CN103265731B - Degradable thermoplastic starch material and preparation method thereof - Google Patents
Degradable thermoplastic starch material and preparation method thereof Download PDFInfo
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- CN103265731B CN103265731B CN201310219775.3A CN201310219775A CN103265731B CN 103265731 B CN103265731 B CN 103265731B CN 201310219775 A CN201310219775 A CN 201310219775A CN 103265731 B CN103265731 B CN 103265731B
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 229920008262 Thermoplastic starch Polymers 0.000 title claims abstract description 46
- 239000004628 starch-based polymer Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920002472 Starch Polymers 0.000 claims abstract description 50
- 239000004902 Softening Agent Substances 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 235000019698 starch Nutrition 0.000 claims abstract description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 38
- -1 methane amide Chemical class 0.000 claims abstract description 32
- 238000001125 extrusion Methods 0.000 claims abstract description 26
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims abstract description 22
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims abstract description 22
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 19
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims abstract description 17
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000008116 calcium stearate Substances 0.000 claims abstract description 17
- 235000013539 calcium stearate Nutrition 0.000 claims abstract description 17
- 239000001069 triethyl citrate Substances 0.000 claims abstract description 17
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000013769 triethyl citrate Nutrition 0.000 claims abstract description 17
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims abstract description 16
- 239000004593 Epoxy Substances 0.000 claims abstract description 16
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 16
- 239000003549 soybean oil Substances 0.000 claims abstract description 16
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 15
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 15
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 15
- 238000005453 pelletization Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 235000013312 flour Nutrition 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 240000003183 Manihot esculenta Species 0.000 claims description 11
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229940100445 wheat starch Drugs 0.000 claims description 10
- 244000017020 Ipomoea batatas Species 0.000 claims description 5
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 5
- 239000003063 flame retardant Substances 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 229920001592 potato starch Polymers 0.000 claims description 5
- ASFAFOSQXBRFMV-LJQANCHMSA-N 3-n-(2-benzyl-1,3-dihydroxypropan-2-yl)-1-n-[(1r)-1-(4-fluorophenyl)ethyl]-5-[methyl(methylsulfonyl)amino]benzene-1,3-dicarboxamide Chemical compound N([C@H](C)C=1C=CC(F)=CC=1)C(=O)C(C=1)=CC(N(C)S(C)(=O)=O)=CC=1C(=O)NC(CO)(CO)CC1=CC=CC=C1 ASFAFOSQXBRFMV-LJQANCHMSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 239000004033 plastic Substances 0.000 abstract description 13
- 229920003023 plastic Polymers 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003921 oil Substances 0.000 abstract description 5
- 235000019198 oils Nutrition 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- AHJKRLASYNVKDZ-UHFFFAOYSA-N DDD Chemical compound C=1C=C(Cl)C=CC=1C(C(Cl)Cl)C1=CC=C(Cl)C=C1 AHJKRLASYNVKDZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 239000008107 starch Substances 0.000 description 9
- 229920002261 Corn starch Polymers 0.000 description 6
- 239000008120 corn starch Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000006378 damage Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000012611 container material Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000003625 amylolytic effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 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
- B29C48/397—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 a single screw
-
- 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
- B29C2948/9258—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
- B29C2948/92819—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of Degradable thermoplastic starch material and preparation method thereof, it is also a kind of plastics equivalent material be easily biodegradable, its composition mainly comprises food-grade starches, epoxy soybean oil, sorbyl alcohol, mono-glycerides, methane amide and 0.2% aqueous sodium polyacrylate, also can add talcum powder, calcium stearate, triethyl citrate, TDE, ammonium polyphosphate according to actual needs, by these components and relevant softening agent according to being uniformly mixed, the order such as high temperature extrusion and pelletizing oven dry can obtain final finished.Degradable thermoplastic starch material provided by the present invention and preparation method, its relative other materials and preparation method, also there is the advantages such as material source is extensive, the mode of production is easy, not only reduce production cost, improve quality product, also reduce the consumption of the Nonrenewable energy resources such as oil, decrease environmental pollution, therefore the Material Fields such as disposable packaging, toy for children, electronic equipments, agricultural cultivation production apparatus can be widely used in.
