CN105985534A - Corn-starch-and-needlebush-fiber-compounded foam material and preparing method thereof - Google Patents
Corn-starch-and-needlebush-fiber-compounded foam material and preparing method thereof Download PDFInfo
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- CN105985534A CN105985534A CN201510163759.6A CN201510163759A CN105985534A CN 105985534 A CN105985534 A CN 105985534A CN 201510163759 A CN201510163759 A CN 201510163759A CN 105985534 A CN105985534 A CN 105985534A
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Abstract
The invention discloses a corn-starch-and-needlebush-fiber-compounded foam material and a preparing method thereof. The corn-starch-and-needlebush-fiber-compounded foam material is a product obtained in the mode that thermoplastic corn starch, needlebush fibers of 50 meshes to 100 meshes, degradable resin, crosslinking agents, composite foaming agents and bulking agents are mixed, subjected to molten mixing and extruding through a screw extruder and foamed. The thermoplastic corn starch is a product obtained in the mode that corn starch and composite plasticizers are mixed in the ratio of 100:(20-40), and the mixture is extruded through a single screw extruder. According to the corn-starch-and-needlebush-fiber-compounded foam material and the preparing method, the corn starch is modified through the plasticizers glycerin into the thermoplastic corn starch; as the degradable resin is added, the melt strength of the foam material is improved, the compression strength of the material is guaranteed, and the water resistance of the material is improved; the needlebush fibers are pretreated with a sodium hydroxide solution of a certain concentration, a part of impurities of hemicellulose, lignin and the like is removed, the fibers have good mechanical strength, and the mechanical performance of the material can be improved. The product is low in cost, good in water resistance and compression strength, capable of achieving complete biodegradation, nontoxic and environmentally friendly.
Description
Technical field
The present invention relates to a kind of amortizing packaging material, particularly relate to a kind of corn starch needle-leaved wood fibre composite foam material and preparation method thereof.
Background technology
The most a large amount of amortizing packaging materials used are still the foam plastics not degrading, and mainly have the foam plasticss such as EPS, EPP, polyurethane, owing to it is difficult to degraded, therefore, define serious city " white pollution ".The main still paper products of existing degradable buffering package material, but paper products are relatively costly, and the most water-fast, resilience is poor.Having the research of the degradable material of plant fiber starch at present, lignocellulosic fiber source enriches, such as Pericarppium arachidis hypogaeae, waste paper powder, straw, wood flour, bamboo fibre, needlebush, straw etc..The addition of Plant fiber can provide certain mechanical strength, improves the hygroscopicity of thermoplastic starch, and is conducive to improving material biodegradability.But its resistance to water is the most limited, easy moisture absorption in humid air for a long time, so that its mechanical strength declines, the quality of impact packaging and effect.Starch is polysaccharide compound, is decomposed by microbial action under natural environment, is finally decomposed to nontoxic CO2And H2O, is therefore one of a now widely used class biodegradable natural polymer raw material.Its wide material sources (corn starch, potato starch, sweet potato starch, potato starch, wheaten starch etc.), and cheap etc..But starch molecular chain contains great amount of hydroxy group, easily and forming hydrogen bond outside strand in strand, therefore indissoluble, infusibility, and poor water resistance, one meets water or for a long time in humid air, easily absorbs moisture, and its stability declines.
Summary of the invention
It is an object of the invention to the shortcoming overcoming existing complete biodegradable expanded material, a kind of corn starch needle-leaved wood fibre composite foam material is provided, to realize improving resistance to water, improves compressive strength, finally meet the requirement of amortizing packaging material, it is achieved the target of " moulding for paper generation ".
