparation method.The invention firstly uses organic acids or acid anhydrides, and the lignin that esterification is prepared in processing is carried out to lignin；Then the starch of oxidation is handled using glacial acetic acid and acetic anhydride, the starch of acetylation is prepared；It will be finally esterified lignin, polylactic acid, the starch of acetylation after mixing, is prepared into starch/lignin full-degradation paper imitation material after extruding pelletization.Through the fake paper material that is prepared of the present invention not only can with complete biodegradable and also water resistance it is good.
Description
Technical field
The invention belongs to the preparations and application technology of the new functional macromolecule material of high molecular material in new material, are related to
Modified plastics technical field, specifically a kind of starch/lignin full-degradation paper imitation material and preparation method thereof.
Background technique
As global pollution is more serious, conventional plastic product causes the extensive pass of people to the huge pollution of environment
Note.The raw material of conventional plastic is non-renewable, and plastics mostly non-degradable, plastic products of every year in terms of hundreds of millions itself are given up
It abandons, also produces little effect even if carrying out " plastic limit ", " white pollution " is still increasing.Therefore research degradation plastic replaces at present
The non-degradable plastics of tradition have become domestic and international researchers are studied one big emphasis.
Paper industry also highly energy-consuming, the industry of high pollution, its pollution level is even than petrochemical industry high score sub-line sometimes
Industry is also serious.There are some plastics fake paper materials on the market at present to replace paper, but more or less contains in these materials
Polyethylene, the polymer difficult to degrade such as polypropylene, prevent imitative paper material is from degradable.Therefore, the imitative paper wood of degradable is developed
Material has great importance.
Summary of the invention
In order to solve the problems, such as that the imitative paper plastic material of tradition is unable to complete biodegradable.Of the invention provides a kind of shallow lake
Powder/lignin full-degradation paper imitation material and preparation method thereof.In order to achieve the above objectives, the present invention will use following technology:
A kind of preparation method of starch/lignin full-degradation paper imitation material, which comprises the following steps:
(1) lignin is soaked in organic acid or acid anhydrides, after a small amount of 1- methylimidazole is added under the conditions of 500-800rpm,
At 120 DEG C, after esterification 24 hours, ice water is added dropwise in reaction mixture under stiring and makes lignin deposit, passed through
Sediment fraction is obtained by filtration, and wash with distilled water to remove remaining 1- methylimidazole and organic acid after, precipitating was placed in
The ethanol solution of diisopropylbenzene (DIPB) is aoxidized, is taken out after impregnating 20-40min, vacuum drying obtains being esterified wooden in 60-80 DEG C of condition
Element；
(2) it is filtered after starch being impregnated 45-60min in hydrogen peroxide solution, oxidation is obtained after 85 DEG C of vacuum drying 20-24h and is formed sediment
Powder；
(3) oxidized starch and glacial acetic acid and acetic anhydride after stirring 1-1.5h under the conditions of 500-800rpm, are placed in ice bath at 40 DEG C
In after 0-4 DEG C of greenhouse cooling, after the concentrated sulfuric acid and glacial acetic acid mixed solution is added, continues after stirring 10min under ice bath, will mix
It, will after the distilled water of 10-20 times of volume to will be added in mixture after object is heated to 60 DEG C, reaction 2 hours under agitation
The sediment of formation filters under vacuum, is dried in vacuo 20-24 hours after being washed with distilled water and at 60 DEG C, obtains acetylation shallow lake
Powder；
(4) after mixing by esterification lignin, polylactic acid, acetylated starch, it is transferred in double screw extruder after, through squeezing out
Starch/lignin full-degradation paper imitation material is prepared into after granulation.
Further, organic acid as described in step (1) is one of acetic acid, n-butyric acie, n-caproic acid, the acid anhydrides
For one of acetic anhydride, crotonic anhydride；The solid-to-liquid ratio of the lignin and organic acid or acid anhydrides is 1:5-10.
Further, 1- methylimidazole additional amount as described in step (1) is the 0.5-1% of lignin quality.
Further, in the ethanol solution of cumyl peroxide as described in step (1) cumyl peroxide it is dense
Degree is 8-15g/L.
Further, the content of hydrogen peroxide is 20-45% in hydrogen peroxide solution described in step (2).
Further, oxidized starch described in step (3) and glacial acetic acid and the mass ratio of acetic anhydride additional amount are 1:3:
3；The concentrated sulfuric acid and glacial acetic acid molar ratio are 1:1 in the concentrated sulfuric acid and glacial acetic acid mixed solution.
