CN1931907A - Biodegradable composition and its prepn process and sheet product - Google Patents
Biodegradable composition and its prepn process and sheet product Download PDFInfo
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- CN1931907A CN1931907A CN 200510103313 CN200510103313A CN1931907A CN 1931907 A CN1931907 A CN 1931907A CN 200510103313 CN200510103313 CN 200510103313 CN 200510103313 A CN200510103313 A CN 200510103313A CN 1931907 A CN1931907 A CN 1931907A
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Abstract
The biodegradable composition contains starch, polylactic acid and polyol. The starch is esterified and/or etherified starch with substitution degree of 0.1-3, and the polylactic acid has fusion index at 190 deg.c of 4-10 g/10 min. The present invention also provides the preparation process and product of the said composition. The said composition is suitable for forming sheet product and the product has complete biodegradability, high simply supported beam impact strength and high tension yield strength.
Description
Technical field
The sheet-like shaped product that the invention relates to a kind of Biodegradable composition and preparation method thereof and contain said composition.
Background technology
At present, degradable starch base resin mainly is divided into two kinds, and a kind of is starch filled incomplete biodegradable disintegration-type resin, and another kind is to be the fully biodegradable resin of main raw material with starch and degradable resin.Though the former starch content can reach more than 60%, but owing to adopt non-biodegradable PE, PP, PS or other to be difficult to biodegradable polymer materials is raw material, therefore except the starch that adds can be degraded, remaining a large amount of non-biodegradable polymkeric substance still remains in and is difficult to degraded, thereby causes the pollution to environment.As disclosed starch-containing resin combination among EP 0409789A2 and the CN 1113918A.This resin combination has and the essentially identical physical and mechanical properties of common polyolefin resin, and cost is lower, can commercially produce.But the raw material polyolefin resin composition in this resin combination can not biological degradation, only is to use the volume of back product to reduce greatly, therefore can't eliminate the pollution of material resin to environment fully.
In recent years, people have dropped into resin and/or its composition of great amount of manpower and material resources research and development fully biodegradable.For example, US 4293539 discloses a kind of resin combination, said composition adopts the polymkeric substance of the alcohol ester with biodegradable or their the multipolymer degraded composition as composition, as poly 3-hydroxy butyrate (PHB), polyvinyl alcohol (PVA), poly-hydroxyl valerate (PHV), PHB-PHV multipolymer and polycaprolactone (PCL).The advantage of this class material is can be fully by biological degradation, but owing to be subjected to the source of raw material and the restriction of synthetic method, this series products price is very expensive, be several times even tens times of common resins, and the goods snappiness made from above-mentioned composition is poor, and unit elongation is little, and product is crisp.Thereby only be suitable for having the purposes of particular requirement.
In addition, in recent years people also found also can be fully by biological degradation by special biological preparation method or the aliphatic polyester that adopts special chemical synthesis process to obtain.But similar with US 4293539, owing to be subjected to the source of raw material and the restriction of synthetic method, this series products price is very expensive, is several times even tens times of common resins.Therefore, the production of its commercial scale and application also are very restricted.
Disclose a kind of biodegradable starch-containing resin combination among the CN 1613901A, said composition mainly contains the starch of 15-80 weight %, the polyvalent alcohol of 3-8 weight %, the ethylene-acrylate copolymer of 0-15 weight %, aliphatic polyester and a spot of other various processing aids of 5-70 weight %.Although said composition uses a large amount of cheap starch to replace expensive aliphatic polyester, but it is described as this document, above-mentioned composition only is suitable for making membrane-based article, and the biological degradation rate (ISO 14855,60 days) of the membrane-based article that makes with said composition only is 50-70%.
Summary of the invention
First purpose of the present invention is in order to overcome the shortcoming that biodegradable starch-containing resin combination in the prior art can not be used to make sheet-like shaped product, a kind of Biodegradable composition that can make sheet-like shaped product to be provided.
Second purpose of the present invention provides a kind of preparation method of Biodegradable composition of the present invention.
The 3rd purpose of the present invention provides a kind of sheet-like shaped product that contains the present composition.
The inventor finds out of a clear sky, by starch is carried out esterification and/or etherification modified, and be 4 to cooperating 190 ℃ melting index less than/10 minutes poly(lactic acid) of 10 grams, can improve the biological degradability of composition greatly, and make said composition can be used in to make sheet-like shaped product.
Biodegradable composition provided by the invention contains starch, poly(lactic acid) and polyvalent alcohol, and wherein, described starch is that substitution value is esterification starch and/or the etherification starch of 0.1-3, and described poly(lactic acid) is 4 to less than 10 grams/10 minutes 190 ℃ melting index.
The method of the described Biodegradable composition of preparation provided by the invention comprises sends into extruding pelletization in the forcing machine after starch, polyvalent alcohol and poly(lactic acid) mixed; Wherein, described starch be substitution value be 0.1-3 esterification starch and/etherification starch, described poly(lactic acid) is 4 to less than 10 grams/10 minutes 190 ℃ melting index.
The present invention also provides a kind of biodegradable sheet-like shaped product, and these goods contain Biodegradable composition provided by the invention.
Owing to do not contain any biodegradable synthetic resins that under natural environmental condition, is difficult in the composition provided by the invention, so composition provided by the invention and goods fully biodegradable thereof, its biological degradation rate is up to 94% (ASTM D5247-92,14 days) and 98% (ISO 14855,60 days), and because used starch is esterification starch and/or etherification starch, therefore the biological degradability of composition provided by the invention and goods thereof is also far above the biological degradation rate of the 50-70% (ISO 14855,60 days) of disclosed composition and membrane-based article thereof among the CN 1613901A.And the tensile yield strength (vertically) of the sheet material based article that makes with composition provided by the invention is (GB/T1040) up to 28 MPas, simple beam impact strength is up to 21 Jiao/rice, thereby the present composition is suitable for making various different types of sheet-like shaped products, for example makes sour milk cup, mess-tin, instant noodle bowl, spontaneous heating snack food product box, beverage cup, the microwave oven packing material with electronic components such as food product containers and mobile phone, batteries.
Embodiment
Contain starch, poly(lactic acid) and polyvalent alcohol according to Biodegradable composition provided by the invention, wherein, described starch is that substitution value is esterification starch and/or the etherification starch of 0.1-3, and described poly(lactic acid) is 4 to less than 10 grams/10 minutes 190 ℃ melting index.
According to Biodegradable composition provided by the invention, be benchmark with the total amount of composition, the content of esterification starch and/or etherification starch is 20-60 weight %, is preferably 30-55 weight %; The content of poly(lactic acid) is 1-70 weight %, is preferably 5-60 weight %; The content of polyvalent alcohol is 2-40 weight %, is preferably 5-40 weight %.