Description
Technical field
The present invention relates to a kind of degredation plastic equivalent material, specifically refer to Degradable thermoplastic starch material and preparation method thereof.
Background technology
Along with Chinese society develops economically, improve constantly to people's living standard, can seedbed demand more and more rely on, particularly to this kind of Nonrenewable energy resources of oil various.Plastics known by us are exactly the direct product of petrochemical industry, and the various products be made of plastics, while bringing convenience to our Economic development, are but affecting our life to the destruction of environment.Therefore, we are in the urgent need to a kind of type material that can replace plastics, both in order to reduce the consumption of this kind of Nonrenewable energy resources of oil, also in order to stop plastic tape to our " white pollution ".At present, also many research is had both at home and abroad for various degradation material, as " a kind of degradable buffering composite material for packaging and preparation method thereof " that disclosed China Patent No. is 201110202137.1, a kind of material be made up of thermoplastic starch, high-density polyethylene resin and some additives etc. is just related in this patent, this material possesses the advantages such as good springiness, intensity is high, shock-absorbing capacity is good, can for the manufacture of buffer pad, tr liner and disposable lunch box etc.Although the thermoplastic starch wherein related to has degradation property, but, after being added into high-density polyethylene resin, still can bring certain obstruction to material degradation, and high-density polyethylene resin needs dependence petroleum-based energy to produce too, this can cause the consumption of Nonrenewable energy resources.Along with constantly the increasing of various consumer goods markets taking plastics as raw material, human consumer also urgently wishes that manufacturer releases that more multimass is stablized, easily processed, cheap easy degradable material, so that replace these plastic materials not easily decomposing and consume Nonrenewable energy resources gradually, jointly safeguard our living environment.
Summary of the invention
The object of the present invention is to provide a kind of steady quality, process Degradable thermoplastic starch material that personality energy is good, cheap, biodegradability is excellent and preparation method thereof, this thermoplastic starch material can replace traditional plastic material, both decrease energy consumption, alleviate environmental pollution again.
Goal of the invention of the present invention is realized by following technical proposal:
A kind of Degradable thermoplastic starch material, its composition mainly comprises food-grade starches, epoxy soybean oil, sorbyl alcohol, mono-glycerides, methane amide and 0.2% aqueous sodium polyacrylate, and the weight part of each component is:
Food-grade starches 36 ~ 85 parts
Epoxy soybean oil 1 ~ 13 part
Sorbyl alcohol 1 ~ 5 part
Mono-glycerides 1 ~ 4 part
Methane amide 4 ~ 12 parts
0.2% aqueous sodium polyacrylate 5 ~ 26 parts.
Described Degradable thermoplastic starch material also adds the one in two or three component in talcum powder 0 ~ 22 part, calcium stearate 0 ~ 17 part, these three kinds of components of triethyl citrate 0 ~ 4 part three kinds or three kinds of components; Described talcum powder fineness is 800 ~ 1200 orders.
Described Degradable thermoplastic starch material also adds TDE 0 ~ 5 part or ammonium polyphosphate 0 ~ 8 part.
Described food-grade starches is one or more in W-Gum, tapioca (flour), yam starch, wheat starch, sweet potato starch, sticky rice flour.
Sodium polyacrylate molecular weight in 0.2% described aqueous sodium polyacrylate is 3000 ~ 5,000 ten thousand.
