CN1931907B - Biodegradable composition and its preparation process and sheet product - Google Patents
Biodegradable composition and its preparation process and sheet product Download PDFInfo
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- CN1931907B CN1931907B CN 200510103313 CN200510103313A CN1931907B CN 1931907 B CN1931907 B CN 1931907B CN 200510103313 CN200510103313 CN 200510103313 CN 200510103313 A CN200510103313 A CN 200510103313A CN 1931907 B CN1931907 B CN 1931907B
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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 the fully biodegradable resin take starch and degradable resin as main raw material.Although the former starch content can reach more than 60%, but be raw material owing to adopting non-biodegradable PE, PP, PS or other to be difficult to biodegradable polymer materials, therefore except the starch that adds can be degraded, remaining a large amount of non-biodegradable polymkeric substance still remains in and hard degradation, thereby causes the pollution to environment.As disclosed starch-containing resin combination in EP 0409789A2 and CN 1113918A.This resin combination has and the essentially identical physical and mechanical properties of common polyolefin resin, and cost compare is low, can commercially produce.But the raw material polyolefin resin composition in this resin combination can not biological degradation, and after just using, the volume of product reduces greatly, therefore can't eliminate material resin fully to the pollution of environment.
In recent years, people have dropped into resin and/or its composition that a large amount of man power and materials researches and develops 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 multipolymer as the degraded composition of 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 to be biodegradable fully, but due to the restriction of the source that is subjected to raw material and synthetic method, this series products price is very expensive, 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 be only suitable in the purposes that particular requirement is arranged.
In addition, people have also found by special biological preparation method or have adopted the aliphatic polyester that special chemical synthesis process obtains also can be biodegradable fully in recent years.But similar with US 4293539, due to the restriction of the source that is subjected to raw material and 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 in CN 1613901A, said composition mainly contains the starch of 15-80 % by weight, the polyvalent alcohol of 3-8 % by weight, the ethylene-acrylate copolymer of 0-15 % by weight, the aliphatic polyester of 5-70 % by weight and other a small amount of various processing aids.Although said composition replaces expensive aliphatic polyester with a large amount of cheap starch, but described as this document, above-mentioned composition is only suitable for be used to making membrane-based article, and the biological degradation rate (ISO 14855,60 days) of the membrane-based article that makes with said composition is only 50-70%.
Summary of the invention
First purpose of the present invention is that in prior art, biodegradable starch-containing resin combination can not for the shortcoming of making sheet-like shaped product, provide a kind of Biodegradable composition that can make sheet-like shaped product in order to overcome.
Second purpose of the present invention is to provide a kind of preparation method of Biodegradable composition of the present invention.
The 3rd purpose of the present invention is to provide 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 coordinate to the poly(lactic acid) less than 10 grams/10 minute the melting index of 190 ℃, can greatly improve the biological degradability of composition, 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 minute the melting index of 190 ℃.
The method of the described Biodegradable composition of preparation provided by the invention comprises sends into extruding pelletization in forcing machine after starch, polyvalent alcohol and poly(lactic acid) are 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 minute the melting index of 190 ℃.
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 not containing any biodegradable synthetic resins that is difficult in composition provided by the invention under natural environmental condition, 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 starch used is esterification starch and/or etherification starch, therefore also (ISO 14855 far above the 50-70% of disclosed composition and membrane-based article thereof in CN 1613901A for the biological degradability of composition provided by the invention and goods thereof, 60 days) biological degradation rate.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, the packing material of electronic components such as manufacturing equipment for prepn. of yoghurt, mess-tin, instant noodle bowl, spontaneous heating lunch box, beverage cup, microwave oven use food product containers and mobile phone, battery.
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 minute the melting index of 190 ℃.
According to Biodegradable composition provided by the invention, take the total amount of composition as benchmark, the content of esterification starch and/or etherification starch is the 20-60 % by weight, is preferably the 30-55 % by weight; The content of poly(lactic acid) is the 1-70 % by weight, is preferably the 5-60 % by weight; The content of polyvalent alcohol is the 2-40 % by weight, is preferably the 5-40 % by weight.
Esterification starch of the present invention refers to the product after partially or completely esterification occurs for hydroxyl in 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 being substituted hydroxyl in 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).One or more in specific embodiment of the invention preferred starch phosphoric acid one ester, starch sulphate, starch acetate, starch hydroxy propionate.
