CN1156154A - Method for preparing biological degredation plastic composition and product prepared by said composition - Google Patents
Method for preparing biological degredation plastic composition and product prepared by said composition Download PDFInfo
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- CN1156154A CN1156154A CN 96118970 CN96118970A CN1156154A CN 1156154 A CN1156154 A CN 1156154A CN 96118970 CN96118970 CN 96118970 CN 96118970 A CN96118970 A CN 96118970A CN 1156154 A CN1156154 A CN 1156154A
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Abstract
A plastic composition superior in both biodegradability and physical properties, comprises a matrix resin which is a blend of polyethylene and a biodegradable aliphatic polyester, starch, a coupling agent, a radical initiator, a starch plasticizer, a starch destructurizing agent and an autooxidizing agent, wherein the starch chemically binds to the matrix resin.
Description
The present invention relates to have the biological degredation plastic composition of excellent biodegradability and physical properties, prepare the method for said composition and the product for preparing with said composition.Specifically, the biological degredation plastic composition that the present invention relates to wherein has thermoplastic treated starch and is chemically bonded on the parent resin that comprises polyethylene with good processibility and physicals and biodegradable aliphatic polyester.The invention still further relates to twin-screw extruder and prepare this biological degredation plastic method for compositions and with the product of this biological degredation plastic preparation of compositions.
In view of the physicals of synthetic plastics is excellent and cheap, all qualifications and the drawback of natural materials have been overcome so it is believed that it.Say liberally, comprise that the various synthetic polymers of plastics have been made huge contribution to the modern science civilization in many fields.
Yet the pollution that the plastics that topple in the whole world cause is threatening human future day by day.For head it off has been taked various measures.Traditional processing comprises that the solid waste way of plastics comprises buries, and burns and reclaims.Yet these measures can not solve problem of environmental pollution fully.
The various research and development of being carried out at present are devoted to can be from the so-called degradable plastics of degraded at environment.These degradable plasticss have three groups: biological degredation plastic, light degredation plastic, and biological and light degredation plastic.Wherein, biological degredation plastic has obtained application the most widely, and this technology also is a purpose of the present invention.
Up to extremely so far, exploitation comprises such as microbial polymer products such as poly-beta-hydroxy-butyrates as the biological degredation plastic of degradable polymer, by biological chemistry synthetic polymkeric substance by microorganisms, the aliphatic polyester of chemosynthesis, natural synthetic polymkeric substance such as chitin, starch etc.
The patentee is the EP304 of Warner-Lambert company, and No. 401 patents just relate to the example of the prior art of biodegradable plastic.Disclosed a processing technology in this patent, when the starch that contains a certain amount of moisture content is mediated with softening agent under the high temperature more than 150 ℃ or 150 ℃ in as enclosed systems such as extrusion machines together, the vapour pressure increase destroys the hydrogen bond between starch molecule, produces to have thermoplastic starch.This technology has related generally to the production of moulded piece.Yet, this technology and be unwell to the high melting intensity of when processing needs, production after the product needed high elongation rate and the production of the film of tensile strength.
The patentee is the EP400 of Novamont, 531 and 400, No. 532 patent has been introduced a kind of method, in the presence of softening agent, under the high temperature more than 150 ℃ or 150 ℃, in extrusion machine, when synthetic resins that can be compatible with starch such as ethylene-vinyl alcohol copolymer and ethylene-acrylic acid copolymer mix with the starch that contains a certain amount of moisture content, key between starch molecule is destroyed, starch with resin chemically or physically bonding form the high biodegradable film of starch content.But for example the such synthetic resins of ethylene-vinyl alcohol copolymer and ethene-ethyl propylene acid copolymer does not show biodegradability and very expensive, so be difficult to replace with film prepared therefrom the plastics film of usual usefulness.
In addition, because aliphatic polyester costs an arm and a leg, so these polyester mix in order to the reduction material price with cheap polyethylene.But these two kinds of polymkeric substance are not compatible with each other, and simple mixing can reduce mechanical property greatly.Have about 60 ℃ the low melting point aliphatic polyester for example, under the polycaprolactone situation, because the so low so that film bubble of its Tc can not fully cooling under atmospheric condition, so it can not be processed as blown film.Thereby additional cooling system that need be as the water cooler.
