CN102492267A - Amylum category complete biodegradable material and preparation method thereof - Google Patents
Amylum category complete biodegradable material and preparation method thereof Download PDFInfo
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- CN102492267A CN102492267A CN201110393591XA CN201110393591A CN102492267A CN 102492267 A CN102492267 A CN 102492267A CN 201110393591X A CN201110393591X A CN 201110393591XA CN 201110393591 A CN201110393591 A CN 201110393591A CN 102492267 A CN102492267 A CN 102492267A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/57—Screws provided with kneading disc-like elements, e.g. with oval-shaped elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/54—Screws with additional forward-feeding elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/55—Screws having reverse-feeding elements
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- Mechanical Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
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Abstract
The invention discloses an amylum category complete biodegradable material and a preparation method thereof. The amylum category complete biodegradable material comprises, by weight, the long-chain branch aliphatic polyester or long-chain branch aliphatic series- aromatic copolyesters 50-70%, the starch 20-30%, the chain extender 0.1-3% and the balance chain extender 9-17%. The preparation method comprises the steps of enabling all components to be mixed in a high speed mixer, feeding in a twin-screw extruder after accurate measurement by means of a measurement scale, and extruding and prilling by adjusting a built-up sequence of a screw and designing different exhaust ports. The amylum category complete biodegradable material and the preparation method of the amylum category complete biodegradable material solve the problems of dispersing, plasticizing and exhausting of starch filler in the twin-screw extruder, and obtained amylum complete biodegradation material not only has complete biodegradation performance, but also has excellent mechanical property and good extrusion molding working quality.
Description
Technical field
The present invention relates to a kind of can be in starch based Biodegradable Materials and preparation method thereof under the composting conditions.
Background technology
In recent years, the development of biodegradable plastic grows with each passing day, use constantly to enlarge, and at wrapping material, disposable tableware, fields such as agricultural mulching and daily goods begin progressively to replace conventional plastic.At present, from performance and price lattice aspect, the performance of comparing biodegradable plastic with conventional plastic is too single, and price is too expensive, and this has all limited further developing of biodegradable plastic greatly.
In the biodegradable polymer plastics, use more have starch, polylactic acid PLA, polycaprolactone (PCL) at present, gather beta-hydroxy alkyl acid esters PHA or the like; POLYACTIC ACID obtains via processes such as amylofermentation, monomer polymerizations; Be one type of aliphatic polyester, mechanical property is suitable with the PET resin, and is more crisp; Heat-drawn wire is low, and machine-shaping device is needed special requirement.Gathering beta-hydroxy alkyl acid esters can obtain by biotechnology or chemical engineering are synthetic, though heat-drawn wire is higher, has the fragility defective equally.Starch uses as weighting agent, has the good biodegradability properties ability, through having excellent compatibility with vibrin after the processing treatment, also have cost advantage, but there is limitation in its processing simultaneously.In sum, present biodegradable polymer plastics exist degradation time long, and it is not thorough to degrade, and poor mechanical property, over-all properties can not satisfy multiple practical requirement in the practical application.
A kind of complete biodegradable starch/polyester plastics and preparation method thereof is disclosed like Chinese patent 200410081265.5.This plastic material is after earlier starch being done mechanical force-chemical modification processing and thermoplasticity processing; In high mixer, carry out melting mixing and graft reaction and mixing with fat-fragrant block polyester material and initiator, properties-correcting agent, stablizer again, cooling is also pulverized after two stepwise double screw rod extruders reaction extruding pelletization makes.This plastic material has excellent physical and mechanical property, and fully biodegradable.But it is in the forcing machine course of processing, and starch filled dose dispersion effect and plasticizing effect are desirable not to the utmost, and the over-all properties of goods remains further to be improved.
Summary of the invention
For solving the deficiency of above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of starch based Biodegradable Materials, and this material not only has biodegradability completely, and has excellent mechanical property and good extrusion moulding processibility.
Another object of the present invention is to provide the preparation method of above-mentioned starch based Biodegradable Materials, solved starch filled dose of scattering problem, plasticizing problem and the exhausting problem in twin screw extruder.