Above-mentioned esterification starch can be purchased and get, and also can get by the self-control of the esterification between starch and esterifying agent.Described esterifying agent can be various esterifying agent of the prior art, as mineral acid and salt, organic acid and derivative thereof, dithiocarbonic anhydride (CS
2), one or more in row machine phosphorus reagent.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 the various organic carboxyl acids of the prior art such as formic acid, acetic acid, 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, 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 % by weight concentration, stirred 10-30 minute under room temperature to 45 ℃, and then stirred 0.5-6 hour under 120-160 ℃, namely get the starch-phosphate product.Described dry method can realize by following technique: esterifying agent is sprayed onto on the dry starch particle with spray pattern, and then mixing, dry moisture, reaction namely get the starch-phosphate product.
Described etherification starch refers to the product after etherification reaction partially or completely occurs for hydroxyl in starch and etherifying agent, can be purchased and gets, and also can get by the self-control of the etherification reaction between starch and 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, cyanamide starch.The general structure of described carboxyl starch 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.The general structure of described cyano group starch 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 following formula (I), wherein R
1Alkylidene group or substituted alkylene, R
2And R
3Can be identical or not identical alkyl, replacement alkane
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 respectively various alkylidene groups, substituted alkylene, aryl, replacement arylidene, and the preferred R of the present invention and R ' are alkylidene group and the derivative thereof of C1-C8, for example, hydroxyethylamyle, hydroxypropylated starch.The general structure of described alkyl starch 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.The general structure of described aryl starch is St-O-Ar, and wherein Ar is aryl or substituted aryl, and the preferred Ar of the present invention is phenyl, tolyl, ethylbenzene, 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 identical or not identical alkyl, substituted alkyl, aryl, substituted aryl, 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 identical or not identical alkyl, 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 identical or not identical alkyl, substituted alkyl, aryl, substituted aryl.Described cyanamide starch refer to contain imido grpup (=NH) starch, general structure is suc as formula shown in (IV),
Wherein, R
1And R
2Can be identical or not identical alkyl, substituted alkyl, aryl, substituted aryl.
One or more in the specific embodiment of the invention in preferred carboxymethyl starch, hydroxypropylated starch, cyanoethyl starch, methyl starch and phenmethyl starch.Described etherifying agent comprises various halogenated carboxylic acids, epoxide, halohydrocarbon, nitrile compounds, sulfuric acid dialkyl and various nitrogenous etherifying agent.
Take the total amount of composition as benchmark, the content of esterification starch and/or etherification starch is the 20-60 % by weight, is preferably the 30-55 % by weight.Under 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 changing-nature and application " (Chemical Industry Press), does not repeat them here.
Substitution value of the present invention refers to the substituted average quantity of hydroxyl in each repeated structural unit of starch.The size of substitution value is 0-3, and the hydroxyl complete end of 0 expression in starch is substituted, and the hydroxyl in 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 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 operation step of aforesaid method does not repeat them here.
Poly(lactic acid) is the polyester material take organic acid lactic acid as raw material production, 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 as shown in formula V:
Under 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 refers to that the melting index of 190 ℃ be 4 to the poly(lactic acid) less than 10 grams/10 minute.More preferably the melting index of 190 ℃ be 4-9.9 gram/10 minute, density be 1.0-1.5 g/cc, elongation at break be 3.1-10.0%, tensile strength be 50-59 MPa, yield strength be 55-80 MPa, tensile modulus be the lucky handkerchief (GPa) of 2.0-3.4, shock strength be 12.6-15 burnt/rice or melt temperature are the poly(lactic acid) of 206-230 ℃.Take the total amount of composition as benchmark, the content of poly(lactic acid) is the 1-70 % by weight, is preferably the 5-60 % by 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 one or more in glycerine, Sorbitol Powder and tetramethylolmethane.Add these polyvalent alcohols can improve the processibility of composition, and can improve to a certain extent the consistency between starch and poly(lactic acid).Described polyvalent alcohol can use separately or two or more is used in conjunction with, and preferably is used in conjunction with.Take the total amount of composition as benchmark, the content of polyvalent alcohol is the 2-40 % by weight, is preferably the 5-40 % by 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, calcium carbonate, Calcium hydrogen carbonate, light calcium carbonate and 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 is brightened and lower production cost.Described additive salt can use separately or two or more is used in conjunction with, and is preferably two kinds and is used in conjunction with.Take the total amount of composition as benchmark, the content of additive salt is preferably the 0-10 % by 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 cane powder, is preferably wood powder.Take the total amount of composition as benchmark, the content of plant powder is preferably the 0-8 % by 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, lubricant.The kind of these additives, content and effect have been conventionally known to one of skill in the art.For example composition 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 use procedure because the factors such as light, heat, oxygen, microorganism cause too early degraded, thereby effectively control 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) one or more in 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.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), 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, and for example, take the total amount of composition as benchmark, the content of above-mentioned other additive is preferably the 0-10 % by weight.
