CN103183936B - Biodegradable composite material prepared by excessive processing materials of high-starch crops and preparation method thereof - Google Patents
Biodegradable composite material prepared by excessive processing materials of high-starch crops and preparation method thereof Download PDFInfo
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- CN103183936B CN103183936B CN201310064845.2A CN201310064845A CN103183936B CN 103183936 B CN103183936 B CN 103183936B CN 201310064845 A CN201310064845 A CN 201310064845A CN 103183936 B CN103183936 B CN 103183936B
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- 229920002472 Starch Polymers 0.000 title claims abstract description 53
- 239000008107 starch Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 58
- 239000004626 polylactic acid Substances 0.000 claims abstract description 51
- -1 polybutylene succinate Polymers 0.000 claims abstract description 38
- 229920002961 polybutylene succinate Polymers 0.000 claims abstract description 35
- 239000004631 polybutylene succinate Substances 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 235000019698 starch Nutrition 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000002893 slag Substances 0.000 claims description 24
- 244000017020 Ipomoea batatas Species 0.000 claims description 21
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 244000061456 Solanum tuberosum Species 0.000 claims description 16
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 16
- 239000002699 waste material Substances 0.000 claims description 16
- 229920002752 Konjac Polymers 0.000 claims description 15
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 14
- 229920002488 Hemicellulose Polymers 0.000 claims description 11
- 229920002678 cellulose Polymers 0.000 claims description 11
- 239000001913 cellulose Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- JMWGZSWSTCGVLX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO JMWGZSWSTCGVLX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229940059574 pentaerithrityl Drugs 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- 238000002203 pretreatment Methods 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000000284 extract Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 5
- 238000002955 isolation Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 5
- 238000001746 injection moulding Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 239000008187 granular material Substances 0.000 description 9
- 238000012216 screening Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 235000006481 Colocasia esculenta Nutrition 0.000 description 1
- 244000205754 Colocasia esculenta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000003413 degradative effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
-
- 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
- B29C2948/92514—Pressure
-
- 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
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a biodegradable composite material prepared by excessive processing materials of high-starch crops and a preparation method thereof. The preparation method for the composite material comprises the following steps: subjecting PLA (polylactic acid), PBS (polybutylene succinate), the excessive materials of the crops, and a cross-linking agent to vacuum drying respectively, and enabling the temperature to be lower than 65 DEG C; sufficiently mixing the dried raw materials in an agitating pan, feeding the uniformly mixed material to a double-screw extruder; and mixing and extruding the material through screws in the double-screw extruder to obtain a granulous product which is the biodegradable composite material prepared by the excessive processing materials of the high-starch crops. The toughness of the biodegradable composite material is better than that of PLA, the tensile strength is slightly poorer than that of PLA but does not affect the utilization, and the material can be subjected to secondary forming processing by a frequently-used plastic processing manner such as injection molding, performing and the like.
Description
Technical field
The present invention relates to Material Field, be specifically related to a kind of biodegradable composite prepared with high starch farm crop processing clout and preparation method thereof.
Background technology
High starch farm crop are planted widely as sweet potato, taro, potato etc. have in China, according to current processing mode, after these farm crop have extracted starch, also have a large amount of farm crop processing clouts.But these farm crop processing clout except after drying with except producing fodder, there is no extensive, Application way efficiently at present; And when some starch isolation factory rules and regulations moulds are less or do not have large plant around factory, these clouts are often directly taken as rubbish and abandon, cause the waste of resource so on the one hand, clout also can cause environmental pollution after rotting on the other hand.Above-mentioned high starch farm crop processing clout is the mixture of multiple Mierocrystalline cellulose, hemicellulose, xylogen, and its main chemical compositions is Mierocrystalline cellulose, hemicellulose.
On the other hand, current biodegradable thermoplastic polymer mainly contains PBS, PLA etc.
Wherein polymer poly succinic acid-butanediol ester (PBS) is a kind of Biodegradable polyester of semicrystalline of chemosynthesis, glass transition temperature Tg is about-38 DEG C, fusing point Tm is about 113 DEG C, and mechanical property and processing characteristics are better, and mechanical property and polyolefin PE, PP are close; PBS easily by the enzyme katabolism in natural multiple-microorganism or animal and plant body, is finally degraded into carbonic acid gas and water.