Esterification starch of the present invention is meant the product after partially or completely esterification takes place for hydroxyl in the starch and esterifying agent, comprise starch-phosphate, starch sulphate, starch nitrate, starch xanthate, starch carboxylicesters (St-OCOR, R is various alkyl, substituted alkyl, aryl, substituted aryl, and wherein St represents the part except that being substituted hydroxyl in the starch) and the esterification products of starch and carboxylic acid derivative in one or more.Described starch-phosphate comprises starch phosphate one ester, starch phosphate diester, starch phosphate three esters; Described starch carboxylicesters comprises starch acetate (St-OCOCH
3), starch propionate, starch butyrate, succinate ester of starch; The esterification products of described starch and carboxylic acid derivative comprises starch carbamate (St-OCONH
2), starch hydroxy propionate (St-OCOCH
2CH
2OH).In specific embodiment of the invention preferred starch phosphoric acid one ester, starch sulphate, starch acetate, the starch hydroxy propionate one or more.
Above-mentioned esterification starch can be purchased and get, and also can get by the self-control of the esterification between starch and the esterifying agent.Described esterifying agent can be a various esterifying agent of the prior art, as mineral acid and salt, organic acid and derivative thereof, dithiocarbonic anhydride (CS
2), in the row machine phosphorus reagent one or more.Described mineral acid and salt thereof can be phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid and their salt and phosphorus oxychloride (POCl
3) in one or more.Described phosphoric acid salt comprises orthophosphoric acid salt (Na
2H
2PO and Na
2PO
4), metaphosphate (Na
4P
2O
7), trimetaphosphate ((NaPO
3)
3).Except the sodium salt of above-mentioned acid, can also be lithium salts, sylvite and the ammonium salt etc. of above-mentioned acid.Described organic acid comprises various organic carboxyl acids of the prior art such as formic acid, acetate, propionic acid, butyric acid, and described organic acid derivatives comprises organic acid acid amides, acyl chlorides, acid anhydrides, and described acid amides comprises urea.Described organophosphorus reagent comprises alkyl phosphate, alkyl pyrophosphate, β-cyanoethyl phosphoric acid ester, N-phosphoryl-N-Methylimidazole muriate, salicyl phosphoric acid ester, N-Benzamido phosphoric acid, 2-alkyl-2-oxazoline etc.The present invention preferably uses various with one or more esterification starchs that esterification obtains as esterifying agent in sodium phosphate salt, salicyl phosphoric acid ester, urea, acetic acid, propionic acid, butyric acid, dithiocarbonic anhydride, the diacetyl oxide.
The esterification process of described starch has been conventionally known to one of skill in the art, and for example the preparation method of starch-phosphate comprises two kinds of wet method and dry method.Described wet method and dry process have been conventionally known to one of skill in the art, for example wet method can realize by following step: will be equivalent to the solid phosphoric acid disodium hydrogen of starch weight 60% and the mixture of 20% SODIUM PHOSPHATE, MONOBASIC and join in the starch emulsion of 45 weight % concentration, room temperature to 45 ℃ following the stirring 10-30 minute, and then under 120-160 ℃, stirred 0.5-6 hour, promptly get the starch-phosphate product.Described dry method can realize by following technology: esterifying agent is sprayed onto on the dry starch particle with spray pattern, and mixing then, dry moisture, reaction promptly get the starch-phosphate product.
Described etherification starch is meant the product after etherification reaction partially or completely takes place for hydroxyl in the starch and etherifying agent, can be purchased and gets, and also can get by the self-control of the etherification reaction between starch and the various etherifying agent of the prior art.Described etherification starch generally includes one or more in carboxyl starch, cyano group starch, amide starches, hydroxyalkyl starch, alkyl starch, aryl starch, primary amine starch ethers, secondary amine starch ethers, tertiary amine starch ethers, kind of starch ether, the cyanamide starch.Described carboxyl starch structure general formula is St-O-R-COONa, and wherein R is various alkyl, substituted alkyl, aryl, substituted aryl; The preferred R of the present invention is various alkyl and the derivative thereof of C1-C8, for example carboxymethyl starch (St-O-CH
2-COONa), propyloic starch, carboxylic propyl group starch, carboxylic sec.-propyl starch.Described cyano group starch structure general formula is St-O-R-CN, and wherein R is various alkylidene groups, substituted alkylene, arylidene, replacement arylidene; The preferred R of the present invention is various alkylidene groups and the derivative thereof of C1-C8, for example cyanoethyl starch (St-O-CH
2CH
2CN).The general structure of described amide starches is shown in the following formula (I), wherein R
1Be alkylidene group or substituted alkylene, R
2And R
3Can be alkyl, replacement alkane identical or inequality
Base, aryl, substituted aryl, R
2And R
3Can also be hydrogen, the preferred R of the present invention
1Be C1-C8 alkylidene group, R
2And R
3Be hydrogen.The general structure of described hydroxyalkyl starch be St-O-R-OH or St-O-(R '-O)
n-ROH, wherein R and R ' are independently selected from various alkylidene groups, substituted alkylene, aryl, replacement arylidene respectively, and preferred R of the present invention and R ' are alkylidene group and the derivative thereof of C1-C8, for example, hydroxyethylamyle, hydroxypropylated starch.Described alkyl starch structure general formula is St-O-R, and wherein R is alkyl or substituted alkyl, and the preferred R of the present invention is the C1-C8 alkyl, for example methyl starch, ethyl starch, propyl group starch.Described aryl starch structure general formula is St-O-Ar, and wherein Ar is aryl or substituted aryl, and the preferred Ar of the present invention is phenyl, tolyl, ethylbenzene base, for example phenyl starch, phenmethyl starch, styroyl starch.The general structure of described primary amine starch ethers, secondary amine starch ethers, tertiary amine starch ethers is as shown in the formula shown in (II), wherein R
1Can be various alkylidene groups, substituted alkylene, the preferred R of the present invention
1Alkylidene group for C1-C8; R
2And R
3Can be alkyl, substituted alkyl, aryl, substituted aryl identical or inequality, R
2And R
3Can also be hydrogen, work as R
2And R
3When all being hydrogen, formula (II) expression primary amine starch ethers is worked as R
2And R
3When one of them was hydrogen, expression secondary amine starch ethers was worked as R
2And R
3During for alkyl identical or inequality, substituted alkyl, aryl, substituted aryl, formula (II) expression tertiary amine starch ethers, the alkyl of the preferred C1-C8 of the present invention.The general structure of described kind of starch ether is as shown in the formula shown in (III), wherein, and R
1Can be various alkylidene groups, substituted alkylene, the preferred R of the present invention
1Alkylidene group for C1-C8; R
2, R
3And R
4Can be alkyl, substituted alkyl, aryl, substituted aryl identical or inequality.Described cyanamide starch be meant contain imido grpup (=NH) starch, general structure is suc as formula shown in (IV),
Wherein, R
1And R
2Can be alkyl, substituted alkyl, aryl, substituted aryl identical or inequality.