Further, each component presses matter when esterification lignin described in step (4), polylactic acid, acetylated starch mixing
Amount number calculation is followed successively by 40-60 parts, 10-15 parts, 45-60 parts.
In addition, starch of the invention/lignin full-degradation paper imitation material, as prepared by above-mentioned preparation method.
Compared with prior art, a kind of starch/lignin full-degradation paper imitation material preparation method of the invention has following
The utility model has the advantages that the raw material using the material of lignin, starch and this kind of degradable of polylactic acid as fake paper material, prepared
The fake paper material arrived can be degradable, will not generate white pollution；Lignin is carried out at esterification using organic acid or acid anhydrides
Reason, not only increase the content of amylase activity group so that its in conjunction with starch material more closely, the lignin after esterification is resistance to
Aqueous increase strengthens the water resistance of fake paper material；After carrying out acetylation process to starch, it is therefore prevented that starch is met water and easily inhaled
Water expansion, further enhances the water resistance of fake paper material.The fake paper material being prepared through the present invention can not only give birth to completely
Object is degraded and water resistance is good.
Specific embodiment
[embodiment 1]
A kind of preparation method of starch/lignin full-degradation paper imitation material, which comprises the following steps:
(1) after mixing lignin by 1:8 mass volume ratio with n-butyric acie, lignin quality 0.7% is added under the conditions of 600rpm
1- methylimidazole after, at 120 DEG C, after esterification 24 hours, ice water, which is added dropwise, in reaction mixture under stiring makes
It obtains lignin deposit and sediment fraction is obtained by filtration, and wash with distilled water to remove remaining 1- methylimidazole and organic acid
Afterwards, it in the ethanol solution for the cumyl peroxide for precipitating being placed in 10g/L, is taken out after impregnating 35min, it is true in 75 DEG C of conditions
It is empty so dry that be esterified lignin；
(2) it is filtered after starch being impregnated 50min in 35% hydrogen peroxide solution, 85 DEG C of vacuum drying obtain oxidation afterwards for 24 hours and form sediment
Powder；
(3) after oxidized starch being mixed with glacial acetic acid and acetic anhydride by the mass volume ratio of 1:3:3, at 40 DEG C, 700rpm condition
It after lower stirring 1h, is placed in ice bath after 0-4 DEG C of greenhouse cooling, it is molten for the concentrated sulfuric acid and the glacial acetic acid mixing of 1:1 that molar ratio is added
After liquid, continue after stirring 10min under ice bath, mixture is heated to 60 DEG C under agitation, after reaction 2 hours, to will mix
The sediment of formation is filtered under vacuum after closing the distilled water that 15 times of volumes are added in object, after being washed with distilled water and at 60 DEG C
Vacuum drying 24 hours, obtains acetylated starch；
(4) by 45 parts be esterified lignin, 10 parts of polylactic acid, 45 parts of acetylations starch by after mixing, after be transferred to double spiral shells
In bar extruder, starch/lignin full-degradation paper imitation material is prepared into after extruding pelletization.
[embodiment 2]
A kind of preparation method of starch/lignin full-degradation paper imitation material, which comprises the following steps:
(1) after mixing lignin by 1:6 mass volume ratio with acetic anhydride, lignin quality 0.5% is added under the conditions of 500rpm
1- methylimidazole after, at 120 DEG C, after esterification 24 hours, ice water, which is added dropwise, in reaction mixture under stiring makes
It obtains lignin deposit and sediment fraction is obtained by filtration, and wash with distilled water to remove remaining 1- methylimidazole and organic acid
Afterwards, it in the ethanol solution for the cumyl peroxide for precipitating being placed in 8g/L, is taken out after impregnating 30min, it is true in 80 DEG C of conditions
It is empty so dry that be esterified lignin；
(2) it is filtered after starch being impregnated 55min in 30% hydrogen peroxide solution, 85 DEG C of vacuum drying obtain oxidation afterwards for 24 hours and form sediment
Powder；
(3) after oxidized starch being mixed with glacial acetic acid and acetic anhydride by the mass volume ratio of 1:3:3, at 40 DEG C, 600rpm condition
It after lower stirring 1h, is placed in ice bath after 0-4 DEG C of greenhouse cooling, it is molten for the concentrated sulfuric acid and the glacial acetic acid mixing of 1:1 that molar ratio is added
After liquid, continue after stirring 10min under ice bath, mixture is heated to 60 DEG C under agitation, after reaction 2 hours, to will mix
The sediment of formation is filtered under vacuum after closing the distilled water that 18 times of volumes are added in object, after being washed with distilled water and at 60 DEG C
Vacuum drying 24 hours, obtains acetylated starch；
(4) by 40 parts be esterified lignin, 10 parts of polylactic acid, 50 parts of acetylations starch by after mixing, after be transferred to double spiral shells
In bar extruder, starch/lignin full-degradation paper imitation material is prepared into after extruding pelletization.