The present invention also provides the preparation method of above-mentioned Biodegradable composition, and the method comprises after the various processing aids that starch, polyvalent alcohol, poly(lactic acid) and selectivity are contained mix sends into extruding pelletization in forcing machine; Wherein, described starch is that substitution value is esterification starch and/or the etherification starch of 0.1-3, and the melting index of 190 ℃ of described poly(lactic acid) is 4 to less than 10 grams/10 minute.
The concrete steps of the method are as follows:
(1) the various processing aids that starch, polyvalent alcohol, poly(lactic acid) and selectivity contained join in stirrer and evenly mix; 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 forcing machine used are conventionally known to one of skill in the art.For example, can adopt twin screw extruder, be 32 in length-to-diameter ratio: 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 refers to 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
The present embodiment is used for explanation 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 (the emerging starch factory production of Beijing power), 20.0 190 ℃ of melting index of weight part are that minute (number-average molecular weight is 20000 in 8.0 grams/10, 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 stirrer and stir at normal temperatures, stirrer is first with 100 rev/mins of low speed mixing approximately 7 minutes, and then with 200 rev/mins of high-speed mixing 8 minutes,
(2) the above-mentioned mixture that stirs is sent in twin screw extruder the 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 respectively 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 175 ℃; The vacuum keep of each section is the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after melting, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after pelletizing, finally make the granule product BSR-06P-HS1 for the preparation of the Biodegradable composition of sheet-like shaped product through die head again.
Embodiment 2
The present embodiment is used for explanation 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 (the emerging starch factory production of Beijing power), 5.0 190 ℃ of melting index of weight part are that minute (number-average molecular weight is 20000 in 9.9 grams/10, 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 stirrer, weight part TNPP and 1.0 weight part antioxidant 1010s stir at normal temperatures, stirrer is first with 80 rev/mins of low speed mixing approximately 5 minutes, and then with 15 rev/mins of high-speed mixing 6 minutes,
(2) the above-mentioned mixture that stirs is sent in twin screw extruder the 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 respectively 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃; The vacuum keep of each section is the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after melting, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after pelletizing, finally make the granule product BSR-06P-HS2 for the preparation of the Biodegradable composition of sheet-like shaped product through die head again.
Comparative Examples 1
This Comparative Examples is used for the explanation prior art for the preparation of the composition and method of making the same of sheet-like shaped product.
Prepare composition and granule product BSR-06C1 thereof according to the described method of example 2, different is, for the preparation of the starch of composition be the common W-Gum without esterification or etherificate, poly(lactic acid) to adopt 190 ℃ of melting index that U.S. combinating carbide company produces be 5.0 poly(lactic acid), wherein for the preparation of the relative weight of starch, poly(lactic acid), Sorbitol Powder, tetramethylolmethane, Zinic stearas, calcium stearate, epoxy soybean oil, antioxidant 1010 and the superfine carbon black of composition than identical.
Embodiment 3
The present embodiment is used for explanation 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 (the emerging starch factory production of Beijing power), 35.0 190 ℃ of melting index of weight part are that minute (number-average molecular weight is 20000 in 4 grams/10, 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 stirrer, weight part UV-531 and 1.0 weight part wood powders stir at normal temperatures, stirrer is first with 80 rev/mins of low speed mixing approximately 5 minutes, and then with 15 rev/mins of high-speed mixing 6 minutes,
(2) the above-mentioned mixture that stirs is sent in twin screw extruder the 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 respectively 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃; The vacuum keep of each section is the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after melting, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after pelletizing, finally make the granule product BSR-06P-HS3 for the preparation of the Biodegradable composition of sheet-like shaped product through die head again.