Polymer poly lactic acid (PLA) is also a kind of biodegradable material, by reproducible plant resources as corn the starch material that extracts make.Starch material makes lactic acid via fermenting process, then converts poly(lactic acid) to by chemosynthesis.PLA has good tensile strength, but toughness is poor, and its elongation at break generally only has 3% to 10%.
Prior art discloses the technical scheme being prepared Biodegradable material by PLA or PBS, such as Chinese patent literature CN1687205A(application number 200510049546.7) disclose a kind of PLA environmental protection complete degradable plastic, after making poly(lactic acid) with W-Gum, add softening agent, lubricant, UV light absorber, white dyes, in high speed mixer, after mixing, PLA degradative plastics is made in granulation oven dry.But the program does not improve the toughness of PLA.Chinese patent literature CN102020773A(application number 200910153129.5) disclose a kind of biodegradable copolymer and preparation method thereof, described multipolymer is prepared from by melt phase polycondensation under catalyst action by poly butylene succinate oligopolymer and polylactic acid low polymer.But prior art is the unexposed biodegradable composite being processed clout manufacture by high starch farm crop also.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of biodegradable composite prepared with high starch farm crop processing clout and preparation method thereof.
The technical scheme realizing the present invention first object is a kind of method preparing biodegradable composite with high starch farm crop processing clout, comprises the following steps:
1. carry out vacuum-drying respectively using as the polylactic acid PLA of reaction mass, poly butylene succinate PBS, pretreated farm crop processing clout and linking agent, make each material water ratio control each part material temperature lower than 65 DEG C lower than 0.4% respectively; Described farm crop processing clout refers to that high starch farm crop extract remaining processing clout after starch, and main chemical compositions is Mierocrystalline cellulose and hemicellulose.Take above-mentioned dried polylactic acid PLA 30 ~ 60 parts, poly butylene succinate PBS0 ~ 30 part, farm crop processing clout 10 ~ 40 parts and 1 ~ 8 part of linking agent stand-by.
2. 1. step is taken polylactic acid PLA, poly butylene succinate PBS, farm crop processing clout and linking agent mixing obtain mixture.
3. the mixture that 2. step obtains is dosed to twin screw extruder, control temperature 120 DEG C ~ 160 DEG C in twin screw extruder, pressure 1.2MPa ~ 3MPa, mixture obtains granular product through the mixing of screw rod and extruding in twin screw extruder, and this granular product is the biodegradable composite prepared with high starch farm crop processing clout.
Described linking agent is tetramethylolmethane three propylene or trimethylolpropane tris methacrylic acid ester or triallyl isocyanurate.
The molecular weight of described polylactic acid PLA is 2 ten thousand to 4 ten thousand, and the molecular weight of described poly butylene succinate PBS is 10 ten thousand to 15 ten thousand.
Described farm crop processing clout is potato slag, sweet potato waste or konjaku slag.
The pre-treatment of described farm crop processing clout carries out drying to the processing clout sieving the Xi shape obtained in starch isolation process, makes its water ratio lower than 10%.
Preferably, also further the processing clout obtained after drying is pulverized, make its particle diameter be less than 300 μm.
As preferably, when 2. described step mixes reaction mass, first polylactic acid PLA is dropped in agitator kettle, stir with the rotating speed of 50rpm ~ 250rpm; Stir after 10 ~ 15min, in agitator kettle, drop into that 1. step take linking agent, after stirring 15 ~ 25min, 1. step is taken farm crop processing clout and poly butylene succinate add in agitator kettle; Stop stirring after continuing stirring 15 ~ 30min and obtain mixture.
The technical scheme realizing the present invention second object is the biodegradable matrix material prepared by above-mentioned method.
The tensile strength of above-mentioned biodegradable composite is 30Mpa ~ 50Mpa, and elongation at break is greater than 50%, and the degradation rate of 6 months is greater than 95%.