A preparation method for Degradable thermoplastic starch material, it comprises the steps:
A, 0.2% aqueous sodium polyacrylate and sorbyl alcohol are poured in reactor, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, be positioned over after mixing in container as softening agent I;
B, epoxy soybean oil and mono-glycerides are poured in reactor, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, be positioned over after mixing in container as softening agent II;
C, food-grade starches and methane amide are poured in mixing machine, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, methane amide is made fully to enter into food-grade starches intramolecule, add softening agent I and softening agent II again, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 500 ~ 1200 revs/min, obtain mixture, this mixture keeps 1 hour at normal temperatures;
D, the mixture that step c obtains is added in single screw extrusion machine and carries out extruding reaction, the extrusion temperature of this mixture from the opening for feed of single screw extrusion machine to discharge port controls at 45 DEG C ~ 85 DEG C, screw speed is 120 ~ 280 revs/min, extrusion pressure is 60 ~ 110bar, and the thermoplastic starch material after discharge port obtains extruding reaction, this thermoplastic starch material carries out pelletizing after cooling, and obtain thermoplastic starch material particle, particle diameter is 1 ~ 10mm;
E, by steps d obtain thermoplastic starch material particle put into thermostatic drying chamber, drying temperature is 80 DEG C ~ 110 DEG C, and being dried to water content according to different demand is 6 ~ 22%, then packs after sifting sort.
Described step c comprises and pours in mixing machine by food-grade starches and methane amide, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, methane amide is made fully to enter into food-grade starches intramolecule, add softening agent I, softening agent II more successively, and talcum powder, calcium stearate, one in two or three component in these three kinds of components of triethyl citrate three kinds or three kinds of components, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 500 ~ 1200 revs/min, obtain mixture, this mixture keeps 1 hour at normal temperatures.
Described step c comprises and pours in mixing machine by food-grade starches and methane amide, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, methane amide is made fully to enter into food-grade starches intramolecule, add softening agent I, softening agent II more successively, and TDE or ammonium polyphosphate, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 500 ~ 1200 revs/min, obtain mixture, this mixture keeps 1 hour at normal temperatures.
Described talcum powder or calcium stearate or triethyl citrate are as lubricant.
Described step c comprises and pours in mixing machine by food-grade starches and methane amide, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, methane amide is made fully to enter into food-grade starches intramolecule, add softening agent I successively again, softening agent II, TDE or ammonium polyphosphate, and talcum powder, calcium stearate, one in two or three component in three kinds in these three kinds of components of triethyl citrate or three kinds of components, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 500 ~ 1200 revs/min, obtain mixture, this mixture keeps 1 hour at normal temperatures.
Described talcum powder or calcium stearate or triethyl citrate are as lubricant; Described TDE or ammonium polyphosphate are as fire retardant.
Difference of the present invention is, with the comparatively cheap food-grade starches of price for major ingredient, adds the softening agent of the environmental protection that is easily degraded and produces the thermoplastic starch material that can be degraded completely.Utilize the characteristic of the water-in-oil type emulsifier of mono-glycerides, when starch hydrogen bond rupture after high temperature gelatinization, methane amide is made to be easy to enter starch molecule inside, and then form more stable hydrogen bond, free water molecules is out encased by mono-glycerides, define hydrophobic layer, thus make this thermoplastic starch material have better water tolerance, add the effect of other softening agent to starch molecular structure, product is possessed, and quality is more stable, processing personality can be good, the advantages such as biodegradability is excellent, greatly reduce the consumption of this kind of Nonrenewable energy resources of oil, also the impact on environment after lightening material degraded, also expanded in Application Areas, can be used for the non-returnable container of food, toy for children, electronic equipments, agricultural cultivation produces the Material Fields such as apparatus.
Embodiment
Degradable thermoplastic starch material composition mainly comprises food-grade starches, epoxy soybean oil, sorbyl alcohol, mono-glycerides, methane amide and 0.2% aqueous sodium polyacrylate, and the weight part of each component is:
Food-grade starches 36 ~ 85 parts
Epoxy soybean oil 1 ~ 13 part
Sorbyl alcohol 1 ~ 5 part
Mono-glycerides 1 ~ 4 part
Methane amide 4 ~ 12 parts
0.2% aqueous sodium polyacrylate 5 ~ 26 parts.
Wherein, food-grade starches mainly adopts one or more in W-Gum, tapioca (flour), yam starch, wheat starch, sweet potato starch, sticky rice flour.And the sodium polyacrylate molecular weight in 0.2% aqueous sodium polyacrylate is 3000 ~ 5,000 ten thousand.
