CN100497457C - Degradable high polymer material of poplar wood pulp cellulose and its preparation method - Google Patents
Degradable high polymer material of poplar wood pulp cellulose and its preparation method Download PDFInfo
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- CN100497457C CN100497457C CNB2007100194825A CN200710019482A CN100497457C CN 100497457 C CN100497457 C CN 100497457C CN B2007100194825 A CNB2007100194825 A CN B2007100194825A CN 200710019482 A CN200710019482 A CN 200710019482A CN 100497457 C CN100497457 C CN 100497457C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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Abstract
The invention discloses a kind of biodegradable macromolecular poplar wood pulp cellulose, comprising resin mixture and plasticity agent; resin mixture comprises acetyl cellulose prepared by using poplar wood pulp cellulose, and one or several of polycaprolactone, polylactic acid, cornstarch; the invention aslo discloses the preparing method. The method comprising following steps: preapring poplar wood pulp cellulose: dispersing poplar woos pulp, adding glacial acetic acid for activation, adding mixture of acetic anhydride, glacial acetic acid and catalyst for esterification, adding dilute acetic acid for hydrolysis to make acetyl cellulose, feeding resin mixture into twin-screw extruder, adding plasticizing agent by liquid pump into the second- class segment; cooling extrudate, drying, cutting into granulate and getting resin granulate. The invention is characterized by enviroment- friendly, low cost, sound comprehensive property, stable product property and wide spread value.
Description
Technical field
The present invention relates to a kind of degradable high polymer material and preparation method thereof, relate in particular to a kind of degradable high polymer material of poplar wood pulp cellulose and preparation method thereof.
Background technology
Poplar is a kind of fast growing wood, and content of lignin is low, and Mierocrystalline cellulose, hemicellulose level height have a wide range of applications on pulping and paper-making.There is abundant quick growth poplar wood resource in China.Cotton wood cellulose receives publicity more with its recyclability, nontoxic, degradable, environment amenable characteristics.Francesco Degli-Innocenti etc. has carried out composting test to starch and cellulosic blend, after more than 40 day, and almost completely degraded.
Water insoluble and the common organic solvents of Mierocrystalline cellulose, chemically reactive a little less than.But, after for example esterification generates cellulose acetate, can give the good toughness of Mierocrystalline cellulose, the transparency etc. through chemical modification.Buchanan etc. adopt stable enrichment culture, and active sludge is joined in the basic salt substratum that contains 5% (volume fraction) Cellulose diacetate and induced growth.After cultivating for 2～3 weeks, discovery Cellulose diacetate (substitution value is 2.5) fiber is degraded in a large number.Carry out ex vivo enrichment with Cellulose diacetate (substitution value is 1.7) film and cultivate, in 4～5d, just have 80% film to be degraded.Cellulose diacetate has best thermoplasticity in all types of cellulose acetates, if just but do not decompose or decolour and can not show enough melting propertieies.Therefore, be necessary to reduce the yield temperature of CA, this just needs to add softening agent.
Existing softening agent has phthalate, phosphoric acid salt, dicarboxylic anhydride and mono-epoxy compounds, polytetramethylene ester, triethyl citrate etc.Monomerics such as usually used phthalate, phosphoric acid salt are because of harmful characteristic of its degradation production, and are not suitable for preparing degradable plastics.Dicarboxylic anhydride and mono-epoxy compounds can improve the thermoplasticity of cellulose acetate under the condition that high temperature is mediated, but the existence of small molecules softening agent will inevitably cause the phenomenon of plasticizer migration to take place.This is that shortage owing to compatibility between softening agent and the resin produces.Cellulose acetate is carried out blend with other macromolecular materials extrude under the situation that adds softening agent, compatilizer, filler etc., can prepare material with good biodegradability properties energy.
Summary of the invention
The objective of the invention is to propose that a kind of environmental protection, cost are low, good combination property, degradable high polymer material of poplar wood pulp cellulose that product performance are stable and preparation method thereof.
The present invention realizes by the following technical solutions:
A kind of poplar wood pulp cellulose biodegradable polymer, comprise the resin compound of 100 parts of quality and the softening agent of 5～30 parts of quality, resin compound comprises the cellulose acetate by the poplar wood pulp cellulose preparation, also comprise polycaprolactone, poly(lactic acid), the mixture of one or more in the W-Gum, wherein, the quality of cellulose acetate is 20～60 parts, the quality of polycaprolactone is 10～40 parts, the quality of poly(lactic acid) is 10～40 parts, the quality of W-Gum is 10～40 parts, this material can prepare by the following method: under 130-250 ℃, resin compound is added the twin screw extruder feed bin, forced feed adds softening agent with liquor pump in stage casing, the twin screw second stage, extrudate is through water-cooled, dry up, after the pelletizing resin particle.
