CN1916062A - Biodegradable composition of resin containing starch, products and prepartion method - Google Patents
Biodegradable composition of resin containing starch, products and prepartion method Download PDFInfo
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- CN1916062A CN1916062A CN 200510090456 CN200510090456A CN1916062A CN 1916062 A CN1916062 A CN 1916062A CN 200510090456 CN200510090456 CN 200510090456 CN 200510090456 A CN200510090456 A CN 200510090456A CN 1916062 A CN1916062 A CN 1916062A
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Abstract
This invention discloses a biodegradable resin composition, which comprises starch, polyol, ethylene-acrylate copolymer, salt additive, polyolefin resin and copolymer of olefin and unsaturated alcohol carboxylate. The composition can be prepared by direct method or master batch method. The composition can be used to produce blow-molded products, press-molded products, injection-molded products and foam products. The products have good heat-sealing performance, good heat resistance and high biodegradability.
Description
Technical field
The invention relates to the preparation method of a kind of biodegradable starch-containing resin combination and goods and said composition.
Background technology
Development of modern industry, the particularly develop rapidly of petrochemical complex, for industrial and agricultural production and people's daily living article provide excellent performance, cheap synthetic resins and plastics, especially plastics film and foam plastic product, promote the industrial and agricultural production development and greatly enriched people's material life, yet the offal treatment after using is not good at, abandon the edge of a field arbitrarily, the river, hill, place such as street corner and park, environment for human survival has also been caused severe contamination, cause one of current social maximum public hazards " white pollution ", caused people's extensive concern.In recent years, make laws one after another in countries in the world, the use of restriction plastics film and porous plastics; Simultaneously, also at biodegradable resin of development research and plastics energetically.
US 4293539 discloses a kind of resin combination, and said composition adopts has the polymkeric substance of biodegradable alcohol ester or their multipolymer, as the degraded composition of PHB (poly 3-hydroxy butyrate) as composition.The advantage of this class material is the energy complete biodegradable, but because the source of raw material and the restriction of synthetic method cause the price of product very expensive, be several times even tens times of common plastics, and when making film, the unit elongation of product is little, thereby only is suitable for having the purposes of particular requirement.
WO 9102023 discloses a kind of resin combination, and said composition adopts starch and wetting ability synthetic resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer and other additive to make.The biodegradable of this based resin composition is good, but its water resisting property is bad, and the performance of product is subjected to the influence of ambient moisture very big, and processing characteristics such as heat sealability are poor.
EP 0409789A2 discloses a kind of resin combination, said composition is that starch, polyethylene, ethylene-vinyl acetate increasing component, softening agent etc. are being had under the condition that adds water, make starch pasting, make polyethylene, ethylene-vinyl acetate and starch blending simultaneously, after extruding excessive moisture, granulation gets Degradable Starch Resin.The characteristics of this method are that gelatinization, the blend of starch once finished, and make the application of starch become possibility.But the starch content in Jia Gong the Degradable Starch Resin is not high in this way, and when starch content was higher than 25%, the product mechanical property was bad, and processing and use are subjected to the influence of humidity very big.When blowing out film, can not obtain thin film, transparency is also bad.Test shows, by the film that this method obtains, thickness will soon embrittlement after storing more than 50 microns and in the exsiccant environment, and unit elongation also sharply descends, and thermalization is very poor.Electron microscope observation finds, starch is dispersed in granularity in the polyethylene between the 30-50 micron, and is dispersed bad.Starch is a kind of strong polar molecule material, and all there is extremely strong hydrogen bond in intermolecular and intramolecularly, and polyvinyl resin then is a kind of nonpolar polymkeric substance, and the consistency of therefore improving starch and polyvinyl resin is the key of this technology.In addition, this blend because starch and synthetic resins is mobile different, is prone to the hole during blowing when being processed into goods.
CN 1113918A discloses a kind of Biodegradable composition and its production and application.In this patent application, said composition contains the starch of 15-68% (weight), the polyvinyl resin of 10-60% (weight), and surplus is that increasing component, softening agent, alkaline additive and a spot of microorganism are as biodegradation promotor.In this resin combination, the mechanical and physical performance of the addition of starch, the goods that made by this resin combination and biodegradable are compared with like product of the prior art all in various degree improvement.But the microorganism of adopting in this patent application is as biodegradation promotor, be subjected to the influence of the processing conditions of resin and technology very big, and the variation of envrionment conditions is also very big to the influence of resin.In addition, though the influence of the characterization of molecules of polyolefin resin to the preparation of resin blend also noticed in this patent application, but just from improving the starch addition, increase Degradable Starch Resin combined physical mechanical property, particularly improving its tearing toughness angle sets out, from the polyolefin resin of routine, select polyolefin resin, and the goods that made by described resin combination are at heat sealability with specific molecular feature, angle tear strength, tensile tear strength, temperature tolerance, easily aspects such as perviousness and degradation property can't satisfy the more and more higher requirement to plastics especially plastic membrane product fully.
A kind of biodegradable resin combination and its production and application is disclosed among the CN 1267680A.In this patent application, said composition contains the starch of 15-65 weight %, the polyvalent alcohol of 3-15 weight %, the ethylene-acrylate copolymer of 3-20 weight %, the additive salt of 8-12 weight %, the plant powder of 0-10 weight %, the polyolefin resin of 8-60 weight % and other auxiliary agent of 0-5 weight %.By selecting the metallocene-polyolefin resin for use, make the physical and mechanical properties of the goods that make by this resin combination and biodegradable all apparently higher than adopting the polyolefinic degradable resin composition of Ziegler-Natta type.But in the product that makes with the disclosed resin combination of this patent application, be that the degradable components content of representative is when higher with starch, because character determines, the heat sealability of product (as sour milk cup, instant noodle bowl, packing bag etc.) reduces greatly, has had a strong impact on the usability and the security of product.
Summary of the invention
The objective of the invention is in order to overcome the bad shortcoming of goods heat sealability that resin combination of the prior art makes, provide a kind of and can make the excellent and biodegradable starch-containing resin combination of heat sealability.
Second purpose of the present invention provides a kind of method for preparing this biodegradable starch-containing resin combination.
The 3rd purpose of the present invention provides a kind of goods that this biodegradable starch-containing resin combination makes that contain.
The invention provides a kind of biodegradable starch-containing resin combination, said composition contains starch, polyvalent alcohol, ethylene-acrylate copolymer, additive salt and polyolefin resin, wherein, said composition also contains the multipolymer of alkene and unsaturated alcohol carboxylicesters.
The preparation method of biodegradable starch-containing resin combination provided by the invention comprises starch, polyvalent alcohol, ethylene-acrylate copolymer, polyolefin resin and additive salt is mixed; The mixture that obtains is sent into extruding pelletization in the forcing machine; Wherein, the multipolymer that when mixing, also adds alkene and unsaturated alcohol carboxylicesters.
The present invention also provides a kind of biodegradable goods, and these goods contain biodegradable starch-containing resin combination provided by the invention.
The goods that make with the composition that contains the multipolymer of alkene and unsaturated alcohol carboxylicesters provided by the invention have the heat sealability of obvious raising, under similarity condition, (the expression heat sealability is poor by A level of the prior art for the heat sealability of goods, difficult heat-sealing) the C level of bringing up to goods of the present invention (represents that heat sealability is good, seal easily), thus the use properties and the security that have improved goods significantly.In addition, alkaline matter can also effectively improve the temperature tolerance of starch in the composition, thereby delayed the thermooxidative degradation speed of starch in the course of processing, make the temperature tolerance of starch in the course of processing bring up to 120-180 ℃ by≤100 ℃, the temperature tolerance that make to use the goods that this composition resin processes is brought up to-5-98 ℃ (as the temperature tolerance of the goods that make with embodiment 7 compositions) by 0-50 ℃.The biodegradable performance of composition provided by the invention also be improved significantly (the biological degradation level is brought up to the 3-5 level by the 1-3 level under ISO 845 testing standards).If contain the angle tear strength that the extremely-low density polyolefin resin can also obviously improve product, make the angle tear strength of product bring up to 50-90N.M in the polyolefin resin in the above-mentioned composition of the present invention by 20-40N.M.
