CN105504363A - Starch and plant fiber composite biodegradable polyester film-blowing grade resin and preparation method - Google Patents
Starch and plant fiber composite biodegradable polyester film-blowing grade resin and preparation method Download PDFInfo
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- CN105504363A CN105504363A CN201610013716.4A CN201610013716A CN105504363A CN 105504363 A CN105504363 A CN 105504363A CN 201610013716 A CN201610013716 A CN 201610013716A CN 105504363 A CN105504363 A CN 105504363A
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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
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/06—Esters
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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 starch and plant fiber composite biodegradable polyester film-blowing grade resin. The starch and plant fiber composite biodegradable polyester film-blowing grade resin is prepared from, by weight, 20-60 parts of aliphatic polyester, 30-60 parts of plant starch, 5-10 parts of natural polymer plant fiber, 0.5-1 part of polyester crystallization auxiliary, 0.2-0.5 part of esterification reaction auxiliary, 10-30 parts of reaction auxiliaries and 1-5 parts of functional auxiliaries. According to the starch and plant fiber composite biodegradable polyester film-blowing grade resin, esterification treatment is conducted on the plant starch and the natural polymer plant fiber through the esterification reaction auxiliary, a transesterification reaction is further conducted through esters and aliphatic polyester in the blending extrusion process, starch graft aliphatic polyester copolymer is generated, and therefore the compatibility between the starch and the aliphatic polyester in a blend is improved.
Description
Technical field
The invention belongs to blown film resin technology field, particularly relate to a kind of starch/vegetable fibre composite biodegradable polyester blown film grade resins and preparation method of low cost.
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, consistency between starch and aliphatic polyester is poor, thus the over-all properties of material can be affected, as tensile property, tear strength, elongation at break etc.
In addition, the cost of Biodegradable polyester blown film grade resins of the prior art is higher, can not meet the demand in market.
In view of this, necessary starch/vegetable fibre composite biodegradable polyester blown film grade resins and the preparation method that a kind of low cost is provided, 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 a kind of starch/vegetable fibre composite biodegradable polyester blown film grade resins and preparation method of low cost are provided, 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:
Starch/vegetable fibre composite biodegradable polyester blown film grade resins, by weight, comprises following component:
Wherein, aliphatic polyester can improve the very sexual function of matrix material, and this composite material toughness is very good, very property increases simultaneously, after can solving current shopping bag for supermarket extract product, long distance puies forward the problems such as fortune easily causes sack and article drawing is oversize, and the cost of material declines to some extent simultaneously;
By the plasticising process to plant amylum, the thermoplastic starch addition after plasticising can improve, and because starch cost is low, therefore makes matrix material cost decline 3% ~ 10%, makes material have more market competition advantage;
Adding of natural polymer vegetable fibre makes the mechanical property of matrix material greatly improve, and only adds the natural polymer vegetable fibre of 5%, the Young's modulus of matrix material and tensile strength just can be made to improve 24% and 16% respectively;
Adding of esterification auxiliary agent makes the consistency of matrix material greatly improve, simultaneously also for the raising of the addition of thermoplastic starch provides favourable condition.
Crystallizing polyester auxiliary agent can improve crystallization velocity and the degree of crystallinity of aliphatic polyester, makes the thermotolerance of matrix material, mechanical property, and resistant to hydrolysis performance improves.The consistency of crystallizing polyester auxiliary agent and poly(lactic acid) is good, to poly(lactic acid), there is good nucleation promoter action, its result can significantly improve its crystallization velocity, shorten the shaping cycle of goods, enhance productivity, improve the physical and mechanical property of goods, improve its heat-drawn wire, Young's modulus and resistance to impact shock.
Starch and cellulose chemistry structural similitude, have good consistency, and by natural fiber and starch blending, starch mechanical property can significantly improve.And vegetable fibre is hydrophobic, starch is hydrophilic, and after adding natural fiber, the water tolerance of starch can significantly improve, and thermostability is also obviously improved.In the mixing material of aliphatic polyester and starch, add natural polymer vegetable fibre can improve its flexural strength.
Natural polymer vegetable fibre has good ductility, elongation at break and mechanical strength, thermoplastic starch and natural polymer vegetable fibre are added enters in aliphatic polyester matrix simultaneously, ensure that goods have good thermotolerance and impact property concurrently simultaneously, synergy is ideal.
