CN105837864A - Fully biodegradable film and preparation method thereof - Google Patents

Fully biodegradable film and preparation method thereof Download PDF

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Publication number
CN105837864A
CN105837864A CN201610394551.XA CN201610394551A CN105837864A CN 105837864 A CN105837864 A CN 105837864A CN 201610394551 A CN201610394551 A CN 201610394551A CN 105837864 A CN105837864 A CN 105837864A
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CN
China
Prior art keywords
parts
starch
water
corn
polyvinyl alcohol
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CN201610394551.XA
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Chinese (zh)
Inventor
徐涛
李庆
孟德
王梦圆
王晓丽
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INNER MONGOLIA DRAGON ZE WATER-SAVING IRRIGATION TECHNOLOGY Ltd Co
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INNER MONGOLIA DRAGON ZE WATER-SAVING IRRIGATION TECHNOLOGY Ltd Co
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Priority to CN201610394551.XA priority Critical patent/CN105837864A/en
Publication of CN105837864A publication Critical patent/CN105837864A/en
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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
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C08L3/06—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/04—Starch derivatives
    • C08J2403/06—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The invention discloses a fully biodegradable film and a preparation method thereof. The fully biodegradable film mainly comprises 30-50 parts of corn starch or esterified starch, 30-50 parts of polyvinyl alcohol, 10-25 parts of corn straw powder, 2-20 parts of polyvinyl alcohol ester, 0.2-5 parts of mineral oil, 5-40 parts of water or ethyl alcohol and 0.2-2 parts of water repellent agent. The method includes: subjecting the corn straw powder to pulverization prior to sieving, subjecting the usable corn straw powder to aftertreatment for 24h, adding the corn starch, the polyvinyl alcohol, lipids, oils and alcohol/water after 24h, blending prior to heating to 50-120 DEG C to form master batch, subjecting the master batch to blow molding prior to cooling shaping, and put into storage after passing inspection. The main raw materials are corn straw cellulose, the corn starch and the polyvinyl alcohol, so that the fully biodegradable film is low in cost and convenient to popularize; crop straw produced in agricultural production can be treated effectively and recycled to promote soil improvement, and organic activity of soil is improved.