In the specific embodiment of the invention in preferred carboxymethyl starch, hydroxypropylated starch, cyanoethyl starch, methyl starch and the phenmethyl starch one or more.Described etherifying agent comprises various halogenated carboxylic acids, epoxide, halohydrocarbon, nitrile compounds, sulfuric acid dialkyl and various nitrogenous etherifying agent.
Total amount with composition is a benchmark, and the content of esterification starch and/or etherification starch is 20-60 weight %, is preferably 30-55 weight %.Under the preferable case, the number-average molecular weight of esterification starch of the present invention and/or etherification starch is 20000-200000.
The condition of esterifying agent of the present invention, etherifying agent, esterification and etherification reaction is described in detail in " natural macromolecular material modification and application " (Chemical Industry Press), does not repeat them here.
Substitution value of the present invention is meant the substituted average quantity of hydroxyl in each repeated structural unit of starch.The size of substitution value is 0-3, and the complete end of hydroxyl in the 0 expression starch is substituted, and the hydroxyl in the 3 expression starch all or substantially all is substituted 3 substituted quantity of hydroxyl of each repeated structural unit in the numeric representation starch between the 0-3.The measuring method of the substitution value of different treated starch (comprising esterification starch and/or etherification starch) is different, concrete measuring method is grasped by those skilled in the art, for example, the measuring method of starch-phosphate substitution value comprises weighting method, atomic absorption method, volumetry, spectrophotometry, potentiometric titration.Wherein, weighting method, volumetry and spectrophotometry are more commonly used.The substitution value of the substitution value of starch-phosphate of the present invention for recording with weighting method.The measuring method of hydroxypropylated starch (etherification starch a kind of) substitution value has high performance liquid chromatography, nuclear magnetic resonance method, spectrophotometry and Zeisel method can.The substitution value of the substitution value of hydroxypropylated starch of the present invention for recording with nuclear magnetic resonance method.The measuring method of starch carboxylicesters substitution value comprises acid base titration and azanol colorimetry.The substitution value of the substitution value of starch carboxylicesters of the present invention for recording with acid base titration.The measuring method of carboxymethyl starch substitution value comprises ashing method, acid wash, complexometry, the precipitator method and spectrophotometry.The substitution value of the substitution value of carboxymethyl starch of the present invention for recording with spectrophotometry.The measuring method of cationic starch (as kind of starch ether) substitution value comprises Kjeldahl determination and potentiometric titration.The concrete operations step of aforesaid method does not repeat them here.
Poly(lactic acid) is to be the polyester material of raw material production with organic acid lactic acid, is a kind of alpha hydroxy acid class aliphatic polyester, has good biodegradable performance, mechanical property and physicals.The structural formula of poly(lactic acid) is shown in formula V:
Under the preferable case, it is 10000-100000 that the value of n makes the number-average molecular weight of poly(lactic acid) of the present invention, is preferably 10000-80000.Poly(lactic acid) can be commercially available, as blocks the EC0-PLA series product that base (Cargill) company produces; The series product of the 2002D model that U.S. the Nature company produces.Poly(lactic acid) of the present invention is meant that 190 ℃ melting index be 4 to less than/10 minutes poly(lactic acid) of 10 grams.Be that 4-9.9 gram/10 minutes, density are that 1.0-1.5 gram/cubic centimetre, elongation at break are that 3.1-10.0%, tensile strength are that 50-59 MPa, yield strength are that 55-80 MPa, tensile modulus are that 2.0-3.4 Ji handkerchief (GPa), shock strength are that Jiao 12.6-15/rice or melt temperature are 206-230 ℃ poly(lactic acid) more preferably 190 ℃ melting index.Total amount with composition is a benchmark, and the content of poly(lactic acid) is 1-70 weight %, is preferably 5-60 weight %.
The kind of described polyvalent alcohol and consumption have been conventionally known to one of skill in the art, for example, described polyvalent alcohol comprises one or more in the incomplete esterification products (as glyceryl monostearate) of ethylene glycol, glycol ether, propylene glycol, glycerine, tetramethylolmethane, Sorbitol Powder or its lower molecular weight condenses (molecular weight≤400) and longer chain fatty acid, is preferably in glycerine, Sorbitol Powder and the tetramethylolmethane one or more.Add these polyvalent alcohols and can improve the processibility of composition, and can improve the consistency between starch and the poly(lactic acid) to a certain extent.Described polyvalent alcohol can use separately or two or more is used, and preferably is used.Total amount with composition is a benchmark, and the content of polyvalent alcohol is 2-40 weight %, is preferably 5-40 weight %.
Composition provided by the invention preferably also contains one or more processing aids, as additive salt, plant powder and other additive.Described additive salt comprises one or more in alkylsulfonate, organic acid molysite, polyhydroxybutyrate salt, stearates, lime carbonate, Calcium hydrogen carbonate, light calcium carbonate and the oyster shell whiting.Described stearate comprises the stearate of Ca, Mg, Zn, Ba, Ce and Fe.Additive salt can improve the dimensional stability of the goods that made by composition of the present invention, goods are brightened and lowers production cost.Described additive salt can use separately or two or more is used, and is preferably two kinds and is used.Total amount with composition is a benchmark, and the content of additive salt is preferably 0-10 weight %.
Composition of the present invention can also contain plant powder.The kind of described plant powder and content are conventionally known to one of skill in the art, and for example, described plant powder can be selected from one or more in wood powder, bajiao banana powder and the cane powder, is preferably wood powder.Total amount with composition is a benchmark, and the content of plant powder is preferably 0-8 weight %.