One as starch of the present invention/vegetable fibre composite biodegradable polyester blown film grade resins is improved, and by weight, this resin comprises following component:
One as starch of the present invention/vegetable fibre composite biodegradable polyester blown film grade resins is improved, by weight, comprise following component: described aliphatic polyester is the mixture of poly-hexanodioic acid/butylene terephthalate and poly(lactic acid), and the mass ratio of the two (9:1) ~ (7:3).The melting index of poly-hexanodioic acid/butylene terephthalate is 3.0 ~ 3.5, and heat seal strength is not less than 15N/m
2.The molecular weight of poly(lactic acid) is more than 10,000, and melting index is between 10 ~ 30.
One as starch of the present invention/vegetable fibre composite biodegradable polyester blown film grade resins is improved, described plant amylum is tapioca (flour), yam starch, W-Gum, wheat starch, pea flour, at least one in husk kind of starch and sweet potato starch, the amylose content (content of amylose starch can affect tensile strength and the elongation at break of matrix material) more than 20% of described plant amylum, its moisture content is less than or equal to 10%, and (degraded of aliphatic polyester and poly(lactic acid) is mainly thermal destruction and hydrolysis, moisture content can affect the degradation cycle of matrix material, also the precipitation of thermoplastic starch can be affected), whiteness is more than or equal to 87 ° (whiteness of plant amylum directly affects the appearance color of blown film resin and membrane product).
One as starch of the present invention/vegetable fibre composite biodegradable polyester blown film grade resins is improved, and described natural polymer vegetable fibre is at least one in stalk fibre, wheat straw fiber, sisal fibers, Caulis Sacchari sinensis fiber, husk fiber and luffa fibers.
One as starch of the present invention/vegetable fibre composite biodegradable polyester blown film grade resins is improved, described natural polymer vegetable fibre is the immersion treatment of the sodium hydroxide solution of 2% ~ 8% through mass concentration, wherein, the mass ratio of described natural polymer vegetable fibre and described sodium hydroxide solution is 1:(15 ~ 25), the order number of described natural polymer vegetable fibre is 30 ~ 100 orders;
In treated natural polymer vegetable fibre, cellulosic content is less than or equal to 2%, the content of pectin is less than 2%, the content of moisture is less than or equal to 5%, pH value is 7-9, and Mierocrystalline cellulose, pectin etc. in natural polymer vegetable fibre are mainly dissolved in the process of natural polymer vegetable fibre NaOH solution, make fiber more refinement, specific surface area increase, thus effectively improve matrix material mechanical property.
One as starch of the present invention/vegetable fibre composite biodegradable polyester blown film grade resins is improved, and described crystallizing polyester auxiliary agent is at least one in multiamide compounds, hydrazide kind compound, phosphenylic acid soap compounds and many hydrazides imine compound.These crystallizing polyester auxiliary agents can improve the crystallization degree of aliphatic polyester, improve thermotolerance and the heat resistanceheat resistant hydrolysis property of matrix material.Blown film grade resins also comprises the 2000 order ~ 4000 object talcum powder through surface-active-treatment of 0.1-0.6 weight part.
These crystallizing polyester auxiliary agents are nontoxic, tasteless, have good nucleation promoter action to aliphatic polyester and poly(lactic acid).Use these crystallization nucleation auxiliary agents can significantly improve its crystallization velocity, shorten shaping cycle, enhance productivity, improve the physical and mechanical property of goods, improve heat-drawn wire, Young's modulus, resistance to impact shock and anti-puncture ability.Hydrazide kind compound also has the effect of compatilizer simultaneously, and it can make thermoplastic starch better at the dispersion effect of matrix material.These crystallizing polyester auxiliary agents can use together in conjunction with the talcum powder through about 3000 orders of surface-active-treatment, talcum powder plays the effect of certain nucleation and crystallization, the combination of the two can make film series products blown film processing procedure more stable, thus significantly improves production efficiency.
One as starch of the present invention/vegetable fibre composite biodegradable polyester blown film grade resins is improved, and described esterification auxiliary agent is at least one in Pyroglutaric acid, Tetra hydro Phthalic anhydride, maleic anhydride, dioctyl maleate and Succinic anhydried.Utilize esterifying agent and starch to react, 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 to generate starch-grafted aliphatic polyester copolymer further by carrying out on the twin screw extruder transesterification reaction, improve the consistency of starch and polyester in blend.
