CN102295816B - Method for preparing full-degradable composite material filled with modified polylactic acid - Google Patents
Method for preparing full-degradable composite material filled with modified polylactic acid Download PDFInfo
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- CN102295816B CN102295816B CN2011101857494A CN201110185749A CN102295816B CN 102295816 B CN102295816 B CN 102295816B CN 2011101857494 A CN2011101857494 A CN 2011101857494A CN 201110185749 A CN201110185749 A CN 201110185749A CN 102295816 B CN102295816 B CN 102295816B
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- zein
- composite material
- polylactic acid
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- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 12
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title description 8
- 229920002494 Zein Polymers 0.000 claims abstract description 52
- 239000005019 zein Substances 0.000 claims abstract description 46
- 229940093612 zein Drugs 0.000 claims abstract description 46
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims description 52
- 108010055615 Zein Proteins 0.000 claims description 48
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 8
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- -1 phosphorous acid ester Chemical class 0.000 claims description 6
- OOZBTDPWFHJVEK-UHFFFAOYSA-N tris(2-nonylphenyl) phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC OOZBTDPWFHJVEK-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 238000005453 pelletization Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 6
- 238000001125 extrusion Methods 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 229920002472 Starch Polymers 0.000 description 14
- 239000008107 starch Substances 0.000 description 14
- 235000019698 starch Nutrition 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 7
- 240000008042 Zea mays Species 0.000 description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 5
- 235000005822 corn Nutrition 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 240000008564 Boehmeria nivea Species 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 239000010899 old newspaper Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000010909 process residue Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
-
- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
-
- 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
- B29C48/92—Measuring, controlling or regulating
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
本发明涉及一种可完全降解的填充改性聚乳酸复合材料的制备方法，属于可完全降解的复合材料的制备方法。将原料聚乳酸、马来酸酐、过氧化物搅拌5~10分钟，温度80℃~120℃；再加入干燥后的玉米蛋白和亚磷酸脂类材料，搅拌5~10分钟，温度100℃~140℃，将混合均匀后的物料投放到双螺杆挤出机中挤出。使用玉米蛋白填充改性聚乳酸不仅可以回收利用玉米蛋白，还可以降低复合材料的成本，而且还可以减少环境污染，玉米蛋白填充改性聚乳酸还能提高聚乳酸的力学性能。The invention relates to a preparation method of a fully degradable filled modified polylactic acid composite material, belonging to a preparation method of a completely degradable composite material. Stir the raw materials polylactic acid, maleic anhydride and peroxide for 5-10 minutes at a temperature of 80°C~120°C; then add dried zein and phosphite materials, stir for 5-10 minutes at a temperature of 100°C~140°C °C, put the uniformly mixed material into a twin-screw extruder for extrusion. The use of zein-filled modified polylactic acid can not only recycle zein, but also reduce the cost of composite materials, and can also reduce environmental pollution. Zein-filled modified polylactic acid can also improve the mechanical properties of polylactic acid.
Description
Technical field
The invention belongs to a kind of preparation method of the matrix material that can degrade fully.
Background technology
China is world's second largest Maize Production state; It also is second largest corn country of consumption; Corn industry consumption increases year by year in China; Industry consumption has accounted for 20% ~ 30% of corn overall consumption, and wherein starch production accounts for the ratio maximum of corn industry consumption, in the W-Gum course of processing, can produce a certain amount of zein.Starch accounts for 75% in corn, and zein accounts for 10.6%, and these zeins are used as waste and arrange, and not only wastes also contaminate environment of resource.
The macromolecule material product that uses in our daily life is the petroleum base polymkeric substance mostly, and its waste is difficult to degraded, cause environmental pollution after discarding, and degradable biomaterial costs an arm and a leg, and limits it and uses widely.In order to reduce the cost of biodegradable composite material, and its product can degrade fully again, free from environmental pollution, use natural animal-plant fiber filled modification biological degradation material mostly.
Chinese patent (CN 101962469 A) discloses a kind of method of utilizing the old and useless newspaper recycled fiber to make the fully-degradable polylactic acid matrix material.After at first old newspaper being soaked 8h in tap water, send into machine,massing and pull an oar to handle and squeeze most of water, obtain recycled fiber, with the diphenylmethanediisocyanate differential fiber again with polylactic acid blend manufacturing matrix material.