The present invention realizes through following technical scheme:
A kind of starch based Biodegradable Materials is characterized in that, by weight percentage, comprises following component:
Long-chain branch aliphatic polyester or long-chain branch aliphatic-aromatic copolyester: 50-70%;
Starch: 20-30%;
Chainextender: 0.1 ~ 3%;
All the other are various auxiliary agent 9-17%;
Wherein, said various auxiliary agent comprises properties-correcting agent, softening agent, oxidation inhibitor and lubricant.
Said long-chain branch aliphatic polyester is that weight-average molecular weight is more than 80000; The long-chain branch aliphatic polyester that its molecular chain is formed by connecting through polyfunctional groups such as polyvalent alcohol or polyprotonic acids at the aliphatic polyester copolymer more than 4000 weight-average molecular weight, and it contains organic dibasic acid residue and organic residue of dihydric alcohol.
Said long-chain branch aliphatic-aromatic copolyester is that weight-average molecular weight is more than 80,000; The long-chain branch aliphatic-aromatic copolyester that its molecular chain is formed by connecting through polyfunctional group mechanisms such as polyvalent alcohols at the aliphatic-aromatic polyester copolymer more than 4000 weight-average molecular weight, and it contains organic dibasic acid residue and organic residue of dihydric alcohol; Specifically comprise and gathering (succinic acid-butanediol ester is the mutual-phenenyl two acid bromide two alcohol ester altogether) PBSA, polycaprolactone (PCL), gather beta-hydroxy alkyl acid esters PHA, poly-PHB, gather one or more the mixture among (the hexanodioic acid butyleneglycol is the mutual-phenenyl two acid bromide two alcohol ester altogether) PBAT.
Said starch is branching or nonbranched starch, is selected from Semen Maydis powder, tapioca(flour), potato starch, the high amylose starch any one.
Said chainextender is selected from 1,4 one phenyl a pair of (2 one dislike beautiful jade), 2-glycidyl ester, two (2 one dislike beautiful jades), tolylene diisocyanate, equal two mixtures of one or more in phthalein amine, novel chainextender ADR-4370, isocyanuric acid three-glycidyl ester, hexamethylene diisocyanate, the isophorone diisocyanate in oneself of benzene four acid anhydrides, diphenylmethanediisocyanate, bischloroformate, isophorone diisocyanate, a benzene two phthalidyls.
Said properties-correcting agent is selected from one or more the mixture in surface active lime carbonate, disactivation lime carbonate, nanometer grade calcium carbonate, the talcum powder.
Said softening agent is selected from the mixture more than two kinds in epoxy soybean oil, polyoxyethylene glycol, Octyl adipate, water, glycerine, trioctyl trimellitate, the tributyl acetylcitrate;
Said oxidation inhibitor is selected from dihydroxyphenyl propane, 1,4-dual-tert-butyl peroxy isopropyl base benzene, N; N '-hexa-methylene two [3; 5-two uncles] base-4-hydroxybenzene propionic acid amide], phosphorous acid dihydroxyphenyl propane ester, β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, four [β (3; 5 one di-t-butyls, one 4-hydroxy phenyl) propionic acid] two or more mixture in the pentaerythritol ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, 4 ' 4 '-two-(α α '-dimethyl benzyl) pentanoic, ten dithio propyl ester, 1,4-dual-tert-butyl peroxy isopropyl base benzene;
Said lubricant is selected from two or more the mixture in the polymer complex ester, ethylene bis stearamide, polyethylene wax of hard esteramides, amine hydroxybenzene, erucicamide, Zinic stearas, metallic soap.
Also comprise end-capping reagent in the said starch based Biodegradable Materials, stabilization aid 0.1～3% such as the reagent that deacidifies, the reagent that dewaters, said stabilization aid is the organic molecule material that contains oxazolyl, NCO, isothiocyanate group, epoxy group(ing), activated silica alkyl or their mixed base.
A kind of preparation method of starch based Biodegradable Materials is characterized in that: may further comprise the steps:
A, two or more softening agent is mixed;
B, starch, long-chain branch aliphatic polyester or long-chain branch aliphatic-aromatic copolyester, properties-correcting agent are joined in the high-speed mixer and mixes; Use microprocessor pump drive quantitatively to spray into the softening agent that mixes simultaneously and make the compound uniform mixing; The back is added various auxiliary agents and is carried out mixed at high speed again, obtains mixture;
C, with mixture by carry out fusion plastification in the weighing balance accurate measurement feeding twin screw extruder, extrude, pelletizing promptly gets.