The inventor's Korea publication 94-11556 and 94-11558 patent have been pointed out with coupling agent and have been come chemical bonding starch and parent resin to overcome because the method that the adding of starch causes the mechanical property variation and reduces production costs by the simplification step.Yet, still exist since the adding of starch make such as biodegradability low with problem such as mechanical property variation.
The inventor's further research has obtained all excellent plastics composite of biodegradability and mechanical property, it is characterized in that making with coupling agent having thermoplastic treated starch and having good processibility and the cheap polyethylene of physical property and the parent resin chemical bonding of biodegradable aliphatic polyester with comprising.Because polyethylene is cheap and have about 100 ℃ of high Tcs, can reduce material cost so polyethylene is carried out reactive mixing with aliphatic polyester, improves the Tc of parent resin, does not need auxiliary facilitys such as water cooler when being processed as blown film.The effect of this coupling agent between polyethylene and aliphatic polyester is the variation that overcomes mechanical property.
Therefore, the purpose of this invention is to provide the biological degredation plastic composition of a kind of wherein starch with the parent resin chemical bonding.
Another object of the present invention provides a kind of preparation biological degredation plastic method for compositions.
A further object of the present invention provides a kind of product with the biological degredation plastic preparation of compositions.
According to an aspect of the present invention, the biological degredation plastic composition that provides comprises: wherein contain by 1: 1-1: 100 parts heavy parent resins of 30 weight ratio blended polyethylene and biodegradable aliphatic polyester, the heavy starch of 10-150 part, the heavy starch softening agent of 0.01-40 part, the heavy starch disrupting agent of 0.01-10 part, the heavy coupling agent of 0.01-10 part, the heavy radical initiator of 0.01-10 part and the heavy autoxidator of 0.01-10 part.
According to another aspect of the present invention, provide biological degredation plastic preparation of compositions method, this method comprises:
(a) will contain by 1: 1-1: the parent resin mixture of 100 parts heavy parent resins of 30 weight ratio blended polyethylene and biodegradable aliphatic polyester, the heavy coupling agent of 0.01-10 part and the heavy radical initiator of 0.01-1.0 part is sent into twin-screw extruder from main hopper, and the starch mixture that will contain the heavy starch of 10-150 part, the heavy starch softening agent of 0.01-40 part, the heavy starch disrupting agent of 0.01-10 part and the heavy autoxidator of 0.01-10 part is sent into said twin-screw extruder from secondary hopper;
(b), described parent resin mixture and described starch mixture are mixed; With
(c), under 150-220 ℃ and screw speed 50-300 rev/min, described mixture is carried out reactive extrusion.
According to a further aspect in the invention, biological degredation plastic composition of the present invention is carried out pelletizing and moulding or extruding granules preparation biological degredation plastic goods.
Read following embodiment with reference to accompanying drawing and can understand other purposes of the present invention and other aspects more:
Fig. 1 is the infrared absorption spectrum of the usual film of Comparative Examples 1;
Fig. 2 is the infrared absorption spectrum of the usual film of Comparative Examples 2;
Fig. 3 is that 2400 times scanning electron photomicrograph copy is amplified in the film square section of Comparative Examples 5;
Fig. 4 is that 2000 times scanning electron photomicrograph copy is amplified in the biodegradable film square section of the embodiment of the invention 4;
The figure of Fig. 5 for being done by the polycaprolactone data that record with dsc (DSC);
Fig. 6 is the figure that does by the data of the composition of the embodiment of the invention 10 that records with dsc (DSC).
The present invention relates to a kind of biological degredation plastic composition, said composition comprises: wherein contain by 1: 1-1: 100 parts heavy parents of the polyethylene that 30 weight ratios are mixed and biodegradable aliphatic polyester Resin, the heavy starch of 10-150 part, the heavy starch plasticizer of 0.01-40 part, 0.01-10 parts heavy starch disrupting agents, the heavy coupling agent of 0.01-10 part, 0.01-1.0 parts weigh free Base initator, the heavy autoxidator of 0.01-10 part, wherein said starch makes its same institute by coupling agent State the matrix resin chemical bonding and modification makes it become thermoplastic starch and owing to adds aliphatic series to a certain degree Polyester and biodegradability is improved.