Chinese patent (CN 101525449 A) discloses the method for modifying that improves POLYACTIC ACID and starch blend consistency and interfacial adhesion.This invention utilizes isocyanic ester to be coupling agent, improves POLYACTIC ACID and starch blend consistency and interfacial adhesion.
Chinese patent (CN 1869107 A) discloses the reinforced polylactic acid composite material for ramie-fabric preparation method.It is the polycaprolactone polydactyl acid of isocyanic ester that this invention utilizes the two ends group; Utilize silane coupling agent γ-An Bingjisanyiyangjiguiwan modification ramie; The γ-An Bingjisanyiyangjiguiwan of ramie upper surface and the isocyanic ester on the POLYACTIC ACID react; Thereby improve the interface compatibility of POLYACTIC ACID and ramie, improve the mechanical property of matrix material.
Except that containing albumen, also contain Mierocrystalline cellulose, wood fibre, starch etc. in the zein, this type material is can degrade and can not produce pollution to environment in physical environment.
Main both at home and abroad at present research zein extracts amino acid and polypeptide, and it studies complicated, and research cost is too high, has limited zein and has used widely in a large number, is unfavorable for recovery and recycling of used resources.Use the document of the filling-modified polymkeric substance of zein also not appear in the newspapers; And the filling-modified POLYACTIC ACID of other vegetable fibre exists problems such as interface compatibility difference; Its consistency difference is not well solved; Also there is serious interface compatibility problem in the starch conversion POLYACTIC ACID, the most important thing is that starch is food, comes filling-modified POLYACTIC ACID to exist serious problems such as waste food with it.
Summary of the invention
The present invention provides a kind of preparation method of the filling-modified lactic acid composite material that can degrade fully, with the problem that cost is high, consistency is poor, zein can not obtain utilizing that solves present biodegradable composite material.
The technical scheme that the present invention takes is to comprise following prescription and step:
Prescription: each raw materials in part by weight ratio is:
100 parts of POLYACTIC ACIDs, 0.6 ~ 3 part of maleic anhydride, 0.1 ~ 1.0 part of superoxide, 0.5 ~ 3 part of phosphorous acid ester, 5 ~ 20 parts of zeins;
Step:
(1) zein vacuum drying 24h in 50 ℃ of baking ovens;
(2) raw material is joined in the impeller by following order stir: POLYACTIC ACID, maleic anhydride, superoxide stirred 1500 ~ 2000 rev/mins of stirring velocitys, 80 ℃ ~ 120 ℃ of temperature 5 ~ 10 minutes; Add dried zein and phosphorous acid lipid material again, stirred 5 ~ 10 minutes, 1500 ~ 2000 rev/mins of stirring velocitys, 100 ℃ ~ 140 ℃ of temperature, the discharging naturally cooling is subsequent use;
(3) material after will mixing is rendered in the twin screw extruder, and extruder temperature is set: 150 ~ 180 ℃, engine speed 100r/min ~ 200r/min is through check rod, cooling, pelletizing, drying, packing.
Described polylactic acid molecule amount 40000 ~ 200000.
Described superoxide is: Di Cumyl Peroxide 99 or Lucidol.
Phosphorous acid lipid material is: triphenyl phosphite, tris(nonyl phenyl) phosphate.
Select for use maleic anhydride (MA) as grafted monomer, its advantage is that maleic anhydride monomer can not form long grafted chain under the grafting condition, and one of which has avoided POLYACTIC ACID (PLA) overall performance to descend; It two has avoided the polarity of grafts excessive, causes and POLYACTIC ACID viscosifying power mutually descends, and it three prevents owing to monomeric homopolymerization reduces grafting efficiency.
Present method adopts and to melt extrude the reaction working method, and it is simple to have an operating procedure, and facility investment is few, can serialization production, and the production technique cost is low.But melt extrude the degraded that the reaction course of processing can cause POLYACTIC ACID; Therefore added phosphorous acid lipid material as the radical catcher among the present invention; Reduce a large amount of radicals that POLYACTIC ACID degraded back forms with this, these radicals can cause the chain type DeR of POLYACTIC ACID.