Meanwhile, what also can add in wherein two or three component in these three kinds of components of talcum powder, calcium stearate and triethyl citrate three kinds or three kinds of components in above-mentioned Degradable thermoplastic starch material is wherein a kind of, using as lubricant.The weight part of three kinds of components is respectively:
Talcum powder 0 ~ 22 part
Calcium stearate 0 ~ 17 part
Triethyl citrate 0 ~ 4 part.
Described talcum powder fineness is 800 ~ 1200 orders.
Also TDE or ammonium polyphosphate can be added, using as fire retardant in above-mentioned Degradable thermoplastic starch material.The weight part of two kinds of components is respectively:
TDE 0 ~ 5 part
Ammonium polyphosphate 0 ~ 8 part.
The preparation method of described Degradable thermoplastic starch material mainly comprises the steps:
A, 0.2% aqueous sodium polyacrylate and sorbyl alcohol are poured in reactor, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, be positioned over after mixing in container as softening agent I;
B, epoxy soybean oil and mono-glycerides are poured in reactor, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, be positioned over after mixing in container as softening agent II;
C, food-grade starches and methane amide are poured in mixing machine, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, make methane amide fully enter into food-grade starches intramolecule, then add softening agent I and softening agent II.Meanwhile, also can add the one in two or three component in talcum powder, calcium stearate, these three kinds of components of triethyl citrate three kinds or three kinds of components again, use mainly as lubricant; Or also can add TDE or ammonium polyphosphate, use mainly as fire retardant.Carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 500 ~ 1200 revs/min after said components adds, obtain mixture, this mixture keeps 1 hour at normal temperatures;
D, the mixture that step c obtains is added in single screw extrusion machine and carries out extruding reaction, the extrusion temperature of this mixture from the opening for feed of single screw extrusion machine to discharge port controls at 45 DEG C ~ 85 DEG C, screw speed is 120 ~ 280 revs/min, extrusion pressure is 60 ~ 110bar, and the thermoplastic starch material after discharge port obtains extruding reaction, this thermoplastic starch material carries out pelletizing after cooling, and obtain thermoplastic starch material particle, particle diameter is 1 ~ 10mm;
E, by steps d obtain thermoplastic starch material particle put into thermostatic drying chamber, drying temperature is 80 DEG C ~ 110 DEG C, and being dried to water content according to different demand is 6 ~ 22%, then packs respectively after sifting sort.
Below by for a more detailed description to the present invention for employing three specific embodiments.
Embodiment 1
First, weigh food-grade corn starch 57kg according to weight part, epoxy soybean oil 2kg, sorbyl alcohol 1kg, mono-glycerides 2kg, methane amide 6kg, 0.2% aqueous sodium polyacrylate 10kg, calcium stearate 8kg, triethyl citrate 1kg.
First 0.2% aqueous sodium polyacrylate 10kg and sorbyl alcohol 1kg is poured in reactor, be 300 revs/min with rotating speed and carry out being uniformly mixed 5 minutes, be positioned in container after mixing, for subsequent use as softening agent I.
Again epoxy soybean oil 2kg and mono-glycerides 4kg is poured in reactor, with rotating speed be 200 revs/min carry out being uniformly mixed 5 minutes after be positioned in container, for subsequent use as softening agent II.
Then, W-Gum 57kg and methane amide 6kg is poured in mixing machine, carry out being uniformly mixed 10 minutes with rotating speed 800 revs/min, make methane amide fully enter into corn starch molecules inside.
Then, add softening agent I, softening agent II, calcium stearate 8kg and triethyl citrate 1kg successively, carry out being uniformly mixed 5 minutes obtain mixture with rotating speed 600 revs/min, this mixture leaves standstill maintenance 1 hour at normal temperatures.
Again then, the said mixture leaving standstill 1 hour is added single screw extrusion machine and carry out extruding reaction.The extrusion temperature of mixture from the opening for feed of single screw extrusion machine to discharge port is respectively 50 DEG C-60 DEG C-70 DEG C, screw speed is at 220 revs/min, and extrusion pressure is 60bar, and the material be extruded is the strip-shaped materials of diameter 3mm, by this strip-shaped materials after air-cooled, cut the particle of growing into 4mm.