Embodiment
Biodegradable starch-containing resin combination provided by the invention contains starch, polyvalent alcohol, ethylene-acrylate copolymer, additive salt and polyolefin resin, and wherein, said composition also contains the multipolymer of alkene and unsaturated alcohol carboxylicesters.
Under the preferable case, total amount with composition is a benchmark, and contents of starch is that the content of 30-65 weight %, polyvalent alcohol is that the content of 2-12 weight %, ethylene-acrylate copolymer is that the content of 3-20 weight %, additive salt is that 0.1-3 weight content %, polyolefin resin is that the content of the multipolymer of 10-60 weight %, alkene and unsaturated alcohol carboxylicesters is 0.1-20 weight %.
The general structure of the multipolymer of described alkene and unsaturated alcohol carboxylicesters is suc as formula shown in (I)::
Wherein, R
1-R
8Can be alkyl or hydrogen identical or inequality, under the preferable case, R
1-R
8Be hydrogen and/or methyl, it is 50,000-200,000 that the value of n makes the weight-average molecular weight of the multipolymer of this alkene and unsaturated alcohol carboxylicesters.The multipolymer of described alkene and unsaturated alcohol carboxylicesters is meant and contains at least 1 carboxylic acid ester groups in each polymer repeat unit, and the carbonyl in the described carboxylic acid ester groups (C=O-) carbon atom on group and the main polymer chain is separated by Sauerstoffatom or other atom.Described alkene can be straight or branched alkene such as ethene, propylene, butylene, iso-butylene, vinylbenzene.Described unsaturated alcohol carboxylicesters normally by unsaturated alcohol and organic carboxyl acid by the product that esterification generates, for example can be in vinyl acetate between to for plastic, acetate propylene, acetic acid butylene, the vinyl propionate one or more.
The structural formula of ethylene-vinyl acetate copolymer is suc as formula shown in (II):
Preferable weight-average molecular weight of the present invention is 50,000-200,000 ethylene-vinyl acetate copolymer.Total amount with composition is a benchmark, and the content of the multipolymer of alkene and unsaturated alcohol carboxylicesters is preferably 0.5-5 weight %.
The present composition can also contain alkaline matter.The adding alkaline matter can improve the temperature tolerance of starch, thereby delay the thermooxidative degradation of starch in the course of processing, improve goods in use to the thermal dimensional stability and the safety in utilization of high calorie packing material, thereby the present composition preferably contains alkaline matter.Total amount with composition is a benchmark, and the content of alkaline matter is 0-15 weight %, is preferably 0.5-5 weight %.
Described alkaline matter can be mineral alkali and/or organic bases, described mineral alkali comprises alkali metal hydroxide and/or alkaline, inorganic salts, and described alkali metal hydroxide comprises one or more in sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, the magnesium hydroxide.Described alkaline, inorganic salts comprises the salt that inorganic strong alkali and inorganic weak acid form.Described organic bases comprises one or more in quaternary ammonium hydroxide, urea, pyridine and the various alkaline carboxylate salt.
The kind of described starch is conventionally known to one of skill in the art, and for example, water content is at the W-Gum below 14%, yam starch, sweet potato starch, tapioca (flour), wheat class and legume starch.Total amount with composition is a benchmark, and described contents of starch is generally 30-65 weight %.
The kind of described ethylene-acrylate copolymer is conventionally known to one of skill in the art, can be in the various ethylene-acrylic acid alkyl ester copolymer of the prior art one or more, described ethylene-acrylic acid alkyl ester copolymer comprises the multipolymer of ethylene-methyl acrylate or the multipolymer of ethylene-propylene acetoacetic ester etc., and the weight-average molecular weight of preferred ethylene-acrylate copolymer is 50,000-200,000.
The kind of described polyvalent alcohol is conventionally known to one of skill in the art, for example, described polyvalent alcohol can be selected from one or more in the incomplete esterification products (as glyceryl monostearate) of ethylene glycol, glycol ether, propylene glycol, glycerine, Sorbitol Powder or its lower molecular weight condenses (molecular weight＜400), tetramethylolmethane and longer chain fatty acid, is preferably in glycerine, Sorbitol Powder and the tetramethylolmethane one or more.Add these polyvalent alcohols and can promote consistency between each component, the consistency of polyolefine and each component especially, and can improve biodegradable and processibility.Described polyvalent alcohol can use separately or two or more is used, and preferably is used.
The kind of described additive salt is conventionally known to one of skill in the art, and for example described additive salt can be 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.Be preferably stearates, particularly as the stearate of Ca, Mg, Zn, Ba, Ce and Fe.Described additive salt can improve goods dimensional stability, brighten and reduce the cost, can also promote the biological degradability of goods.Described additive can use separately or two or more is used, and is preferably two kinds and is used.
In the composition provided by the invention, but described polyolefin resin can be selected from various known polyolefin resines as the Biodegradable compositions component, for example adopt the polyolefin resin of new generation of metallocene catalysts, for example the homopolymer of ethene such as new LDPE (film grade) (LDPE), high density polyethylene(HDPE) (HDPE), LLDPE (LLDPE); The homopolymer of propylene such as isotatic polypropylene (PP), syndiotactic polypropylene (S-PP), and the binary of ethene and propylene or terpolymer etc.Adopt the metallocene-polyolefin resin, the physical mechanical strength of the membrane product that is made by resin combination of the present invention is increased substantially.The example of above-mentioned metallocene-polyolefin resin comprises that the trade names that Mitsui oiling company produces are that the trade names that EVOLUE and american exxon chemical company produce are the metallocene-polyolefin resin of EXXPOL, and the trade names of U.S. DOW chemical company production are the metallocene PE resin of 2045AC etc.
Polyolefin resin described in the composition of the present invention is preferably above-mentioned metallocene-polyolefin resin, but according to the requirement of goods varieties and characteristics with from cost consideration, also can other polyolefin resin of all or part of employing, as the Ziegler-Natta type polyolefin resin, for example HDPE of Ziegler-Natta type, PP, regeneration PE or polystyrene (PS).For example, if when resin combination of the present invention is used for making foam article, described polyolefin resin preferably adopts the mixture of metallocene PE and Ziegler-Natta type PS.
Under the preferable case, polyolefin resin of the present invention comprises the extremely-low density polyolefin resin.Total amount with polyolefin resin is a benchmark, and the content of extremely-low density polyolefin resin is generally 0-50 weight %, is preferably 10-45 weight %.Described extremely-low density polyolefin resin is meant that density is the polyolefin resin of 0.580-0.900 gram/cubic centimetre, and it can be selected from ultra-low density polyethylene, polypropylene, vinylbenzene, the ethylene-propylene copolymer one or more.The present inventor is surprised to find that the adding of above-mentioned extremely-low density polyolefin resin can significantly increase the angle tear strength of product.
According to the variant production requirement, resin combination of the present invention can also contain other auxiliary agent of 0-5% (weight).Described other auxiliary agent comprises one or more in oxidation inhibitor, light (heat) stablizer, antifogging agent, fire retardant, static inhibitor, coupling agent, whipping agent, tinting material, the lubricant.The kind of these auxiliary agents, content and act as conventionally known to one of skill in the art.Composition for example provided by the invention can also contain oxidation inhibitor and/or light (heat) stablizer, to prevent and to suppress starch and resin alloy system in the course of processing or in the use, because factors such as light, heat, oxygen, microorganism or bacterium cause too early degraded, particularly in degradative plastic film, add oxidation inhibitor and/or light (heat) stablizer and can control and delay superpolymer autoxidation speed effectively, or suppress effectively or slow down ultraviolet solarization, thereby reach the purpose of effective author's preface ground control mulch film cracking phase (inductive phase).Oxidation inhibitor can be selected from four (3-(3 ', 5 '-di-t-butyl-4 '-its phenyl of hydroxyl) 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 (heat) stablizer can be selected from one or more in UV-series light (heat) stablizer, carbon black, organic tin light (heat) stablizer, trisnonyl phenyl phosphite (TNPP), the epoxy soybean oil.Wherein, UV-series light (heat) stablizer can be Alpha-hydroxy-4-oxy-octyl benzophenone (being called for short UV-531).Described organic tin light (heat) stablizer 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.These auxiliary agents cooperate can play synergistic effect, and result of use is better.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 described plant powder is 0-8 weight %.