The present invention has positive effect:
(1) main chemical compositions in high starch farm crop processing clout used in the present invention is Mierocrystalline cellulose, hemicellulose, above-mentioned Mierocrystalline cellulose, hemicellulose are after treatment, certain orientation can be produced, there is good elasticity and surface reaction activity in a certain direction; After crosslinked with suitable biodegradable material, can obtain performance meets the matrix material that product manufacturing, low cost of manufacture keep biological degradation character simultaneously.
The toughness of biodegradable composite of the present invention is better than PLA, but tensile strength is slightly poorer than PLA does not affect use; Cost is starkly lower than PLA; Described biodegradable composite can with conventional as the plastic working such as injection moulding, compressing tablet mode post-forming process.
(2) the high starch farm crop processing clout in the raw materials of biodegradable composite of the present invention is cheap and easy to get, and therefore cost is lower than existing other biological degradable material; The use of a large amount of farm crop clout is not only increased economic efficiency, and avoids clout and arbitrarily bank up to the destruction of environment.
(3) method preparing biodegradable composite of the present invention utilizes polymer blended, crosslinked, in twin screw extruder high temperature, high pressure environment under, make active function groups and PLA, PBS body generation partial cross-linking of Mierocrystalline cellulose in farm crop clout or hemicellulose components, produce secondary crystal and crystallization reconstruct, prepared material produces the scorching of local, thus obtain over-all properties balance, the material that toughness and tensile strength are all applicable to.
(4) tensile strength of biodegradable composite of the present invention is 30Mpa ~ 50Mpa, and elongation at break is greater than 50%, and the degradation rate of 6 months is greater than 95%.
Embodiment
(embodiment 1)
High starch farm crop processing clout described in the present embodiment is that Ipomoea batatas extracts remaining residue after sweet potato starch through existing technique.The extraction process of the sweet potato starch of current mechanize mainly comprise select materials, clean, pulverize, sieve, remove sand, precipitate, dewater, dry, packaging and other steps; Farm crop processing clout wherein described in the present embodiment obtains in screening step.When sieving, due to the fiber that sweet potato waste is elongated, volume is greater than starch granules, the coefficient of expansion is also greater than starch granules, proportion is lighter than starch granules again, and adding water in the magma obtained after pulverizing, take water as medium, the Starchy pulps contained in sweet potato waste is leached from sieve, and the Ipomoea batatas that is that starch slurry filters above complete sieve processes clout.The main chemical compositions of Ipomoea batatas processing clout is Mierocrystalline cellulose, hemicellulose.
Carry out pre-treatment to the processing clout sweet potato waste obtained after screening, described pre-treatment carries out drying to the sweet potato waste of Xi shape, makes its water ratio lower than 10%.If the particle diameter of the sweet potato waste of the powdery obtained after drying is comparatively large, then further powdery sweet potato waste is pulverized, preferably make its particle diameter be less than 300 μm.The method preparing biodegradable composite with high starch farm crop processing clout of the present embodiment comprises the following steps:
1. will be the poly(lactic acid) (PLA of 20,000 as the molecular weight of reaction mass, CAS NO:51063-13-9), molecular weight is the poly butylene succinate (PBS) of 100,000 ~ 150,000, pretreated powdery farm crop processing clout sweet potato waste and the triallyl isocyanurate (TAIC as linking agent, CAS NO:1025-15-6) at 100 DEG C, carry out vacuum-drying respectively, make the water ratio of each material control each part material temperature lower than 65 DEG C lower than 0.4% respectively.
Take above-mentioned dried poly(lactic acid) 40 parts, poly butylene succinate (PBS) 20 parts, farm crop processing clout powdery sweet potato waste 38 parts and the triallyl isocyanurate 2 parts as linking agent stand-by.
2. polylactic acid PLA step 1. taken drops in agitator kettle, stirs with the rotating speed (for 60rpm in the present embodiment) being greater than 50rpm; Stirring in 10 ~ 15min(the present embodiment is 10min) after, in agitator kettle, drop into the linking agent triallyl isocyanurate that 1. step takes, dried sweet potato waste step 1. taken after stirring 15min and poly butylene succinate add in agitator kettle; Stop stirring after continuing to stir 20min and obtain mixture.
