CN105504704A - Ethanolamine activated Na-montmorillonite and polymer composite biodegradable film blowing resin and preparation method - Google Patents
Ethanolamine activated Na-montmorillonite and polymer composite biodegradable film blowing resin and preparation method Download PDFInfo
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- CN105504704A CN105504704A CN201610013690.3A CN201610013690A CN105504704A CN 105504704 A CN105504704 A CN 105504704A CN 201610013690 A CN201610013690 A CN 201610013690A CN 105504704 A CN105504704 A CN 105504704A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention belongs to the technical field of film blowing resin and particularly relates to ethanolamine activated Na-montmorillonite and polymer composite biodegradable film blowing resin. The resin is prepared from, by weight, 50-80 parts of polyester polymer, 20-50 parts of plant starch, 5-8 parts of ethanolamine activated Na-montmorillonite, 0.5-1 part of a grafting auxiliary, 0.5-1 part of maltitol, 10-25 parts of a reactive assistant and 1-5 parts of a functional assistant. According to the resin, plant starch serves as a raw material and is subjected to gelatinization and starch compound plastification modification, the composite materials are mixed through ethanolamine activated Na-montmorillonite, the lamellar structure of modified montmorillonite is evenly dispersed in the mixture so that the molecular structure of the mixture can be more stable, then the grafting auxiliary is added for grafting of starch and copolymerization of starch and polymer, the molecular structure of starch and polyester in the composite materials is changed, and accordingly the aims of improving tensile strength and tear strength of the composite material, increasing the breaking elongation of the composite material, reducing cost and the like are achieved.
Description
Technical field
The invention belongs to blown film resin technology field, particularly relate to a kind of thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin and preparation method.
Background technology
As everyone knows, present white pollution is constantly destroying the environment that we depend on for existence, and the whole world is being out for the harm that way elimination " white pollution " brings, the underproduction of many good farmlands, desertification, and river blocks, and causes flood.
For this reason, biodegradable blown film resin should be pregnant and give birth to, and biodegradable blown film resin refers to that microorganism that a class exists by nature causes the resin of degraded as the effect of bacterium, mould (fungi) and algae.Desirable biodegradable blown film resin be a kind of there is excellent use properties, discarded after can be decomposed completely by environmental microorganism, finally by inorganization and become the macromolecular material of an integral part of occurring in nature Carbon cycle.
Poly(lactic acid) (PLA), also referred to as polylactide, belongs to polyester family.Poly(lactic acid) is that main raw material is polymerized the polymkeric substance obtained with lactic acid, and raw material sources are abundant and can regenerate.The production process of poly(lactic acid) is pollution-free, and product can biological degradation, and realizing the circulation at occurring in nature, is therefore desirable Green Polymer Material.Have a hydroxyl and a carboxyl in single lactic acid molecules, together ,-COOH the dehydrating condensation of-OH and other molecule ,-OH the dehydrating condensation of-COOH and other molecule, like this, they define polymkeric substance hand in hand to multiple lactic acid molecules.
Poly(lactic acid) (H-[OCHCH
3cO]
n-OH) Heat stability is good, processing temperature 170 ~ 230 DEG C, the good solubility-resistence had, available various ways is processed, as extruding, spinning, biaxial stretch-formed, injection blow molding.Outside the product decapacitation biological degradation of being made up of poly(lactic acid), biocompatibility, glossiness, the transparency, feel and good heat resistance, have good biodegradability, can be degradable by occurring in nature microorganism after using, final generation carbonic acid gas and water, free from environmental pollution.Although its tensile strength is comparatively large, its shock strength is limited.
PBAT belongs to thermoplastic biodegradable's plastics, is the multipolymer of tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester, has the characteristic of PBA and PBT concurrently, and existing good ductility and elongation at break, also have good thermotolerance and impact property; In addition, also having excellent biological degradability, is enliven very much in the research of current biodegradable plastic to apply one of best degradable material with market.PBAT is a kind of semicrystalline polymer, and usual Tc is near 110 DEG C, and fusing point is at about 130 DEG C, and density is between 1.18g/ml ~ 1.3g/ml.The degree of crystallinity of PBAT is probably about 30%, and shore hardness is more than 85.PBAT is aliphatics and aromatic multipolymer, combines the excellent degradation property of aliphatic polyester and the excellent mechanical performances of aromatic polyester.But the tensile strength of PBAT is inadequate.