According to the biodegradable biodegradable starch-containing resin combination provided by the invention that contains provided by the invention.
By the composition of adjustment composition and the consumption of each component, composition of the present invention can utilize equipment such as blow moulding equipment, extrusion apparatus and the injection-moulding device of conventional LDPE of processing and HDPE to be processed into various plastics, blow-molded article for example is as agricultural mulching or packing bag etc.; Extrudate such as pallet, food box and beverage cup etc.; Injection-molded item such as flowerpot, knife and fork/chopsticks, toy etc. or foaming product etc., resulting product has favorable mechanical performance and biodegradable performance.
First kind of preparation method of biodegradable starch-containing resin combination provided by the invention comprises starch, polyvalent alcohol, ethylene-acrylate copolymer, polyolefin resin and additive salt mixed; With the mixture extruding pelletization that obtains; Wherein, the multipolymer that when mixing, also adds alkene and unsaturated alcohol carboxylicesters.This method is called direct method.
The concrete steps of described direct method are as follows:
(1) multipolymer of starch, polyvalent alcohol, ethylene-acrylate copolymer, polyolefin resin, additive salt, alkene and unsaturated alcohol carboxylicesters and the alkaline matter of selectivity adding are joined 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 50-150 rev/min; Described alkaline matter is preferably one or more in sodium hydroxide, potassium hydroxide, the urea, usually with them directly or to be mixed with concentration be that the aqueous solution form of 5-60 weight % adds in the stirrer;
(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, and screw speed 150-1200 rev/min, each zone temperatures is respectively extruding pelletization under the condition of 90-125 ℃, 115-145 ℃, 130-170 ℃, 130-170 ℃, 110-140 ℃, 105-155 ℃.
Second kind of preparation method of biodegradable starch-containing resin combination provided by the invention comprises starch, polyvalent alcohol and additive salt mixed; Ethylene-acrylate copolymer and polyolefin resin are mixed; With above-mentioned two kinds of compounds that obtain respectively by sending into extruding pelletization in the forcing machine; Wherein, when ethylene-acrylate copolymer and polyolefin resin are mixed, also add the multipolymer of alkene and unsaturated alcohol carboxylicesters.This preparation method is called the master batch method.
The concrete steps of described mother material are as follows:
(1) to join stirrer for mixing even for the alkaline matter that starch, polyvalent alcohol, additive salt and selectivity are contained, obtain powder, wherein, the temperature and time of blended under agitation is conventionally known to one of skill in the art, 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 50-150 rev/min; Described alkaline matter is preferably one or more in sodium hydroxide, potassium hydroxide, the urea,, usually directly or to be mixed with concentration be that the aqueous solution form of 5-60 weight % adds in the stirrer with them;
(2) multipolymer and the polyolefin resin with ethylene-acrylate copolymer, alkene and unsaturated alcohol carboxylicesters mixes in mixing tank, obtain powder, wherein, the temperature and time of blended under agitation is conventionally known to one of skill in the art, for example, the temperature of blended under agitation can be 25-65 ℃, and the time of blended under agitation can be 5-15 minute;
(3) compound of step (1) and (2) is sent into extruding pelletization in the forcing machine.Wherein, the method for feeding manner and extruding pelletization, condition and used forcing machine are conventionally known to one of skill in the art.For example, powder and pellet are sent in the forcing machine by powder feeding device, pellet feeder respectively, 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 extruding pelletization under the condition of 90-125 ℃, 115-145 ℃, 130-170 ℃, 130-170 ℃, 110-140 ℃, 105-155 ℃.
The preferred master batch legal system of using is equipped with composition particle product in the specific embodiment of the invention.
The present invention is further illustrated by the following examples.
One, film class
Embodiment 1
Present embodiment is used to illustrate starch-containing resin combination provided by the invention and preparation method thereof.
Adopt the master batch method to prepare biodegradable starch-containing resin combination provided by the invention, concrete operations are as follows:
(1) polyol component of forming with the W-Gum (dry weight basis) of 45.0 weight parts, by the glycerine of the Sorbitol Powder of 6.0 weight parts and 4.0 weight parts and join stirrer for mixing by the additive salt component that the Zinic stearas of the calcium stearate of 0.5 weight part and 0.5 weight part is formed and evenly obtain pellet, wherein, the rotating speed of blended under agitation is 90 rev/mins, the temperature of blended under agitation is 35 ℃, and the time of blended under agitation is 10 minutes;
(2) 9.0 weight part weight-average molecular weight being trade names that 150,000 ethylene-methyl acrylate copolymer (EAA), 5.0 parts by weight of ethylene-acetate ethylene copolymer and 30.0 weight part DOW chemical companies produce is that the metallocene PE resin of 2045AC mixes in mixing tank and obtains powder, wherein, the speed of blended under agitation is 100 rev/mins, the temperature of blended under agitation is 50 ℃, and the time of blended under agitation is 15 minutes;
(3) compound of step (1) and (2) is sent into extruding pelletization in the forcing machine.Wherein, powder and pellet are sent into twin screw extruder by powder feeding device, pellet feeder respectively, in length-to-diameter ratio is 48: 1,1000 rev/mins of screw speeds, each zone temperatures is respectively extruding pelletization under 100 ℃, 115 ℃, 130 ℃, 140 ℃, 145 ℃, 150 ℃ the condition, obtains composition S1 provided by the invention.The composition of S1 is as shown in table 1.Said composition is suitable for the preparation of common film based article.
The composition (weight %) of table 1 composition S1
| Starch | Sorbitol Powder | Glycerine | EAA | Metallocene PE | Zinic stearas | Calcium stearate | Ethylene-vinyl acetate copolymer |
| 45.0 | 6.0 | 4.0 | 9.0 | 30.0 | 0.5 | 0.5 | 5.0 |
Embodiment 2
Present embodiment is used to illustrate composition of the present invention and preparation method.
Adopt direct method to prepare biodegradable starch-containing resin combination provided by the invention and carry out granulation, concrete operations are as follows:
(1) with the W-Gum (dry weight basis) of 35.5 weight parts, the polyol component of forming by the glycerine of the Sorbitol Powder of 5.0 weight parts and 3.0 weight parts, 10.0 the weight-average molecular weight of weight part is 150,000 ethylene-ethyl acrylate copolymer, 39.0 the trade names that the DOW chemical company of weight part produces are the metallocene PE resin of 2045AC, 5.0 the weight-average molecular weight of weight part is 140,000 ethylene-vinyl acetate copolymer, 0.2 the additive salt component that the Zinic stearas of the calcium stearate of weight part and 0.2 weight part is formed and by the epoxy soybean oil of 0.8 weight part, 0.2 the antioxidant 1010 of weight part, 0.3 the UV-531 of weight part, uniform mixing obtains mixture in the stirrer 0.7 the additive that the ultra-fine carbon black of the DSTP of weight part and 0.1 weight part is formed joins, wherein, stirring velocity is 90 rev/mins, the temperature of blended under agitation is 65 ℃, and the time of blended under agitation is 15 minutes;
(2) with the mixture extruding pelletization that obtains.Wherein, mixture extruding pelletization in twin screw extruder obtains granule product, twin screw extruder is that 45: 1, screw speed are that 1200 rev/mins, each zone temperatures are respectively extruding pelletization under 90 ℃, 115 ℃, 130 ℃, 145 ℃, 150 ℃, 155 ℃ the condition in length-to-diameter ratio, obtains composition S2 provided by the invention.The composition of S2 is as shown in table 2.
The composition (weight %) of table 2 composition S2
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Ethylene-vinyl acetate copolymer | Calcium stearate | |
| 35.5 | 5.0 | 3.0 | 0.8 | 5.0 | 0.2 | |
| UV-531 | Antioxidant 1010 | EAA | The metallocene PE resin | DSTP | Ultra-fine carbon black | Zinic stearas |
| 0.3 | 0.2 | 10.0 | 39.0 | 0.7 | 0.1 | 0.2 |
In application facet, the composition that present embodiment provides can be made the more special goods that are adapted at outdoor application, as the agricultural mulching based article, that is: in use, need within a certain period of time, can resist the product of ultraviolet ray ageing in the sunlight, (heat) oxidation etc., and possess the specialty products that have biological degradation function after discarded using simultaneously.For example: cable sheath prevents to be laid on the film or the lamella of seepage ground surface and to be used for fixing grid of hillside, continental rise etc. or the like.