Biological degredation plastic composition according to the present invention also comprises heavily copolymerization usefulness of 0.01-10 part Monomer and/or 0.01-10 part heavy phase are held the catalyzed copolymerization monomer.
All cheap polyethylene and the biodegradable aliphatic series of excellence are gathered to be used in processability and physical property The purpose that ester admixture is made matrix resin is to improve biodegradability and processability and physical property. Should be poly-Ethene is preferentially selected low density polyethylene (LDPE), LLDPE and high density polyethylene (HDPE). Can for biology The aliphatic polyester of degraded, the preferred use comprises PCL, PLA, and dihydroxylic alcohols and binary acid The aliphatic polyester of polycondensation or its mixture.
Described starch is selected from such as grain starch, farina and rice starch, acid-treated starch, ester Change starch, the general starch that cationic starch is such and its mixture. The starch preferable amount is 10-15 0 part of weight. For example, be lower than 10 parts of weights such as the starch consumption, the resulting composition biodegradation is too slow. The opposing party Face, greater than 150 parts of weights, the physical property of resulting composition is variation then such as the starch consumption. In order to obtain giving birth to Thing degradation capability and physical property be the composition of excellence all, and most preferred quantities 60-120 part of starch is heavy.
Can use maleic anhydride, methacrylic anhydride or maleimide to make coupling agent.
Preferred free-radical initiator example comprises: benzoyl peroxide, peroxidating two-tert-butyl group, azo Bis-isobutyronitrile, TBHP, dicumyl peroxide, Lupersol 101 (Pennwalt company The business men name of an article, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane) and Perkadox-14 (the Akzo company business men name of an article, 1,3-pairs-(tert-butyl peroxy isopropyl base) benzene).
But spent glycol, propane diols, polyethylene glycol, D-sorbite, glycerine (glycerine) or its mixture Make the starch plasticizer.
Urea, right-amino toluene sulphonyl or melamine are the starch disrupting agents that suits.
The autoxidator that used promotion polyethylene decomposes be selected from oleic acid, stearic acid, magnesium oleate, dolomol, Iron oleate (II), ferric stearate (II) and its mixture.
The preferred example of comonomer comprises acrylonitrile, styrene, ethyl acrylate and its mixture.
Promptly have the compatible catalyzed copolymerization that catalytic activity has consistency again and comprise vinylformic acid and/or methacrylic acid with monomeric preferred example.
According to the present invention,, adopt twin-screw extruder that described composition is carried out reactive extrusion behind the adding starch in order to reduce production costs by simplified processing process and to make the reduction of physicals remain on minimum level.Say in detail, use the twin-screw extruder that is provided with two hoppers and two feeders by following way: will contain by 1: 1-1: 100 parts of maternal resins of weight of 30 weight ratio blended polyethylene and biodegradable aliphatic polyester, the heavy coupling agent of 0.01-10 part, the heavy radical initiator of 0.01-1.0 part and the heavy autoxidator of 0.01-10 part add from main hopper, and the starch mixture that will contain the heavy starch of 1-150 part, the heavy starch softening agent of 0.01-40 part and the heavy starch disrupting agent of 0.01-10 part simultaneously adds from the secondary hopper that is positioned at the extrusion machine middle part.In twin-screw extruder, the mixture of sending into from two hoppers mediated and under 150-220 ℃ and screw speed 50-300 change, divide, described mixture is carried out reactive extrusion.During reactive extrusion, coupling agent is grafted on the Polyethylene Chain consistency that increases between polyethylene and aliphatic polyester, is chemically bonded to biological degredation plastic composition on the parent resin thereby obtain starch wherein with intermolecular destructive starch esterification simultaneously.
According to the present invention, when the preparation said composition, just the heavy comonomer of 0.01-10 part and/or 0.01-10 part heavy phase capacitive catalyzed copolymerization are together added to increase graft ratio and consistency with monomer and coupling agent.