Embodiment 4
The present embodiment is used for explanation 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 (the emerging starch factory production of Beijing power), 20.0 190 ℃ of melting index of weight part are that minute (number-average molecular weight is 20000 in 6.0 grams/10, 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 stirrer, weight part ester group tin and 0.5 weight part antioxidant 1010 stir at normal temperatures, stirrer is first with 80 rev/mins of low speed mixing approximately 5 minutes, and then with 15 rev/mins of high-speed mixing 6 minutes,
(2) the above-mentioned mixture that stirs is sent in twin screw extruder the 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 respectively 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃; The vacuum keep of each section is the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after melting, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after pelletizing, finally make the granule product BSR-06P-HS4 for the preparation of the Biodegradable composition of sheet-like shaped product through die head again.
Embodiment 5
The present embodiment is used for the preparation of explanation 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 (the emerging starch factory production of Beijing power), 20.0 190 ℃ of melting index of weight part are that minute (number-average molecular weight is 20000 in 8.0 grams/10, 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 stirrer and stir at normal temperatures, stirrer is first with 100 rev/mins of low speed mixing approximately 7 minutes, and then with 200 rev/mins of high-speed mixing 8 minutes,
(2) the above-mentioned mixture that stirs is sent in twin screw extruder the 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 respectively 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 175 ℃; The vacuum keep of each section is (0.02)-(0.09) MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after melting, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after pelletizing, finally make the granule product BSR-06P-HS5 for the preparation of the Biodegradable composition of sheet-like shaped product through die head again.
Embodiment 6
The present embodiment is used for explanation 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 (the emerging starch factory production of Beijing power), 5.0 190 ℃ of melting index of weight part are that minute (number-average molecular weight is 20000 in 9.9 grams/10, 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 stirrer, weight part TNPP and 1.0 weight part antioxidant 1010s stir at normal temperatures, stirrer is first with 80 rev/mins of low speed mixing approximately 5 minutes, and then with 15 rev/mins of high-speed mixing 6 minutes,
(2) the above-mentioned mixture that stirs is sent in twin screw extruder the 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 respectively 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃; The vacuum keep of each section is the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after melting, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after pelletizing, finally make the granule product BSR-06P-HS6 for the preparation of the Biodegradable composition of sheet-like shaped product through die head again.
Embodiment 7
The present embodiment is used for explanation 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 (the emerging starch factory production of Beijing power), 35.0 190 ℃ of melting index of weight part are that minute (number-average molecular weight is 20000 in 4 grams/10, 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 stirrer, weight part UV-531 and 1.0 weight part TNPP stir at normal temperatures, stirrer is first with 80 rev/mins of low speed mixing approximately 5 minutes, and then with 15 rev/mins of high-speed mixing 6 minutes,
(2) the above-mentioned mixture that stirs is sent in twin screw extruder the 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 respectively 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃; The vacuum keep of each section is the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after melting, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after pelletizing, finally make the granule product BSR-06P-HS7 for the preparation of the Biodegradable composition of sheet-like shaped product through die head again.
Embodiment 8
The present embodiment is used for explanation 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 (the emerging starch factory production of Beijing power), 20.0 190 ℃ of melting index of weight part are that minute (number-average molecular weight is 20000 in 6.0 grams/10, 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 stirrer, weight part wood powder and 0.5 weight part antioxidant 1010 stir at normal temperatures, stirrer is first with 80 rev/mins of low speed mixing approximately 5 minutes, and then with 15 rev/mins of high-speed mixing 6 minutes,
(2) the above-mentioned mixture that stirs is sent in twin screw extruder the 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 respectively 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃; The vacuum keep of each section is the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after melting, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after pelletizing, finally make the granule product BSR-06P-HS8 for the preparation of the Biodegradable composition of sheet-like shaped product through die head again.