Because starch belongs to macromolecular compound, can be degradable, also can film forming separately, but matter is crisp, and meet water-solubleization.In order to reach intensity, the toughness of starch plastic, people start to develop a kind of new degradative plastics, namely utilize modified starch to add polyolefins material, as polyethylene, polypropylene, EVA and EAA etc., to reach the use properties of plastics.Owing to including polyolefins material, can not be degradable, add the reason of mechanical means and the problem of production technology, its price is higher than protopetroleum chemical plastic, and current development prospect is also pessimistic.
For this reason, people by adding poly(lactic acid) and poly-hexanodioic acid/butylene terephthalate etc. in starch, the performance of resin can be improved to a certain extent, but, the mechanical property such as tensile property, tear strength, elongation at break of biodegradable blown film resin of the prior art still can not satisfy the demands, and cost is higher.
In view of this, necessaryly a kind of thanomin is provided to activate sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin and preparation method, it can improve the over-all properties such as tensile property, tear strength, elongation at break of matrix material, and can reduce costs.
Summary of the invention
An object of the present invention is: for the deficiencies in the prior art, and provide a kind of thanomin to activate sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin and preparation method, it can improve the over-all properties such as tensile property, tear strength, elongation at break of matrix material, and can reduce costs.
In order to achieve the above object, the present invention adopts following technical scheme:
Thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin, by weight, comprises following component:
Water absorbing properties through the starch/polyester blend material of maltose alcohol plasticizing obviously improves, water-intake rate under relative humidity 95% is only about 30%, and (degraded of biological degradable composite material is mainly pyrolysis and hydrolysis, the water-intake rate of matrix material is low, degradation cycle can extend, the quality guaranteed period of product and the shelf life extension of goods are active influence to the processing of goods and sale).Purity>=98% of maltose alcohol, molecular formula is C
12h
24o
11, relative molecular mass is 344.31.Maltose alcohol is white crystalline powder or water white neutral thick liquid, and soluble in water, be insoluble to methyl alcohol and ethanol, it has superpower water absorbing properties, Chang Zuowei sweetening agent, is the bio-based materials of safety non-toxic; And the interpolation of maltose alcohol can also make the fragrance of matrix material denseer sweeter, in addition, maltose alcohol is viscous liquid, adds more convenient.
The water dispersible of sodium-based montmorillonite is good, the thixotropy of its soliquid, viscosity, oilness and Heat stability is good.Sodium-based montmorillonite is through modified, and interlamellar spacing expands, and makes poly(lactic acid) fusion intercalation easier.Simultaneously, owing to adding thanomin activation sodium-based montmorillonite in poly(lactic acid), compared with traditional lactic acid composite material, the present invention not only can improve the thermotolerance of material, pure poly-lactic acid material intensity can also be overcome low, the defect that toughness is not high, improves its mechanical property, expands the Application Areas of this material.There are a large amount of hydrogen bond and hydroxyethyl in thanomin, use the easier thermoplastic starch of its modification sodium-based montmorillonite, and interact with the hydroxyl in polyester, play the effect of toughener.The distinctive laminated structure of sodium-based montmorillonite after utilizing thanomin to activate can be dispersed in the molecule of plant amylum, and dispersion is more even, thus make the molecular structure of thermoplastic starch (plant amylum after maltose alcohol plasticizing) more stable, utilize the polar interaction between the wetting ability of sodium-based montmorillonite and plant amylum, again can the overall water vapour percent of pass improving thermoplastic starch; Use the nano level polynite blending and modifying of thanomin modification, polynite is in the polymer dispersed with nanoscale, and the interfacial effect produced due to the small-size effect of montmorillonite layer and huge specific surface area and quantum effect, macro quanta tunnel effect etc. give the over-all properties of nano composite material excellence and special function physical property.Thanomin activates sodium-based montmorillonite/polyester composite biodegradable blown film resin except having the performance of general nano material, also because the distinctive laminated structure of polynite makes the thermotolerance of composite biological material, dimensional stability, gas-liquid barrier and flame retardant resistance etc. be improved.