Wherein, said screw rod is a starch filled type of degradative plastics special combination screw rod, and screw combinations is the assembled arrangement of high-shear element, banburying element, kneading member, conveying original paper and 2-4 venting port arranged, preferred 3 venting ports or 4 venting ports.
Said twin screw extruder can be selected cocurrent and parallel twin screw extruder, anisotropic parallel twin-screw extruding machine or conical double screw extruder for use; Forcing machine needs with the pairing heads venting port design of screw design, and needs two of outfits or above vacuum pump to dock with venting port; Its length-to-diameter ratio is 40:1,56:1 or 60:1, preferred 56:1; The power of forcing machine is 65D type or 75A model.
Said high-speed mixer is the frequency-conversion high-speed mixing machine, and metering is called weight-loss metering and claims.
The mode of said pelletizing is that tie rod is crossed tank and got into the granulation of white steel knife dicing machine, underwater cutpellet or water ring pelletizing.
The present invention compared with prior art has following advantage:
(1) the present invention is to be main weighting agent with starch, and is consistent with the biodegradable plastic consistency, is aided with lubricant efficiently simultaneously, effectively stoped the reunion of filler, guaranteed the dispersiveness of weighting agent in extrusion, improves its processing characteristics; The adding of chainextender is such as two (2 one dislike beautiful jade) and bischloroformate etc., and the molecular weight that has improved degradative plastics has guaranteed the tensile property that finished product are good; The adding of properties-correcting agent such as lime carbonate or talcum powder etc. make moderate progress to the crystallinity of finished product, have guaranteed the blowing processing characteristics that finished product are good;
(2) gordian technique of the present invention more is on the basis of above-mentioned compsn through the various shearing screw thread of adjustment screw rod original paper; Carry the built-up sequence of original paper and the exhaust that designs different screw rod and barrel; Solved starch filled dose of scattering problem, plasticizing problem and the exhausting problem in twin screw extruder; The dispersion effect and the plasticizing effect of weighting agent have been guaranteed from complete processing; Not only have under the composting conditions biodegradability completely thereby obtained the starch based Biodegradable Materials, and have excellent mechanical property and good extrusion moulding processibility;
(3) starch based Biodegradable Materials provided by the present invention can prepare the membrane product of good physical and chemical performance through the method for blow molding; The biological degradation of this membrane product is degraded under composting conditions; Physical and chemical performance at 1 year inner membrance material satisfies daily user demand, is widely used in packaging industry and product for agriculture.
Description of drawings
Fig. 1 is embodiment 1 a used screw combinations structural representation;
Fig. 2 is the enlarged view of embodiment 1 used screw combinations A part;
Fig. 3 is the enlarged view of embodiment 1 used screw combinations B part;
Fig. 4 is embodiment 2 used screw combinations structural representations;
Fig. 5 is the enlarged view of embodiment 2 used screw combinations A parts;
Fig. 6 is the enlarged view of embodiment 2 used screw combinations B parts;
Fig. 7 is embodiment 3 used screw combinations structural representations;
Fig. 8 is embodiment 4 used screw combinations structural representations.
Embodiment
Further specify the present invention through embodiment below, following examples are preferred implementation of the present invention, but embodiment of the present invention does not receive the restriction of following embodiment.