A kind of preparation method of poplar wood pulp cellulose biodegradable polymer, preparation process may further comprise the steps:
The first step, the preparation of poplar cellulose acetate; After the poplar wood pulp is uniformly dispersed, adding Glacial acetic acid activates, activation temperature is 30～90 ℃, soak time is 2～24 hours, add acetic anhydride then, Glacial acetic acid, mixture of catalysts is carried out esterification, wherein, the quality of Glacial acetic acid is cellulosic 1～100 times, catalyst quality is cellulosic 0.5～15%, the mol ratio of acetic anhydride and cotton wood cellulose is (1～3): 1, and the reaction times is 1～3 hour, esterification finishes back adding dilute acetic acid and is hydrolyzed into cellulose acetate, hydrolysis is 1～20% with the concentration of dilute acetic acid, and the acetic acid quality is cellulosic 5～15%;
Second step, under 130-250 ℃, the resin compound of 100 parts of quality is added the twin screw extruder feed bin, forced feed, the softening agent that adds 5～30 parts of quality with liquor pump in stage casing, the twin screw second stage, extrudate is through water-cooled, dry up, after the pelletizing resin particle, wherein resin compound is by above-mentioned cellulose acetate and polycaprolactone, poly(lactic acid), mixture in the W-Gum, wherein, the quality of cellulose acetate is 20～60 parts, the quality of polycaprolactone is 10～40 parts, and the quality of poly(lactic acid) is 10～40 parts, and the quality of W-Gum is 10～40 parts.
In the technical program, α in the poplar raw material of wood pulp-Mierocrystalline cellulose quality percentage composition is 70%～80%.Catalyzer is one or more a mixture of the vitriol oil, phosphoric acid, perchloric acid.Softening agent is one or more the mixture in glycerine triacetate, two glycerol mono acetate bulks, triethyl citrate, the tributyl citrate.
The present invention obtains following technique effect:
1. cotton wood cellulose receives publicity more with its recyclability, nontoxic, degradable, environment amenable characteristics.The present invention adopts common papermaking poplar wood pulp to produce cellulose acetate, α in the poplar wood pulp-Mierocrystalline cellulose quality percentage composition is 70%～80%, all the other are hemicellulose etc., and cotton fibre or high pure pulp are generally all adopted in the production of industrial cellulose acetate, and its cost for purification is higher.On the one hand, directly adopt common poplar wood pulp both to save the cotton fibre of excellent property, avoided producing the pollution that high pure pulp is brought, do not need to purify, reduced cost, on the other hand, the biodegradable components such as hemicellulose (in common cellulose acetate production, being regarded as impurity) in the poplar wood pulp have also been made full use of, these compositions are not only biodegradable, and on the other hand, its existence has also improved simultaneously the processing characteristics of degradation material to a certain extent.
2. the softening agent such as glycerine triacetate selected for use of the present invention have not only played the plastifying effect, improved polycaprolactone or poly(lactic acid) simultaneously and the acetyl cellulose that adopted between consistency, the phenomenon of phase separation of mixture is alleviated greatly; The toughness and the ductility of material have been improved.
3. the parallel dual-screw extrusion way that adopts among the present invention not only has the effect of good dispersing and mixing polymkeric substance, and because the consistency of softening agent and cellulose acetate affects the thermoplasticity of material to a great extent, use twin screw extruder to implement the cellulosic reaction processing of Dichlorodiphenyl Acetate and can obtain effective plasticizing process, and prevent being separated of blend.
4. gained material of the present invention has plasticizing capacity under 200 ℃, its tensile strength of material reaches 40MPa, and elongation at break is greater than 200%.
5. the polycaprolactone among the present invention (PCL) is a kind of aliphatic polyester that can partial crystallization, one of its specific performance be can with many polymer formation thermodynamic compatibilities or the compatible co-mixing system of part.Polycaprolactone has excellent biological compatibility, and is biodegradable, can be applicable to the aspects such as carrier, sutures and wrapping material of controlled release drug.Because it is the lower tensile strength of polycaprolactone, therefore that itself and other polymer blending is significant.