Description

A kind of biological whole degrading film and preparation method thereof
Technical field
The invention belongs to biodegradable plastic film product technique field, particularly relate to a kind of biological complete Degradable film and preparation method thereof.
Background technology
Complete biodegradable plastics refer to microorganism such as antibacterial, mycete that a class exists by nature, fungus and The effect of algae and cause the plastics of degraded, preferable biodegradable plastic is a kind of to have excellent usability Can, discarded after can be decomposed completely by environmental microorganism, finally by inorganization and become Carbon cycle in nature The macromolecular material of an ingredient, biodegradable plastic is to have paper and synthetic plastic both materials concurrently The macromolecular material of character.Complete biodegradable thin film of the prior art mainly has the U.S. NOVON, Mater-Bi, the BIOPOT of Britain and the BIONOLE of Japan of Italy, and from product The factors such as mechanical property, degradation property, production technology and production scale consider, really form internationalized production The Mater-Bi of only Italy.And the deficiency of Mater-Bi company complete biodegradable film product it Place is that the performance under high temperature, high humidity environment of its product is poor, and the scope of application of product is narrower, the most applicable In temperature 0 DEG C～50 DEG C, relative humidity 30 parts～the environment of 80 parts, and the price of Mater-Bi product Up to 7000 dollars, it is difficult to worldwide large scale application.
Summary of the invention
The deficiency that the present invention exists to overcome prior art, it is provided that a kind of application range of products is relatively wide, cost Biological whole degrading film of cheap, energy-conserving and environment-protective and preparation method thereof.
The present invention is achieved by the following technical solutions: a kind of biological whole degrading film, it is mainly by following The raw material composition of weight portion: starch 30 parts～50 parts, polyvinyl alcohol 30 parts～50 parts, corn stalk powder 10 parts～25 parts, polyethylene alcohol ester 2 parts～20 parts, mineral oil 0.2 part～5 parts, plasticizer auxiliary agent 5 parts～40 parts and water-repelling agent 0.2 part～2 parts, starch is corn starch or esterification starch, plasticizer auxiliary agent For water, ethanol or methanol.
As the preferred embodiment of the present invention, biological whole degrading film of the present invention is mainly by following weight parts Raw material forms: starch 34 parts～45 parts, polyvinyl alcohol 42 parts～48 parts, corn stalk powder 10 parts～13 Part, polyethylene alcohol ester 8 parts～15 parts, mineral oil 1 part～4 parts, plasticizer auxiliary agent 21 parts～37 parts With water-repelling agent 0.4 part～1 part.
As the preferred forms of the present invention, biological whole degrading film of the present invention is mainly by following weight parts Raw material forms: starch 40 parts, polyvinyl alcohol 45 parts, corn stalk powder 13 parts, polyethylene alcohol ester 12 Part, mineral oil 2 parts, plasticizer auxiliary agent 30 parts and water-repelling agent 0.7 part.
The preparation method of biological whole degrading film of the present invention comprises the steps: a, first by corn stalk powder Sieve after broken, make corn stalk powder, the corn stalk powder that can use is carried out post processing, finishing time For 24h；B, be then passed through 24h after be sequentially added in corn stalk powder corn starch, polyvinyl alcohol, Polyethylene alcohol ester, mineral oil, water or ethanol, water-repelling agent, above-mentioned material is blended post-heating to 50 DEG C～ 120 DEG C, make biological whole degrading film masterbatch；C, finally by biological whole degrading film masterbatch in blow moulding machine It is blow molded, cools down molding, put in storage through after the assay was approved, prepare finished product.
Biological whole degrading film in the present invention uses the plasticizer auxiliary agent including water, in pelletize, blowing During form, by gelatinized starch etc., the material that resistance to water is good.
The invention has the beneficial effects as follows: corn straw is given the most effectively to utilize by the present invention, reduces environment dirty Dye, the primary raw material of the present invention is corn stalk fiber element, corn starch and polyvinyl alcohol, its cost of manufacture Cheap, it is simple to the whole nation is promoted.The crop material produced in agricultural production can be effectively treated by the present invention, And recycled, and soil improvement can be promoted, improve the organic active of soil；Stop peasant big Area burns crop material, has effectively administered environmental pollution.In prior art, Italy Mater-Bi produces Product, in the case of high temperature resistant, moisture-proof and thin film high-content of starch, have shortcoming dry, that wet strength is the highest, The advance of key technology of the present invention shows and overcomes what world-renowned Italy Mater-Bi product existed Defect, the biological whole degrading film in the present invention can use the strong agent of reinforcing agent, temperature and cold-resistant agent to expand product The range of application of product, and use plasticized starch to substitute ative starch, improve the mobility of film article raw material, Accelerate blown film speed, improve the quality of film article.
By application and the practicality of Biodegradable starch plastic of analyzing plastics goods, in the present invention Biological full degradation starch plastic can have following four big classes enter society production and sphere of life:
One is packing articles field: it includes daily packaging, such as shopping bag, refuse bag etc., food and food and drink Packaging such as mess-tin, cup, dish, aviation tableware, Sofe drink bottle, candy, cosmetics, shampoo, Cleaning mixture etc. are packed, industrial and agricultural products packaging such as equipment, instrument antirust anti-electric disk pack dress, agricultural byproducts transport Packaging etc., and other the articles for daily use packaging.
Two is industrial or agricultural field of plastic products: object form has plastic pipe for industrial use, various component and bag Holding tool；Various mulch films, sunshade net, fly net, non-woven fabrics, Reflecting curtain, insulation composite sheet material, insulation The slow-releasing covering material of curtain, insulation quilt, seedling culture basin, pot for growing seedlings, seedling growth greenhouse and pesticide and fertilizer, Preservative film, cultivation equipment, sowing coating etc..
Three is various daily necessities fields: relating to the articles for daily use, office appliance and stationery etc., goods mainly have Such as diaper, laundry bag, disposable underclothes, slippers, physiological hygiene articles for use, computer casing, keyboard, tape Dish and tape and IC base plate, portable phone, writing case, pen stand, file, disposable ball pen Deng.
Four is civil engineering articles for use fields: relate to urban construction, greening, road construction, wasteland control of desert Deng, product includes wasteland, desert afforestation water conservation base material, vegetation net, water-retaining agent, industrial water conservation plate, soil Wood member type frame, bank protection and solid soil engineering material etc..
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1: a kind of biological whole degrading film, it is mainly made up of the raw material of following weight parts: Semen Maydis Starch 30 parts, polyvinyl alcohol 30 parts, corn stalk powder 10 parts, polyethylene alcohol ester 2 parts, mineral oil 0.2 part, water or ethanol 5 parts and water-repelling agent 0.2 part.
The preparation method of biological whole degrading film of the present invention comprises the steps: a, first by corn straw 10 Part grinding and sieving, makes corn stalk powder, the corn stalk powder that can use is carried out post processing, post processing Time is 24h；B, be then passed through 24h after in 10 parts of corn stalk powders, be sequentially added into corn starch 30 Part, polyvinyl alcohol 30 parts, polyethylene alcohol ester 2 parts, mineral oil 0.2 part, water or ethanol 5 parts, dredge 0.2 part of water preparation, is blended post-heating to 50 DEG C～120 DEG C by above-mentioned material, makes biological whole degrading film female Material；C, finally biological whole degrading film masterbatch is blow molded in blow moulding machine, cools down molding, through inspection Warehousing after passing, prepares finished product.
Embodiment 2: a kind of biological whole degrading film, it is mainly made up of the raw material of following weight parts: be esterified Starch 40 parts, polyvinyl alcohol 45 parts, corn stalk powder 13 parts, polyethylene alcohol ester 12 parts, mineral oil 2 parts, water or methanol 30 parts and water-repelling agent 0.7 part, preparation method is with embodiment 1.
Embodiment 3: a kind of biological whole degrading film, it is mainly made up of the raw material of following weight parts: Semen Maydis Starch 50 parts, polyvinyl alcohol 50 parts, corn stalk powder 25 parts, polyethylene alcohol ester 20 parts, mineral oil 5 parts, 40 parts of water and water-repelling agent 2 parts, preparation method is with embodiment 1.
Last it should be noted that, above content is only in order to illustrate technical scheme, rather than to this The restriction of bright protection domain, those of ordinary skill in the art simply repaiies what technical scheme was carried out Change or equivalent, all without departing from the spirit and scope of technical solution of the present invention.