Under 150-220 ℃ and screw speed 50-150 rev/min, available single-screw extrusion machine pushes the biological degredation plastic composition and obtains general blow moulded polyethyene mould.Can produce injection moulding or moulded work by general technology with the biological degredation plastic composition that obtains like this.
Non-limiting example by the property of the following describes can better be understood the present invention.
In the Henschel mixing tank, (melt index=1g/10 minute, density was 0.919g/cm to add the 2.5kg Linear low-density polyethylene
3) and (the Union Carbide Corporation's sale of 2.5Kg polycaprolactone, commodity are called " TONE P-787 "), coated with containing 100g maleic anhydride, 10g oleic acid, 30g benzoyl peroxide, 20g magnesium oleate, 50g vinylformic acid and the cinnamic acetone of 50ml (100ml) solution.In another Hensohel mixing tank, with 500g contain cereal starch, 50g glycerine and the 50g of 10% (weight meter) moisture content right-the amino toluene sulphonyl mixes.These mixtures are sent into temperature maintenance by two independent loaders and are carried out reactive extrusion at 170 ℃, screw speed in 250 rev/mins extrusion machine and obtain starch wherein and be chemically bound in biological degredation plastic composition hopper on the parent resin.This pellet is prepared as film, and its mechanical property and biodegradability are listed in the table below in 1.
Embodiment 1I-VI
Method with similar embodiment I prepares biodegradable composition pellet, just presses the listed amount of table 1 and adds starch.With this pellet system film and test its physicals and the biodegradable ability.Test-results is listed in the table below in 1.With the film cross section that the sem observation EXAMPLE IV obtains, Fig. 3 is the scanning electron photomicrograph of 2000 times of amplifications.
Comparative Examples I
Method with similar embodiment I prepares composition, but not addition polymerization caproic acid lactone and starch.With the composition blowing that obtains is film, and its biodegradability is listed in the table below in 1.
The infrared absorption spectrum of this film is shown in Fig. 1.
Contrast row II
Method with similar embodiment I prepares composition, but without polycaprolactone, with the ester bond that confirms to form between parent resin and starch.With the composition blowing that obtains is film, and its biodegradability is listed in the table below in 1.The infrared absorption spectrum of this film is shown in Fig. 2.
Comparative Example II I
Method with similar embodiment I prepares composition, but without starch and maleic anhydride, coupling agent.With the composition blowing that obtains is film, and its physical properties and biodegradability are listed in the table below in 1.
Comparative Examples I V
Method with similar embodiment I prepares composition, but without starch.With the composition blowing that obtains is film, and its physical properties and biodegradability are listed in the table below in 1.
Comparative Examples V
Method with similar embodiment IV prepares composition, but starch is not plastified.With the composition blowing that obtains is film, and its physical properties and biodegradability are listed in the table below in 1.The cross section of the film that observe to obtain with scanning electronic microscope (amplifying 2400 times), the copy pattern of electron micrograph is shown in Fig. 3.
Comparative Examples VI
Method with similar embodiment IV prepares composition, but without the maleic anhydride coupling agent.With the composition blowing that obtains is film, and its physical properties and biodegradability are listed in the table below in 1.
Elongation biological degradation when tensile strength was destroyed when table 1 embodiment starch content destroyed
(weight part) (kg/cm
2) (%) ability C.E.*I 0--0C.E.II 10--1C.E.III 0 200 400 2C.E.IV 0 350 600 2C.E.V 90 150 300 4C.E.VI 90 170 370 4 I 10 340 600 2 II 30 330 580 3III 60 310 550 4 IV 90 280 530 4 V 120 220 450 4 VI 150 120 300 4*C.E. mean Comparative Examples
Test the biodegradability of this film by the regulation of ASTM G21-70.Promptly measure the mould that was covered on the film at least 21 days, measurement result is shown as follows by following table of grading:
0： 0％
1： 10％
2： 10-30％
3： 30-60％
4： 60-100％
With many tensile strength and elongations of measuring film with trier (UTM).
Example VII A-XIII
Method with similar embodiment IV prepares biodegradable film, but the linear low density polyethylene of polycaprolactone (Union Carbide Corporation sells, and commodity are called " TONE-787 ") with following table 2 amounts of giving mixed.Its physicals and biodegradability are listed in the table below 2.The composition data of the embodiment X that records with dsc is shown in Fig. 6.