Described other additive comprises one or more in oxidation inhibitor, light/thermo-stabilizer, photooxidant, antifogging agent, fire retardant, static inhibitor, coupling agent, tinting material, the lubricant.The kind of these additives, content and effect have been conventionally known to one of skill in the art.Composition for example provided by the invention can also contain oxidation inhibitor and/or light/thermo-stabilizer, with prevent and suppress starch and resin alloy system in the course of processing or in the use because factors such as light, heat, oxygen, microorganism cause too early degraded, thereby control effectively and delay superpolymer autoxidation speed, or effectively suppress or slow down ultraviolet solarization.Oxidation inhibitor can be selected from four (3-(3 ', 5 '-di-t-butyl)-4 '-hydroxy phenyl) in the propionic acid pentaerythritol ester (abbreviation antioxidant 1010), thio-2 acid SUNSOFT Q-182S (being called for short oxidation inhibitor DSTP), phosphorous acid esters, composite antioxidant PKY, dihydroxyphenyl propane one or more.Light/thermo-stabilizer can be selected from one or more in UV-series light/thermo-stabilizer, carbon black, organic tin light/thermo-stabilizer, trisnonyl phenyl phosphite (TNPP), the epoxy soybean oil.Wherein, UV-series light/thermo-stabilizer can be Alpha-hydroxy-4-oxy-octyl benzophenone (being called for short UV-531).Described organic tin light/thermo-stabilizer can be selected from one or more in dibutyl tin laurate, the different monooctyl ester diformazan of dithioglycol ester group ethylidene tin (being called for short ester group tin), ester group tin RWS-784, two (the different monooctyl ester of sulfo-glycolic acid) dioctyltin (being called for short capital tin 8831), two toxilic acid dibutyl tins, the different monooctyl ester dibutyl tin of sulfo-glycol.The kind of above-mentioned various additives and the selection of consumption have been that those of ordinary skills are known, for example, are benchmark with the total amount of composition, and above-mentioned other content of additive is preferably 0-10 weight %.
The present invention also provides the preparation method of above-mentioned Biodegradable composition, and this method comprises after the various processing aids that starch, polyvalent alcohol, poly(lactic acid) and selectivity are contained mix sends into extruding pelletization in the forcing machine; Wherein, described starch is that substitution value is esterification starch and/or the etherification starch of 0.1-3,190 ℃ melting index of described poly(lactic acid) be 4 to less than 10 the gram/10 minutes.
The concrete steps of this method are as follows:
(1) the various processing aids that starch, polyvalent alcohol, poly(lactic acid) and selectivity are contained join uniform mixing in the stirrer; Wherein, the temperature and time of blended under agitation is conventionally known to one of skill in the art, and for example, the temperature of blended under agitation can be 25-65 ℃, and the time of blended under agitation can be 5-15 minute, and the rotating speed of blended under agitation is 50-300 rev/min;
(2) with the mixture extruding pelletization that obtains.Wherein, the method for mixture extruding pelletization, condition and used forcing machine are conventionally known to one of skill in the art.For example, can adopt twin screw extruder, in length-to-diameter ratio is 32: 1-52: 1, screw speed 150-1200 rev/min, each zone temperatures is respectively 90-155 ℃, 115-165 ℃, 120-175 ℃, 130-185 ℃, 110-180 ℃, 120-185 ℃, and the vacuum tightness of each section is extruding pelletization under the condition of 0.02-0.09 MPa.Vacuum tightness herein is meant the absolute value (absolute pressure is less than barometric point) of the difference of absolute pressure and barometric point.
The present invention is further illustrated by the following examples.
Embodiment 1
Present embodiment is used to illustrate Biodegradable composition of the present invention and preparation method thereof.
(1) be 200000 with 50.0 weight parts (dry basis) number-average molecular weight, substitution value is 1.0 starch phosphate one ester (emerging starch factory production is weighed in Beijing), 20.0 190 ℃ of melting index of weight part are that (number-average molecular weight was 20000 to 8.0 grams in/10 minutes, elongation at break is 6.0%, tensile strength is 53 MPas, yield strength is 60 MPas, tensile modulus is 3.0 lucky handkerchiefs, shock strength is 12.8 Jiao/rice, melt temperature is 206 ℃) poly(lactic acid) and 30.0 weight part tetramethylolmethanes add in the stirrer and stir at normal temperatures, stirrer is earlier with about 7 minutes of 100 rev/mins of low speed mixing, and then with 200 rev/mins of high-speed mixing 8 minutes;
(2) the above-mentioned mixture that stirs is sent in the twin screw extruder length-to-diameter ratio L of forcing machine: D=48: 1, screw diameter is 58 millimeters of Φ.Adjust the rotating speed of screw rod, make it progressively rise to 200 rev/mins, 300 rev/mins, 400 rev/mins, 500 rev/mins, 700 rev/mins, 900 rev/mins from 100 rev/mins, each zone temperatures is controlled at 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 175 ℃ respectively; The vacuum tightness of each section remains the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after fusion, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after the pelletizing, finally make the granule product BSR-06P-HS1 of the Biodegradable composition that is used to prepare sheet-like shaped product through die head again.
Embodiment 2
Present embodiment is used to illustrate Biodegradable composition of the present invention and preparation method thereof.
(1) be 180000 with 50.0 weight parts (dry basis) number-average molecular weight, substitution value is 1.0 starch sulphate (emerging starch factory production is weighed in Beijing), 5.0 190 ℃ of melting index of weight part are that (number-average molecular weight was 20000 to 9.9 grams in/10 minutes, elongation at break is 6.0%, tensile strength is 56 MPas, yield strength is 62 MPas, tensile modulus is 3.2 lucky handkerchiefs, shock strength is 13.8 Jiao/rice, melt temperature is 210 ℃) poly(lactic acid), 20.0 weight part glycerine, 20.0 weight part Sorbitol Powder, 1.0 weight part Zinic stearas, 1.0 weight part calcium stearate, 1.0 weight part epoxy soybean oil, 1.0 adding in the stirrer, weight part TNPP and 1.0 weight part antioxidant 1010s stir at normal temperatures, stirrer is earlier with about 5 minutes of 80 rev/mins of low speed mixing, and then with 15 rev/mins of high-speed mixing 6 minutes;
(2) the above-mentioned mixture that stirs is sent in the twin screw extruder length-to-diameter ratio L of forcing machine: D=48: 1, screw diameter is 72 millimeters of Φ.Adjust the rotating speed of screw rod, make it progressively rise to 200 rev/mins, 300 rev/mins, 400 rev/mins, 500 rev/mins, 700 rev/mins, 900 rev/mins from 100 rev/mins, each zone temperatures is controlled at 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃ respectively; The vacuum tightness of each section remains the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after fusion, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after the pelletizing, finally make the granule product BSR-06P-HS2 of the Biodegradable composition that is used to prepare sheet-like shaped product through die head again.
Comparative Examples 1
This Comparative Examples is used for illustrating that prior art is used to prepare the composition and method of making the same of sheet-like shaped product.
Prepare composition and granule product BSR-06C1 thereof according to example 2 described methods, different is, 190 ℃ of melting index that the starch that is used to prepare composition is the common W-Gum without esterification or etherificate, poly(lactic acid) adopts U.S. combinating carbide company to produce are 5.0 poly(lactic acid), and the starch, poly(lactic acid), Sorbitol Powder, tetramethylolmethane, Zinic stearas, calcium stearate, epoxy soybean oil, antioxidant 1010 and the ultra-fine sooty relative weight that wherein are used to prepare composition are than identical.
Embodiment 3
Present embodiment is used to illustrate Biodegradable composition of the present invention and preparation method thereof.