Comparative Examples 1
This Comparative Examples is used for illustrating that prior art is used to prepare the composition and the preparation method of film based article.
Prepare composition C1 according to example 2 described methods, different is, does not add ethylene-vinyl acetate copolymer, and the weight ratio of all the other components is identical in the said composition.
Embodiment 3
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S3 provided by the invention with the method identical with embodiment 2, different is that wherein the add-on of starch is 54.0 weight parts (dry weight basis), the add-on of Sorbitol Powder is 5.0 weight parts, the add-on of glycerine is 3.0 weight parts, the add-on of epoxy soybean oil is 0.8 weight part, the add-on of Zinic stearas is 0.3 weight part, the add-on of calcium stearate is 0.2 weight part, the add-on of EAA is 6.2 weight parts, the add-on of metallocene PE is 10.5 weight parts, the add-on of ethylene-vinyl acetate copolymer is 20.0 weight parts.Shown in the table 3 composed as follows of S3.
The composition (weight %) of table 3 composition S3
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Zinic stearas | Calcium stearate |
| 54.0 | 5.0 | 3.0 | 0.8 | 0.3 | 0.2 |
| EAA | Metallocene PE | Ethylene-vinyl acetate copolymer | |||
| 6.2 | 10.5 | 20.0 | |||
In application facet, the composition that present embodiment provides can be made and be adapted at the film product that packaging field is used, particularly requiring this packing film to have certain transparency, can observe packaged commodity and heat sealability better products, for example: clothes or food packaging film etc.
Embodiment 4
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S4 provided by the invention with the method identical with embodiment 2, different is that wherein the add-on of starch is 40.0 weight parts (dry weight basis), the add-on of Sorbitol Powder is 5.0 weight parts, the add-on of glycerine is 3.0 weight parts, the add-on of epoxy soybean oil is 0.5 weight part, the add-on of Zinic stearas is 0.2 weight part, the add-on of calcium stearate is 0.3 weight part, the add-on of EAA is 9.0 weight parts, the add-on of metallocene PE is 35.0 weight parts, metallic aluminium powder 〉=300 purpose add-ons are 5.0 weight parts, the add-on of ultra-low density polyethylene resin is 5.0 weight parts, the add-on of potassium hydroxide is 2.0 weight parts (aqueous solution form with 60 weight % adds), the add-on of ethylene-vinyl acetate copolymer is 5.0 weight parts.Shown in the table 4 composed as follows of S4.
The composition (weight %) of table 4 composition S4
| Starch | Sorbitol Powder | Glycerine | Zinic stearas | Metallic aluminium powder 〉=300 orders | Calcium stearate | EAA | |
| 40.0 | 5.0 | 3.0 | 0.2 | 5.0 | 0.3 | 9.0 | |
| The ultra-low density polyethylene resin | Metallocene PE | Epoxy soybean oil | Potassium hydroxide | Ethylene-vinyl acetate copolymer | |||
| 5.0 | 25.0 | 0.5 | 2.0 | 5.0 | |||
In application facet, the composition that present embodiment provides can be made film product very special, that be applied in packaging field, particularly be applied in and require this packing film to have certain heat sealability, high tear strength, some light is seen through or produce the film product of special optical reaction, for example: the film that is used to plant tobacco of containing metal aluminium powder, the film of some disease and pest can be killed, the film of some light etc. can be completely cut off.
Embodiment 5
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S5 provided by the invention with the method identical with embodiment 2, different is that wherein the add-on of starch is 45.0 weight parts (dry weight basis), the add-on of Sorbitol Powder is 5.0 weight parts, the add-on of glycerine is 3.0 weight parts, the add-on of epoxy soybean oil is 0.5 weight part, the add-on of Zinic stearas is 0.5 weight part, the add-on of calcium stearate is 0.4 weight part, the add-on of EAA is 7.0 weight parts, the add-on of metallocene PE is 27.5 weight parts, the add-on of two lauric acid dioctyl tins is 0.1 weight part, the add-on of ultra-low density polyethylene-propylene copolymer is 27.5 weight parts, the add-on of urea is 5.0 weight parts, the add-on of ethylene-vinyl acetate copolymer is 3.0 weight parts.Shown in the table 5 composed as follows of S5.
The composition (weight %) of table 5 composition S5
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Ultra-low density polyethylene-propylene copolymer | Calcium stearate | |
| 45.0 | 5.0 | 3.0 | 0.5 | 3.0 | 0.4 | |
| Two lauric acid dioctyl tins | EAA | Metallocene PE | Zinic stearas | EEA | Urea | |
| 0.1 | 7.0 | 27.5 | 0.5 | 3.0 | 5.0 | |
In application facet, the composition that present embodiment provides is fit to be formed in the industrial film product (not relating to the Application Areas of sanitary index) that packaging field is used, and is particularly requiring this packing film to have certain heat sealability, high tear strength, resistant to elevated temperatures film product.
Embodiment 6
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S6 provided by the invention with the method identical with embodiment 2, different is that wherein the add-on of starch is 60.0 weight parts (dry weight basis), the add-on of Sorbitol Powder is 6.0 weight parts, the add-on of glycerine is 4.0 weight parts, the add-on of epoxy soybean oil is 0.5 weight part, the add-on of iron stearate is 0.5 weight part, the add-on of calcium stearate is 0.5 weight part, the add-on of EAA is 5.0 weight parts, the add-on of metallocene PE is 13.5 weight parts, the add-on of ultra-low density polyethylene (density is 0.660 gram/cubic centimetre) is 5.0 weight parts, the add-on of ethylene-vinyl acetate copolymer is 5.0 weight parts.Shown in the table 6 composed as follows of S6.
The composition (weight %) of table 6 composition S6
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Iron stearate |
| 60.0 | 6.0 | 4.0 | 0.5 | 0.5 |
| Calcium stearate | Ultra-low density polyethylene | EAA | Metallocene PE | Ethylene-vinyl acetate copolymer |
| 0.5 | 5.0 | 5.0 | 13.5 | 5.0 |
In application facet, the composition that present embodiment provides is suitable for being formed in the film product that light packaging field is used, particularly requiring this packing film except less demanding to physical and mechanical properties, requirement has the film product of good heat sealability, quick degradation property, for example: the packing material of medicated napkin etc.
Two, plastic uptake sheet material class
Embodiment 7
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S7 provided by the invention with the method identical with embodiment 1, different is that wherein the add-on of starch is 45.0 weight parts (dry weight basis), the add-on of Sorbitol Powder is 4.0 weight parts, the add-on of glycerine is 2.0 weight parts, the add-on of epoxy soybean oil is 0.6 weight part, the add-on of Zinic stearas is 0.5 weight part, the add-on of calcium stearate is 0.4 weight part, the add-on of EAA is 5.0 weight parts, the add-on of metallocene polypropylene is 25.5 weight parts, the add-on of extremely-low density acrylic resin is 4.0 weight parts, the add-on of sodium hydroxide is 5.0 weight parts (adding with 50 weight % aqueous solution forms), the add-on of ethylene-vinyl acetate copolymer is 5.0 weight parts.And the screw speed of duplex forcing machine is 300-600 rev/min, and each zone temperatures is respectively: 155 ℃, 165 ℃, 175 ℃, 170 ℃, 170 ℃ and 175 ℃, vacuum degree control is about-0.09 MPa.Shown in the table 7 composed as follows of S7.