The present invention selects degradable polyester polymers and poly(lactic acid) to carry out compound, while the mechanical property improving material, also there is excellent biological degradability, can be degradable in physical environment, can not produce Soil structure after decomposition and destroy, can effectively solve " white pollution ".
In a word, the present invention take plant amylum as raw material, by to plant amylum gelation, starch compound plasticization and modification, blended to matrix material with thanomin activation polynite, the laminated structure of modified montmorillonoid is utilized to make it in the blend dispersed, make blend molecular structure more stable, add grafting auxiliary agent graft starch and polymkeric substance copolyreaction again, change the molecular structure of starch and polyester in matrix material, thus reach raising matrix material tensile property, tear strength, elongation at break, the object such as to reduce costs.
One as thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin of the present invention is improved, and by weight, comprises following component:
One as thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin of the present invention is improved, described polyester polymers is the mixture of poly-hexanodioic acid/butylene terephthalate and poly(lactic acid), and the mass ratio of the two (9:1) ~ (7:3).
One as thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin of the present invention is improved, and described plant amylum is at least one in tapioca (flour), yam starch, W-Gum, wheat starch, pea flour, husk kind of starch and sweet potato starch.
One as thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin of the present invention is improved, the preparation method of described thanomin activation sodium-based montmorillonite is: thanomin is soluble in water, then sodium-based montmorillonite is added, stirred by homogenizer, at the thermostatic drying chamber inner drying 4 ~ 8h of 100 DEG C ~ 120 DEG C.
One as thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin of the present invention is improved, and described grafting auxiliary agent is at least one in Pyroglutaric acid, Tetra hydro Phthalic anhydride, Succinic anhydried and maleic anhydride.Utilize dibasic acid anhydride class grafting auxiliary agent and starch generation esterification, make starch molecular structure produces active group, to increase the consistency between starch and polymkeric substance, improve the mechanical property of blend.Carboxylate and aliphatic polyester carry out blendedly can also carrying out transesterification reaction further on the twin screw extruder and generating starch-grafted aliphatic polyester copolymer, to improve the consistency of starch and polyester in blend.
One as thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin of the present invention is improved, and the purity of described maltose alcohol is more than or equal to 98%.
One as thanomin of the present invention activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin is improved, and described reactive assistant is at least one in softening agent and coupling agent;
Described softening agent is at least two kinds in glycerol, propylene glycol, water, methane amide, urea, Xylitol and sorbyl alcohol; Softening agent can carry out gel, plasticising process, improve elasticity and thermoplasticity plant amylum, and adding of softening agent can make the toughness of material be significantly improved, and the comprehensive mechanical property of resin significantly promotes, thus can improve the competitive power of resin.
Described coupling agent is at least one in silane based coupling agents, titanate coupling agent and Aluminate coupling agent, carries out active modification, make it have hydrophobicity to the surface of plant amylum and polyester polymers.
One as thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin of the present invention is improved, and described functional aid is at least one in oxidation inhibitor, dispersion moisture agent, slipping agent and toughner;
Described oxidation inhibitor is at least one of antioxidant 1010, irgasfos 168, oxidation inhibitor 619, antioxidant 2246, antioxidant BHT, oxidation inhibitor B215, to increase the aging resistance of matrix material.
Described dispersion moisture agent is at least one in EBS, polyethylene wax, paraffin, EBH, Tegin 55G, stearic acid and Zinic stearas, to improve dispersing property and the wettability of each composition in matrix material;
Described slipping agent is at least one in ethylene bis stearic acid amide, stearylamide, stearic amide, amine hydroxybenzene, erucicamide and meteorological silicon-dioxide, to improve the opening smoothness in material processing;
Described toughner is tributyl citrate, acetylize tributyl citrate, polyethyleneglycol diacrylate, at least one in the toughner with nucleocapsid structure and methyl methacrylate/ethyl acrylate/vinylformic acid/butyl ester and styrene copolymer; the core with the toughner of nucleocapsid structure is Afpol; shell is polymethylmethacrylate; improve with the consistency to matrix material, toughness, to improve the comprehensive tensile property of material.