[embodiment 3]
A kind of preparation method of starch/lignin full-degradation paper imitation material, which comprises the following steps:
(1) after mixing lignin by 1:8 mass volume ratio with acetic anhydride, lignin quality 0.6% is added under the conditions of 600rpm
1- methylimidazole after, at 120 DEG C, after esterification 24 hours, ice water, which is added dropwise, in reaction mixture under stiring makes
It obtains lignin deposit and sediment fraction is obtained by filtration, and wash with distilled water to remove remaining 1- methylimidazole and organic acid
Afterwards, precipitating is placed in the ethanol solution of the cumyl peroxide of 12g/L, is taken out after impregnating 25min, the vacuum in 80 DEG C of conditions
It is so dry that be esterified lignin；
(2) it is filtered after starch being impregnated 60min in 35% hydrogen peroxide solution, 85 DEG C of vacuum drying obtain oxidation afterwards for 24 hours and form sediment
Powder；
(3) after oxidized starch being mixed with glacial acetic acid and acetic anhydride by the mass volume ratio of 1:3:3, at 40 DEG C, 600rpm condition
It after lower stirring 1.5h, is placed in ice bath after 0-4 DEG C of greenhouse cooling, the concentrated sulfuric acid and glacial acetic acid mixing that molar ratio is 1:1 is added
After solution, continue after stirring 10min under ice bath, after mixture to be heated to 60 DEG C, reaction 2 hours under agitation, Xiang Jiang
The sediment of formation is filtered under vacuum after the distilled water of 20 times of volumes is added in mixture, simultaneously 60 DEG C after being washed with distilled water
Lower vacuum drying 24 hours, obtains acetylated starch；
(4) by 40 parts be esterified lignin, 15 parts of polylactic acid, 45 parts of acetylations starch after mixing, after be transferred to twin-screw
In extruder, starch/lignin full-degradation paper imitation material is prepared into after extruding pelletization.
For the ordinary skill in the art, specific embodiment is only exemplarily described the present invention,
Obviously the present invention specific implementation is not subject to the restrictions described above, as long as use the inventive concept and technical scheme of the present invention into
The improvement of capable various unsubstantialities, or not improved the conception and technical scheme of the invention are directly applied to other occasions
, it is within the scope of the present invention.
Claims (8)
1. a kind of starch/lignin full-degradation paper imitation material preparation method, which comprises the following steps:
(1) lignin is soaked in organic acid or acid anhydrides, after a small amount of 1- methylimidazole is added under the conditions of 500-800rpm,
At 120 DEG C, after esterification 24 hours, ice water is added dropwise in reaction mixture under stiring and makes lignin deposit, passed through
Sediment fraction is obtained by filtration, and wash with distilled water to remove remaining 1- methylimidazole and organic acid after, precipitating was placed in
The ethanol solution of diisopropylbenzene (DIPB) is aoxidized, is taken out after impregnating 20-40min, vacuum drying obtains being esterified wooden in 60-80 DEG C of condition
Element；
(2) it is filtered after starch being impregnated 45-60min in hydrogen peroxide solution, oxidation is obtained after 85 DEG C of vacuum drying 20-24h and is formed sediment
Powder；
(3) oxidized starch and glacial acetic acid and acetic anhydride after stirring 1-1.5h under the conditions of 500-800rpm, are placed in ice bath at 40 DEG C
In after 0-4 DEG C of greenhouse cooling, after the concentrated sulfuric acid and glacial acetic acid mixed solution is added, continues after stirring 10min under ice bath, will mix
It, will after the distilled water of 10-20 times of volume to will be added in mixture after object is heated to 60 DEG C, reaction 2 hours under agitation
The sediment of formation filters under vacuum, is dried in vacuo 20-24 hours after being washed with distilled water and at 60 DEG C, obtains acetylation shallow lake
Powder；
(4) after mixing by esterification lignin, polylactic acid, acetylated starch, it is transferred in double screw extruder after, through squeezing out
Starch/lignin full-degradation paper imitation material is prepared into after granulation.