Embodiment 1
Press column weight amount per-cent and take by weighing each component:
| Form | Ratio % |
| PBSA | 60 |
| W-Gum | 20 |
| |
10 |
| |
5 |
| |
2 |
| Tolylene diisocyanate | 1 |
| 1,4 one phenyl a pair of (2 one dislike beautiful jade) | 1.5 |
| Phosphorous acid dihydroxyphenyl propane ester | 0.1 |
| Ten dithio propyl ester | 0.1 |
| Amine hydroxybenzene | 0.1 |
| Ethylene bis stearamide | 0.2 |
Preparation technology is following:
Be transferred to microprocessor pump drive after glycerine and DOA mixed;
With PBSA and W-Gum, lime carbonate drops into the frequency-conversion high-speed mixing machine by proportioning and mixes, and opens behind microprocessor pump drive accurate measurement oil spout the mixings 135s adding auxiliary agent simultaneously and changes simultaneously and mixture is transferred to weight-loss metering behind the mixed at high speed 40s and claims;
Use in the weighing balance accurate measurement feeding forcing machine;
The forcing machine length-to-diameter ratio is 56:1,4 venting ports of host design;
Forcing machine power and model: 75A type, cocurrent and parallel twin screw extruder;
Melting temperature is following: one section 60-70 ℃; Two sections 90-100 ℃; Three sections 120-130 ℃; Four sections 150-160 ℃; Five sections 170-180 ℃; Six sections 170-180 ℃; Seven sections 170-180 ℃; Eight sections 170-180 ℃; Nine sections 170-180 ℃; Ten sections 170-180 ℃; 11 sections 160-170 ℃; 12 sections 160-170 ℃; 13 sections 160-170 ℃; Head 170-180 ℃;
Screw combinations is shown in Fig. 1-3: 1 is helical pitch 96, length 96 transfer block; 2 is helical pitch 72, length 72 transfer block; 3 is helical pitch 56, length 56 transfer block; 4 is helical pitch 56, length 56 major thread transfer block; 5 are 5 mediates 45 degree that sheet is formed, the shearing threaded block of length 56; 6 are 5 mediates 90 degree that sheet is formed, the shearing threaded block of length 56;
7 are 5 mediates 45 degree that sheet is formed, the shearing threaded block of length 36; 8 are 5 mediates 45 degree that sheet is formed, and the left-hand of length 36 is sheared threaded block; 9 is helical pitch 76, and length 36 is done to transfer block; 10 is feed opening; 11 is venting port; 14 are 5 mediates 45 degree that sheet is formed, and the left-hand of length 56 is sheared threaded block;
Select for use underwater cutpellet to make goods.Obtain goods and see table 1 according to the results of property that GB tests.
Press column weight amount per-cent and take by weighing each component:
| Form | Ratio % |
| PCL | 50 |
| W-Gum | 30 |
| |
10 |
| |
5 |
| |
2 |
| Tolylene diisocyanate | 1 |
| 2-glycidyl ester, two (2 one dislike beautiful jade) | 1.5 |
| Phosphorous acid dihydroxyphenyl propane ester | 0.1 |
| Ten dithio propyl ester | 0.1 |
| Amine hydroxybenzene | 0.1 |
| Ethylene bis stearamide | 0.2 |
Preparation technology is following:
Be transferred to microprocessor pump drive after G & W mixed;
With PCL and W-Gum, lime carbonate drops into the frequency-conversion high-speed mixing machine by proportioning and mixes, and opens behind microprocessor pump drive accurate measurement oil spout the mixings 135s adding auxiliary agent simultaneously and changes simultaneously and mixture is transferred to weight-loss metering behind the mixed at high speed 40s and claims;
Use weighing balance accurate measurement feeding forcing machine;
The forcing machine length-to-diameter ratio is 56:1, three venting ports of host design;
Forcing machine power and model: 75A type, cocurrent and parallel twin screw extruder;
Melting temperature is following: one section 60-70 ℃; Two sections 90-100 ℃; Three sections 120-130 ℃; Four sections 150-160 ℃; Five sections 170-180 ℃; Six sections 170-180 ℃; Seven sections 170-180 ℃; Eight sections 170-180 ℃; Nine sections 170-180 ℃; Ten sections 170-180 ℃; 11 sections 170-180 ℃; 12 sections 160-170 ℃; 13 sections 160-170 ℃; Head 170-180 ℃;
Screw combinations is shown in Fig. 4-6: 1 is helical pitch 96, length 96 transfer block; 2 is helical pitch 72, length 72 transfer block; 3 is helical pitch 56, length 56 transfer block; 4 is helical pitch 56, length 56 major thread transfer block; 5 are 5 mediates 45 degree that sheet is formed, the shearing threaded block of length 56; 6 are 5 mediates 90 degree that sheet is formed, the shearing threaded block of length 56; 7 are 5 mediates 45 degree that sheet is formed, the shearing threaded block of length 36; 8 are 5 mediates 45 degree that sheet is formed, and the left-hand of length 36 is sheared threaded block; 9 is helical pitch 76, length 36 left-hand transfer block; 10 is feed opening; 11 is venting port; 14 are 5 mediates 45 degree that sheet is formed, and the left-hand of length 56 is sheared threaded block;
Selecting for use tie rod to cross 15 meters tanks gets into the granulation of white steel knife dicing machine and makes goods.Obtain goods and see table 1 according to the results of property that GB tests.