Superoxide is radical initiator again; It has double effects; Under the situation of heating, can cause POLYACTIC ACID and maleic anhydride and produce radical; When the freedom of maleic anhydride and the combined with radical of POLYACTIC ACID must arrive the POLYACTIC ACID grafted maleic anhydride to a time-out, superoxide also possibly cause a spot of POLYACTIC ACID cross-linking products simultaneously.
The present invention uses the filling-modified POLYACTIC ACID of zein; The degradability of zein can not cause environmental pollution; Use the filling-modified POLYACTIC ACID of zein not only can recycle zein; Can also reduce the cost of matrix material, but also can reduce environmental pollution, have great realistic meaning.Because the consistency of zein and POLYACTIC ACID is poor, in the course of processing, impel the POLYACTIC ACID degraded again, in order to overcome above problem; The present invention uses superoxide to be initiator; Cause the reaction of POLYACTIC ACID and maleic anhydride, again with the zein blend, zein has more active α-H atom; React easily, thereby improve the consistency of POLYACTIC ACID and zein with the maleic anhydride that reacts with POLYACTIC ACID.The amido linkage of zein, hydroxyl impel the POLYACTIC ACID degraded easily, use superoxide to cause POLYACTIC ACID, make POLYACTIC ACID generation self-crosslinking, thereby reduce the degraded of POLYACTIC ACID.
Use at present mostly starch filled polydactyl acid, starch is hydroaropic substance, and POLYACTIC ACID is a hydrophobicity, and the two consistency extreme difference has had a strong impact on the mechanical property of its matrix material.The staple of zein is a protein; Mainly be prolamine matter; Prolamine matter is lyophobic dust; With POLYACTIC ACID certain consistency is arranged; The amino acid of zein further improves the interface compatibility of POLYACTIC ACID and zein with reacting with the maleic anhydride of POLYACTIC ACID reaction in the blend process, so the interface compatibility of the filling-modified POLYACTIC ACID of zein good than starch filled polydactyl acid shows as that zein is filling-modified to have mechanical property preferably than starch filled polydactyl acid.Starch is food, and zein is the food-processing waste, and the cost of zein is more much lower than starch; So the filling-modified POLYACTIC ACID of zein more has superiority; Use the filling-modified POLYACTIC ACID of zein not only can recycle zein, can also reduce the cost of matrix material, but also can reduce environmental pollution; Have great realistic meaning, the filling-modified POLYACTIC ACID of zein can also improve the mechanical property of POLYACTIC ACID.
Description of drawings
Figure 1A is field emission scanning electron microscope (ESEM) figure of zein;
Figure 1B is field emission scanning electron microscope (ESEM) figure of zein, unmodified polylactic acid PLA;
Fig. 1 C is field emission scanning electron microscope (ESEM) figure of zein, maleic anhydride MA polydactyl acid PLA;
Fig. 2 is the amino acid reaction principle figure of maleic anhydride and POLYACTIC ACID, zein.
Embodiment
The sub product that zein of the present invention is produced when being the wet method starch production.
Embodiment 1
Prescription: each raw materials in part by weight ratio is:
100 parts of POLYACTIC ACIDs, molecular weight 40000,0.6 part of maleic anhydride, 0.1 part of Di Cumyl Peroxide 99,0.5 part of triphenyl phosphite, 5 parts of zeins;
Step:
(1) zein vacuum drying 24h in 50 ℃ of baking ovens;
(2) raw material is joined in the impeller by following order stir: POLYACTIC ACID, maleic anhydride, Di Cumyl Peroxide 99 stirred 1500 rev/mins of stirring velocitys, 80 ℃ of temperature 5 minutes; Add dried zein and triphenyl phosphite again, stirred 5 minutes, 1500 rev/mins of stirring velocitys, 100 ℃ of temperature, the discharging naturally cooling is subsequent use;
(3) material after will mixing is rendered in the twin screw extruder, and extruder temperature is set: 150 ℃, engine speed 100r/min is through check rod, cooling, pelletizing, drying, packing.