6. the poly(lactic acid) among the present invention (PLA) is the representative of synthesizing biological degradable material, has excellent biological compatibility and security, and is nontoxic to human body, reaches degraded gradually in the physical environment in vivo, finally becomes CO
2And H
2O.Poly(lactic acid) can adopt traditional plastic working method to extrude and compression molding production, is fit to industrial requirement.Independent PLA causes the elongation at break of institute's prepared material not meet the demands because toughness is not enough, can adopt the measure of blending and modifying to improve tensile property.
7. among the present invention, the cotton wood cellulose molecule is the straight chain stiff molecule, also there is strong hydrogen bond action each other, can remedy the defective of polycaprolactone undercapacity, exist rotatable covalent linkage on the carbochain of polycaprolactone, have certain flexibility, also can remedy Mierocrystalline cellulose, defective that polylactic acid molecule toughness is not enough.Therefore adopt cellulose acetate, poly(lactic acid), polycaprolactone and W-Gum can learn from other's strong points to offset one's weaknesses, realize the optimization of material property for the method that the main raw material blend prepares the cellulose based degradable plastics.
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1;
A kind of poplar wood pulp cellulose biodegradable polymer comprises the resin compound of 100 parts of quality and the softening agent of 5～30 parts of quality, and the mass fraction of softening agent can be chosen for 5 parts, 7 parts, 8 parts, 10 parts, 13 parts, 15 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 27 parts, 29 parts, resin compound comprises by the cellulose acetate of poplar wood pulp cellulose preparation, also comprises polycaprolactone, poly(lactic acid), the mixture of one or more in the W-Gum, wherein, the quality of cellulose acetate is 20～60 parts, for example can be chosen for 25 parts, 28 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 52 parts, 55 parts, 58 parts, the quality of polycaprolactone is 10～40 parts, for example can be chosen for 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 28 parts, 30 parts, 33 parts, 36 parts, 38 parts, the quality of poly(lactic acid) is 10～40 parts, for example can be chosen for: 13 parts, 16 parts, 19 parts, 21 parts, 22 parts, 28 parts, 30 parts, 32 parts, 34 parts, 37 parts, the quality of W-Gum is 10～40 parts, for example can be chosen for: 11 parts, and 12 parts, 16 parts, 21 parts, 24 parts, 27 parts, 32 parts, 34 parts, 35 parts, 39 parts, this material can prepare by the following method: under 130-250 ℃, resin compound is added the twin screw extruder feed bin, for example temperature can be chosen for 150 ℃, and 180 ℃, 200 ℃, 220 ℃, 230 ℃, 240 ℃, forced feed, add softening agent in stage casing, the twin screw second stage with liquor pump, extrudate is through water-cooled, dry up, after the pelletizing resin particle.
In the present embodiment, α in the poplar raw material of wood pulp-Mierocrystalline cellulose quality percentage composition is 70%～80%.Catalyzer is one or more a mixture of the vitriol oil, phosphoric acid, perchloric acid, if be mixture, can be any ratio, and it is 98% the vitriol oil that the vitriol oil can make mass concentration.Softening agent is one or more the mixture in glycerine triacetate, two glycerol mono acetate bulks, triethyl citrate, the tributyl citrate, and the proportioning of mixture can be any proportioning.
Embodiment 2:
A kind of preparation method of poplar wood pulp cellulose biodegradable polymer may further comprise the steps:
The first step, the preparation of poplar cellulose acetate: after the poplar wood pulp is uniformly dispersed, add Glacial acetic acid and activate, activation temperature is 30～90 ℃, and activation temperature can be chosen for 35 ℃, 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 85 ℃, 88 ℃, soak time is 2h～24h, and soak time can be chosen for: 2 hours, and 4 hours, 5 hours, 8 hours, 9 hours, 11 hours, 12 hours, 14 hours, 18 hours, 20 hours, 22 hours, 23 hours, add acetic anhydride then, Glacial acetic acid, mixture of catalysts is carried out esterification, wherein, the quality of Glacial acetic acid is cellulosic 1～100 times, for example can be chosen for 8 times, 15 times, 20 times, 30 times, 43 times, 52 times, 60 times, 70 times, 82 times, 85 times, 90 times, catalyst quality is 0.5～15% of a cotton wood cellulose, for example can be chosen for: 0.8%, 1.2%, 1.5%, 2%, 3%, 4%, 5%, 8%, 9%, 11%, 12%, 14%, the mol ratio of acetic anhydride and cotton wood cellulose is (1-3): 1, for example can be chosen for 1:1,1.2:1,1.5:1,2:1,2.2:1,2.8:1, the reaction times is 1～3 hour, for example can be chosen for 1.5 hours, 2 hours, 2.2 hours, 2.8 hour, esterification finishes back adding dilute acetic acid and is hydrolyzed into cellulose acetate, and hydrolysis is 1～20% with the mass concentration of dilute acetic acid, for example can be chosen for 10%, 15%, the acetic acid quality is cellulosic 5～15%, for example can be chosen for 8%, 9%, 12%, 14%; Reaction finishes posthydrolysis, and to become substitution value be 1.5～2.5 poplar cellulose acetate.