Claims (4)

1. a biological whole degrading film, it is characterised in that: described biological whole degrading film is mainly by following The raw material composition of weight portion: starch 30 parts～50 parts, polyvinyl alcohol 30 parts～50 parts, corn stalk powder 10 parts～25 parts, polyethylene alcohol ester 2 parts～20 parts, mineral oil 0.2 part～5 parts, plasticizer auxiliary agent 5 parts～40 parts and water-repelling agent 0.2 part～2 parts, described starch is corn starch or esterification starch, described increasing Moulding agent aid is water, ethanol or methanol.
A kind of biological whole degrading film the most according to claim 1, it is characterised in that: described biology Whole degrading film is mainly made up of the raw material of following weight parts: starch 34 parts～45 parts, polyvinyl alcohol 42 Part～48 parts, corn stalk powder 10 parts～13 parts, polyethylene alcohol ester 8 parts～15 parts, mineral oil 1 Part～4 parts, plasticizer auxiliary agent 21 parts～37 parts and water-repelling agent 0.4 part～1 part.
A kind of biological whole degrading film the most according to claim 2, it is characterised in that: described biology Whole degrading film is mainly made up of the raw material of following weight parts: starch 40 parts, polyvinyl alcohol 45 parts, Semen Maydis Powder of straw 13 parts, polyethylene alcohol ester 12 parts, mineral oil 2 parts, plasticizer auxiliary agent 30 parts and water-repelling agent 0.7 part.
The preparation method of biological whole degrading film the most according to claim 1, it is characterised in that: institute The preparation method stating biological whole degrading film comprises the steps:
A, first sieve after corn straw smashing, make corn stalk powder, the corn straw that will use Powder carries out post processing, and finishing time is 24h；
B, be then passed through 24h after in corn stalk powder, be sequentially added into corn starch, polyvinyl alcohol, poly-second Enol fat, mineral oil, water or ethanol, water-repelling agent, be blended post-heating to 50 DEG C～120 DEG C by above-mentioned material, Make biological whole degrading film masterbatch；
C, finally biological whole degrading film masterbatch is blow molded in blow moulding machine, cools down molding, through inspection Warehousing after passing, prepares finished product.
CN201610394551.XA 2016-06-07 2016-06-07 Fully biodegradable film and preparation method thereof Pending CN105837864A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106633202A (en) * 2016-10-19 2017-05-10 中国农业大学 Degradable film and preparation method thereof
CN107383436A (en) * 2017-06-22 2017-11-24 陕西理工大学 A kind of Biodegradable mulch
CN107501822A (en) * 2017-09-13 2017-12-22 安徽鼎正包装材料有限公司 A kind of processing method of compounding raw material for PVA water soluble films
CN118144201A (en) * 2024-03-31 2024-06-07 杭州中平化工有限公司 Manufacturing process of environment-friendly degradable plastic

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101580642A (en) * 2009-06-10 2009-11-18 普正汇利生物科技（北京）有限公司 Full-biodegradation natural polymer alloy and preparation method thereof
CN101885231A (en) * 2009-05-15 2010-11-17 上海交福新材料科技有限公司 Preparation method of fully-degradable polymer wood plastic composite
CN104910426A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Full-degradable plastic film taking surface hydrophobically modified starch as base material and preparation method thereof
CN104910441A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Agriculture plastic film capable of increasing soil activity directly after degradation and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885231A (en) * 2009-05-15 2010-11-17 上海交福新材料科技有限公司 Preparation method of fully-degradable polymer wood plastic composite
CN101580642A (en) * 2009-06-10 2009-11-18 普正汇利生物科技（北京）有限公司 Full-biodegradation natural polymer alloy and preparation method thereof
CN104910426A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Full-degradable plastic film taking surface hydrophobically modified starch as base material and preparation method thereof
CN104910441A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Agriculture plastic film capable of increasing soil activity directly after degradation and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106633202A (en) * 2016-10-19 2017-05-10 中国农业大学 Degradable film and preparation method thereof
CN107383436A (en) * 2017-06-22 2017-11-24 陕西理工大学 A kind of Biodegradable mulch
CN107501822A (en) * 2017-09-13 2017-12-22 安徽鼎正包装材料有限公司 A kind of processing method of compounding raw material for PVA water soluble films
CN118144201A (en) * 2024-03-31 2024-06-07 杭州中平化工有限公司 Manufacturing process of environment-friendly degradable plastic

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