Above-mentioned linking agent triallyl isocyanurate also can be replaced by the trimethylolpropane tris methacrylic acid ester of equal portions or tetramethylolmethane three propylene.
3. the mixture that 2. step obtains is dosed to twin screw extruder, controlling temperature 120 DEG C ~ 160 DEG C in twin screw extruder, is 1.5MPa in pressure 1.2MPa ~ 3MPa(the present embodiment); Mixture obtains granular product through the mixing of screw rod and extruding in twin screw extruder, and this granular product is the biodegradable composite prepared with high starch farm crop processing clout.
The tensile strength of biodegradable composite prepared by the present embodiment is 35Mpa, and elongation at break is greater than 50%, and obtained biodegradable composite can be used for the preparation of plastic uptake technique as the disposable product such as disposable food or beverage container, disposable daily necessities.The biodegradable composite biological degradation rate of 6 months prepared by the present embodiment is 95.5%.
The method preparing biodegradable composite of the present invention utilizes polymer blended, crosslinked, in twin screw extruder high temperature, high pressure environment under, make active function groups and PLA, PBS body generation partial cross-linking of Mierocrystalline cellulose in farm crop clout or hemicellulose components, produce secondary crystal and crystallization reconstruct, prepared material produces the scorching of local, thus obtain over-all properties balance, the material that toughness and tensile strength are all applicable to.
In order to improve the antioxidant property of the biodegradable composite of gained, also in step mixture 2., can add food grade antioxidant further, the add-on of oxidation inhibitor is 0.1% ~ 1% of mixture gross weight.
(embodiment 2)
High starch farm crop processing clout described in the present embodiment is that potato extracts remaining residue after starch through existing technique.Similar to the sweet potato waste in embodiment 1, the farm crop processing clout potato slag of the present embodiment obtains in screening step.When sieving, due to the fiber that potato slag is elongated, volume is greater than starch granules, the coefficient of expansion is also greater than starch granules, proportion is lighter than starch granules again, and adding water in the magma obtained after pulverizing, take water as medium, the Starchy pulps contained in potato slag is leached from sieve, and the potato that is that starch slurry filters above complete sieve processes clout.The main chemical compositions of potato processing clout is Mierocrystalline cellulose, hemicellulose.
Carry out pre-treatment to the processing clout potato slag obtained after screening, described pre-treatment is that Xi shape potato slag is dry, makes its water ratio lower than 10%.If the particle diameter of the potato slag of the powdery obtained after drying is comparatively large, then further powdery potato slag is pulverized, make its particle diameter be less than 300 μm.
The method preparing biodegradable composite with high starch farm crop processing clout of the present embodiment comprises the following steps:
1. will be the poly(lactic acid) (PLA of 40,000 as the molecular weight of reaction mass, CAS NO:51063-13-9), molecular weight is the poly butylene succinate (PBS) of 100,000 ~ 150,000, pretreated farm crop processing clout potato slag and tetramethylolmethane three propylene (PTEA) vacuum-drying at 100 DEG C respectively as linking agent, makes the water ratio of each material control each part material temperature lower than 65 DEG C lower than 0.4% respectively.
Take above-mentioned dried molecular weight be 40,000 polylactic acid PLA 35 parts, poly butylene succinate PBS20 part, farm crop processing clout potato slag 30 parts and linking agent tetramethylolmethane three propylene PETA5 part stand-by.
2. dried polylactic acid PLA step 1. taken drops in agitator kettle, stirs with the rotating speed (for 100rpm in the present embodiment) being greater than 50rpm; Stirring in 10 ~ 15min(the present embodiment is 15min) after, in agitator kettle, drop into dried linking agent tetramethylolmethane three propylene that 1. step takes, dried potato slag step 1. taken after stirring 20min and poly butylene succinate add in agitator kettle; Stop stirring after continuing to stir 20min and obtain mixture.
Above-mentioned linking agent tetramethylolmethane three propylene also can be replaced by the trimethylolpropane tris methacrylic acid ester of equal portions or triallyl isocyanurate.