Table 2 embodiment weight ratio
*Elongation biodegradability when tensile strength is destroyed during destruction
(kg/cm
2) (%) 1: 30 350 620 4** polyethylene of 1: 1 280 530 4 VII, 1: 5 320 560 4 IX, 1: 9 330 590 4 XI, 1: 20 340 620 4XIII of 1: 15 340 600 4 XII of 1: 7 330 580 4 X of 1: 3 310 550 4VIII of IV are with the PCL weight ratio
Embodiment XIV-XIX
Method with similar embodiment I prepares biodegradable film, but adds starch by the amount that following table 3 is given, and makes coupling agent with methacrylic anhydride and replaces maleic anhydride, and methacrylic acid is made compatible catalyzed copolymerization and replaced vinylformic acid with monomer.The physicals of this film and biodegradability are listed in the table below in 3.
Elongation biodegradability when tensile strength was destroyed when table 3 embodiment starch content destroyed
(weight part) (kg/cm
2) (％) I 10 340 600 2 XIV 10 280 550 2 XV 30 270 530 3 XVI 60 250 500 4XVII 90 200 410 4XVIII 120 180 330 4 XIX 150 70 250 4
Embodiment XX-XXIII
Method with similar embodiment XVII prepares biodegradable film, but the linear low density polyethylene of polycaprolactone (Union Carbide Corporation sells, and commodity are called " TONE P-787 ") with following table 4 amounts of giving mixed.Its physicals and biodegradability are listed in the table below 4.
Table 4 embodiment weight ratio
*Elongation biodegradability when tensile strength is destroyed during destruction
(kg/cm
2) (%) 1: 9 230 480 4** polyethylene of XVII 1: 3 210 420 4 XXI, 1: 7 220 460 4XXIII of 1: 5 210 450 4XXII of 1: 1 200 410 4 XX are with the PCL weight ratio
Can clearly find out from embodiment 1-6 and Comparative Examples 1-6, comprise that starch and/or aliphatic polyester film are biodegradable films, and the film of 1 not starch-containing and aliphatic polyester not be biodegradable as a comparison case.The Comparative Examples 3 that does not contain coupling agent and starch is compared with starch free Comparative Examples 4, comprises that the Comparative Examples 3 of the parent resin that wherein is mixed with polyethylene and the poly-adoption ester of fat is poorer than the consistency of Comparative Examples 4, like this bad mechanical property of Comparative Examples 3.The data of EXAMPLE III and embodiment XVI show, greater than 60 parts when heavy, the biodegradability of film just improves as the add-on of starch.As indicated in EXAMPLE V and the XVIII, the amount of starch of existence is 120 parts heavy or 120 parts more than the weight, and its biodegradability is good but tensile strength and elongation are had disadvantageous effect.Like this can be by hoping material product physical properties desired and biodegradability select to comprise the plastics composite of sufficient quantity starch.When said composition comprised the starch of 60-120 part weight, most of film of the present invention was if not whole, and its physicals and biodegradability are all good.
In addition, confirmed between starch and parent resin, to have the formation of chemical bond with infrared absorption spectrum.Fig. 1 and 2 shows Infrared spectroscopy.As Fig. 1 infrared spectra 1800-1760cm
-1Shown in, when coupling agent does not add the polyvinyl resin grafting of starch and polycaprolactone together (Comparative Examples 1), the absorption peak of this coupling agent acid anhydrides appears.On the contrary, as shown in Figure 2, when polyvinyl resin carries out reactive extrusion together with starch (Comparative Example II), absorption peak is at 1760-1680cm
-1The place, and not at 1800-1761cm
-1, this proof is because the coupling agent acid anhydrides has newly formed ester bond with the starch hydroxyl reaction, as shown in Figure 2.Only the reason of making the parent resin of Comparative Examples 1 and 2 with polyethylene is overlapping with the aliphatic polyester absorption peak of the absorption peak of the ester bond that prevents that chemical bonding forms between parent resin and starch.