The composition (weight %) of table 7 composition S7
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Zinic stearas | Calcium stearate | The extremely-low density acrylic resin |
| 45.0 | 4.0 | 2.0 | 0.6 | 0.5 | 0.4 | 4.0 |
| EAA | Sodium hydroxide | Ethylene-vinyl acetate copolymer | Metallocene polypropylene | |||
| 8.0 | 5.0 | 5.0 | 25.5 | |||
In application facet, the composition that present embodiment provides is fit to make the product that is applied in sheet material plastics sucking moulding packaging field, particularly be applied in and require this packaging vessel (for example: the microwave oven heating to have certain sealing property, transparency, anti-certain high temperature, splendid attire 60-98 ℃ heat product etc.) product, for example: sour milk cup, mess-tin, instant noodle bowl, spontaneous heating snack food product box, other food box, beverage cup, microwave oven are with food product containers etc.
Comparative Examples 2
This Comparative Examples is used for illustrating that prior art is used to prepare the composition and the preparation method of plastic uptake sheet material based article.
Prepare composition C2 according to example 7 described methods, different is, does not add ethylene-vinyl acetate copolymer, sodium hydroxide and extremely-low density acrylic resin, and the weight ratio of all the other components is identical in the said composition.
Embodiment 8
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S8 provided by the invention according to the method described in the embodiment 7, different is, wherein the add-on of starch is that the add-on of 46.0 weight parts (dry weight basis), Sorbitol Powder is that the add-on of 6.0 weight parts, glycerine is that the add-on of 4.0 weight parts, Zinic stearas is that the add-on of 0.5 weight part, calcium stearate is that the add-on of 0.5 weight part, EAA is that the add-on of 9.0 weight parts, metallocene polypropylene is that the add-on of 30.0 weight parts, ethylene-vinyl acetate copolymer is 4.0 weight parts.Shown in the table 8 composed as follows of S8.
The composition (weight %) of table 8 composition S8
| Starch | Sorbitol Powder | Glycerine | EAA | Metallocene polypropylene | Zinic stearas | Calcium stearate | EEA |
| 46.0 | 6.0 | 4.0 | 9.0 | 30.0 | 0.5 | 0.5 | 4.0 |
In application facet, the composition that present embodiment provides is fit to make more common extrusion sheet-plastics sucking moulding resinoid product.
Embodiment 9
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S9 provided by the invention according to the method described in the embodiment 7, different is that wherein the add-on of starch is 38.5 weight parts (dry weight basis), the add-on of Sorbitol Powder is 5.0 weight parts, the add-on of glycerine is 3.0 weight parts, the add-on of epoxy soybean oil is 0.8 weight part, the add-on of Zinic stearas is 0.2 weight part, the add-on of calcium stearate is 0.2 weight part, the add-on of EAA is 10.0 weight parts, the add-on of metallocene polypropylene is 31.0 weight parts, the add-on of antioxidant 1010 is 0.2 weight part, the add-on of UV-531 is 0.3 weight part, the add-on of oxidation inhibitor DSTP is 0.7 weight part, ultra-fine sooty add-on is 0.1 weight part, the add-on of ethylene-vinyl acetate copolymer is 5 weight parts.Shown in the table 9 composed as follows of S9.
The composition (weight %) of table 9 composition S9
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Ethylene-vinyl acetate copolymer | Calcium stearate | |
| 43..5 | 5.0 | 3.0 | 0.8 | 5.0 | 0.2 | |
| UV-531 | Antioxidant 1010 | EAA | Metallocene polypropylene | Oxidation inhibitor DSTP | Ultra-fine carbon black | Zinic stearas |
| 0.3 | 0.2 | 10.0 | 31.0 | 0.7 | 0.1 | 0.2 |
In application facet, the composition that present embodiment provides is suitable for being formed in product outdoor application, more special, that is: in use, need to resist within a certain period of time ultraviolet ray ageing in the sunlight, (heat) oxidation etc. and possess the specialty products that have biodegradable function after discarded using simultaneously.
Embodiment 10
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S10 provided by the invention according to the method described in the embodiment 7, different is that wherein the add-on of starch is 55.0 weight parts (dry weight basis), the add-on of Sorbitol Powder is 4.0 weight parts, the add-on of glycerine is 3.0 weight parts, the add-on of epoxy soybean oil is 1.0 weight parts, the add-on of Zinic stearas is 0.3 weight part, the add-on of calcium stearate is 0.2 weight part, the add-on of EAA is 6.0 weight parts, the add-on of metallocene PE is 10.5 weight parts, the add-on of ethene-vinyl propionate multipolymer is 20 weight parts.Shown in the table 10 composed as follows of S10.
The composition (weight %) of table 10 composition S10
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Zinic stearas | Calcium stearate |
| 55.0 | 4.0 | 3.0 | 1.0 | 0.3 | 0.2 |
| EAA | Metallocene PE | Ethene-vinyl propionate multipolymer | |||
| 6.0 | 10.5 | 20.0 | |||
In application facet, the composition that present embodiment provides is suitable for making the plastic uptake sheet material series products that is fit to be applied in packaging field, particularly can observe packaged commodity, heat sealability better products requiring this packing material to have certain transparency, for example food box etc.
Embodiment 11
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S11 provided by the invention according to the method described in the embodiment 7, different is that wherein the add-on of starch is 40.0 weight parts (dry weight basis), the add-on of Sorbitol Powder is 4.0 weight parts, the add-on of glycerine is 3.5 weight parts, the add-on of epoxy soybean oil is 0.5 weight part, the add-on of Zinic stearas is 0.45 weight part, the add-on of calcium stearate is 0.55 weight part, the add-on of EAA is 7.0 weight parts, the add-on of metallocene polypropylene is 22.5 weight parts, metallic aluminium powder 〉=300 purpose add-ons are 5.0 weight parts, the add-on of extremely-low density acrylic resin (density is 0.700 gram/cubic centimetre) is 6.0 weight parts, the add-on of sodium hydroxide is 2.0 weight parts (adding with 50 weight % solution forms), the add-on of EEA is 8.0 weight parts.Shown in the table 11 composed as follows of S11.
The composition (weight %) of table 11 composition S11
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Zinic stearas | Calcium stearate | The extremely-low density acrylic resin | |
| 40.5 | 4.0 | 3.5 | 0.5 | 0.45 | 0.55 | 6.0 | |
| Metallic aluminium powder 〉=300 orders | Metallocene polypropylene | EAA | Sodium hydroxide | EEA | |||
| 5.0 | 22.5 | 7.0 | 2.0 | 8.0 | |||
In application facet, the composition that present embodiment provides is suitable for making class plastic uptake sheet material series products very special, that be applied in packaging field, is particularly requiring this packing material to have certain heat sealability, high tear strength, some light is seen through or is producing the product etc. of special optical reaction.
Embodiment 12
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S12 provided by the invention according to the method described in the embodiment 7, different is that wherein the add-on of starch is 45.0 weight parts (dry weight basis), the add-on of Sorbitol Powder is 5.0 weight parts, the add-on of glycerine is 3.0 weight parts, the add-on of epoxy soybean oil is 0.5 weight part, the add-on of Zinic stearas is 0.4 weight part, the add-on of calcium stearate is 0.5 weight part, the add-on of EAA is 11.0 weight parts, the add-on of metallocene PE is 17.5 weight parts, metallic aluminium powder 〉=300 purpose add-ons are 5.0 weight parts, the add-on of extremely-low density acrylic resin (density is 0.700 gram/cubic centimetre) is 5.0 weight parts, the add-on of two lauric acid dioctyl tins is 0.1 weight part, the add-on of urea is 2.0 weight parts (adding with 50 weight % solution forms), the add-on of EEA is 8.0 weight parts.Shown in the table 12 composed as follows of S12.
The composition (weight %) of table 12 composition S12
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | EEA | Calcium stearate | |
| 45.0 | 5.0 | 3.0 | 0.5 | 8.0 | 0.5 | |
| Two lauric acid dioctyl tins | EAA | Metallocene PE | Ultra-low density polyethylene | Zinic stearas | Urea | |
| 0.1 | 11.0 | 17.5 | 5.0 | 0.4 | 4.0 | |
In application facet, the composition that present embodiment provides is suitable for making the industrial film product (not relating to the Application Areas of sanitary index) that is fit to be applied in packaging field, is particularly requiring this product to have certain heat sealability, high tear strength, resistant to elevated temperatures product.