The one that present invention also offers the preparation method of a kind of thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin is improved, and comprises the following steps:
S1, pours into plant amylum in high mixer, then in high mixer, adds reactive assistant, mixes 3min ~ 15min, carry out gelation process, plasticization and modification to plant amylum at 60 DEG C ~ 70 DEG C;
S2, adds the sodium-based montmorillonite of thanomin activation in high mixer, and continue mixing 1min ~ 15min, rotating speed is set to 2000r/min ~ 2500r/min, and temperature remains on 60 DEG C ~ 70 DEG C;
S3, maltose alcohol is poured in high mixer, mixing 1min ~ 15min, and then polyester polymers is poured in high mixer, then add grafting auxiliary agent and functional aid, and temperature is controlled at 150 DEG C ~ 160 DEG C, time controling is in 10min, then stop mixing, cooling 5min ~ 15min, obtains compound;
S4; compound is poured in dual-screw-stem machine; sectional set temperature; wherein; the temperature of leading portion and back segment is all set to 120 DEG C ~ 130 DEG C; the temperature of interlude is set to 130 DEG C ~ 140 DEG C, then in twin screw strand granulator top brace, pelletizing, oven dry, packaging, produces faint yellow cylindrical particle material.
Relative to prior art, present invention process is simple, it take plant amylum as raw material, by to plant amylum gelation, starch compound plasticization and modification, blended to matrix material with thanomin activation polynite, the laminated structure of modified montmorillonoid is utilized to make it in the blend dispersed, make blend molecular structure more stable, add grafting auxiliary agent graft starch and polymkeric substance copolyreaction again, change the molecular structure of starch and polyester in matrix material, thus reach the tensile property improving matrix material, tear strength, elongation at break, the object such as to reduce costs.
Embodiment
Embodiment 1
A kind of thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin that the present embodiment provides, by weight, comprises following component:
Wherein, polyester polymers is the mixture of poly-hexanodioic acid/butylene terephthalate and poly(lactic acid), and the mass ratio 8:2 of the two.The preparation method of thanomin activation sodium-based montmorillonite is: thanomin is soluble in water, then sodium-based montmorillonite is added, stirred by homogenizer, at the thermostatic drying chamber inner drying 6h of 110 DEG C, reactive assistant is the mixture of glycerol, water and silane based coupling agents, the mass ratio of three is 1:1:2, and functional aid is the mixture of antioxidant 1010 and tributyl citrate, and the mass ratio of the two is 1:1.
Its preparation method comprises the steps:
S1, pours into plant amylum in high mixer, then in high mixer, adds reactive assistant, at 65 DEG C, mix 10min, carries out gelation process, plasticization and modification to plant amylum;
S2, in high mixer, add the sodium-based montmorillonite of dried thanomin activation, continue mixing 3min, rotating speed is set to 2200r/min, and temperature remains on 65 DEG C;
S3, pours maltose alcohol in high mixer, mixing 3min, and then pours polyester polymers in high mixer, add grafting auxiliary agent and functional aid again, and control temperature at 155 DEG C, time controling is in 10min, then stop mixing, cooling 10min, obtains compound;
S4, pours into compound in dual-screw-stem machine, sectional set temperature, and wherein, the temperature distribution of each section is as follows:
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district | 8th district |
| 125℃ | 135℃ | 135℃ | 135℃ | 135℃ | 135℃ | 130℃ | 125℃ |
Wherein, a district and 8th district are respectively leading portion and back segment, and two districts of district to seven are then interlude.Then in twin screw strand granulator top brace, pelletizing, oven dry, packaging, faint yellow cylindrical particle material is produced.