(1) be 190000 with 30.0 weight parts (dry basis) number-average molecular weight, substitution value is 1.5 starch acetate (emerging starch factory production is weighed in Beijing), 35.0 190 ℃ of melting index of weight part are that (number-average molecular weight was 20000 to 4 grams in/10 minutes, elongation at break is 7.0%, tensile strength is 55 MPas, yield strength is 61 MPas, tensile modulus is 3.5 lucky handkerchiefs, shock strength is 13.0 Jiao/rice, melt temperature is 220 ℃) poly(lactic acid), 15.0 weight part glycerine, 15.0 weight part Sorbitol Powder, 1.0 weight part Zinic stearas, 1.0 weight part calcium stearate, 1.0 weight part oxidation inhibitor DSTP, 1.0 adding in the stirrer, weight part UV-531 and 1.0 weight part wood powders stir at normal temperatures, stirrer is earlier with about 5 minutes of 80 rev/mins of low speed mixing, and then with 15 rev/mins of high-speed mixing 6 minutes;
(2) the above-mentioned mixture that stirs is sent in the twin screw extruder length-to-diameter ratio L of forcing machine: D=48: 1, screw diameter is 58 millimeters of Φ.Adjust the rotating speed of screw rod, make it progressively rise to 200 rev/mins, 300 rev/mins, 400 rev/mins, 500 rev/mins, 700 rev/mins, 900 rev/mins from 100 rev/mins, each zone temperatures is controlled at 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃ respectively; The vacuum tightness of each section remains the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after fusion, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after the pelletizing, finally make the granule product BSR-06P-HS3 of the Biodegradable composition that is used to prepare sheet-like shaped product through die head again.
Embodiment 4
Present embodiment is used to illustrate Biodegradable composition of the present invention and preparation method thereof.
(1) be 200000 with 48.0 weight parts (dry basis) number-average molecular weight, substitution value is 1.8 starch propionate (emerging starch factory production is weighed in Beijing), 20.0 190 ℃ of melting index of weight part are that (number-average molecular weight was 20000 to 6.0 grams in/10 minutes, elongation at break is 5.9%, tensile strength is 52 MPas, yield strength is 59 MPas, tensile modulus is 2.0 lucky handkerchiefs, shock strength is 12.9 Jiao/rice, 207 ℃ of melt temperatures) poly(lactic acid), 15.0 weight part glycerine, 15.0 weight part Sorbitol Powder, 0.3 weight part Zinic stearas, 0.2 weight part calcium stearate, 0.5 weight part UV-531,0.5 adding in the stirrer, weight part ester group tin and 0.5 weight part antioxidant 1010 stir at normal temperatures, stirrer is earlier with about 5 minutes of 80 rev/mins of low speed mixing, and then with 15 rev/mins of high-speed mixing 6 minutes;
(2) the above-mentioned mixture that stirs is sent in the twin screw extruder length-to-diameter ratio L of forcing machine: D=48: 1, screw diameter is 58 millimeters of Φ.Adjust the rotating speed of screw rod, make it progressively rise to 200 rev/mins, 300 rev/mins, 400 rev/mins, 500 rev/mins, 700 rev/mins, 900 rev/mins from 100 rev/mins, each zone temperatures is controlled at 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃ respectively; The vacuum tightness of each section remains the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after fusion, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after the pelletizing, finally make the granule product BSR-06P-HS4 of the Biodegradable composition that is used to prepare sheet-like shaped product through die head again.
Embodiment 5
Present embodiment is used to illustrate the preparation of Biodegradable composition of the present invention.
(1) be 200000 with 50.0 weight parts (dry basis) number-average molecular weight, substitution value is 1.5 carboxymethyl starch (emerging starch factory production is weighed in Beijing), 20.0 190 ℃ of melting index of weight part are that (number-average molecular weight was 20000 to 8.0 grams in/10 minutes, elongation at break is 3.1%, tensile strength is 53 MPas, yield strength is 60 MPas, tensile modulus is 3.3 lucky handkerchiefs, shock strength is 12.8 Jiao/rice, melt temperature is 210 ℃) poly(lactic acid) and 30.0 weight part glycerine add in the stirrer and stir at normal temperatures, stirrer is earlier with about 7 minutes of 100 rev/mins of low speed mixing, and then with 200 rev/mins of high-speed mixing 8 minutes;
(2) the above-mentioned mixture that stirs is sent in the twin screw extruder length-to-diameter ratio L of forcing machine: D=48: 1, screw diameter is 58 millimeters of Φ.Adjust the rotating speed of screw rod, make it progressively rise to 200 rev/mins, 300 rev/mins, 400 rev/mins, 500 rev/mins, 700 rev/mins, 900 rev/mins from 100 rev/mins, each zone temperatures is controlled at 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 175 ℃ respectively; The vacuum tightness of each section remains (0.02)-(0.09) MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after fusion, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after the pelletizing, finally make the granule product BSR-06P-HS5 of the Biodegradable composition that is used to prepare sheet-like shaped product through die head again.
Embodiment 6
Present embodiment is used to illustrate Biodegradable composition of the present invention and preparation method thereof.
(1) be 180000 with 50.0 weight parts (dry basis) number-average molecular weight, substitution value is 2.0 hydroxypropylated starch (emerging starch factory production is weighed in Beijing), 5.0 190 ℃ of melting index of weight part are that (number-average molecular weight was 20000 to 9.9 grams in/10 minutes, elongation at break is 5.8%, tensile strength is 51 MPas, yield strength is 62 MPas, tensile modulus is 3.1 lucky handkerchiefs, shock strength is 13.8 Jiao/rice, melt temperature is 210 ℃) poly(lactic acid), 20.0 weight part glycerine, 20.0 weight part Sorbitol Powder, 1.0 weight part Zinic stearas, 1.0 weight part calcium stearate, 1.0 weight part epoxy soybean oil, 1.0 adding in the stirrer, weight part TNPP and 1.0 weight part antioxidant 1010s stir at normal temperatures, stirrer is earlier with about 5 minutes of 80 rev/mins of low speed mixing, and then with 15 rev/mins of high-speed mixing 6 minutes;
(2) the above-mentioned mixture that stirs is sent in the twin screw extruder length-to-diameter ratio L of forcing machine: D=48: 1, screw diameter is 58 millimeters of Φ.Adjust the rotating speed of screw rod, make it progressively rise to 200 rev/mins, 300 rev/mins, 400 rev/mins, 500 rev/mins, 700 rev/mins, 900 rev/mins from 100 rev/mins, each zone temperatures is controlled at 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃ respectively; The vacuum tightness of each section remains the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after fusion, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after the pelletizing, finally make the granule product BSR-06P-HS6 of the Biodegradable composition that is used to prepare sheet-like shaped product through die head again.