In second step, with the resin compound adding twin screw extruder feed bin of 100 parts of quality, forced feed is with the softening agent of liquor pump in 5～30 parts of quality of stage casing, twin screw second stage adding, for example can be chosen for 5 parts, 7 parts, 8 parts, 10 parts, 13 parts, 15 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 27 parts, 29 parts, extrudate is through water-cooled, dry up, after the pelletizing resin particle, wherein resin compound is by above-mentioned cellulose acetate and polycaprolactone, poly(lactic acid), mixture in the W-Gum, wherein, the quality of cellulose acetate is 20～60 parts, for example can be chosen for 5 parts, 7 parts, and 8 parts, 10 parts, 13 parts, 15 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 27 parts, 29 parts, the quality of polycaprolactone is 10～40 parts, for example can be chosen for 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 28 parts, 30 parts, 33 parts, 36 parts, 38 parts, the quality of poly(lactic acid) is 10～40 parts, for example can be chosen for: 13 parts, 16 parts, 19 parts, 21 parts, 22 parts, 28 parts, 30 parts, 32 parts, 34 parts, 37 parts, the quality of W-Gum is 10～40 parts, for example can be chosen for: 11 parts, 12 parts, 16 parts, 21 parts, 24 parts, 27 parts, 32 parts, 34 parts, 35 parts, 39 parts.
In the present embodiment, α in the poplar raw material of wood pulp-Mierocrystalline cellulose quality percentage composition is 70%～80%.Catalyzer is one or more a mixture of the vitriol oil, phosphoric acid, perchloric acid, if be mixture, can be any ratio, and it is 98% the vitriol oil that the vitriol oil can make mass concentration.Softening agent is one or more the mixture in glycerine triacetate, two glycerol mono acetate bulks, triethyl citrate, the tributyl citrate, and the proportioning of mixture can be any proportioning.
The poplar wood pulp obtains poplar through operations such as boiling, defibrination, screening, bleachings.The plasticizing forming of resin compound has adopted the parallel dual-screw processing mode, screw diameter 20mm, and length-to-diameter ratio is 36, is divided into five temperature control sections by the feeding section to head, temperature respectively is 165 ℃, 180 ℃, 175 ℃, 170 ℃, 145 ℃.Add softening agent with liquor pump in stage casing, the second stage, through water-cooled, dry up, after the pelletizing plastic grain.
Embodiment 3:
Take by weighing poplar wood pulp 10Kg in the reactor of 500L, the chuck water-bath is 40 ℃, the Glacial acetic acid that drips 100Kg under continuous stirring condition activates Mierocrystalline cellulose, treat the abundant swollen of Mierocrystalline cellulose after, the acetic anhydride and the 0.5Kg catalyzer that add 28.33Kg carry out esterification.When reaction presented the solution of homogeneous transparent, the dilute acetic acid that adds 12Kg made the substitution value hydrolysis to 2.3 of product.The solution system that obtains was placed on through precipitation, filtration, washing, drying in 60 ℃ the baking oven and was dried to constant weight this moment.
Embodiment 4:
Take by weighing poplar wood pulp 10Kg in the reactor of 500L, the chuck water-bath is 40 ℃, the Glacial acetic acid that drips 200Kg under continuous stirring condition activates Mierocrystalline cellulose, treat the abundant swollen of Mierocrystalline cellulose after, the acetic anhydride and the 1.0Kg catalyzer that add 28.33Kg carry out esterification.When reaction presented the solution of homogeneous transparent, the dilute acetic acid that adds 15Kg made the substitution value hydrolysis to 2.3 of product.The solution system that obtains was placed on through precipitation, filtration, washing, drying in 60 ℃ the baking oven and was dried to constant weight this moment.