Embodiment 2
A kind of thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin that the present embodiment provides, by weight, comprises following component:
Wherein, polyester polymers is the mixture of poly-hexanodioic acid/butylene terephthalate and poly(lactic acid), and the mass ratio 9:1 of the two.The preparation method of thanomin activation sodium-based montmorillonite is: thanomin is soluble in water, then sodium-based montmorillonite is added, stirred by homogenizer, at the thermostatic drying chamber inner drying 5h of 115 DEG C, reactive assistant is the mixture of propylene glycol, Xylitol and titanate coupling agent, the mass ratio of the two is 2:1:1, and functional aid is the mixture of irgasfos 168, polyethylene wax, stearylamide, and the mass ratio of three is 3:2:1.
Its preparation method comprises the steps:
S1, pours into yam starch in high mixer, then in high mixer, adds reactive assistant, at 60 DEG C, mix 8min, carries out gelation process, plasticization and modification to yam starch;
S2, adds the sodium-based montmorillonite of thanomin activation in high mixer, and continue mixing 8min, rotating speed is set to 2300r/min, and temperature remains on 60 DEG C;
S3, pours maltose alcohol in high mixer, mixing 8min, and then pours polyester polymers in high mixer, add grafting auxiliary agent and functional aid again, and control temperature at 150 DEG C, time controling is in 10min, then stop mixing, cooling 8min, obtains compound;
S4, pours into compound in dual-screw-stem machine, sectional set temperature, and wherein, the temperature of each section is as follows:
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district | 8th district |
| 128℃ | 132℃ | 132℃ | 132℃ | 132℃ | 132℃ | 130℃ | 128℃ |
Then in twin screw strand granulator top brace, pelletizing, oven dry, packaging, faint yellow cylindrical particle material is produced.
Embodiment 3
A kind of thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin that the present embodiment provides, by weight, comprises following component:
Wherein, polyester polymers is the mixture of poly-hexanodioic acid/butylene terephthalate and poly(lactic acid), and the mass ratio 7:3 of the two.The preparation method of thanomin activation sodium-based montmorillonite is: thanomin is soluble in water, then sodium-based montmorillonite is added, stirred by homogenizer, at the thermostatic drying chamber inner drying 7h of 105 DEG C, reactive assistant is Aluminate coupling agent, functional aid is the mixture of antioxidant 2246, paraffin and stearic amide, and the mass ratio of three is 1:2:3.
Its preparation method comprises the steps:
S1, pours into W-Gum in high mixer, then in high mixer, adds reactive assistant, at 70 DEG C, mix 13min, carries out gelation process, plasticization and modification to W-Gum;
S2, adds the sodium-based montmorillonite of thanomin activation in high mixer, and continue mixing 4min, rotating speed is set to 2400r/min, and temperature remains on 70 DEG C;
S3, pours maltose alcohol in high mixer, mixing 4min, and then pours polyester polymers in high mixer, add grafting auxiliary agent and functional aid again, and control temperature at 160 DEG C, time controling is in 10min, then stop mixing, cooling 8min, obtains compound;
S4, pours into compound in dual-screw-stem machine, sectional set temperature, and wherein, the temperature of each section is as follows:
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district | 8th district |
| 126℃ | 134℃ | 134℃ | 134℃ | 134℃ | 134℃ | 131℃ | 126℃ |
Then in twin screw strand granulator top brace, pelletizing, oven dry, packaging, faint yellow cylindrical particle material is produced.
Embodiment 4
A kind of thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin that the present embodiment provides, by weight, comprises following component:
Wherein, polyester polymers is the mixture of poly-hexanodioic acid/butylene terephthalate and poly(lactic acid), and the mass ratio 7.5:2.5 of the two.The preparation method of thanomin activation sodium-based montmorillonite is: the preparation method of thanomin activation sodium-based montmorillonite is: thanomin is soluble in water, then sodium-based montmorillonite is added, stirred by homogenizer, at the thermostatic drying chamber inner drying 5h of 110 DEG C, reactive assistant is the mixture of methane amide and urea, the mass ratio of the two is 1:3, and functional aid is the mixture of EBH, erucicamide and polyethyleneglycol diacrylate, and the mass ratio of three is 2:1:1.