3. the mixture that 2. step obtains is dosed to twin screw extruder, controlling temperature 120 DEG C ~ 160 DEG C in twin screw extruder, is 2.5MPa in pressure 1.2MPa ~ 3MPa(the present embodiment); Mixture obtains granular product through the mixing of screw rod and extruding in twin screw extruder, and this granular product is the biodegradable composite prepared with high starch farm crop processing clout.
In injector, carry out sample preparation according to the requirement of GB/T17037-1997 with obtained granular product, then carry out tensile property test according to the requirement of GB/T1040-2006 and GB/T2918-1998.
The tensile strength of biodegradable composite prepared by the present embodiment is 40Mpa, and elongation at break is greater than 80%, and obtained material can be used for Shooting Technique and prepares non-durable daily necessities.The biodegradable composite biological degradation rate of 6 months prepared by the present embodiment is 96.5%.
(embodiment 3)
High starch farm crop processing clout described in the present embodiment is that konjaku extracts remaining residue after starch through existing technique.Similar to the sweet potato waste in embodiment 1, the farm crop processing clout konjaku slag of the present embodiment obtains in screening step.When sieving, due to the fiber that konjaku slag is elongated, volume is greater than starch granules, the coefficient of expansion is also greater than starch granules, proportion is lighter than starch granules again, and adding water in the magma obtained after pulverizing, take water as medium, the Starchy pulps contained in konjaku slag is leached from sieve, and clout processed by the konjaku that is that starch slurry filters above complete sieve.The main chemical compositions of konjaku processing clout is Mierocrystalline cellulose, hemicellulose.
Carry out pre-treatment to the processing clout konjaku slag obtained after screening, described pre-treatment is that the konjaku slag of Xi shape is dry, makes its water ratio lower than 10%.If the particle diameter of the konjaku slag of the powdery obtained after drying is comparatively large, then further powdery konjaku slag is pulverized, preferably make its particle diameter be less than 300 μm.
The method preparing biodegradable composite with high starch farm crop processing clout of the present embodiment comprises the following steps:
1. will be the poly(lactic acid) (PLA of 30,000 as the molecular weight of reaction mass, CAS NO:51063-13-9), molecular weight is the poly butylene succinate (PBS) of 100,000 ~ 150,000, pretreated farm crop processing clout konjaku slag and trimethylolpropane tris methacrylic acid ester (TMPA) vacuum-drying at 100 DEG C respectively as linking agent, makes the water ratio of each material control each part material temperature lower than 65 DEG C lower than 0.4% respectively.
Take above-mentioned dried molecular weight be 30,000 polylactic acid PLA 50 parts, poly butylene succinate PBS20 part, farm crop processing clout konjaku slag 27 parts and linking agent trimethylolpropane tris methacrylic acid ester TMPA3 part stand-by.
2. dried polylactic acid PLA step 1. taken drops in agitator kettle, stirs with the rotating speed (for 200rpm in the present embodiment) being greater than 50rpm; Stirring in 10 ~ 15min(the present embodiment is 12min) after, in agitator kettle, drop into the dried linking agent trimethylolpropane tris methacrylic acid ester that 1. step takes, dried konjaku slag step 1. taken after stirring 25min and poly butylene succinate add in agitator kettle; Stop stirring after continuing to stir 20min and obtain mixture.
Above-mentioned linking agent trimethylolpropane tris methacrylic acid ester also can be replaced by tetramethylolmethane three propylene of equal portions or triallyl isocyanurate.
3. the mixture that 2. step obtains is dosed to twin screw extruder, controlling temperature 120 DEG C ~ 160 DEG C in twin screw extruder, is 3MPa in pressure 1.2MPa ~ 3MPa(the present embodiment); Mixture obtains granular product through the mixing of screw rod and extruding in twin screw extruder, and this granular product is the biodegradable composite prepared with high starch farm crop processing clout.
The tensile strength of biodegradable composite prepared by the present embodiment is 36Mpa, and elongation at break is greater than 80%, and obtained material can be used for plastic uptake technique and prepares non-durable daily necessities, office appliance etc.The biodegradable composite biological degradation rate of 6 months prepared by the present embodiment is 96.0%.