Finally, this particle is put into thermostatic drying chamber and carries out drying with 110 DEG C, obtain the thermoplasticity W-Gum material product of water content 13 ~ 15%.Pack after sifting sort.
In above-described embodiment 1, strip-shaped materials after extruding reaction, due to not through high-temperature fusion, this makes the hydrogen bond between corn starch molecules not be changed, but the hydrogen bond between corn starch molecules is affected due to the effect of softening agent I and softening agent II.Simultaneously, after increasing temperature outside this thermoplasticity W-Gum material is subject to or extruding, hydrogen bond between corn starch molecules is weakened and destruction at once, obtain the product of alternative plastics, directly again be injection molded into various product by injection moulding machine, corn starch molecules after shaping is more stable, can be widely used in non-returnable container material, tableware, toy for children etc.
Embodiment 2
First, weigh food grade tapioca (flour) 65kg according to weight part, epoxy soybean oil 3kg, sorbyl alcohol 2kg, mono-glycerides 3kg, methane amide 10kg, 0.2% aqueous sodium polyacrylate 16kg, TDE 1kg, triethyl citrate 1kg.
First 0.2% aqueous sodium polyacrylate 16kg and sorbyl alcohol 2kg is poured in reactor, be 300 revs/min with rotating speed and carry out being uniformly mixed 5 minutes, be positioned in container after mixing, for subsequent use as softening agent I.
Again epoxy soybean oil 3kg and mono-glycerides 3kg is poured in reactor, with rotating speed be 220 revs/min carry out being uniformly mixed 5 minutes after be positioned in container, for subsequent use as softening agent II.
Then, tapioca (flour) 65kg and methane amide 10kg is poured in mixing machine, carry out being uniformly mixed 10 minutes with rotating speed 800 revs/min, make methane amide fully enter into tapioca (flour) intramolecule.
Then, add softening agent I, softening agent II, TDE 1kg and triethyl citrate 1kg successively, carry out being uniformly mixed 5 minutes obtain mixture with rotating speed 500 revs/min, this mixture leaves standstill maintenance 1 hour at normal temperatures.
Again then, the said mixture leaving standstill 1 hour is added single screw extrusion machine and carry out extruding reaction.The extrusion temperature of mixture from the opening for feed of single screw extrusion machine to discharge port is respectively 60 DEG C-70 DEG C-80 DEG C, screw speed is at 200 revs/min, and extrusion pressure is 50bar, and the material be extruded is the strip-shaped materials of diameter 3mm, by this strip-shaped materials after air-cooled, cut the particle of growing into 4mm.
Finally, this particle is put into thermostatic drying chamber and carries out drying with 110 DEG C, obtain the thermoplastic wood sweet potato starch material product of water content 15 ~ 17%.Pack after sifting sort.
In above-described embodiment 2, strip-shaped materials after extruding reaction, due to not through high-temperature fusion, it is less that this makes the hydrogen bond between tapioca (flour) molecule change, tapioca (flour) is under the effect of softening agent I and softening agent II, and the characteristic of tapioca (flour) molecule is changed.Simultaneously, after increasing temperature outside this thermoplastic wood sweet potato starch material is subject to or extruding, hydrogen bond between tapioca (flour) molecule is weakened and destruction at once, obtain the product of alternative plastics, directly again be injection molded into various product by injection moulding machine, tapioca (flour) molecule after shaping is more stable, can be widely used in non-returnable container material, toy for children, decorative building material etc.
Embodiment 3
First, weigh food grade wheat starch 60kg according to weight part, epoxy soybean oil 3kg, sorbyl alcohol 2kg, mono-glycerides 4kg, methane amide 8kg, 0.2% aqueous sodium polyacrylate 16kg, ammonium polyphosphate 3kg, talcum powder 14kg, calcium stearate 10kg.
First 0.2% aqueous sodium polyacrylate 16kg and sorbyl alcohol 2kg is poured in reactor, be 300 revs/min with rotating speed and carry out being uniformly mixed 5 minutes, be positioned in container after mixing, for subsequent use as softening agent I.