Its preparation method comprises the steps:
S1, pours into wheat starch in high mixer, then in high mixer, adds reactive assistant, at 68 DEG C, mix 11min, carries out gelation process, plasticization and modification to wheat starch;
S2, adds the sodium-based montmorillonite of thanomin activation in high mixer, and continue mixing 7min, rotating speed is set to 2400r/min, and temperature remains on 68 DEG C;
S3, pours maltose alcohol in high mixer, mixing 4min, and then pours polyester polymers in high mixer, add grafting auxiliary agent and functional aid again, and control temperature at 151 DEG C, time controling is in 10min, then stop mixing, cooling 7min, obtains compound;
S4, pours into compound in dual-screw-stem machine, sectional set temperature, and wherein, the temperature of each section is as follows:
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district | 8th district |
| 123℃ | 138℃ | 138℃ | 138℃ | 138℃ | 138℃ | 134℃ | 123℃ |
Then in twin screw strand granulator top brace, pelletizing, oven dry, packaging, faint yellow cylindrical particle material is produced.
Embodiment 5
A kind of thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin that the present embodiment provides, by weight, comprises following component:
Wherein, polyester polymers is the mixture of poly-hexanodioic acid/butylene terephthalate and poly(lactic acid), and the mass ratio 8.5:1.5 of the two.The preparation method of thanomin activation sodium-based montmorillonite is: the preparation method of thanomin activation sodium-based montmorillonite is: thanomin is soluble in water, then sodium-based montmorillonite is added, stirred by homogenizer, at the thermostatic drying chamber inner drying 8h of 100 DEG C, reactive assistant is the mixture of Xylitol and sorbyl alcohol, the mass ratio of the two is 3:1, functional agent is oxidation inhibitor B215, Zinic stearas, meteorological silicon-dioxide and there is the mixture of toughner of nucleocapsid structure, the mass ratio of four is 1:2:1:3, the core with the toughner of nucleocapsid structure is Afpol, shell is polymethylmethacrylate.
Its preparation method comprises the steps:
S1, pours in high mixer by sweet potato starch, then in high mixer, adds reactive assistant, at 62 DEG C, mix 6min, carries out gelation process, plasticization and modification to sweet potato starch;
S2, adds the sodium-based montmorillonite of thanomin activation in high mixer, and continue mixing 4min, rotating speed is set to 2250r/min, and temperature remains on 62 DEG C;
S3, pours maltose alcohol in high mixer, mixing 2min, and then pours polyester polymers in high mixer, add grafting auxiliary agent and functional aid again, and control temperature at 158 DEG C, time controling is in 10min, then stop mixing, cooling 8min, obtains compound;
S4, pours into compound in dual-screw-stem machine, sectional set temperature, wherein,
The temperature of each section is as follows:
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district | 8th district |
| 124℃ | 137℃ | 137℃ | 137℃ | 137℃ | 137℃ | 133℃ | 124℃ |
Then in twin screw strand granulator top brace, pelletizing, oven dry, packaging, faint yellow cylindrical particle material is produced.
By the material landfill of embodiment 1 to 5 in soil, calculate the mass loss after 30 days, 90 days and 150 days, acquired results is as shown in table 1:
Table 1: the mass loss of material landfill in soil after 30 days, 90 days and 150 days of embodiment 1 to 5
As can be seen from Table 1: the present invention has good biological degradability.
The material that embodiment 1 to 5 obtains is added in twin screw inflation film manufacturing machine and carries out blown film machine-shaping, obtain Biodegradable film, belong to the biological plastics of Wholly-degradable, U.S. ASTMD6400 and European Union EN13432JIANGJIE standard can be met, the singe screw length-to-diameter ratio of twin screw inflation film manufacturing machine is 44: 1, is numbered Y1 to Y5 respectively.
The Biodegradable film being numbered Y1 to Y5 is carried out the test of elongation at break and tensile strength according to GB1040-79, its test result is as shown in table 2.
Table 2: the physicals being numbered the Biodegradable film of Y1 to Y5
As shown in Table 2, the present invention has the over-all propertieies such as good tensile property, tear strength, elongation at break, and its raw materials cost adopted is low, therefore, it is possible to reduce costs.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change above-mentioned embodiment and revise.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.In addition, although employ some specific terms in this specification sheets, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin, is characterized in that, by weight, comprise following component:
2. thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin according to claim 1, is characterized in that, by weight, comprise following component:
3. thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin according to claim 1 and 2, it is characterized in that: described polyester polymers is the mixture of poly-hexanodioic acid/butylene terephthalate and poly(lactic acid), and the mass ratio of the two (9:1) ~ (7:3).
4. thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin according to claim 1 and 2, is characterized in that: described plant amylum is at least one in tapioca (flour), yam starch, W-Gum, wheat starch, pea flour, husk kind of starch and sweet potato starch.
5. thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin according to claim 1 and 2, it is characterized in that, the preparation method of described thanomin activation sodium-based montmorillonite is: thanomin is soluble in water, then sodium-based montmorillonite is added, stirred by homogenizer, at the thermostatic drying chamber inner drying 4 ~ 8h of 100 DEG C ~ 120 DEG C.
6. thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin according to claim 1 and 2, is characterized in that: described grafting auxiliary agent is at least one in Pyroglutaric acid, Tetra hydro Phthalic anhydride, Succinic anhydried and maleic anhydride.
7. thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin according to claim 1 and 2, is characterized in that: the purity of described maltose alcohol is more than or equal to 98%.
8. thanomin according to claim 1 and 2 activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin, is characterized in that: described reactive assistant is at least one in softening agent and coupling agent;
Described softening agent is at least two kinds in glycerol, propylene glycol, water, methane amide, urea, Xylitol and sorbyl alcohol;
Described coupling agent is at least one in silane based coupling agents, titanate coupling agent and Aluminate coupling agent.
9. thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin according to claim 1 and 2, is characterized in that: described functional aid is at least one in oxidation inhibitor, dispersion moisture agent, slipping agent and toughner;
Described oxidation inhibitor is at least one of antioxidant 1010, irgasfos 168, oxidation inhibitor 619, antioxidant 2246, antioxidant BHT, oxidation inhibitor B215;
Described dispersion moisture agent is at least one in EBS, polyethylene wax, paraffin, EBH, Tegin 55G, stearic acid and Zinic stearas;
Described slipping agent is at least one in ethylene bis stearic acid amide, stearylamide, stearic amide, amine hydroxybenzene, erucicamide and meteorological silicon-dioxide;
Described toughner is tributyl citrate, acetylize tributyl citrate, polyethyleneglycol diacrylate, at least one in the toughner with nucleocapsid structure and methyl methacrylate/ethyl acrylate/vinylformic acid/butyl ester and styrene copolymer; the core with the toughner of nucleocapsid structure is Afpol, and shell is polymethylmethacrylate.
10. a preparation method for thanomin activation sodium-based montmorillonite/polymkeric substance composite biodegradable blown film resin according to claim 1, is characterized in that, comprise the following steps:
S1, pours into plant amylum in high mixer, then in high mixer, adds reactive assistant, mixes 3min ~ 15min, carry out gelation process, plasticization and modification to plant amylum at 60 DEG C ~ 70 DEG C;
S2, adds the sodium-based montmorillonite of thanomin activation in high mixer, and continue mixing 1min ~ 15min, rotating speed is set to 2000r/min ~ 2500r/min, and temperature remains on 60 DEG C ~ 70 DEG C;
S3, maltose alcohol is poured in high mixer, mixing 1min ~ 15min, and then polyester polymers is poured in high mixer, then add grafting auxiliary agent and functional aid, and temperature is controlled at 150 DEG C ~ 160 DEG C, time controling is in 10min, then stop mixing, cooling 5min ~ 15min, obtains compound;
S4; compound is poured in dual-screw-stem machine; sectional set temperature; wherein; the temperature of leading portion and back segment is all set to 120 DEG C ~ 130 DEG C; the temperature of interlude is set to 130 DEG C ~ 140 DEG C, then in twin screw strand granulator top brace, pelletizing, oven dry, packaging, produces faint yellow cylindrical particle material.
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| CN111500029A (en) * | 2020-05-08 | 2020-08-07 | 深圳国至新材料科技有限公司 | Bio-based degradable knife and fork material and preparation method thereof |
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