(embodiment 4)
The present embodiment prepare the method for biodegradable composite with high starch farm crop processing clout all the other are identical with embodiment 1, difference is: the poly(lactic acid) (PLA that 1. step as the molecular weight of reaction mass will be 20,000, CAS NO:51063-13-9), pretreated powdery farm crop processing clout sweet potato waste and the triallyl isocyanurate (TAIC as linking agent, CAS NO:1025-15-6) at 100 DEG C, carry out vacuum-drying respectively, make the water ratio of each material control each part material temperature lower than 65 DEG C lower than 0.4% respectively.
Take above-mentioned dried poly(lactic acid) 60 parts, farm crop processing clout powdery sweet potato waste 38 parts and the triallyl isocyanurate 2 parts as linking agent stand-by.
Each embodiment is the explanation to the specific embodiment of the present invention above; but not limitation of the present invention; person skilled in the relevant technique without departing from the spirit and scope of the present invention; can also make various conversion and change and obtain corresponding equivalent technical scheme, therefore all equivalent technical schemes all should be included into scope of patent protection of the present invention.
Claims (7)
1. prepare a method for biodegradable composite with high starch farm crop processing clout, it is characterized in that comprising the following steps:
1. carry out vacuum-drying respectively using as the polylactic acid PLA of reaction mass, poly butylene succinate PBS, pretreated farm crop processing clout and linking agent, make each material water ratio control each part material temperature lower than 65 DEG C lower than 0.4% respectively; Described farm crop processing clout refers to that high starch farm crop extract remaining processing clout after starch, and main chemical compositions is Mierocrystalline cellulose and hemicellulose; Take above-mentioned dried polylactic acid PLA 30 ~ 60 parts, poly butylene succinate PBS20 ~ 30 part, farm crop processing clout 10 ~ 40 parts and 1 ~ 8 part of linking agent stand-by; The pre-treatment of described farm crop processing clout carries out drying to the processing clout sieving the Xi shape obtained in starch isolation process, makes its water ratio lower than 10%, pulverize the processing clout obtained after drying, make its particle diameter be less than 300 μm;
2. polylactic acid PLA step 1. taken, poly butylene succinate PBS, farm crop processing clout and linking agent mixing obtain mixture;
3. the mixture that 2. step obtains is dosed to twin screw extruder, control temperature 120 DEG C ~ 160 DEG C in twin screw extruder, pressure 1.2MPa ~ 3 MPa, mixture obtains granular product through the mixing of screw rod and extruding in twin screw extruder, and this granular product is the biodegradable composite prepared with high starch farm crop processing clout.
2. the method preparing biodegradable composite with high starch farm crop processing clout according to claim 1, is characterized in that: described linking agent is tetramethylolmethane three propylene or trimethylolpropane tris methacrylic acid ester or triallyl isocyanurate.
3. the method preparing biodegradable composite with high starch farm crop processing clout according to claim 1, it is characterized in that: the molecular weight of described polylactic acid PLA is 2 ten thousand to 4 ten thousand, the molecular weight of described poly butylene succinate PBS is 10 ten thousand to 15 ten thousand.
4. the method preparing biodegradable composite with high starch farm crop processing clout according to claim 1, is characterized in that: described farm crop processing clout is potato slag, sweet potato waste or konjaku slag.
5. the method preparing biodegradable composite with high starch farm crop processing clout according to claim 1, it is characterized in that: when 2. step mixes reaction mass, first polylactic acid PLA is dropped in agitator kettle, stir with the rotating speed of 50rpm ~ 250 rpm; After stirring 10 ~ 15min, drop into the linking agent that 1. step takes in agitator kettle, farm crop processing clout step 1. taken after stirring 15 ~ 25min and poly butylene succinate add in agitator kettle; Stop stirring after continuing stirring 15 ~ 30min and obtain mixture.
6. the biodegradable matrix material prepared of the method for claim 1.
7. biodegradable composite according to claim 6, is characterized in that: the tensile strength of biodegradable composite is 30MPa ~ 50 MPa, and elongation at break is greater than 50%, and the degradation rate of 6 months is greater than 95%.
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