Again epoxy soybean oil 3kg and mono-glycerides 4kg is poured in reactor, with rotating speed be 200 revs/min carry out being uniformly mixed 5 minutes after be positioned in container, for subsequent use as softening agent II.
Then, wheat starch 60kg and methane amide 8kg is poured in mixing machine, carry out being uniformly mixed 10 minutes with rotating speed 800 revs/min, make methane amide fully enter into wheat starch intramolecule.
Then, add softening agent I, softening agent II, ammonium polyphosphate 3kg successively, talcum powder 14kg and calcium stearate 10kg, carry out being uniformly mixed 5 minutes obtain mixture with rotating speed 500 revs/min, this mixture leaves standstill maintenance 1 hour at normal temperatures.
Again then, the said mixture leaving standstill 1 hour is added single screw extrusion machine and carry out extruding reaction.The extrusion temperature of mixture from the opening for feed of single screw extrusion machine to discharge port is respectively 50 DEG C-60 DEG C-70 DEG C, screw speed is at 180 revs/min, and extrusion pressure is 80bar, and the material be extruded is the strip-shaped materials of diameter 4mm, by this strip-shaped materials after air-cooled, cut the particle of growing into 5mm.
Finally, this particle is put into thermostatic drying chamber and carries out drying with 110 DEG C, obtain the thermoplasticity wheat starch material product of water content 12 ~ 15%.Pack after sifting sort.
In above-described embodiment 3, strip-shaped materials after extruding reaction, due to not through high-temperature fusion, this makes the hydrogen bond between wheat starch molecule not be changed, but the hydrogen bond between wheat starch molecule is affected due to the effect of softening agent I and softening agent II.Meanwhile, with the addition of ammonium polyphosphate and talcum powder in this thermoplasticity wheat starch material, make this material have certain flame retardant effect, electronic equipments, toy for children, Industrial materials etc. can be widely used in.
The present invention is mainly based on the requirement to recyclability and biodegradability, take food-grade starches as main raw material, with water and various softening agent for carrier, through a series of production processes such as mixing, extrusion reaction and oven dry, therefore the hydrogen bond action that can change the starch molecular structure a large amount of hydroxyl in surface and produce, thus obtain the thermoplastic starch material being similar to plastics.
Food-grade starches selected by the present invention is also a kind of abundance, the renewable cycle is short, under the effect of microorganism, be easy to the environment-friendly materials that are degraded.Because starch is polyol, be easy to form a large amount of intermolecular, intramolecular hydrogen bond, the equilibrium water raised in starch granules along with temperature will lose, and makes amylolysis.Therefore, need to add and can keep balancing with starch molecule and form the softening agent of hydrogen bond, thus change starch molecular structure, the obtained thermoplastic starch material that can replace plastics.And recrystallization phenomenon can be there is in view of starch molecule, avoid high temperature on amylolytic impact, the present invention finally extrudes mixture extruding reaction and material and adopts temperature between 45 DEG C-85 DEG C.The product processed eventually through injection moulding machine is more stable, and this materials application is more extensive.
Claims (10)
1. a Degradable thermoplastic starch material, it is characterized in that this Degradable thermoplastic starch material composition mainly comprises food-grade starches, epoxy soybean oil, sorbyl alcohol, mono-glycerides, methane amide and 0.2% aqueous sodium polyacrylate, the weight part of each component is:
Food-grade starches 36 ~ 85 parts
Epoxy soybean oil 1 ~ 13 part
Sorbyl alcohol 1 ~ 5 part
Mono-glycerides 1 ~ 4 part
Methane amide 4 ~ 12 parts
0.2% aqueous sodium polyacrylate 5 ~ 26 parts.
2. Degradable thermoplastic starch material according to claim 1, is characterized in that the one in two or three component that described Degradable thermoplastic starch material also adds in talcum powder 0 ~ 22 part, calcium stearate 0 ~ 17 part, these three kinds of components of triethyl citrate 0 ~ 4 part three kinds or three kinds of components; Described talcum powder fineness is 800 ~ 1200 orders.