One as starch of the present invention/vegetable fibre composite biodegradable polyester blown film grade resins is improved, and described reaction promoter is softening agent or coupling agent; Wherein, coupling agent add the surfactivity improving starch, improve the effect of starch thermoplastic;
Described softening agent is the one in following combination: the mixture of methane amide and urea, the mixture of methane amide and ethanamide, the mixture of methane amide and ethylene glycol, the mixture of sorbyl alcohol and maltose, water, glycerol and propylene glycol mixture, the mixture of glycerol and citric acid; These softening agent can plasticized starch.
Described coupling agent is at least one in silane based coupling agents, titanate coupling agent and aluminate coupling agent, and these coupling agents, to the modifying surface of starch, increase the activity degree on starch surface;
Described functional agent is antiaging agent and/or dispersion moisture agent;
Described antiaging agent is at least one in antioxidant 1010, antioxidant 1076, irgasfos 168, oxidation inhibitor 622, oxidation inhibitor 215, oxidation inhibitor B215, oxidation inhibitor B561, antioxidant BHT, oxidation inhibitor T502, oxidation inhibitor DSTOP and vitamin-E; Oxidation inhibitor add the oxidation resistent susceptibility and aging resistance that can improve material, materials processing performance is improved.These oxidation inhibitor can absorbing wavelength be effectively the ultraviolet of 280nm ~ 400nm, improve the aging resistance of material;
Described dispersion moisture agent is at least one in EBS, polyethylene wax, paraffin, EBH, Tegin 55G, stearic acid and Zinic stearas.Dispersion moisture agent add the dispersion effect and wetting effect that improve thermoplastic starch and aliphatic polyester, thermoplastic starch is uniformly dispersed in polyester, and over-all properties is uniform and stable.
Another object of the present invention is the preparation method providing a kind of starch of the present invention/vegetable fibre composite biodegradable polyester blown film grade resins, comprises the following steps:
S1, natural macromolecule plant fiber is soaked with the sodium hydroxide solution that concentration is 2% ~ 8%, soak time is 4h ~ 10h, wherein, the mass ratio of described natural polymer vegetable fibre and described sodium hydroxide solution is 1:(15 ~ 25), then freeze-day with constant temperature 1h ~ 2h at 60 DEG C ~ 90 DEG C, sealing is deposited stand-by;
S2, adds plant amylum in high mixer, is then added by reaction promoter in this high mixer, carries out gelation, plastics processing to plant amylum, and the temperature in high mixer controls at 80 DEG C ~ 90 DEG C, and the time of mixing is 2min-20min;
S3, the natural polymer vegetable fibre obtained by S1 is poured in high mixer, and adds the functional agent of 30% ~ 60%, and mixing 2min-20min, then adds in high mixer by esterification auxiliary agent, continues mixing 1min-10min; Successively crystallizing polyester auxiliary agent, remaining functional agent and aliphatic polyester are added in high mixer again, at 145 DEG C-160 DEG C, mix 5min-30min, after cooling, obtain 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, the present invention at least has following beneficial effect:
First, the present invention utilizes chemistry, physical reaction combines, gelation, surface modification treatment are carried out to plant amylum, change the molecular structure of starch, thus the compound plasticising realized plant amylum, and then the hydrophobic performance of raising matrix material, thermoplastic property and physicals, improve the ratio of thermoplastic starch in composite biological material, thus reach the object reduced costs;
Second, the present invention's esterification auxiliary agent carries out esterification treatment to plant amylum and natural polymer vegetable fibre, make it in blending extrusion process, utilize carboxylate and aliphatic polyester to carry out transesterification reaction further, generate starch-grafted aliphatic polyester copolymer, thus improve the consistency in blend between starch and aliphatic polyester;
3rd, the present invention's crystallizing polyester auxiliary agent carries out crystallization treatment to aliphatic polyester, the degree of crystallinity of aliphatic polyester can be improved, and then improve its thermotolerance and intensity, and add some functional agents, the aging resistance of matrix material, processing heat stability etc. can be improved, improve the over-all properties of matrix material.
Embodiment
Embodiment 1
A kind of starch that the present embodiment provides/vegetable fibre composite biodegradable polyester blown film grade resins, 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 of the two is 8:2, and the melting index of poly-hexanodioic acid/butylene terephthalate is 3.0 ~ 3.5, and heat seal strength is not less than 15N/m
2.The molecular weight of poly(lactic acid) is more than 10,000, and melting index is between 10 ~ 30.