Embodiment 5:
With the cellulose acetate among the 6Kg embodiment 3, the 2Kg polycaprolactone, the mixture of 2Kg poly(lactic acid) adds feed bin, forced feed.The 1Kg glycerine triacetate adds in stage casing, the second stage with liquor pump, through water-cooled, dry up, after the pelletizing plastic grain.
Embodiment 6:
With the cellulose acetate among the 6Kg embodiment 3, the 2Kg polycaprolactone, the mixture of 2Kg poly(lactic acid) adds feed bin, forced feed.1Kg two glycerol mono acetate bulks add in stage casing, the second stage with liquor pump, through water-cooled, dry up, after the pelletizing plastic grain.
Embodiment 7:
With the cellulose acetate among the 6Kg embodiment 3, the 2Kg polycaprolactone, the 1Kg poly(lactic acid), the mixture of 1Kg W-Gum adds feed bin, forced feed.The 1Kg triethyl citrate adds in stage casing, the second stage with liquor pump, through water-cooled, dry up, after the pelletizing plastic grain.
Embodiment 8:
With the cellulose acetate among the 6Kg embodiment 3, the 2Kg polycaprolactone, the 1Kg poly(lactic acid), the mixture of 1Kg W-Gum adds feed bin, forced feed.1Kg tributyl citrate, 0.5Kg two glycerol mono acetate bulks add in stage casing, the second stage with liquor pump, through water-cooled, dry up, after the pelletizing plastic grain.
Embodiment 9:
With the cellulose acetate among the 6Kg embodiment 3, the 3Kg poly(lactic acid), the mixture of 1Kg W-Gum adds feed bin, forced feed.0.5Kg glycerine triacetate adds in stage casing, the second stage with liquor pump, through water-cooled, dry up, after the pelletizing plastic grain.
Embodiment 10:
With the cellulose acetate among the 6Kg embodiment 3, the 3Kg polycaprolactone, the mixture of 1Kg W-Gum adds feed bin, forced feed.1.5Kg two glycerol mono acetate bulks add in stage casing, the second stage with liquor pump, through water-cooled, dry up, after the pelletizing plastic grain.
| CA ％ | PCL ％ | PLA ％ | W-Gum % | Glycerine triacetate % | Two glycerol mono acetate bulk % | Triethyl citrate % | Tributyl citrate % | Tensile strength MPa | Elongation at break % |
| 60 | 20 | 20 | 0 | 10 | 0 | 0 | 0 | 62 | 151 |
| 60 | 20 | 20 | 0 | 0 | 10 | 0 | 0 | 65 | 133 |
| 60 | 20 | 10 | 10 | 0 | 0 | 10 | 0 | 58 | 128 |
| 60 | 20 | 10 | 10 | 0 | 5 | 0 | 10 | 51 | 139 |
| 60 | 0 | 30 | 10 | 5 | 0 | 0 | 0 | 55 | 89 |
| 60 | 30 | 0 | 10 | 0 | 15 | 0 | 0 | 36 | 166 |
| 60 | 20 | 20 | 0 | 0 | 0 | 0 | 0 | 45 | 30 |
| 60 | 40 | 0 | 0 | 10 | 0 | 0 | 0 | 35 | 157 |
| 60 | 0 | 40 | 0 | 10 | 0 | 0 | 0 | 59 | 27 |
Claims (4)
1. poplar wood pulp cellulose biodegradable polymer, it is characterized in that, comprise the resin compound of 100 parts of quality and the softening agent of 5～30 parts of quality, resin compound comprises the cellulose acetate by the poplar wood pulp cellulose preparation, also comprise polycaprolactone, poly(lactic acid), the mixture of one or more in the W-Gum, wherein, the quality of cellulose acetate is 20～60 parts, the quality of polycaprolactone is 10～40 parts, the quality of poly(lactic acid) is 10～40 parts, the quality of W-Gum is 10～40 parts, this material prepares by the following method: under 130～250 ℃, resin compound is added the twin screw extruder feed bin, forced feed, add softening agent in stage casing, the twin screw second stage with liquor pump, softening agent is a glycerine triacetate, two glycerol mono acetate bulks, triethyl citrate, the mixture of one or more in the tributyl citrate, extrudate is through water-cooled, dry up, after the pelletizing resin particle.