Embodiment 2
Prescription: each raw materials in part by weight ratio is:
100 parts of POLYACTIC ACIDs, molecular weight 100000,1.8 parts of maleic anhydrides, 0.5 part of Lucidol, 1.8 parts of tris(nonyl phenyl) phosphates, 12.5 parts of zeins;
Step:
(1) zein vacuum drying 24h in 50 ℃ of baking ovens;
(2) raw material is joined in the impeller by following order stir: POLYACTIC ACID, maleic anhydride, Lucidol stirred 1800 rev/mins of stirring velocitys, 100 ℃ of temperature 7 minutes; Add dried zein and tris(nonyl phenyl) phosphate again, stirred 8 minutes, 1800 rev/mins of stirring velocitys, 120 ℃ of temperature, the discharging naturally cooling is subsequent use;
(3) material after will mixing is rendered in the twin screw extruder, and extruder temperature is set: 165 ℃, engine speed 150r/min is through check rod, cooling, pelletizing, drying, packing.
Embodiment 3
Prescription: each raw materials in part by weight ratio is: 100 parts of POLYACTIC ACIDs, molecular weight 200000,3 parts of maleic anhydrides, 1.0 parts of Di Cumyl Peroxide 99s, 3 parts of tris(nonyl phenyl) phosphates, 20 parts of zeins;
Step:
(1) zein vacuum drying 24h in 50 ℃ of baking ovens;
(2) raw material is joined in the impeller by following order stir: POLYACTIC ACID, maleic anhydride, Di Cumyl Peroxide 99 stirred 2000 rev/mins of stirring velocitys, 120 ℃ of temperature 10 minutes; Add dried zein and tris(nonyl phenyl) phosphate again, stirred 10 minutes, 2000 rev/mins of stirring velocitys, 140 ℃ of temperature, the discharging naturally cooling is subsequent use;
(3) material after will mixing is rendered in the twin screw extruder, and extruder temperature is set: 180 ℃, engine speed 200r/min is through check rod, cooling, pelletizing, drying, packing.
Claims (4)
1. the preparation method of the filling-modified lactic acid composite material that can degrade fully is characterized in that: comprise following prescription and step:
Prescription: each raw materials in part by weight ratio is:
100 parts of POLYACTIC ACIDs, 0.6 ~ 3 part of maleic anhydride, 0.1 ~ 1.0 part of superoxide, 0.5 ~ 3 part of phosphorous acid ester, 5 ~ 20 parts of zeins;
Step:
(1) zein vacuum drying 24h in 50 ℃ of baking ovens;
(2) raw material is joined in the impeller by following order stir: POLYACTIC ACID, maleic anhydride, superoxide stirred 1500 ~ 2000 rev/mins of stirring velocitys, 80 ℃ ~ 120 ℃ of temperature 5 ~ 10 minutes; Add dried zein and phosphorous acid esters material again, stirred 5 ~ 10 minutes, 1500 ~ 2000 rev/mins of stirring velocitys, 100 ℃ ~ 140 ℃ of temperature, the discharging naturally cooling is subsequent use;
(3) material after will mixing is rendered in the twin screw extruder, and extruder temperature is set: 150 ~ 180 ℃, engine speed 100r/min ~ 200r/min is through check rod, cooling, pelletizing, drying, packing.
2. the preparation method of a kind of filling-modified lactic acid composite material that can degrade fully as claimed in claim 1 is characterized in that: described polylactic acid molecule amount 40000 ~ 200000.
3. the preparation method of a kind of filling-modified lactic acid composite material that can degrade fully as claimed in claim 1 is characterized in that: described superoxide is Di Cumyl Peroxide 99 or Lucidol.
4. the preparation method of a kind of filling-modified lactic acid composite material that can degrade fully as claimed in claim 1 is characterized in that: described phosphorous acid ester is triphenyl phosphite, tris(nonyl phenyl) phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN110204956A (en) * | 2019-07-15 | 2019-09-06 | 深圳市裕同包装科技股份有限公司 | A kind of biodegradable green printing ink binder, ink and preparation method thereof |
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| CN101851424B (en) * | 2009-03-31 | 2011-08-10 | 西南科技大学 | Thermoplastic plant protein/polylactic acid blend material and preparation method thereof |
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