Find that with the cross section of sem observation EXAMPLE IV and Comparative Examples V film because the breaking of key between starch molecule, the granularity that makes starch granules is reduced to 1 μ m or below the 1 μ m (Fig. 4) from 7-20 μ m (Fig. 3).
When observing the Tc of polycaprolactone (Fig. 5) and embodiment X (Fig. 6) with dsc, because use coupling agent that polyethylene and thermoplastic starch are mixed with polycaprolactone, the Tc of polycaprolactone is increased to 29 ℃ (Fig. 6) from 17 ℃ (Fig. 5).But also find that just occur crystallization in the time of about 100 ℃ recently, this just means when processing film owing to promoted cooling, and the processing characteristics of film is improved.From above table 2, can clearly be seen that and obtained good physicals and biodegradability and processing film well.
The present invention schematically is described since then, certain used term is to be to illustrate the present invention, rather than restriction the present invention.
Can do various modifications and change to the present invention according to above-mentioned instruction, but all within the scope of the claim that application is awaited the reply, can implement the present invention not according to the method for introducing in this specification sheets.
Claims (18)
1, a kind of biological degredation plastic composition, said composition comprises: wherein contain by 1: 1-1: 100 parts heavy parent resins of 30 weight ratio blended polyethylene and biodegradable aliphatic polyester, the heavy starch of 10-150 part, the heavy starch softening agent of 0.01-40 part, the heavy starch disrupting agent of 0.01-10 part, the heavy coupling agent of 0.01-10 part, the heavy radical initiator of 0.01-1.0 part and the heavy autoxidator of 0.01-10 part, described in view of the above starch is with described parent resin chemical bonding.
2, according to the biological degredation plastic composition of claim 1, said composition also comprises the heavy comonomer of 0.01-10 part and/or 0.01-10 part heavy phase appearance catalyzed copolymerization monomer.
3, according to the biological degredation plastic composition of claim 2, wherein said comonomer is selected from vinyl cyanide, vinylbenzene, ethyl propenoate and its mixture.
4. according to the biological degredation plastic composition of claim 2, wherein said compatible catalyzed copolymerization is selected from vinylformic acid, methacrylic acid and composition thereof with monomer.
5, according to the biological degredation plastic composition of claim 1, wherein said polyethylene is new LDPE (film grade), linear low density polyethylene or high density polyethylene(HDPE).
6. according to the biological degredation plastic composition of claim 1, wherein said biodegradable aliphatic polyester is selected from polycaprolactone, poly-lactic acid, by aliphatic polyester and its mixture of dibasic alcohol and diprotic acid polycondensation.
7. according to the biological degredation plastic composition of claim 1, the consumption of wherein said starch is heavy for 60-120 part.
8. according to the biological degredation plastic composition of claim 1, wherein said starch is selected from the common starch that comprises cereal starch, yam starch and Starch rice, acid-treated starch, esterification starch, cationic starch and its mixture.
9. according to the biological degredation plastic composition of claim 1, wherein said starch softening agent is selected from ethylene glycol, propylene glycol, polyoxyethylene glycol, Sorbitol Powder, glycerine and its mixture.
10, according to the biological degredation plastic composition of claim 1, wherein said starch disrupting agent is selected from urea, right-the amino toluene sulphonyl, melamine and its mixture.
11, according to the biological degredation plastic composition of claim 1, wherein said coupling agent is selected from maleic anhydride, methacrylic anhydride or maleimide.
12, according to the biological degredation plastic composition of claim 1, wherein said radical is selected from benzoyl peroxide, peroxidation two-tertiary butyl, Diisopropyl azodicarboxylate, tertbutyl peroxide, dicumyl peroxide, 1, two (the tert-butyl hydrogen peroxide sec.-propyl) benzene and 2 of 3-, 5-dimethyl-2,5-two (t-butyl peroxy) hexane.
13,, wherein saidly be selected from oleic acid, stearic acid, magnesium oleate, Magnesium Stearate, iron oleate (II), iron stearate (II) and its mixture from antioxidant according to the biological degredation plastic composition of claim 1.