The corn starch needle-leaved wood fibre composite foam material of the present invention, by the product obtained through screw extruder melt blending extrusion foaming after thermoplasticity corn starch, the needle-leaved wood fibre of 50 ~ 100 mesh (preferably 80 mesh), degradable resin, cross-linking agent, composite foamable agent, bulking agent mixing.Wherein thermoplasticity corn starch is 40 ~ 60 parts (preferably 50 parts)；The needle-leaved wood fibre of 50 ~ 100 mesh 5 ~ 15 parts (preferably 10 parts)；Degradable resin 20 ~ 40 parts (preferably 30 parts)；Cross-linking agent 4 ~ 10 parts (preferably 6 parts)；Bulking agent 4 ~ 10 parts (preferably 6 parts).
Described thermoplasticity corn starch is according to corn starch by corn starch and plasticizer: the preferred 100:30 of mixed plasticizer=100:20 ~ 40() mixing, is extruded the product obtained by screw extruder.
Described composite elasticizer is the mixture of glycerol and carbamide, its glycerol: the preferred 2:3 of carbamide=2:1 ~ 4().
Described needle-leaved wood fibre (first-selected Masson Pine) is through pulverizing by needlebush, cross 50 ~ 100 mesh sieves, then the mass percent being immersed in temperature 30 DEG C ~ 40 DEG C (preferably 35 DEG C) is 5% ~ 12%(preferably 7%) sodium hydroxide aqueous solution in the preferred 20min of 10 ~ 30min(), wherein, needle-leaved wood fibre and sodium hydrate aqueous solution mass ratio are the preferred 1:1 of 1:0.5 ~ 1.5(), then be placed in the constant temperature oven of 50 DEG C ~ 70 DEG C (preferably 60 DEG C) through the preferred 36h of 24h ~ 48h() it is dried the product of gained.
Described degradable resin is the mixture of polylactic acid (PLA) and water, PLA: water=1:0.03 ~ 0.12(preferred 1:0.1).
Described cross-linking agent is calcium hydroxide.
Described composite foamable agent is azodicarbonamide, zinc oxide and water, and the mass ratio of three is the preferred 2:2:0.5 of 2:1 ~ 3:0.5 ~ 1(), quality summation accounts for the 1 ~ 5%(preferably 3% of unclassified stores sum).
Described bulking agent is ethylene-vinyl acetate copolymer (EVA).
Its preparation method comprises the following steps:
(1) by corn starch with composite elasticizer according to corn starch: composite elasticizer is mixed in 100:20 ~ 40 ratio, by single screw extrusion machine extrusion obtain thermoplastic starch, stand-by；
(2) needlebush is pulverized in plant pulverizer, cross 50 ~ 100 mesh sieves, 10 ~ 30min in the aqueous solution of the sodium hydroxide that mass percent is 5 ~ 12% being then immersed in temperature 30 ~ 40 DEG C, wherein, needle-leaved wood fibre and sodium hydrate aqueous solution mass ratio are 1:0.5 ~ 1.5, then are placed on the product being dried gained in the constant temperature oven of 50 ~ 70 DEG C through 24 ~ 48h；
(3) get the raw materials ready: be 40 ~ 60 parts according to thermoplasticity corn starch；The needle-leaved wood fibre of 50 ~ 100 mesh 5 ~ 15 parts；Degradable resin 20 ~ 40 parts；Cross-linking agent 4 ~ 10 parts；Bulking agent 4 ~ 10 parts is got the raw materials ready；
(4) needle-leaved wood fibre 5 ~ 15 parts by thermoplastic starch 40 ~ 60 parts, handled well, degradable resin 20 ~ 40 parts, bulking agent 4 ~ 10 parts, the preferred 10min of 8 ~ 15min(is mixed) in high-speed mixer, add cross-linking agent 4 ~ 10 parts, composite foamable agent account for the 1 ~ 5% of unclassified stores sum in high-speed mixer the preferred 10min of 10 ~ 15min()；
(5) by double screw extruder extrusion foaming, controlling head temperature is 120 ~ 150 DEG C (preferably 130 DEG C), the preferred 10MPa of head pressure 0.5 ~ 50MPa(), screw speed 100 ~ 120r/min(preferably 110 r/min).