2. the preparation method of a poplar wood pulp cellulose biodegradable polymer according to claim 1 is characterized in that preparation process may further comprise the steps:
The first step, the preparation of poplar cellulose acetate: after the poplar wood pulp is uniformly dispersed, adding Glacial acetic acid activates, activation temperature is 30～90 ℃, soak time is 2～24 hours, add acetic anhydride then, Glacial acetic acid, mixture of catalysts is carried out esterification, wherein, the quality of Glacial acetic acid is cellulosic 1～100 times, and catalyst quality is cellulosic 0.5～15%, and the mol ratio of acetic anhydride and cotton wood cellulose is (1～3): 1, reaction times is 1～3 hour, esterification finishes back adding dilute acetic acid and is hydrolyzed into cellulose acetate, and hydrolysis is 1～20% with the mass concentration of dilute acetic acid, and the acetic acid quality is cellulosic 5～15%;
Second step, under 130～250 ℃, the resin compound of 100 parts of quality is added the twin screw extruder feed bin, forced feed, the softening agent that adds 5～30 parts of quality with liquor pump in stage casing, the twin screw second stage, extrudate is through water-cooled, dry up, after the pelletizing resin particle, wherein resin compound is above-mentioned cellulose acetate and polycaprolactone, poly(lactic acid), the mixture of one or more in the W-Gum, wherein, the quality of cellulose acetate is 20～60 parts, the quality of polycaprolactone is 10～40 parts, and the quality of poly(lactic acid) is 10～40 parts, and the quality of W-Gum is 10～40 parts.
3. the preparation method of poplar wood pulp cellulose biodegradable polymer according to claim 2 is characterized in that alpha-cellulose quality percentage composition is 70%～80% in the poplar raw material of wood pulp.
4. the preparation method of biodegradable polymer according to claim 2 is characterized in that catalyzer is one or more a mixture of the vitriol oil, phosphoric acid, perchloric acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011184520A (en) * | 2010-03-05 | 2011-09-22 | Fujifilm Corp | Method for producing cellulose-based resin composition |
| CN101942118B (en) * | 2010-10-25 | 2012-03-21 | 曾广胜 | Plant fiber starch fully-biodegradable material and preparation method thereof |
| CN102108196B (en) * | 2010-12-30 | 2013-03-13 | 广东上九生物降解塑料有限公司 | Method for preparing polylactic acid degradable material |
| CN102250389B (en) * | 2011-06-17 | 2013-06-19 | 中国林业科学研究院林产化学工业研究所 | Biodegradable polymer material compatibilized and blended by lignocellulose and preparation method thereof |
| ITMI20112181A1 (en) * | 2011-11-30 | 2013-05-31 | Es Laminati Estrusi Termoplasti Ci S P A | BIODEGRADABLE PLASTIC MATERIAL BASED ON CELLULOSE ACETATE AND RELATED ARTICLES |
| CN102585297A (en) * | 2012-01-18 | 2012-07-18 | 姚岚 | Biodegradable cellulose acetate plastic and preparation method thereof |
| CN103223687B (en) * | 2013-05-07 | 2015-08-19 | 中国林业科学研究院林产化学工业研究所 | A kind of acetylize modification processing method of Poplar Powder |
| CN103865107B (en) * | 2014-03-26 | 2016-03-02 | 苏州汉丰新材料股份有限公司 | The preparation method of complete biodegradable resin prepared by non-staple food grain complex denaturation hydrophobic starch and preparation facilities thereof |
| CN105440610A (en) * | 2015-04-21 | 2016-03-30 | 湖南工业大学 | Polylactic acid composite material |
| CN106317229A (en) * | 2016-08-22 | 2017-01-11 | 四川北方硝化棉股份有限公司 | Production method for preparing low-substituted cellulose acetate |
| CN111438910A (en) * | 2019-01-16 | 2020-07-24 | 纪腾萦 | Environment-friendly straw and manufacturing method thereof |
| CN114031903A (en) * | 2021-11-29 | 2022-02-11 | 南通醋酸纤维有限公司 | Biodegradable material and film product and application thereof |
| WO2023151041A1 (en) * | 2022-02-11 | 2023-08-17 | 广东省贵来新材料科技有限公司 | Cellulose-based polymer material for degradable product and preparation method therefor |
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