Embodiment 13
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S13 provided by the invention according to the method described in the embodiment 7, different is, wherein the add-on of starch is that the add-on of 60.0 weight parts (dry weight basis), Sorbitol Powder is that the add-on of 6.0 weight parts, glycerine is that the add-on of 4.0 weight parts, epoxy soybean oil is that the add-on of 0.5 weight part, iron stearate is that the add-on of 0.5 weight part, EAA is that the add-on of 5.0 weight parts, metallocene PE is that the add-on of 19.0 weight parts, EEA is 5.0 weight parts.Shown in the table 13 composed as follows of S13.
The composition (weight %) of table 13 composition S13
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Iron stearate |
| 60.0 | 6.0 | 4.0 | 0.5 | 0.5 |
| EAA | Metallocene PE | Ethylene-vinyl acetate copolymer | ||
| 5.0 | 19.0 | 5.0 | ||
In application facet, the composition that present embodiment provides is suitable for making the plastic uptake sheet material series products that a class is fit to be applied in light packaging field, particularly requiring this packing material except less demanding to physical and mechanical properties, requirement has the film product of good heat sealability, quick degradation property, for example: the packing material of mobile phone, battery and other electronic component etc. etc.
Three, injection molding class
Embodiment 14
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S14 provided by the invention according to the method described in the embodiment 7, different is that wherein the add-on of starch is 45.0 weight parts (dry weight basis), the add-on of Sorbitol Powder is 4.0 weight parts, the add-on of glycerine is 2.0 weight parts, the add-on of epoxy soybean oil is 0.5 weight part, the add-on of Zinic stearas is 0.5 weight part, the add-on of calcium stearate is 0.5 weight part, the add-on of EAA is 8.0 weight parts, the add-on of metallocene polypropylene is 24.5 weight parts, the add-on of extremely-low density acrylic resin (density is 0.720 gram/cubic centimetre) is 5.0 weight parts, the add-on of sodium hydroxide is 5.0 weight parts (adding with 50 weight % solution forms), the add-on of EEA is 5.0 weight parts.Shown in the table 14 composed as follows of S14.
The composition (weight %) of table 14 composition S14
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Zinic stearas | Calcium stearate | EAA |
| 45.0 | 4.0 | 2.0 | 0.5 | 0.5 | 0.5 | 8.0 |
| The extremely-low density acrylic resin | Metallocene polypropylene | Sodium hydroxide | EEA | |||
| 5.0 | 24.5 | 5.0 | 5.0 | |||
In application facet, the composition that present embodiment provides is suitable for making the product that a class is fit to be applied in the injection molding packaging field, particularly be applied in and require this product to have certain welding property, transparency, certain resistance to elevated temperatures (for example: the microwave oven heating, splendid attire 60-98 ℃ heat product, Deng) product, for example: the cutter that adopts injection molding processing, fork, spoon, chopsticks, golf ball T, shaver, the farm crop support, the sour milk cup, mess-tin, instant noodle bowl, spontaneous heating snack food product box, other food box, beverage cup, microwave oven is with food product containers etc.
Comparative Examples 3 these Comparative Examples are used for illustrating that prior art is used to prepare the composition and the preparation method of injection molding based article.
Prepare composition C3 according to example 14 described methods, different is, does not add ethylene-vinyl acetate copolymer, sodium hydroxide and extremely-low density acrylic resin, and the weight ratio of all the other components is identical in the said composition.
Embodiment 15
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S15 provided by the invention according to the method described in the embodiment 7, different is, wherein the add-on of starch is that the add-on of 46.0 weight parts (dry weight basis), Sorbitol Powder is that the add-on of 6.0 weight parts, glycerine is that the add-on of 4.0 weight parts, Zinic stearas is that the add-on of 0.5 weight part, calcium stearate is that the add-on of 0.5 weight part, EAA is that the add-on of 9.0 weight parts, metallocene polypropylene is that the add-on of 30.0 weight parts, EEA is 4.0 weight parts.Shown in the table 15 composed as follows of S15.
The composition (weight %) of table 15 composition S15
| Starch | Sorbitol Powder | Glycerine | EAA | Metallocene polypropylene | Zinic stearas | Calcium stearate | EEA |
| 46.0 | 6.0 | 4.0 | 9.0 | 30.0 | 0.5 | 0.5 | 4.0 |
In application facet, the composition that present embodiment obtains is suitable for making the more general employing injection molding resinoid product of a class.
Embodiment 16
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S16 provided by the invention according to the method described in the embodiment 7, different is that wherein the add-on of starch is 38.5 weight parts (dry weight basis), the add-on of Sorbitol Powder is 5.0 weight parts, the add-on of glycerine is 3.0 weight parts, the add-on of epoxy soybean oil is 0.8 weight part, the add-on of Zinic stearas is 0.3 weight part, the add-on of calcium stearate is 0.3 weight part, the add-on of EAA is 9.4 weight parts, the add-on of metallocene polypropylene is 18.0 weight parts, the add-on of metallocene PE resin is 14.0 weight parts, the add-on of antioxidant 1010 is 0.3 weight part, the add-on of UV-531 is 0.2 weight part, the add-on of propylene-acetate propylene multipolymer is 5.0 weight parts.Shown in the table 16 composed as follows of S16.
The composition (weight %) of table 16 composition S16
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Calcium stearate | Propylene-acetate propylene multipolymer | |
| 38.5 | 5.0 | 3.0 | 0.8 | 0.3 | 5.0 | |
| UV-531 | Antioxidant 1010 | EAA | Metallocene PE | Metallocene polypropylene | Ultra-fine carbon black | Zinic stearas |
| 0.2 | 0.3 | 14.5 | 14.0 | 18.0 | 0.1 | 0.3 |
In application facet, the composition that present embodiment provides is suitable for making a class and is adapted at outdoor application, more special injection molding series products, that is: in use, need to resist within a certain period of time ultraviolet ray ageing in the sunlight, (heat) oxidation etc. and possess the specialty products that have biological degradation function after discarded using simultaneously.
Embodiment 17
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S17 provided by the invention according to the method described in the embodiment 7, different is that wherein the add-on of starch is 51.0 weight parts (dry weight basis), the add-on of Sorbitol Powder is 5.0 weight parts, the add-on of glycerine is 3.0 weight parts, the add-on of epoxy soybean oil is 1.0 weight parts, the add-on of Zinic stearas is 0.3 weight part, the add-on of calcium stearate is 0.3 weight part, the add-on of EAA is 9.0 weight parts, the add-on of metallocene polypropylene is 10.5 weight parts, the add-on of EEA is 20.0 weight parts.Shown in the table 17 composed as follows of S17.
The composition (weight %) of table 17 composition S17
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Zinic stearas | Calcium stearate |
| 51.0 | 5.0 | 3.0 | 1.0 | 0.3 | 0.2 |
| EAA | Metallocene polypropylene | EEA | |||
| 9.0 | 10.5 | 20.0 | |||
In application facet, the composition that present embodiment provides is suitable for making the injection molding series products that a class is fit to be applied in packaging field, particularly can observe packaged commodity, heat sealability better products requiring this packing material to have certain transparency, for example: food box etc.
Embodiment 18
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S18 provided by the invention according to the method described in the embodiment 7, different is that wherein the add-on of starch is 41.2 weight parts (dry weight basis), the add-on of Sorbitol Powder is 5.0 weight parts, the add-on of glycerine is 3.0 weight parts, the add-on of epoxy soybean oil is 0.5 weight part, the add-on of Zinic stearas is 0.1 weight part, the add-on of calcium stearate is 0.2 weight part, the add-on of EAA is 7.0 weight parts, the add-on of metallocene polypropylene is 22.5 weight parts, metallic aluminium powder 〉=300 purpose add-ons are 5.0 weight parts, the add-on of extremely-low density acrylic resin (density is 0.700 gram/cubic centimetre) is 6.0 weight parts, the add-on of potassium hydroxide is 2.0 weight parts (adding with 50 weight % solution forms), the add-on of EEA is 8.0 weight parts.Shown in the table 18 composed as follows of S18.