The present invention takes full advantage of biodegradable, environmentally friendly, the aboundresources of Plant fiber and starch, the advantage such as cheap, plays effective coordinative role and complementary action on material property.Particularly needle-leaved wood fibre has the advantage that intensity is high, impurity is few, is conducive to improving the crushing resistance of composite foam material.Corn starch is obtained thermoplastic starch with composite elasticizer (glycerol and carbamide) by double screw extruder extrusion, owing to carbamide and glycerol are all little molecules, hydrogen bond can be formed with the hydroxyl in starch, so that carbamide and glycerol play the effect of plasticising corn starch, give starch thermoplastic processability.Adding again degradable resin, melt fluidity is good, and mechanical strength is high, therefore can be as binding agent and reinforcing agent, and be effectively improved between Plant fiber with starch uniformly mixes, and improves resistance to water and the compressive strength of expanded material.Bulking agent EVA can reduce the mutual frictional force improving storeroom, improves the interfacial interaction power of storeroom, on the one hand advantageously ensures that the mechanical property of material, on the other hand can improve production efficiency.Calcium hydroxide is as cross-linking agent, and a small amount of addition can improve the resistance to water of material, dimensional stability.This product is inexpensive, resistance to water and compressive strength good, and fully biodegradable, asepsis environment-protecting.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
(1) by corn starch 10 Kg, mix with plasticizer (glycerol 1 Kg, carbamide 1 Kg), obtain thermoplastic starch 12 Kg by single screw extrusion machine extrusion, stand-by；
(2) needlebush is pulverized in plant pulverizer, through 50 mesh sieves, obtain needle-leaved wood fibre, 30min in the aqueous solution of the sodium hydroxide that mass percent is 5% being then immersed in 30 DEG C, wherein, waste paper pulp fiber and sodium hydrate aqueous solution mass ratio are 1:0.5, then are placed in the constant temperature oven of 50 DEG C and are dried through 48h, the needle-leaved wood fibre that must handle well；
(3) needle-leaved wood fibre 2 Kg that by thermoplastic starch 12 Kg, handles well, degradable resin polylactic acid 3.8 Kg, water 0.2 Kg, bulking agent EVA 1Kg, mix 15min in high-speed mixer.Add cross-linking agent calcium hydroxide 1 Kg, azodicarbonamide 0.1 Kg, zinc oxide 0.1 Kg, water 0.05 Kg, high-speed mixer mixes 10min.Last at head temperature 120 DEG C, head pressure 2MPa, the double screw extruder extrusion foaming of screw speed 100r/min.
The new material of preparation contrasts such as following table with the hot strength of thermoplastic starch expanded material, compressive strength and water absorption rate
Embodiment 2:
(1) corn starch 5 Kg is mixed with plasticizer (glycerol 0.5 Kg, carbamide 0.5 Kg), obtain thermoplastic starch 6 Kg by single screw extrusion machine extrusion, stand-by；
(2) needlebush is pulverized in plant pulverizer, through 70 mesh sieves, obtain needle-leaved wood fibre, 30min in the aqueous solution of the sodium hydroxide that mass percent is 5% being then immersed in 30 DEG C, wherein, waste paper pulp fiber and sodium hydrate aqueous solution mass ratio are 1:0.5, then are placed in the constant temperature oven of 50 DEG C and are dried, through 48h, the needle-leaved wood fibre that gained is handled well, stand-by；
(3) needle-leaved wood fibre 0.5 Kg that by thermoplastic starch 6 Kg, handles well, degradable resin polylactic acid 1.9 Kg, water 0.1 Kg, bulking agent EVA 0.5 Kg, mix 15min in high-speed mixer.Add cross-linking agent calcium hydroxide 1 Kg, azodicarbonamide 0.1 Kg, zinc oxide 0.1 Kg, water 0.05 Kg, high-speed mixer mixes 10min.Last at head temperature 120 DEG C, head pressure 3MPa, the double screw extruder extrusion foaming of screw speed 100r/min.