Embodiment 7
Present embodiment is used to illustrate Biodegradable composition of the present invention and preparation method thereof.
(1) be 210000 with 30.0 weight parts (dry basis) number-average molecular weight, substitution value is 1.5 cyanoethyl starch (emerging starch factory production is weighed in Beijing), 35.0 190 ℃ of melting index of weight part are that (number-average molecular weight was 20000 to 4 grams in/10 minutes, elongation at break is 6.7%, tensile strength is 58 MPas, yield strength is 61 MPas, tensile modulus is 3.0 lucky handkerchiefs, shock strength is 13.0 Jiao/rice, melt temperature is 200 ℃) poly(lactic acid), 15.0 weight part glycerine, 15.0 weight part Sorbitol Powder, 1.0 weight part Zinic stearas, 1.0 weight part calcium stearate, 1.0 weight part DSTP, 1.0 adding in the stirrer, weight part UV-531 and 1.0 weight part TNPP stir at normal temperatures, stirrer is earlier with about 5 minutes of 80 rev/mins of low speed mixing, and then with 15 rev/mins of high-speed mixing 6 minutes;
(2) the above-mentioned mixture that stirs is sent in the twin screw extruder length-to-diameter ratio L of forcing machine: D=48: 1, screw diameter is 58 millimeters of Φ.Adjust the rotating speed of screw rod, make it progressively rise to 200 rev/mins, 300 rev/mins, 400 rev/mins, 500 rev/mins, 700 rev/mins, 900 rev/mins from 100 rev/mins, each zone temperatures is controlled at 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃ respectively; The vacuum tightness of each section remains the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after fusion, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after the pelletizing, finally make the granule product BSR-06P-HS7 of the Biodegradable composition that is used to prepare sheet-like shaped product through die head again.
Embodiment 8
Present embodiment is used to illustrate Biodegradable composition of the present invention and preparation method thereof.
(1) be 200000 with 48.0 weight parts (dry basis) number-average molecular weight, substitution value is 1.8 phenmethyl starch (emerging starch factory production is weighed in Beijing), 20.0 190 ℃ of melting index of weight part are that (number-average molecular weight was 20000 to 6.0 grams in/10 minutes, elongation at break is 6.0%, tensile strength is 5.9 MPas, yield strength is 59 MPas, tensile modulus is 3.2 lucky handkerchiefs, shock strength is 12.9 Jiao/rice, melt temperature is 209 ℃) poly(lactic acid), 15.0 weight part glycerine, 15.0 weight part Sorbitol Powder, 0.3 weight part Zinic stearas, 0.2 weight part calcium stearate, 0.5 weight part UV-531,0.5 adding in the stirrer, weight part wood powder and 0.5 weight part antioxidant 1010 stir at normal temperatures, stirrer is earlier with about 5 minutes of 80 rev/mins of low speed mixing, and then with 15 rev/mins of high-speed mixing 6 minutes;
(2) the above-mentioned mixture that stirs is sent in the twin screw extruder length-to-diameter ratio L of forcing machine: D=48: 1, screw diameter is 58 millimeters of Φ.Adjust the rotating speed of screw rod, make it progressively rise to 200 rev/mins, 300 rev/mins, 400 rev/mins, 500 rev/mins, 700 rev/mins, 900 rev/mins from 100 rev/mins, each zone temperatures is controlled at 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃ respectively; The vacuum tightness of each section remains the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after fusion, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after the pelletizing, finally make the granule product BSR-06P-HS8 of the Biodegradable composition that is used to prepare sheet-like shaped product through die head again.
Embodiment 9
Present embodiment is used to illustrate Biodegradable composition of the present invention and preparation method thereof.
(1) be 200000 with 28.0 weight parts (dry basis) number-average molecular weight, substitution value is 1.8 phenmethyl starch (emerging starch factory production is weighed in Beijing), 20.0 the parts by weight average molecular weight is 180000, substitution value is 2.0 starch acetate, 20.0 190 ℃ of melting index of weight part are that (number-average molecular weight was 20000 to 6.0 grams in/10 minutes, elongation at break is 9.9%, tensile strength is 53 MPas, yield strength is 79 MPas, tensile modulus is 3.4 lucky handkerchiefs, shock strength is 14.9 Jiao/rice, melt temperature is 225 ℃) poly(lactic acid), 15.0 weight part glycerine, 15.0 weight part Sorbitol Powder, 0.3 weight part Zinic stearas, 0.2 weight part calcium stearate, 0.5 weight part UV-531,0.5 adding in the stirrer, weight part wood powder and 0.5 weight part ester group tin stirs at normal temperatures, stirrer is earlier with about 5 minutes of 80 rev/mins of low speed mixing, and then with 15 rev/mins of high-speed mixing 6 minutes;
(2) the above-mentioned mixture that stirs is sent in the twin screw extruder length-to-diameter ratio L of forcing machine: D=48: 1, screw diameter is 58 millimeters of Φ.Adjust the rotating speed of screw rod, make it progressively rise to 200 rev/mins, 300 rev/mins, 400 rev/mins, 500 rev/mins, 700 rev/mins, 900 rev/mins from 100 rev/mins, each zone temperatures is controlled at 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃ respectively; The vacuum tightness of each section remains the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after fusion, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after the pelletizing, finally make the granule product BSR-06P-HS9 of the Biodegradable composition that is used to prepare sheet-like shaped product through die head again.