The amylose content of tapioca (flour) is more than 20%, and its moisture content is less than or equal to 10%, and whiteness is more than or equal to 87 °.
Stalk fibre is the immersion treatment of the sodium hydroxide solution of 5% through mass concentration, and wherein, the mass ratio of stalk fibre and sodium hydroxide solution is 1:20, and the order number of stalk fibre is 40 orders;
In treated stalk fibre, cellulosic content is less than or equal to 2%, the content of pectin is less than 2%, the content of moisture is less than or equal to 5%, pH value is 7-9, and Mierocrystalline cellulose, pectin etc. in stalk fibre are mainly dissolved in the process of stalk fibre NaOH solution, make fiber more refinement, specific surface area increase, thus effectively improve matrix material mechanical property.
Crystallizing polyester auxiliary agent is multiamide compounds TMP-3000, esterification auxiliary agent is Pyroglutaric acid, and reaction promoter is the mixture of methane amide and urea, and the mass ratio of the two is 1:1, functional agent is the mixture of antioxidant 1010 and EBS, and the mass ratio of the two is 1:1.
Its preparation method comprises the steps:
S1, soak stalk fibre with the sodium hydroxide solution that concentration is 5%, soak time is 6h, and wherein, the mass ratio of institute's stalk fibre and sodium hydroxide solution is 1:20, then freeze-day with constant temperature 1.5h at 70 DEG C, and sealing is deposited stand-by;
S2, adds tapioca (flour) in high mixer, is then added by reaction promoter in this high mixer, carries out gelation, plastics processing to tapioca (flour), and the temperature in high mixer controls at 85 DEG C, and the time of mixing is 10min;
S3, the treated stalk fibre obtained by S1 is poured in high mixer, and adds the functional agent of 50%, and mixing 10min, then adds in high mixer by esterification auxiliary agent, continues mixing 5min; Successively crystallizing polyester auxiliary agent, remaining functional agent and aliphatic polyester are added in high mixer again, at 150 DEG C, mix 10min, after cooling, obtain 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 starch that the present embodiment provides/vegetable fibre composite biodegradable polyester blown film grade resins, 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 of the two is 7:3, and the melting index of poly-hexanodioic acid/butylene terephthalate is 3.0 ~ 3.5, and heat seal strength is not less than 15N/m
2.The molecular weight of poly(lactic acid) is more than 10,000, and melting index is between 10 ~ 30.
The amylose content of yam starch is more than 20%, and its moisture content is less than or equal to 10%, and whiteness is more than or equal to 87 °.
Wheat straw fiber is the immersion treatment of the sodium hydroxide solution of 4% through mass concentration, and wherein, the mass ratio of wheat straw fiber and sodium hydroxide solution is 1:18, and the order number of wheat straw fiber is 60 orders;
In treated wheat straw fiber, cellulosic content is less than or equal to 2%, the content of pectin is less than 2%, the content of moisture is less than or equal to 5%, pH value is 7-9, and Mierocrystalline cellulose, pectin etc. in wheat straw fiber are mainly dissolved in the process of wheat straw fiber NaOH solution, make fiber more refinement, specific surface area increase, thus effectively improve matrix material mechanical property.
Crystallizing polyester auxiliary agent is hydrazide kind compound, and esterification auxiliary agent is Tetra hydro Phthalic anhydride, and reaction promoter is silane based coupling agents, and functional agent is the mixture of antioxidant 1076 and polyethylene wax, and the mass ratio of the two is 2:1.Talcum powder is the 3000 object talcum powder through surface-active-treatment.
Its preparation method comprises the steps:
S1, soak wheat straw fiber with the sodium hydroxide solution that concentration is 4%, soak time is 8h, and wherein, the mass ratio of wheat straw and sodium hydroxide solution is 1:22, then freeze-day with constant temperature 2h at 80 DEG C, and sealing is deposited stand-by;
S2, adds yam starch in high mixer, is then added by reaction promoter in this high mixer, carries out gelation, plastics processing to yam starch, and the temperature in high mixer controls at 90 DEG C, and the time of mixing is 12min;
S3, the treated wheat straw fiber obtained by S1 is poured in high mixer, and adds the functional agent of 40%, and mixing 8min, then adds in high mixer by esterification auxiliary agent, continues mixing 6min; Successively crystallizing polyester auxiliary agent, talcum powder, remaining functional agent and aliphatic polyester are added in high mixer again, at 155 DEG C, mix 10min, after cooling, obtain 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 starch that the present embodiment provides/vegetable fibre composite biodegradable polyester blown film grade resins, 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 melting index of poly-hexanodioic acid/butylene terephthalate is 3.0 ~ 3.5, and heat seal strength is not less than 15N/m
2.The molecular weight of poly(lactic acid) is more than 10,000, and melting index is between 10 ~ 30.