Embodiment 3
Press column weight amount per-cent and take by weighing each component:
| Form | Ratio % |
| PHA | 70 |
| W-Gum | 20 |
| |
5 |
| Lime carbonate | 1 |
| |
2 |
| Tolylene diisocyanate | 1 |
| 2-glycidyl ester, two (2 one dislike beautiful jade) | 0.5 |
| Phosphorous acid dihydroxyphenyl propane ester | 0.1 |
| Ten dithio propyl ester | 0.1 |
| Amine hydroxybenzene | 0.1 |
| Ethylene bis stearamide | 0.2 |
Preparation technology is following:
Be transferred to microprocessor pump drive after glycerine and DOA mixed;
With PHA and W-Gum, lime carbonate drops into the frequency-conversion high-speed mixing machine by proportioning and mixes, and opens behind microprocessor pump drive accurate measurement oil spout the mixings 135s adding auxiliary agent simultaneously and changes simultaneously and mixture is transferred to weight-loss metering behind the mixed at high speed 40s and claims;
Use weighing balance accurate measurement feeding forcing machine;
The forcing machine length-to-diameter ratio is 56:1, three venting ports of host design;
Forcing machine power and model: 65D type, cocurrent and parallel twin screw extruder;
Melting temperature is following: one section 60-70 ℃; Two sections 90-100 ℃; Three sections 120-130 ℃; Four sections 150-160 ℃; Five sections 170-180 ℃; Six sections 170-180 ℃; Seven sections 170-180 ℃; Eight sections 170-180 ℃; Nine sections 170-180 ℃; Ten sections 170-180 ℃; 11 sections 170-180 ℃; 12 sections 160-170 ℃; 13 sections 160-170 ℃; Head 170-180 ℃;
Screw combinations is as shown in Figure 7: 1 is helical pitch 96, length 96 transfer block; 2 is helical pitch 72, length 72 transfer block; 3 is helical pitch 56, length 56 transfer block; 4 is helical pitch 56, length 56 major thread transfer block; 5 are 5 mediates 45 degree that sheet is formed, the shearing threaded block of length 56; 6 are 5 mediates 90 degree that sheet is formed, the shearing threaded block of length 56; 7 are 5 mediates 45 degree that sheet is formed, the shearing threaded block of length 36; 8 are 5 mediates 45 degree that sheet is formed, and the left-hand of length 36 is sheared threaded block; 9 is helical pitch 76, length 36 left-hand transfer block; 10 is feed opening; 11 is venting port; 12 is helical pitch 44, length 44 transfer block; 13 are 6 mediates 30 degree that sheet is formed, and the left-hand of length 56 is sheared threaded block; 14 are 5 mediates 45 degree that sheet is formed, and the left-hand of length 56 is sheared threaded block; 15 is helical pitch 44, length 22 left-hand transfer block; 16 is helical pitch 44, length 22 transfer block; 17 is helical pitch 56, length 28 transfer block;
Select for use underwater cutpellet to make goods.Obtain goods and see table 1 according to the results of property that GB tests.