The new material of preparation contrasts such as following table with the hot strength of thermoplastic starch expanded material, compressive strength and water absorption rate
Embodiment 3:
(1) by corn starch 3.8 Kg, mix with plasticizer (glycerol 0.8 Kg, carbamide 0.4 Kg), obtain thermoplastic starch 5 kilograms by single screw extrusion machine extrusion, stand-by；
(2) needlebush is pulverized in plant pulverizer, through 80 mesh sieves, obtain needle-leaved wood fibre, then 35min in the sodium hydrate aqueous solution that mass percent is 8% of 35 DEG C it is immersed in, wherein, waste paper pulp fiber and sodium hydrate aqueous solution mass ratio are 1:1, then are placed on the product being dried gained in the constant temperature oven of 60 DEG C through 40h；
(3) the needle-leaved wood fibre 1Kg that by thermoplastic starch 5Kg, handles well, degradable resin polylactic acid 2.9Kg, water 0.1Kg, bulking agent EVA 0.5Kg, mix 10min in high-speed mixer.Add cross-linking agent calcium hydroxide 0.5Kg, azodicarbonamide 0.1Kg, zinc oxide 0.1Kg, water 0.05Kg, 10min in high-speed mixer.Last at head temperature 140 DEG C, head pressure 10MPa, the double screw extruder extrusion foaming of screw speed 130r/min.
The new material of preparation contrasts such as following table with the hot strength of thermoplastic starch expanded material, compressive strength and water absorption rate
Claims (3)
1. corn starch needle-leaved wood fibre composite foam material and preparation method thereof, it is characterised in that: by the product obtained through double screw extruder melt blending extrusion foaming after thermoplasticity corn starch, the needle-leaved wood fibre of 50 ~ 100 mesh, degradable resin, cross-linking agent, composite foamable agent, bulking agent mixing.
2. according to the composite foam material described in claims 1, it is characterised in that: described composite elasticizer is the mixture of glycerol and carbamide, its glycerol: carbamide=2:1 ~ 4, and degradable resin is the mixture of polylactic acid (PLA) and water；PLA: water=1:0.03 ~ 0.12；Cross-linking agent is calcium hydroxide；Composite foamable agent is azodicarbonamide, zinc oxide and water, and the mass ratio of three is 2:1 ~ 3:0.5 ~ 1, and its quality summation accounts for the 1 ~ 5% of unclassified stores sum；Bulking agent is ethylene-vinyl acetate copolymer (EVA).
3. according to composite foam material described in claims 1 and preparation method thereof, it is characterised in that comprise the following steps:
(1) by corn starch with composite elasticizer according to corn starch: composite elasticizer=100:20 ~ 40 ratio mixes, by single screw extrusion machine extrusion obtain thermoplastic starch, stand-by；
(2) needlebush is pulverized in plant pulverizer, cross 50 ~ 100 mesh sieves, 10 ~ 30min in the aqueous solution of the sodium hydroxide that mass percent is 5 ~ 12% being then immersed in temperature 30 ~ 40 DEG C, wherein, needle-leaved wood fibre and sodium hydrate aqueous solution mass ratio are 1:0.5 ~ 1.5, then are placed on the product being dried gained in the constant temperature oven of 50 ~ 70 DEG C through 24 ~ 48h；
(3) get the raw materials ready: according to thermoplasticity corn starch be 40 ~ 60 parts, the needle-leaved wood fibre 5 ~ 15 parts of 50 ~ 100 mesh, degradable resin 20 ~ 40 parts, cross-linking agent 4 ~ 10 parts, bulking agent 4 ~ 10 parts get the raw materials ready；