The amylose content of W-Gum is more than 20%, and its moisture content is less than or equal to 10%, and whiteness is more than or equal to 87 °.
Sisal fibers is the immersion treatment of the sodium hydroxide solution of 7% through mass concentration, and wherein, the mass ratio of sisal fibers and sodium hydroxide solution is 1:18, and the order number of sisal fibers is 80 orders;
In treated sisal fibers, cellulosic content is less than or equal to 2%, the content of pectin is less than 2%, the content of moisture is less than or equal to 5%, pH value is 7-9, and Mierocrystalline cellulose, pectin etc. in sisal fibers are mainly dissolved in the process of sisal fibers NaOH solution, make fiber more refinement, specific surface area increase, thus effectively improve matrix material mechanical property.
Crystallizing polyester auxiliary agent is phosphenylic acid soap compounds, esterification auxiliary agent is maleic anhydride, reaction promoter is the mixture (mass ratio of the two is 1:2) of methane amide and ethanamide, and phthalate ester coupling agent, the mixture of methane amide and ethanamide and the mass ratio of phthalate ester coupling agent are 1:3, functional agent is the mixture of irgasfos 168 and paraffin, and the mass ratio of the two is 3:1.
Its preparation method comprises the steps:
S1, soak sisal fibers, soak time 7h with the sodium hydroxide solution that concentration is 3%, wherein, the mass ratio of sisal hemp and sodium hydroxide solution is 1:21, then freeze-day with constant temperature 1h at 65 DEG C, and sealing is deposited stand-by;
S2, adds W-Gum in high mixer, is then added by reaction promoter in this high mixer, carries out gelation, plastics processing to W-Gum, and the temperature in high mixer controls at 80 DEG C ~ 90 DEG C, and the time of mixing is 2min-20min;
S3, the sisal fibers obtained by S1 is poured in high mixer, and adds the functional agent of 35%, and mixing 15min, then adds in high mixer by esterification auxiliary agent, continues mixing 2min; Successively crystallizing polyester auxiliary agent, remaining functional agent and aliphatic polyester are added in high mixer again, at 155 DEG C, mix 25min, after cooling, obtain compound;
S4, pours into compound in dual-screw-stem machine, sectional set temperature, and wherein, the temperature of each section is as follows:
Then in twin screw strand granulator top brace, pelletizing, oven dry, packaging, faint yellow cylindrical particle material is produced.
Embodiment 4
A kind of starch that the present embodiment provides/vegetable fibre composite biodegradable polyester blown film grade resins, 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 melting index of poly-hexanodioic acid/butylene terephthalate is 3.0 ~ 3.5, and heat seal strength is not less than 15N/m
2.The molecular weight of poly(lactic acid) is more than 10,000, and melting index is between 10 ~ 30.
The amylose content of wheat starch is more than 20%, and its moisture content is less than or equal to 10%, and whiteness is more than or equal to 87 °.
Caulis Sacchari sinensis fiber is the immersion treatment of the sodium hydroxide solution of 7% through mass concentration, and wherein, the mass ratio of Caulis Sacchari sinensis fiber and sodium hydroxide solution is 1:16, and the order number of Caulis Sacchari sinensis fiber is 70 orders;
In treated Caulis Sacchari sinensis fiber, cellulosic content is less than or equal to 2%, the content of pectin is less than 2%, the content of moisture is less than or equal to 5%, pH value is 7-9, and Mierocrystalline cellulose, pectin etc. in Caulis Sacchari sinensis fiber are mainly dissolved in the process of Caulis Sacchari sinensis fiber NaOH solution, make fiber more refinement, specific surface area increase, thus effectively improve matrix material mechanical property.