14, preparation biological degredation plastic method for compositions, this method comprises the steps:
(a) will contain by 1: 1-1: the parent resin mixture of 100 parts heavy parent resins of 30 weight ratio blended polyethylene and biodegradable aliphatic polyester, the heavy coupling agent of 0.01-10 part and the heavy radical initiator of 0.01-10 part is sent into twin-screw extruder from main hopper; The starch mixture that will contain the heavy starch of 10-150 part, the heavy starch softening agent of 0.01-40 part, the heavy starch disrupting agent of 0.01-10 part and the heavy autoxidator of 0.01-10 part is sent into said twin-screw extruder from secondary hopper;
(b), described parent resin mixture and described starch mixture are mixed; With
(c), under 150-220 ℃ and screw speed 50-300 rev/min, described mixture is carried out reactive extrusion, make starch with the parent resin chemical bonding in view of the above.
15, according to the method for claim 14, wherein said parent resin also comprises the heavy comonomer of 0.01-10 part and/or 0.01-10 part heavy phase appearance catalyzed copolymerization monomer.
16, according to the method for claim 15, wherein said comonomer is selected from vinyl cyanide, vinylbenzene, ethyl propenoate and its mixture.
17, according to the method for claim 15, wherein said compatible catalyzed copolymerization is selected from vinylformic acid, methacrylic acid and composition thereof with monomer.
18, by the biological degredation plastic product of each claim Biodegradable compositions preparation of 1-14, wherein said starch is with described parent resin chemical bonding.
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| CN 96118970 CN1156154A (en) | 1995-12-06 | 1996-12-06 | Method for preparing biological degredation plastic composition and product prepared by said composition |
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| KR48168/95 | 1995-12-06 | ||
| CN 96118970 CN1156154A (en) | 1995-12-06 | 1996-12-06 | Method for preparing biological degredation plastic composition and product prepared by said composition |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093550C (en) * | 1998-04-30 | 2002-10-30 | 陈宏伟 | Biodegradated material and preparation thereof |
| CN1099439C (en) * | 1998-10-29 | 2003-01-22 | 孙国榆 | Process for making fully-biodegradable containers of food or beverage with potato |
| CN1297598C (en) * | 2002-12-13 | 2007-01-31 | 张沛生 | Fully-biodegradable plastic and its product preparing method |
| CN103122079A (en) * | 2012-09-20 | 2013-05-29 | 湖南工业大学 | Starch-based composite blown film and preparation process of same |
| CN103408804A (en) * | 2013-07-24 | 2013-11-27 | 吴江龙硕金属制品有限公司 | Degradable plastic |
| CN103497361A (en) * | 2013-09-29 | 2014-01-08 | 中国林业科学研究院林产化学工业研究所 | Preparation method of thermoplastic starch material based on non-grain woody plant oil and fat |
| CN107835837A (en) * | 2015-06-30 | 2018-03-23 | 白鸥逻辑股份有限公司 | Objects formed from biodegradable materials |
-
1996
- 1996-12-06 CN CN 96118970 patent/CN1156154A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093550C (en) * | 1998-04-30 | 2002-10-30 | 陈宏伟 | Biodegradated material and preparation thereof |
| CN1099439C (en) * | 1998-10-29 | 2003-01-22 | 孙国榆 | Process for making fully-biodegradable containers of food or beverage with potato |
| CN1297598C (en) * | 2002-12-13 | 2007-01-31 | 张沛生 | Fully-biodegradable plastic and its product preparing method |
| CN103122079A (en) * | 2012-09-20 | 2013-05-29 | 湖南工业大学 | Starch-based composite blown film and preparation process of same |
| CN103408804A (en) * | 2013-07-24 | 2013-11-27 | 吴江龙硕金属制品有限公司 | Degradable plastic |
| CN103497361A (en) * | 2013-09-29 | 2014-01-08 | 中国林业科学研究院林产化学工业研究所 | Preparation method of thermoplastic starch material based on non-grain woody plant oil and fat |
| CN103497361B (en) * | 2013-09-29 | 2015-09-02 | 中国林业科学研究院林产化学工业研究所 | Based on the preparation method of the thermoplastic starch material of non-grain xylophyta grease |
| CN107835837A (en) * | 2015-06-30 | 2018-03-23 | 白鸥逻辑股份有限公司 | Objects formed from biodegradable materials |
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