The composition (weight %) of table 18 composition S18
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Zinic stearas | Calcium stearate | The extremely-low density acrylic resin |
| 41.2 | 5.0 | 3.0 | 0.5 | 0.1 | 0.2 | 6.0 |
| Metallocene polypropylene | EAA | Metallic aluminium powder 〉=300 orders | Potassium hydroxide | EEA | ||
| 22.5 | 7.0 | 5.0 | 2.0 | 8.0 | ||
In application facet, the composition that present embodiment provides is suitable for making class injection molding series products very special, that be applied in packaging field, is particularly requiring this product to have certain heat sealability, high tear strength, some light is seen through or is producing the specialty products etc. of special optical reaction.
Embodiment 19
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S19 provided by the invention according to the method described in the embodiment 7, different is that wherein the add-on of starch is 47.7 weight parts (dry weight basis), the add-on of Sorbitol Powder is 5.0 weight parts, the add-on of glycerine is 3.0 weight parts, the add-on of epoxy soybean oil is 0.5 weight part, the add-on of Zinic stearas is 0.1 weight part, the add-on of calcium stearate is 0.1 weight part, the add-on of EAA is 8.0 weight parts, the add-on of metallocene PE is 22.5 weight parts, the add-on of two lauric acid dioctyl tins is 0.1 weight part, the add-on of extremely-low density polystyrene resin (density is 0.780 gram/cubic centimetre) is 6.0 weight parts, the add-on of urea is 3.0 weight parts, the add-on of EEA is 1.0 weight parts.Shown in the table 19 composed as follows of S19.
The composition (weight %) of table 19 composition S19
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | EEA | Calcium stearate | |
| 47.7 | 5.0 | 3.0 | 0.5 | 1.0 | 0.1 | |
| Two lauric acid dioctyl tins | EAA | Metallocene PE | The extremely-low density polystyrene | Zinic stearas | Urea | |
| 0.1 | 8.0 | 25.5 | 6.0 | 0.1 | 3.0 | |
In application facet, the composition that present embodiment provides is suitable for making the Industrial products (not relating to the Application Areas of sanitary index) that a class is fit to be applied in packaging field, is particularly requiring this product to have certain heat sealability, high tear strength, resistance to elevated temperatures etc.
Embodiment 20
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S20 provided by the invention according to the method described in the embodiment 7, different is that wherein the add-on of starch is 60.0 weight parts (dry weight basis), the add-on of Sorbitol Powder is 5.0 weight parts, the add-on of glycerine is 5.0 weight parts, the add-on of epoxy soybean oil is 0.5 weight part, the add-on of iron stearate is 0.3 weight part, the add-on of EAA is 5.0 weight parts, the add-on of metallocene polypropylene is 10.7 weight parts, the add-on of extremely-low density acrylic resin (density is 0.700 gram/cubic centimetre) is 9.5 weight parts, the add-on of ethylene-vinyl acetate copolymer is 4.0 weight parts.Shown in the table 20 composed as follows of S20.
The composition (weight %) of table 20 composition S20
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Iron stearate |
| 60.0 | 5.0 | 5.0 | 0.5 | 0.3 |
| The extremely-low density polypropylene | EAA | Metallocene polypropylene | Ethylene-vinyl acetate copolymer | |
| 9.5 | 5.0 | 10.7 | 4.0 | |
In application facet, the composition that present embodiment provides is suitable for making the injection molding series products that a class is fit to be applied in light packaging field, particularly requiring this product except less demanding to physical and mechanical properties, requirement has the injection series products of good heat sealability, quick degradation property.
Four, foaming kind
Embodiment 21
Present embodiment is used to illustrate composition of the present invention and preparation method.
Prepare biodegradable starch-containing resin combination S21 provided by the invention according to the method described in the embodiment 7, different is that wherein the add-on of starch is 40.0 weight parts (dry weight basis), the add-on of Sorbitol Powder is 4.0 weight parts, the add-on of glycerine is 2.0 weight parts, the add-on of epoxy soybean oil is 0.5 weight part, the add-on of Zinic stearas is 0.1 weight part, the add-on of calcium stearate is 0.2 weight part, the add-on of EAA is 5.0 weight parts, the add-on of metallocene polypropylene is 24.9 weight parts, the add-on of polystyrene is 8.3 weight parts, the add-on of extremely-low density acrylic resin (density is 0.700 gram/cubic centimetre) is 6.0 weight parts, the add-on of sodium hydroxide is 4.0 weight parts (adding with 50 weight % solution forms), the add-on of EEA is 5.0 weight parts.Shown in the table 21 composed as follows of S21.
The composition (weight %) of table 21 composition S21
| Starch | Sorbitol Powder | Glycerine | Epoxy soybean oil | Zinic stearas | Calcium stearate | The extremely-low density acrylic resin |
| 40 | 4.0 | 2.0 | 0.5 | 0.1 | 0.2 | 6.0 |
| EAA | Metallocene polypropylene | Sodium hydroxide | Polystyrene | EEA | ||
| 5.0 | 24.9 | 4.0 | 8.3 | 5.0 | ||
In application facet, the composition that present embodiment provides is suitable for making the product that a class is fit to be applied in physical blowing formed package field, particularly be applied in and require this product (for example: the microwave oven heating to have certain welding property, transparency, certain resistance to elevated temperatures, splendid attire 60-98 ℃ heat product, Deng) product, for example: the mess-tin, instant noodle bowl, spontaneous heating snack food product box, other food box, microwave oven that adopts the processing of physical blowing molding mode is with food product containers etc.
Comparative Examples 4 these Comparative Examples are used for illustrating that prior art is used to prepare the composition and the preparation method of foamed product.
Prepare composition C4 according to example 21 described methods, different is, does not add ethylene-vinyl acetate copolymer, sodium hydroxide and extremely-low density acrylic resin, and the weight ratio of all the other components is identical in the said composition.
Performance test
According to method in the prior art particle product that the foregoing description 1-6 and Comparative Examples 1 make is made the film based article, numbering is respectively MS1-6 and MC1; The particle product that the foregoing description 7-13 and Comparative Examples 2 make is made plastic uptake sheet material based article, and numbering is respectively PS7-13 and PC2; The particle product that the foregoing description 14-20 and Comparative Examples 3 make is made the injection molding based article, and numbering is respectively ZS14-20 and ZC3; The foregoing description 21 and Comparative Examples 4 gained particle products are made the foaming based article, numbering is respectively FS21 and FC4, and they are carried out heat sealability, temperature tolerance, tensile break strength and direct tear strength test, and getting its mean value, the result is shown in table 22-25.According to GB 13022-91 said products is carried out the tensile break strength test; Carry out the angle tear strength test according to QB/T1130-91; The mould-growth level that biodegradable adopts American I SO 845 standard laws to detect represents that be divided into the 0-5 level usually, 5 grades of expressions have extraordinary biodegradable or fully biodegradable.Carry out the heat sealability test according to U.S. ASTMD 3985.Among the table 22-25, heat sealability represents that with A, B and C A represents that heat sealability is poor, is difficult for heat-sealing; B represents that heat sealability is medium; C represents that heat sealability is good, easily heat-sealing.