Embodiment 9
The present embodiment is used for explanation 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 (the emerging starch factory production of Beijing power), 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 minute (number-average molecular weight is 20000 in 6.0 grams/10, 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 stirrer, weight part wood powder and 0.5 weight part ester group tin stirs at normal temperatures, stirrer is first with 80 rev/mins of low speed mixing approximately 5 minutes, and then with 15 rev/mins of high-speed mixing 6 minutes,
(2) the above-mentioned mixture that stirs is sent in twin screw extruder the 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 respectively 150 ℃, 165 ℃, 165 ℃, 175 ℃, 165 ℃ and 170 ℃; The vacuum keep of each section is the 0.02-0.09 MPa; Mixture is in the screw rod and cylindrical shell of above-mentioned forcing machine, after melting, shearing, dispersion, reaction, compression, exhaust, plastifying, extrude, extrude, after pelletizing, finally make the granule product BSR-06P-HS9 for the preparation of the Biodegradable composition of 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 composition of table 2 granule product BSR-06P-HS5-BSR-06P-HS9
Performance test
Above-mentioned granule product is extruded with Φ 90 type forcing machines (Shantou, Guangdong gold alliance wrapping mechanism factory make) 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.
Adopt following standard method to carry out the properties test to above-mentioned sheet material products, test result is as shown in table 3 below:
Measure the tensile yield strength of goods with the method for stipulating in GB/T1040;
Measure the simple beam impact strength of goods with the method rigid plastics charpy impact test method of stipulating in GB/T1043-93;
Measure the biological degradation rate of goods with the method for regulation in ASTM D5247-92 (U.S.);
Measure mould degraded level and the biological degradation rate of goods with the method for regulation in ISO14855 (U.S.).
The performance perameter of table 3 sheet-like shaped product
can find out from the result of upper table 3, 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 in prior art, high (goods of the present invention can be realized complete biodegradable with based article, 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% in CN 1613901A, thereby composition provided by the invention is compared with disclosed composition in CN 1613901A, has more excellent 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. 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, and described poly(lactic acid) is 4 to less than 10 grams/10 minute the melting index of 190 ℃.
2. composition according to claim 1, wherein, described poly(lactic acid) is 4-9.9 gram/10 minute the melting index of 190 ℃.
3. composition according to claim 1, wherein, take the total amount of composition as benchmark, the content of described esterification starch and/or etherification starch is the 20-60 % by weight; The content of poly(lactic acid) is the 1-70 % by weight; The content of polyvalent alcohol is the 2-40 % by weight.
4. composition according to claim 3, wherein, the content of described esterification starch and/or etherification starch is the 30-55 % by weight; The content of poly(lactic acid) is the 5-60 % by weight; The content of polyvalent alcohol is the 5-40 % by 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, 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 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 g/cc, 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 12.6-15.0 Jiao/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, 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, calcium carbonate, Calcium hydrogen carbonate, light calcium carbonate and oyster shell whiting, take the total amount of composition as benchmark, the content of described additive salt is the 0-10 % by weight.
14. composition according to claim 13, wherein, described stearate is selected from one or more in Zinic stearas, calcium stearate, 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 cane powder, and take the total amount of composition as benchmark, the content of plant powder is the 0-8 % by 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, lubricant; Take the total amount of composition as benchmark, the content of described other additive is the 0-10 % by weight.
17. the preparation method of the described composition of claim 1, the method comprises sends into extruding pelletization in forcing machine after starch, poly(lactic acid) and polyvalent alcohol are 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 minute the melting index of 190 ℃.
18. preparation method according to claim 17, wherein, take the total amount of composition as benchmark, the add-on of described esterification starch and/or etherification starch is the 30-55 % by weight; The add-on of poly(lactic acid) is the 5-60 % by weight; The add-on of polyvalent alcohol is the 5-40 % by weight.
19. a biodegradable sheet-like shaped product, wherein, these goods contain the described composition of any one in claim 1-16.
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| CN1415651A (en) * | 2002-12-10 | 2003-05-07 | 中国科学院长春应用化学研究所 | Method for preparing amylaceous fully degradable plastic |
| CN1613901A (en) * | 2003-11-07 | 2005-05-11 | 李小鲁 | Biological degradable blow-moulding resin composition containing starch and its preparation |
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| CN1415651A (en) * | 2002-12-10 | 2003-05-07 | 中国科学院长春应用化学研究所 | Method for preparing amylaceous fully degradable plastic |
| CN1613901A (en) * | 2003-11-07 | 2005-05-11 | 李小鲁 | Biological degradable blow-moulding resin composition containing starch and its preparation |
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| JP特开2003-335934A 2003.11.28 |
| JP特开2004-189770A 2004.07.08 |
| JP特开平9-137069A 1997.05.27 |
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