The composition of table 1 granule product BSR-06P-HS1-BSR-06P-HS4 and BSR-06C1
| The embodiment numbering | Embodiment 1 | Embodiment 2 | Comparative Examples 1 | Embodiment 3 | Embodiment 4 | |
| The granule product numbering | BSR-06P-HS1 | BSR-06P-HS2 | BSR-06C1 | BSR-06P-HS3 | BSR-06P-HS4 | |
| Starch | Type | Starch phosphate one ester | Starch sulphate | Common starch | Starch acetate | Starch propionate |
| Substitution value | 1.0 | 1.0 | 0 | 1.5 | 1.8 | |
| Content (weight %) | 50.0 | 50.0 | 50.0 | 30.0 | 48.0 | |
| Poly(lactic acid) | 190 ℃ of melting index (restraining/10 minutes) | 8.0 | 9.9 | 5.0 | 4.0 | 6.0 |
| Tensile strength (MPa) | 53 | 56 | 55 | 55 | 52 | |
| Yield strength (MPa) | 60 | 62 | 61 | 61 | 59 | |
| Tensile modulus (Ji Pa) | 3.0 | 3.2 | 3.4 | 3.4 | 2.0 | |
| Elongation at break (%) | 6.0 | 6.0 | 7.0 | 7.0 | 5.9 | |
| Shock strength (Jiao/rice) | 12.8 | 13.8 | 13.0 | 13.0 | 12.9 | |
| Melt temperature (℃) | 206 | 210 | 220 | 220 | 207 | |
| Content (weight %) | 20.0 | 15.0 | 15.0 | 35.0 | 20.0 | |
| Sorbitol Powder (weight %) | - | 10.0 | 10.0 | 15.0 | 15.0 | |
| Glycerine (weight %) | - | 20.0 | 20.0 | 15.0 | 15.0 | |
| Tetramethylolmethane (weight %) | 30.0 | - | - | - | - | |
| Zinic stearas (weight %) | - | 1.0 | 1.0 | 1.0 | 0.3 | |
| Calcium stearate (weight %) | - | 1.0 | 1.0 | 1.0 | 0.2 | |
| Epoxy soybean oil (weight %) | - | 1.0 | 1.0 | - | - | |
| Oxidation inhibitor DSTP (weight %) | - | - | - | 1.0 | - | |
| Antioxidant 1010 (weight %) | - | 1.0 | 1.0 | - | 0.5 | |
| UV-531 (weight %) | - | - | - | 1.0 | 0.5 | |
| Ester group tin (weight %) | - | - | - | - | 0.5 | |
| Wood powder ((weight %)) | - | - | - | 1.0 | - | |
| TNPP (weight %) | - | 1.0 | 1.0 | - | - | |
| Total amount (weight %) | 100 | 100 | 100 | 100 | 100 | |
The composition of table 2 granule product BSR-06P-HS5-BSR-06P-HS9
| The embodiment numbering | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| The granule product numbering | BSR-06P-HS5 | BSR-06P-HS6 | BSR-06P-HS7 | BSR-06P-HS8 | BSR-06P-HS9 | |
| Starch | Type | Carboxymethyl starch | Hydroxypropylated starch | Cyanoethyl starch | Phenmethyl starch | Phenmethyl starch+starch acetate |
| Substitution value | 0.5 | 2.0 | 1.5 | 1.8 | 1.8+2.0 | |
| Content (weight %) | 50.0 | 50.0 | 30.0 | 48.0 | 20.0+28.0 | |
| Poly(lactic acid) | 190 ℃ of melting index (restraining/10 fens) | 8.0 | 9.9 | 4.0 | 6.0 | 6.0 |
| Tensile strength (MPa) | 53 | 56 | 58 | 55 | 59 | |
| Yield strength (MPa) | 60 | 62 | 61 | 59 | 79 | |
| Tensile modulus (Ji Pa) | 3.3 | 3.1 | 3.0 | 3.2 | 3.4 | |
| Elongation at break (%) | 3.1 | 5.8 | 6.7 | 5.9 | 9.9 | |
| Shock strength (Jiao/rice) | 12.8 | 13.8 | 13.0 | 12.9 | 14.9 | |
| Melt temperature (℃) | 210 | 210 | 200 | 209 | 225 | |
| Content (weight %) | 20.0 | 5.0 | 35.0 | 20.0 | 20.0 | |
| Sorbitol Powder (weight %) | - | 20.0 | 15.0 | 15.0 | 15.0 | |
| Glycerine (weight %) | - | 20.0 | 15.0 | 15.0 | 15.0 | |
| Tetramethylolmethane (weight %) | 30.0 | - | - | - | - | |
| Zinic stearas (weight %) | - | 1.0 | 1.0 | 0.3 | 0.3 | |
| Calcium stearate (weight %) | - | 1.0 | 1.0 | 0.2 | 0.2 | |
| Epoxy soybean oil (weight %) | - | 1.0 | - | - | - | |
| Oxidation inhibitor DSTP (weight %) | - | - | 1.0 | - | - | |
| Antioxidant 1010 (weight %) | - | 1.0 | - | 0.5 | - | |
| UV-531 (weight %) | - | - | 1.0 | 0.5 | 0.5 | |
| Ester group tin (weight %) | - | - | - | - | 0.5 | |
| Wood powder ((weight %)) | - | - | - | 0.5 | 0.5 | |
| TNPP (weight %) | - | 1.0 | 1.0 | - | - | |
| Total amount (weight %) | 100 | 100 | 100 | 100 | 100 | |
Performance test
Above-mentioned granule product is extruded the sheet-like shaped product HS1-HS9 and the C1 that obtain being of a size of 680 millimeters (wide) * 0.8 millimeter (thick) * double centner/volume with Φ 90 type forcing machines (manufacturing of Shantou, Guangdong Jin Meng wrapping mechanism factory).
Adopt following standard method that above-mentioned sheet material products is carried out every performance test, test result is as shown in table 3 below:
Measure the tensile yield strength of goods with the method for stipulating among the GB/T1040;
Measure the simple beam impact strength of goods with the method rigid plastics charpy impact test method of stipulating among the GB/T1043-93;
Measure the biological degradation rate of goods with the method for regulation among the ASTM D5247-92 (U.S.);
Measure the mould degraded level and the biological degradation rate of goods with the method for regulation among the ISO14855 (U.S.).
The performance perameter of table 3 sheet-like shaped product
| Test event | HS1 | HS2 | Cl | HS3 | HS4 | HS5 | HS6 | HS7 | HS8 | HS9 | Requirement | |
| Appearance features | Light yellow material, free from extraneous odour, differently smell, foreign matter | |||||||||||
| Water content (weight %) | 0.7 | 0.8 | 0.8 | 0.5 | 0.6 | 0.5 | 0.6 | 0.8 | 0.5 | 0.7 | ≤1.2 | |
| Biological degradation rate (%, 14 days) | 95 | 96 | 65 | 94 | 93 | 96 | 96 | 95 | 96 | 95 | ≥90 | |
| Biological degradation rate (%, 60 days) | 95 | 96 | 70 | 98 | 95 | 96 | 98 | 97 | 96 | 98 | ≥90 | |
| Mould-growth level (level, 21 days) | 5 | 5 | 4 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
| Simple beam impact strength (Jiao/rice) | 25 | 23 | 14 | 28 | 29 | 25 | 27 | 24 | 26 | 28 | ≥20 | |
| Rockwell hardness (R scale) | 35 | 36 | 13 | 33 | 37 | 34 | 39 | 40 | 36 | 38 | ≥28 | |
| Tensile yield strength (MPa) | Vertical | 33 | 33 | 10 | 36 | 32 | 30 | 31 | 38 | 35 | 33 | ≥20 |
| Horizontal | 28 | 30 | 15 | 34 | 29 | 28 | 28 | 34 | 33 | 30 | ||
From the result of last table 3 as can be seen, the biological degradation rate of the goods that make with composition provided by the invention is up to 98%, the mould-growth level also reaches 5 grades, more than (goods of the present invention can be realized complete biodegradable with the based article height in the prior art, and all can not realize complete biodegradable with based article), even compare also high with the biological degradation rate (recording under the same test condition) of disclosed membrane-based article 70% among the CN 1613901A, thereby composition provided by the invention compares with disclosed composition among the CN 1613901A, has excellent more biological degradability.The more important thing is, the goods that make with composition provided by the invention have good simple beam impact strength, Rockwell hardness and tensile yield strength, the performance requirement that meets sheet-like shaped product fully, therefore, composition provided by the invention can be used in makes sheet-like shaped product.