The performance perameter of table 22 film based article
| Goods | Performance | ||||||
| Tensile tear strength (MPa) | Angle tear strength (N.M) | Heat sealability | Temperature tolerance (℃) | Biodegradable (ISO845, level) | |||
| Laterally | Vertically | Laterally | Vertically | ||||
| MS1 | 15 | 16 | 50 | 38 | C | 0-55 | 3-4 |
| MS2 | 17 | 17 | 53 | 41 | C | 0-55 | 2-3 |
| MC1 | 14.6 | 15.5 | 46 | 38 | A | 0-50 | 2-3 |
| MS3 | 18 | 16 | 46 | 39 | C | -5-55 | 4-5 |
| MS4 | 20 | 25 | 89 | 70 | C | -15-80 | 3-4 |
| MS5 | 22 | 24 | 88 | 76 | C | -15-85 | 3-4 |
| MS6 | 16 | 16 | 56 | 54 | C | 0-55 | 5 |
The performance perameter of table 23 plastic uptake sheet material based article
| Goods | Performance | ||||||
| Tensile tear strength (MPa) | Angle tear strength (N.M) | Heat sealability | Temperature tolerance (℃) | Biodegradable (ISO845, level) | |||
| Laterally | Vertically | Laterally | Vertically | ||||
| PS7 | 27 | 29 | 99 | 98 | C | -5-98 | 4-5 |
| PS8 | 23 | 26 | 52 | 46 | C | 0-55 | 4-5 |
| PS9 | 23 | 27 | 58 | 49 | C | -15-55 | 3-4 |
| PS10 | 26 | 30 | 61 | 44 | C | -5-55 | 5 |
| PS11 | 30 | 35 | 171 | 155 | C | -15-85 | 3-4 |
| PS12 | 31 | 34 | 160 | 145 | C | 0-90 | 4-5 |
| PS13 | 20 | 24 | 52 | 45 | C | 0-55 | 5 |
| PC2 | 22 | 24 | 51 | 40 | A | 0-50 | 4-5 |
The performance perameter of table 24 injection molding based article
| Goods | Performance | ||||||
| Tensile tear strength (MPa) | Angle tear strength (N.M) | Heat sealability | Temperature tolerance (℃) | Biodegradable (ISO845, level) | |||
| Laterally | Vertically | Laterally | Vertically | ||||
| ZS14 | 19 | 26 | 137 | 98 | C | -5-90 | 4-5 |
| ZS15 | 20 | 26 | 53 | 36 | C | 0-55 | 4-5 |
| ZS16 | 19 | 24 | 55 | 41 | C | -5-55 | 3-4 |
| ZS17 | 24 | 26 | 60 | 42 | C | 0-55 | 5 |
| ZS18 | 35 | 45 | 189 | 177 | C | -15-95 | 3-4 |
| ZS19 | 30 | 35 | 123 | 100 | B | -5-90 | 3-5 |
| ZS20 | 18 | 29 | 99 | 90 | C | -5-55 | 5 |
| ZC3 | 17 | 22 | 50 | 35 | A | 0-40 | 3-4 |
The performance perameter of table 25 foaming based article
| Goods | Performance | ||||||
| Tensile tear strength (MPa) | Angle tear strength (N.M) | Heat sealability | Temperature tolerance (℃) | Biodegradable (ISO845, level) | |||
| Laterally | Vertically | Laterally | Vertically | ||||
| FS21 | 19 | 26 | 97 | 88 | C | -5-90 | 4-5 |
| FC4 | 14 | 15 | 33 | 21 | A | 0-40 | 3-4 |
As can be seen from the above table, compared with prior art, under the suitable situation of tensile tear strength, use the heat sealability of the goods that composition provided by the invention makes to improve greatly; And when containing alkaline matter in the composition, the goods that make with said composition are compared with based article with prior art, and temperature tolerance is able to obvious raising; When containing the extremely-low density polyolefin resin in the polyolefin resin in the composition, the angle tear strength of goods also increases significantly.
Claims (23)
1, a kind of biodegradable starch-containing resin combination, said composition contains starch, polyvalent alcohol, ethylene-acrylate copolymer, additive salt and polyolefin resin, it is characterized in that said composition also contains the multipolymer of alkene and unsaturated alcohol carboxylicesters.
2, composition according to claim 1 wherein, is a benchmark with the total amount of composition, and contents of starch is 30-65 weight %; The content of polyvalent alcohol is 2-12 weight %; The content of ethylene-acrylate copolymer is 3-20 weight %; The content of additive salt is 0.1-3 weight %; The content of polyolefin resin is 10-60 weight %; The content of the multipolymer of alkene and unsaturated alcohol carboxylicesters is 0.1-20 weight %.
3, composition according to claim 2, wherein, the content of the multipolymer of described alkene and unsaturated alcohol carboxylicesters is 0.5-5 weight %.
4, composition according to claim 1, wherein, the multipolymer of described alkene and unsaturated alcohol carboxylicesters is selected from one or more in ethylene-vinyl acetate copolymer, propylene-acetate propylene multipolymer, EEA, the ethene-vinyl propionate multipolymer.
5, composition according to claim 4, wherein, the multipolymer of described alkene and unsaturated alcohol carboxylicesters is an ethylene-vinyl acetate copolymer.
6, according to claim 1 or 4 described compositions, wherein, the weight-average molecular weight of the multipolymer of described alkene and unsaturated alcohol carboxylicesters is 50,000-200,000.
7, composition according to claim 1, wherein, said composition also contains alkaline matter, is benchmark with the total amount of composition, and the content of alkaline matter is 0-15 weight %.
8, composition according to claim 7, wherein, the content of described alkaline matter is 0.5-5 weight %.
9, according to claim 7 or 8 described compositions, wherein, described alkaline matter is mineral alkali and/or organic bases.
10, composition according to claim 9, wherein, described mineral alkali is alkali metal hydroxide and/or alkaline inorganic acid salt.
11, composition according to claim 10, wherein, described alkali metal hydroxide comprises one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, the magnesium hydroxide.
12, composition according to claim 9, wherein, described organic bases comprises one or more in urea, quaternary ammonium hydroxide, the alkaline carboxylate salt.
13, composition according to claim 1, wherein, described polyolefin resin is polyethylene, polypropylene, polystyrene and/or ethylene-propylene copolymer.
14, according to claim 1 or 13 described compositions, wherein, described polyolefin resin comprises the extremely-low density polyolefin resin of density between 0.5-0.9 gram/cubic centimetre; Content with polyolefin resin is benchmark, and the content of described extremely-low density polyolefin resin is 0-50 weight %.
15, composition according to claim 14 wherein, is a benchmark with the content of polyolefin resin, and the content of described extremely-low density polyolefin resin is 10-45 weight %.
16, the preparation method of the described biodegradable starch-containing resin combination of claim 1, this method comprise starch, polyvalent alcohol and additive salt are mixed; Ethylene-acrylate copolymer and polyolefin resin are mixed; Above-mentioned two kinds of compounds that obtain are sent into extruding pelletization in the forcing machine respectively; Wherein, with ethylene-acrylate copolymer and polyolefin resin mixing the time, also add the multipolymer of alkene and unsaturated alcohol carboxylicesters.
17, preparation method according to claim 16 wherein, when starch, polyvalent alcohol and additive salt are mixed, also adds alkaline matter or its solution.
18, preparation method according to claim 17, wherein, described alkaline matter is one or more in sodium hydroxide, potassium hydroxide, the urea, the concentration of the described aqueous solution is 5-60 weight %.
19, the preparation method of the described biodegradable starch-containing resin combination of claim 1, this method comprise starch, polyvalent alcohol, ethylene-acrylate copolymer, polyolefin resin and additive salt are mixed; With the mixture extruding pelletization that obtains; Wherein, the multipolymer that when mixing, also adds alkene and unsaturated alcohol carboxylicesters.
20, preparation method according to claim 19 wherein, also adds alkaline matter or its solution.
21, preparation method according to claim 20, wherein, described alkaline matter is one or more in sodium hydroxide, potassium hydroxide, the urea, the concentration of the described aqueous solution is 5-60 weight %.
22, a kind of biodegradable articles, wherein, these goods contain any described biodegradable starch-containing resin combination in the claim 1,2 or 7.
23, goods according to claim 22, wherein, described goods are blow-molded article, injection-molded item, extrudate or foaming product.
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| CN 200510090456 CN1916062A (en) | 2005-08-15 | 2005-08-15 | Biodegradable composition of resin containing starch, products and prepartion method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775644A (en) * | 2012-03-16 | 2012-11-14 | 江西禾尔斯环保科技有限公司 | Nanocomposite starch micro-foaming biodegradable material |
| CN104618533A (en) * | 2015-01-19 | 2015-05-13 | 蒲绪萍 | Method for pasting phone screen with peony seeds |
-
2005
- 2005-08-15 CN CN 200510090456 patent/CN1916062A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775644A (en) * | 2012-03-16 | 2012-11-14 | 江西禾尔斯环保科技有限公司 | Nanocomposite starch micro-foaming biodegradable material |
| CN102775644B (en) * | 2012-03-16 | 2015-04-22 | 江西禾尔斯环保科技有限公司 | Nanocomposite starch micro-foaming biodegradable material |
| CN104618533A (en) * | 2015-01-19 | 2015-05-13 | 蒲绪萍 | Method for pasting phone screen with peony seeds |
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