(4) needle-leaved wood fibre 10 ~ 20 parts by thermoplastic starch 40 ~ 60 parts, handled well, degradable resin 20 ~ 40 parts, bulking agent 4 ~ 10 parts, 8 ~ 15min is mixed in high-speed mixer, adding cross-linking agent 4 ~ 10 parts, composite foamable agent accounts for the 1 ~ 5% of unclassified stores sum and mixes 10 ~ 15min in high-speed mixer；
(5) by double screw extruder extrusion foaming, controlling head temperature is 120 ~ 150 DEG C, head pressure 0.5 ~ 50MPa, screw speed 100 ~ 120r/min.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108587086A (en) * | 2018-01-24 | 2018-09-28 | 广西壮族自治区农业科学院 | A kind of preparation method preparing expanded material using banana nanofiber |
| CN110330694A (en) * | 2019-05-16 | 2019-10-15 | 湖南工业大学 | A kind of starch base composite foam material freezing foaming and its preparation |
| CN111187451A (en) * | 2020-02-11 | 2020-05-22 | 陕西科技大学 | Degradable starch fiber composite foam material and preparation method thereof |
| CN111423707A (en) * | 2020-05-26 | 2020-07-17 | 安徽颍美科技股份有限公司 | Environment-friendly composite material for packaging and preparation method thereof |
| CN112457534A (en) * | 2020-11-19 | 2021-03-09 | 杭州金焱包装彩印有限公司 | Biodegradable thermoplastic starch resin for food packaging material and preparation method thereof |
| CN112761030A (en) * | 2020-12-16 | 2021-05-07 | 江西中竹生物质科技有限公司 | Bamboo pulp foaming material and preparation method thereof |
| CN114031820A (en) * | 2021-10-26 | 2022-02-11 | 南京五瑞生物降解新材料研究院有限公司 | Heat-resistant biodegradable composite foam material and preparation method thereof |
| CN115873312A (en) * | 2022-12-30 | 2023-03-31 | 福建冠中科技有限公司 | Biodegradable buffer packaging composite material and preparation method thereof |
| CN117089121A (en) * | 2023-08-17 | 2023-11-21 | 佛山市南海区百兴玩具有限公司 | Environment-friendly nontoxic starch plastic for toy |
| WO2023240669A1 (en) * | 2022-06-17 | 2023-12-21 | 宋伟杰 | Degradable automobile floor mat material and preparation method therefor |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108587086A (en) * | 2018-01-24 | 2018-09-28 | 广西壮族自治区农业科学院 | A kind of preparation method preparing expanded material using banana nanofiber |
| CN110330694A (en) * | 2019-05-16 | 2019-10-15 | 湖南工业大学 | A kind of starch base composite foam material freezing foaming and its preparation |
| CN110330694B (en) * | 2019-05-16 | 2021-08-13 | 湖南工业大学 | Freezing foaming method and starch-based composite foaming material prepared by freezing foaming method |
| CN111187451A (en) * | 2020-02-11 | 2020-05-22 | 陕西科技大学 | Degradable starch fiber composite foam material and preparation method thereof |
| CN111423707A (en) * | 2020-05-26 | 2020-07-17 | 安徽颍美科技股份有限公司 | Environment-friendly composite material for packaging and preparation method thereof |
| CN112457534A (en) * | 2020-11-19 | 2021-03-09 | 杭州金焱包装彩印有限公司 | Biodegradable thermoplastic starch resin for food packaging material and preparation method thereof |
| CN112761030A (en) * | 2020-12-16 | 2021-05-07 | 江西中竹生物质科技有限公司 | Bamboo pulp foaming material and preparation method thereof |
| CN114031820A (en) * | 2021-10-26 | 2022-02-11 | 南京五瑞生物降解新材料研究院有限公司 | Heat-resistant biodegradable composite foam material and preparation method thereof |
| WO2023240669A1 (en) * | 2022-06-17 | 2023-12-21 | 宋伟杰 | Degradable automobile floor mat material and preparation method therefor |
| CN115873312A (en) * | 2022-12-30 | 2023-03-31 | 福建冠中科技有限公司 | Biodegradable buffer packaging composite material and preparation method thereof |
| CN117089121A (en) * | 2023-08-17 | 2023-11-21 | 佛山市南海区百兴玩具有限公司 | Environment-friendly nontoxic starch plastic for toy |
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