Claims (19)
1, a kind of Biodegradable composition, said composition contains starch, poly(lactic acid) and polyvalent alcohol, it is characterized in that described starch is that substitution value is esterification starch and/or the etherification starch of 0.1-3, described poly(lactic acid) is 4 to less than 10 grams/10 minutes 190 ℃ melting index.
2, composition according to claim 1, wherein, described poly(lactic acid) is 4-9.9 gram/10 minutes 190 ℃ melting index.
3, composition according to claim 1 wherein, is a benchmark with the total amount of composition, and the content of described esterification starch and/or etherification starch is 20-60 weight %; The content of poly(lactic acid) is 1-70 weight %; The content of polyvalent alcohol is 2-40 weight %.
4, composition according to claim 3, wherein, the content of described esterification starch and/or etherification starch is 30-55 weight %; The content of poly(lactic acid) is 5-60 weight %; The content of polyvalent alcohol is 5-40 weight %.
5, composition according to claim 1, wherein, the substitution value of described esterification starch and/or etherification starch is 0.5-2.5.
6, composition according to claim 1, wherein, described esterification starch and/or etherification starch are selected from one or more in primary amine starch ethers, secondary amine starch ethers, tertiary amine starch ethers, kind of starch ether, cyanamide starch, starch-phosphate, starch sulphate, starch nitrate, starch xanthate, starch carboxylicesters, carboxyl starch, hydroxyalkyl starch, cyano group starch, alkyl starch, the aryl starch.
7, composition according to claim 6, wherein, described esterification starch and/or etherification starch are selected from one or more in starch phosphate one ester, starch phosphate diester, starch phosphate three esters, starch sulphate, starch acetate, starch propionate, carboxymethyl starch, hydroxypropylated starch, cyanoethyl starch, methyl starch, ethyl starch and the phenmethyl starch.
8, composition according to claim 1, wherein, the number-average molecular weight of described poly(lactic acid) is that 10000-100000, elongation at break are 3.1-10.0%.
9, composition according to claim 8, wherein, the density of described poly(lactic acid) is that 1.0-1.5 gram/cubic centimetre, tensile strength are the 50-54 MPa.
10, composition according to claim 9, wherein, the yield strength of described poly(lactic acid) is that 55-80 MPa, tensile modulus are the lucky handkerchief of 2.0-3.4.
11, composition according to claim 10, wherein, the shock strength of described poly(lactic acid) is that Jiao 12.6-15.0/rice, melt temperature are 206-230 ℃.
12, composition according to claim 1, wherein, described polyvalent alcohol is selected from one or more in Sorbitol Powder, glycerine, the tetramethylolmethane.
13, composition according to claim 1, wherein, said composition also contains additive salt, described additive salt is selected from one or more in alkylsulfonate, organic acid molysite, polyhydroxybutyrate salt, stearates, lime carbonate, Calcium hydrogen carbonate, light calcium carbonate and the oyster shell whiting, total amount with composition is a benchmark, and the content of described additive salt is 0-10 weight %.
14, composition according to claim 13, wherein, described stearate is selected from one or more in Zinic stearas, calcium stearate, the iron stearate.
15, composition according to claim 1, wherein, said composition also contains plant powder, and described plant powder is selected from one or more in wood powder, bajiao banana powder and the cane powder, is benchmark with the total amount of composition, and the content of plant powder is 0-8 weight %.
16, composition according to claim 1, wherein, said composition also contains other additive, and described other additive comprises one or more in oxidation inhibitor, light/thermo-stabilizer, photooxidant, antifogging agent, fire retardant, static inhibitor, coupling agent, tinting material, the lubricant; Total amount with composition is a benchmark, and described other content of additive is 0-10 weight %.
17, the described preparation of compositions method of claim 1, this method comprises sends into extruding pelletization in the forcing machine after starch, poly(lactic acid) and polyvalent alcohol mixed, wherein, described starch is that substitution value is esterification starch and/or the etherification starch of 0.1-3, and described poly(lactic acid) is 4 to less than 10 grams/10 minutes 190 ℃ melting index.
18, preparation method according to claim 17 wherein, is a benchmark with the total amount of composition, and the add-on of described esterification starch and/or etherification starch is 30-55 weight %; The add-on of poly(lactic acid) is 5-60 weight %; The add-on of polyvalent alcohol is 5-40 weight %.
19, a kind of biodegradable sheet-like shaped product, wherein, these goods contain any described composition among the claim 1-16.
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| CN102268155A (en) * | 2011-07-04 | 2011-12-07 | 王庆昭 | Additive and preparation method thereof as well as full-degradable polyethylene nano compound material and products thereof |
| CN102443195A (en) * | 2010-10-09 | 2012-05-09 | 于瑞德 | Biodegradable plastic and preparation method thereof |
| CN105209227A (en) * | 2013-06-21 | 2015-12-30 | 乐金华奥斯株式会社 | Board comprising biodegradable resin and wooden flour and method of manufacturing the same |
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| CN1169869C (en) * | 2002-12-10 | 2004-10-06 | 中国科学院长春应用化学研究所 | Method for preparing amylaceous fully degradable plastic |
| CN1307246C (en) * | 2003-11-07 | 2007-03-28 | 李小鲁 | Biological degradable blow-moulding resin composition containing starch and its preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102443195A (en) * | 2010-10-09 | 2012-05-09 | 于瑞德 | Biodegradable plastic and preparation method thereof |
| CN102268155A (en) * | 2011-07-04 | 2011-12-07 | 王庆昭 | Additive and preparation method thereof as well as full-degradable polyethylene nano compound material and products thereof |
| CN102268155B (en) * | 2011-07-04 | 2013-11-20 | 王庆昭 | Additive and preparation method thereof as well as full-degradable polyethylene nano compound material and products thereof |
| CN105209227A (en) * | 2013-06-21 | 2015-12-30 | 乐金华奥斯株式会社 | Board comprising biodegradable resin and wooden flour and method of manufacturing the same |
| CN107840994A (en) * | 2017-11-14 | 2018-03-27 | 成都新柯力化工科技有限公司 | It is a kind of can degradable starch-based bio plastic foil preparation method |
| CN109770905A (en) * | 2019-03-12 | 2019-05-21 | 长兴县人民医院 | A kind of offline Exhaled nitric oxide detection device |
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