3. Degradable thermoplastic starch material according to claim 1, is characterized in that described Degradable thermoplastic starch material also adds TDE 0 ~ 5 part or ammonium polyphosphate 0 ~ 8 part.
4. Degradable thermoplastic starch material according to claim 1, is characterized in that described food-grade starches is one or more in W-Gum, tapioca (flour), yam starch, wheat starch, sweet potato starch.
5. Degradable thermoplastic starch material according to claim 1, is characterized in that the sodium polyacrylate molecular weight in 0.2% described aqueous sodium polyacrylate is 3000 ~ 5,000 ten thousand.
6. a preparation method for Degradable thermoplastic starch material according to claim 1, is characterized in that the method comprises the steps:
A, 0.2% aqueous sodium polyacrylate and sorbyl alcohol are poured in reactor, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, be positioned over after mixing in container as softening agent I;
B, epoxy soybean oil and mono-glycerides are poured in reactor, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, be positioned over after mixing in container as softening agent II;
C, food-grade starches and methane amide are poured in mixing machine, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, methane amide is made fully to enter into food-grade starches intramolecule, add softening agent I and softening agent II again, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 500 ~ 1200 revs/min, obtain mixture, this mixture keeps 1 hour at normal temperatures;
D, the mixture that step c obtains is added in single screw extrusion machine and carries out extruding reaction, the extrusion temperature of this mixture from the opening for feed of single screw extrusion machine to discharge port controls at 45 DEG C ~ 85 DEG C, screw speed is 120 ~ 280 revs/min, extrusion pressure is 60 ~ 110bar, and the thermoplastic starch material after discharge port obtains extruding reaction, this thermoplastic starch material carries out pelletizing after cooling, and obtain thermoplastic starch material particle, particle diameter is 1 ~ 10mm;
E, by steps d obtain thermoplastic starch material particle put into thermostatic drying chamber, drying temperature is 80 DEG C ~ 110 DEG C, and being dried to water content according to different demand is 6 ~ 22%, then packs after sifting sort.
7. the preparation method of Degradable thermoplastic starch material according to claim 6, it is characterized in that described step c comprises pours in mixing machine by food-grade starches and methane amide, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, methane amide is made fully to enter into food-grade starches intramolecule, add softening agent I successively again, softening agent II, and talcum powder, calcium stearate, one in two or three component in three kinds in these three kinds of components of triethyl citrate or three kinds of components, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 500 ~ 1200 revs/min, obtain mixture, this mixture keeps 1 hour at normal temperatures.
8. the preparation method of Degradable thermoplastic starch material according to claim 6, it is characterized in that described step c comprises pours in mixing machine by food-grade starches and methane amide, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, methane amide is made fully to enter into food-grade starches intramolecule, add softening agent I, softening agent II more successively, and TDE or ammonium polyphosphate, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 500 ~ 1200 revs/min, obtain mixture, this mixture keeps 1 hour at normal temperatures.
9. the preparation method of Degradable thermoplastic starch material according to claim 6, it is characterized in that described step c comprises pours in mixing machine by food-grade starches and methane amide, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 200 ~ 1000 revs/min, methane amide is made fully to enter into food-grade starches intramolecule, add softening agent I successively again, softening agent II, TDE or ammonium polyphosphate, and talcum powder, calcium stearate, one in two or three component in three kinds in these three kinds of components of triethyl citrate or three kinds of components, carry out being uniformly mixed 5 ~ 10 minutes with rotating speed 500 ~ 1200 revs/min, obtain mixture, this mixture keeps 1 hour at normal temperatures.
10. the preparation method of Degradable thermoplastic starch material according to claim 9, is characterized in that described talcum powder or calcium stearate or triethyl citrate are as lubricant; Described TDE or ammonium polyphosphate are as fire retardant.
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| CN108424549B (en) * | 2018-03-31 | 2021-05-04 | 苏州汉丰新材料股份有限公司 | Heat-resistant fully-degradable thermoplastic starch and preparation method and application thereof |
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