2. a kind of preparation method of starch/lignin full-degradation paper imitation material according to claim 1, which is characterized in that
Organic acid as described in step (1) is one of acetic acid, n-butyric acie, n-caproic acid, and the acid anhydrides is acetic anhydride, crotonic anhydride
One of；The solid-to-liquid ratio of the lignin and organic acid or acid anhydrides is 1:5-10.
3. a kind of preparation method of starch/lignin full-degradation paper imitation material according to claim 1, which is characterized in that
1- methylimidazole additional amount as described in step (1) is the 0.5-1% of lignin quality.
4. a kind of preparation method of starch/lignin full-degradation paper imitation material according to claim 1, which is characterized in that
The concentration of cumyl peroxide is 8-15g/L in the ethanol solution of cumyl peroxide as described in step (1).
5. a kind of preparation method of starch/lignin full-degradation paper imitation material according to claim 1, which is characterized in that
The content of hydrogen peroxide is 20-45% in hydrogen peroxide solution described in step (2).
6. a kind of preparation method of starch/lignin full-degradation paper imitation material according to claim 1, which is characterized in that
Oxidized starch described in step (3) and glacial acetic acid and the mass ratio of acetic anhydride additional amount are 1:3:3；The concentrated sulfuric acid and ice
The concentrated sulfuric acid and glacial acetic acid molar ratio are 1:1 in acetic acid mixed solution.
7. a kind of preparation method of starch/lignin full-degradation paper imitation material according to claim 1, which is characterized in that
Each component is figured by mass parts when esterification lignin described in step (4), polylactic acid, acetylated starch mixing is followed successively by 40-
60 parts, 10-15 parts, 45-60 parts.
8. a kind of starch/lignin full-degradation paper imitation material, the preparation method as described in -7 any one according to claim 1
It is prepared.
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| CN201811263120.5A CN109467752A (en) | 2018-10-27 | 2018-10-27 | A kind of starch/lignin full-degradation paper imitation material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110408180A (en) * | 2019-08-19 | 2019-11-05 | 南京工业大学 | A kind of Biodegradable polyester material and preparation method thereof that lignin-starch composition master batch is compound |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403496A (en) * | 2002-10-28 | 2003-03-19 | 汕头市奇佳机械厂有限公司 | Completely degradable paper-like material with starch as basic material and its prepn |
| CN101608058A (en) * | 2009-07-16 | 2009-12-23 | 任伟 | A kind of full-degradation paper imitation material and preparation method thereof |
| CN101735482A (en) * | 2008-11-21 | 2010-06-16 | 姚日鹏 | Method for preparing degradable fake paper material |
| CN101759879A (en) * | 2008-11-12 | 2010-06-30 | 李圣震 | Method for preparing papery material capable of being degraded completely |
| CN101914294A (en) * | 2010-08-26 | 2010-12-15 | 成都新柯力化工科技有限公司 | Paper-imitating biodegradable resin and preparation method |
-
2018
- 2018-10-27 CN CN201811263120.5A patent/CN109467752A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403496A (en) * | 2002-10-28 | 2003-03-19 | 汕头市奇佳机械厂有限公司 | Completely degradable paper-like material with starch as basic material and its prepn |
| CN101759879A (en) * | 2008-11-12 | 2010-06-30 | 李圣震 | Method for preparing papery material capable of being degraded completely |
| CN101735482A (en) * | 2008-11-21 | 2010-06-16 | 姚日鹏 | Method for preparing degradable fake paper material |
| CN101608058A (en) * | 2009-07-16 | 2009-12-23 | 任伟 | A kind of full-degradation paper imitation material and preparation method thereof |
| CN101914294A (en) * | 2010-08-26 | 2010-12-15 | 成都新柯力化工科技有限公司 | Paper-imitating biodegradable resin and preparation method |
Non-Patent Citations (4)
| Title |
|---|
| 上海文化用品采购供应站 等: "《文化用品商品学 纸张》", 31 December 1959, 上海科学技术出版社 * |
| 张力田 等: "《碳水化合物化学 第2版》", 31 July 2013, 中国轻工业出版社 * |
| 新知互动: "《平面广告设计与印前技术 全新版》", 31 May 2016, 中国铁道出版社 * |
| 李坚: "《木材科学》", 31 August 2002, 高等教育出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110408180A (en) * | 2019-08-19 | 2019-11-05 | 南京工业大学 | A kind of Biodegradable polyester material and preparation method thereof that lignin-starch composition master batch is compound |
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