Crystallizing polyester auxiliary agent is many hydrazides imine compound, esterification auxiliary agent is dioctyl maleate, reaction promoter is the mixture (mass ratio of the two is 1:3) of sorbyl alcohol and maltose, and silane based coupling agents, the mixture of sorbyl alcohol and maltose and the mass ratio of silane based coupling agents are 1:4, functional agent is the mixture of vitamin-E and Zinic stearas, and the mass ratio of the two is 2:1.Talcum powder is the 2500 object talcum powder through surface-active-treatment.
Its preparation method comprises the steps:
S1, soak Caulis Sacchari sinensis fiber with the sodium hydroxide solution that concentration is 3.5%, soak time is 7h, and wherein, the mass ratio of sugarcane and sodium hydroxide solution is 1:15, then freeze-day with constant temperature 1.2h at 85 DEG C, and sealing is deposited stand-by;
S2, adds wheat starch in high mixer, is then added by reaction promoter in this high mixer, carries out gelation, plastics processing to wheat starch, and the temperature in high mixer controls at 82 DEG C, and the time of mixing is 15min;
S3, the Caulis Sacchari sinensis fiber obtained by S1 is poured in high mixer, and adds the functional agent of 55%, and mixing 16min, then adds in high mixer by esterification auxiliary agent, continues mixing 6min; Successively crystallizing polyester auxiliary agent, talcum powder, remaining functional agent and aliphatic polyester are added in high mixer again, at 152 DEG C, mix 10min, after cooling, obtain 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 starch that the present embodiment provides/vegetable fibre composite biodegradable polyester blown film grade resins, 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 melting index of poly-hexanodioic acid/butylene terephthalate is 3.0 ~ 3.5, and heat seal strength is not less than 15N/m
2.The molecular weight of poly(lactic acid) is more than 10,000, and melting index is between 10 ~ 30.
The amylose content of pea flour is more than 20%, and its moisture content is less than or equal to 10%, and whiteness is more than or equal to 87 °.
Husk fiber and luffa fibers are the immersion treatment of the sodium hydroxide solution of 5.5% through mass concentration, and wherein, the mass ratio that the total mass of husk fiber and luffa fibers states sodium hydroxide solution is 1:15, and the order number of institute's husk fiber and luffa fibers is 50 orders;
In treated husk fiber and luffa fibers, cellulosic content is less than or equal to 2%, the content of pectin is less than 2%, the content of moisture is less than or equal to 5%, pH value is 7-9, and Mierocrystalline cellulose, pectin etc. in husk fiber and luffa fibers are mainly dissolved in husk fiber and the process of luffa fibers NaOH solution, make fiber more refinement, specific surface area increase, thus effectively improve matrix material mechanical property.
Crystallizing polyester auxiliary agent is the mixture (mass ratio of the two is 1:2) of many hydrazides imine compound and multiamide compounds, esterification auxiliary agent is Succinic anhydried, reaction promoter be water, glycerol and propylene glycol mixture (mass ratio of three is 1:2:3), and aluminate coupling agent, glycerol and propylene glycol mixture and the mass ratio of aluminate coupling agent be 1:2, functional agent is the mixture of oxidation inhibitor DSTOP and Zinic stearas, and the mass ratio of the two is 1:3.
Its preparation method comprises the steps:
S1, soak husk fiber and luffa fibers with the sodium hydroxide solution that concentration is 5.5%, soak time is 4h ~ 10h, wherein, the total mass of husk fiber and luffa fibers and the mass ratio of sodium hydroxide solution are 1:17, then freeze-day with constant temperature 2h at 80 DEG C, and sealing is deposited stand-by;
S2, adds pea flour in high mixer, is then added by reaction promoter in this high mixer, carries out gelation, plastics processing to pea flour, and the temperature in high mixer controls at 82 DEG C, and the time of mixing is 10min;
S3, the husk fiber obtained by S1 and luffa fibers are poured in high mixer, and add the functional agent of 45%, and mixing 10min, then adds in high mixer by esterification auxiliary agent, continue mixing 4min; Successively crystallizing polyester auxiliary agent, remaining functional agent and aliphatic polyester are added in high mixer again, at 145 DEG C, mix 20min, after cooling, obtain 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 |
| 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 singe 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 singe screw inflation film manufacturing machine is 25: 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. starch/vegetable fibre composite biodegradable polyester blown film grade resins, is characterized in that, by weight, comprise following component:
2. starch according to claim 1/vegetable fibre composite biodegradable polyester blown film grade resins, is characterized in that, by weight, comprise following component:
3. starch according to claim 1 and 2/vegetable fibre composite biodegradable polyester blown film grade resins, it is characterized in that, by weight, comprise following component: described aliphatic polyester 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. starch according to claim 1 and 2/vegetable fibre composite biodegradable polyester blown film grade resins, it 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, the amylose content of described plant amylum is more than 20%, and its moisture content is less than or equal to 10%.