Embodiment 4
Press column weight amount per-cent and take by weighing each component:
| Form | Ratio % |
| PBAT | 55 |
| W-Gum | 25 |
| |
10 |
| |
5 |
| |
2 |
| Tolylene diisocyanate | 1 |
| 1,4 one phenyl a pair of (2 one dislike beautiful jade) | 1.5 |
| Phosphorous acid dihydroxyphenyl propane ester | 0.1 |
| Ten dithio propyl ester | 0.1 |
| Amine hydroxybenzene | 0.1 |
| Ethylene bis stearamide | 0.2 |
Preparation technology is following:
Be transferred to microprocessor pump drive after G & W mixed;
With PBAT and W-Gum, lime carbonate drops into the frequency-conversion high-speed mixing machine by proportioning and mixes, and opens behind microprocessor pump drive accurate measurement oil spout the mixings 135s adding auxiliary agent simultaneously and changes simultaneously and mixture is transferred to weight-loss metering behind the mixed at high speed 40s and claims;
Use weighing balance accurate measurement feeding such as forcing machine;
The forcing machine length-to-diameter ratio is 56:1, two venting ports of host design;
Forcing machine power and model: 65D type, cocurrent and parallel twin screw extruder;
Melting temperature is following: one section 60-70 ℃; Two sections 90-100 ℃; Three sections 120-130 ℃; Four sections 150-160 ℃; Five sections 170-180 ℃; Six sections 170-180 ℃; Seven sections 170-180 ℃; Eight sections 170-180 ℃; Nine sections 170-180 ℃; Ten sections 170-180 ℃; 11 sections 170-180 ℃; 12 sections 160-170 ℃; 13 sections 160-170 ℃; Head 170-180 ℃;
Screw combinations is as shown in Figure 8, and 1 is helical pitch 96, length 96 transfer block; 2 is helical pitch 72, length 72 transfer block; 3 is helical pitch 56, length 56 transfer block; 4 is helical pitch 56, length 56 major thread transfer block; 5 are 5 mediates 45 degree that sheet is formed, the shearing threaded block of length 56; 6 are 5 mediates 90 degree that sheet is formed, the shearing threaded block of length 56; 7 are 5 mediates 45 degree that sheet is formed, the shearing threaded block of length 36; 8 are 5 mediates 45 degree that sheet is formed, and the left-hand of length 36 is sheared threaded block; 9 is helical pitch 76, length 36 left-hand transfer block; 10 is feed opening; 11 is venting port; 12 is helical pitch 44, length 44 transfer block; 13 are 6 mediates 30 degree that sheet is formed, and the left-hand of length 56 is sheared threaded block; 14 are 5 mediates 45 degree that sheet is formed, and the left-hand of length 56 is sheared threaded block; 15 is helical pitch 44, length 22 left-hand transfer block; 16 is helical pitch 44, length 22 transfer block; 17 is helical pitch 56, length 28 transfer block;
Select for use the water ring pelletizing to make goods.Obtain goods and see table 1 according to the results of property that GB tests.
Table 1 embodiment 1 ~ 4 The performance test results
| Test event | Embodiment 1 | |
Embodiment 3 | Embodiment 4 |
| Tensile strength | 15.3 | 14.3 | 13.8 | 14.1 |
| Elongation at break | 357 | 306 | 325.6 | 302.7 |
| Flexural strength | 3.6 | 5.6 | 5.8 | 5.2 |
| Modulus in flexure | 135 | 128 | 135 | 152 |
| Melt index | 3.24 | 2.8 | 2.9 | 3.14 |
| Density | 1.28 | 1.29 | 1.29 | 1.28 |
Said products degradation rate of 90 days under composting conditions reaches 90%.
Claims (10)
1. a starch based Biodegradable Materials is characterized in that, by weight percentage, comprises following component:
Long-chain branch aliphatic polyester or long-chain branch aliphatic-aromatic copolyester: 50-70%;
Starch: 20-30%;
Chainextender: 0.1 ~ 3%;
All the other are various auxiliary agent 9-17%;
Wherein, said various auxiliary agent comprises properties-correcting agent, softening agent, oxidation inhibitor and lubricant.
2. starch based Biodegradable Materials according to claim 1; It is characterized in that: said long-chain branch aliphatic polyester is that weight-average molecular weight is more than 80000; The long-chain branch aliphatic polyester that its molecular chain is formed by connecting through polyfunctional groups such as polyvalent alcohol or polyprotonic acids at the aliphatic polyester copolymer more than 4000 weight-average molecular weight, and it contains organic dibasic acid residue and organic residue of dihydric alcohol.
3. starch based Biodegradable Materials according to claim 1; It is characterized in that: said long-chain branch aliphatic-aromatic copolyester is that weight-average molecular weight is more than 80,000; The long-chain branch aliphatic-aromatic copolyester that its molecular chain is formed by connecting through polyfunctional group mechanisms such as polyvalent alcohols at the aliphatic-aromatic polyester copolymer more than 4000 weight-average molecular weight, and it contains organic dibasic acid residue and organic residue of dihydric alcohol; Specifically comprise and gathering (succinic acid-butanediol ester is the mutual-phenenyl two acid bromide two alcohol ester altogether) PBSA, polycaprolactone (PCL), gather beta-hydroxy alkyl acid esters PHA, poly-PHB, gather one or more the mixture among (the hexanodioic acid butyleneglycol is the mutual-phenenyl two acid bromide two alcohol ester altogether) PBAT.