5. starch according to claim 1 and 2/vegetable fibre composite biodegradable polyester blown film grade resins, it is characterized in that, described natural polymer vegetable fibre is at least one in stalk fibre, wheat straw fiber, sisal fibers, Caulis Sacchari sinensis fiber, husk fiber and luffa fibers.
6. starch according to claim 5/vegetable fibre composite biodegradable polyester blown film grade resins, it is characterized in that, described natural polymer vegetable fibre is the immersion treatment of the sodium hydroxide solution of 2% ~ 8% through mass concentration, wherein, the mass ratio of described natural polymer vegetable fibre and described sodium hydroxide solution is 1:(15 ~ 25), the order number of described natural polymer vegetable fibre is 30 ~ 100 orders;
In treated natural polymer vegetable fibre, cellulosic content is less than or equal to 2%, and the content of pectin is less than 2%, and the content of moisture is less than or equal to 5%.
7. starch according to claim 1 and 2/vegetable fibre composite biodegradable polyester blown film grade resins, it is characterized in that, described crystallizing polyester auxiliary agent is at least one in multiamide compounds, hydrazide kind compound, phosphenylic acid soap compounds and many hydrazides imine compound;
Blown film grade resins also comprises the 2000 order ~ 4000 object talcum powder through surface-active-treatment of 0.1-0.6 weight part.
8. starch according to claim 1 and 2/vegetable fibre composite biodegradable polyester blown film grade resins, is characterized in that: described esterification auxiliary agent is at least one in Pyroglutaric acid, Tetra hydro Phthalic anhydride, maleic anhydride, dioctyl maleate and Succinic anhydried.
9. starch according to claim 1 and 2/vegetable fibre composite biodegradable polyester blown film grade resins, it is characterized in that, described reaction promoter is softening agent or coupling agent;
Described softening agent is the one in following combination: the mixture of methane amide and urea, the mixture of methane amide and ethanamide, the mixture of methane amide and ethylene glycol, the mixture of sorbyl alcohol and maltose, water, glycerol and propylene glycol mixture, the mixture of glycerol and citric acid;
Described coupling agent is at least one in silane based coupling agents, titanate coupling agent and aluminate coupling agent;
Described functional agent is antiaging agent and/or dispersion moisture agent;
Described antiaging agent is at least one in antioxidant 1010, antioxidant 1076, irgasfos 168, oxidation inhibitor 622, oxidation inhibitor 215, oxidation inhibitor B215, oxidation inhibitor B561, antioxidant BHT, oxidation inhibitor T502, oxidation inhibitor DSTOP and vitamin-E;
Described dispersion moisture agent is at least one in EBS, polyethylene wax, paraffin, EBH, Tegin 55G, stearic acid and Zinic stearas.
10. a preparation method for starch according to claim 1/vegetable fibre composite biodegradable polyester blown film grade resins, is characterized in that, comprise the following steps:
S1, natural macromolecule plant fiber is soaked with the sodium hydroxide solution that concentration is 2% ~ 8%, soak time is 4h ~ 10h, wherein, the mass ratio of described natural polymer vegetable fibre and described sodium hydroxide solution is 1:(15 ~ 25), then freeze-day with constant temperature 1h ~ 2h at 60 DEG C ~ 90 DEG C, sealing is deposited stand-by;
S2, adds plant amylum in high mixer, is then added by reaction promoter in this high mixer, carries out gelation, plastics processing to plant amylum, and the temperature in high mixer controls at 80 DEG C ~ 90 DEG C, and the time of mixing is 2min-20min;
S3, the natural polymer vegetable fibre obtained by S1 is poured in high mixer, and adds the functional agent of 30% ~ 60%, and mixing 2min-20min, then adds in high mixer by esterification auxiliary agent, continues mixing 1min-10min; Successively crystallizing polyester auxiliary agent, remaining functional agent and aliphatic polyester are added in high mixer again, at 145 DEG C-160 DEG C, mix 5min-30min, after cooling, obtain 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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