4. starch based Biodegradable Materials according to claim 1 is characterized in that: said starch is branching or nonbranched starch, is selected from W-Gum, tapioca(flour), potato starch, the high amylose starch any one.
5. starch based Biodegradable Materials according to claim 1; It is characterized in that: said chainextender is selected from 1,4 one phenyl a pair of (2 one dislike beautiful jade), 2-glycidyl ester, two (2 one dislike beautiful jades), tolylene diisocyanate, equal two mixtures of one or more in phthalein amine, novel chainextender ADR-4370, isocyanuric acid three-glycidyl ester, hexamethylene diisocyanate, the isophorone diisocyanate in oneself of benzene four acid anhydrides, diphenylmethanediisocyanate, bischloroformate, isophorone diisocyanate, a benzene two phthalidyls.
6. starch based Biodegradable Materials according to claim 1 is characterized in that: said properties-correcting agent is selected from one or more the mixture in lime carbonate, disactivation lime carbonate, nanometer grade calcium carbonate and the talcum powder; Said softening agent is selected from the mixture more than two kinds in epoxy soybean oil, polyoxyethylene glycol, Octyl adipate, water, glycerine, trioctyl trimellitate, the tributyl acetylcitrate; Said oxidation inhibitor is selected from dihydroxyphenyl propane, 1,4-dual-tert-butyl peroxy isopropyl base benzene, N; N '-hexa-methylene two [3; 5-two uncles] base-4-hydroxybenzene propionic acid amide], phosphorous acid dihydroxyphenyl propane ester, β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, four [β (3; 5 one di-t-butyls, one 4-hydroxy phenyl) propionic acid] two or more mixture in the pentaerythritol ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, 4 ' 4 '-two-(α α '-dimethyl benzyl) pentanoic, ten dithio propyl ester, 1,4-dual-tert-butyl peroxy isopropyl base benzene; Said lubricant is selected from two or more the mixture in the polymer complex ester, ethylene bis stearamide, polyethylene wax of hard esteramides, amine hydroxybenzene, erucicamide, Zinic stearas, metallic soap.
7. starch based Biodegradable Materials according to claim 1; It is characterized in that: also comprise end-capping reagent, stabilization aid 0.1～3% such as the reagent that deacidifies, the reagent that dewaters, said stabilization aid is the organic molecule material that contains oxazolyl, NCO, isothiocyanate group, epoxy group(ing), activated silica alkyl or their mixed base.
8. the preparation method of each described starch based Biodegradable Materials of claim 1 ~ 7 is characterized in that: may further comprise the steps:
A, two or more softening agent is mixed;
B, starch, long-chain branch aliphatic polyester or long-chain branch aliphatic-aromatic copolyester, properties-correcting agent are joined in the high-speed mixer and mixes; Use microprocessor pump drive quantitatively to spray into the softening agent that mixes simultaneously and make the compound uniform mixing; The back is added various auxiliary agents and is carried out mixed at high speed again, obtains mixture;
C, with mixture by carry out fusion plastification in the weighing balance accurate measurement feeding twin screw extruder, extrude, pelletizing promptly gets;
Wherein, said screw rod is a starch filled type of degradative plastics special combination screw rod, and screw combinations is high-shear element, banburying element, kneading member, conveying original paper assembled arrangement and 2-4 venting port arranged.
9. the preparation method of starch based Biodegradable Materials according to claim 8 is characterized in that: said twin screw extruder is cocurrent and parallel twin screw extruder, anisotropic parallel twin-screw extruding machine or conical double screw extruder; Its length-to-diameter ratio is 40:1,56:1 or 60:1.
10. the preparation method of starch based Biodegradable Materials according to claim 8 is characterized in that: the mode of said pelletizing is that tie rod is crossed tank and got into the granulation of white steel knife dicing machine, underwater cutpellet or water ring pelletizing.
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