CN105315442A - Preparation method of starch modified polycaprolactone plastic material - Google Patents
Preparation method of starch modified polycaprolactone plastic material Download PDFInfo
- Publication number
- CN105315442A CN105315442A CN201510865121.7A CN201510865121A CN105315442A CN 105315442 A CN105315442 A CN 105315442A CN 201510865121 A CN201510865121 A CN 201510865121A CN 105315442 A CN105315442 A CN 105315442A
- Authority
- CN
- China
- Prior art keywords
- preparation
- add
- starch
- 40min
- completes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a preparation method of a starch modified polycaprolactone plastic material, and belongs to the field of preparation of polycaprolactone plastic materials. According to the preparation method, a mold preparation is prepared by virtue of starch modification, then cyclohexanone is used as a raw material to react with bivalent manganese and concentrated sulfuric acid, then bottom aeration is performed, then starch and the mold preparation are added to perform oxidation reaction so as to obtain caprolactone, and the caprolactone is subjected to polymerization reaction under the action of stannous iso-caprylate to prepare a polycaprolactone plastic material. The preparation method disclosed by the invention has the following beneficial effects: the preparation process is good in safety, and the obtained product is good in hydrophilic property and high in biodegradation rate; and the bivalent manganese and concentrated sulfuric acid are adopted to oxidize with the starch and the mold preparation after the bottom aeration to generate caprolactone, so that the defect that explosion happens easily during production is solved, and the preparation method is worthy of popularization and application.
Description
Technical field
The present invention relates to a kind of preparation method of starch conversion polycaprolactone plastic material, belong to polycaprolactone plastic material preparation field.
Background technology
Since the sixties in 20th century, polycaprolactone (PCLpolycaprolacton), with its superior biodegradable and memory, starts to obtain extensive concern, and its relevant research is also developed rapidly.PCL is a kind of semicrystalline polymer, and its fusing point is 59 ~ 64 DEG C, and second-order transition temperature is-60 DEG C.Its structural repeat unit has 5 nonpolar methylene radical-CH2-and polar ester groups-coo-, namely-(COO-CH2CH2CH2CH2CH2CH2---) Pn, such structure makes PCL have good snappiness and processibility, and this material has good biocompatibility simultaneously.This constructional feature, makes it have shape memory on the one hand, has the goods of original shape, after deformation is fixing, is stimulated the process of means, it can be made again to recover the phenomenon of original shape by external conditionss such as heating.On the other hand, this material such as material and starch is blended, can obtain Biodegradable Materials.At present, the characteristic of these two aspects is applied in a lot of field, especially in medical, as adhesive tape, bandage, rectifier, suture line, medicinal slow release agent etc., the annual growth rate of demand more than 50%, but produces employing with hydrogen peroxide oxidation Cyclohexanone Production caprolactone, and oxidizing reaction is complicated violent, easily blast, so supply falls short of demand both at home and abroad.Because polycaprolactone molecular chain is more regular and submissive, crystallinity is comparatively strong, and the existence of five methylene radical makes the wetting ability of polycaprolactone poor, biological degradation rate is low, quality weight, and there is no domestic polycaprolactone product due to domestic at present, basic dependence import, causes product cost high.Therefore work out a kind of method that polycaprolactone biological degradation rate is high, production process security is good, have great practical value.
Summary of the invention
Technical problem to be solved by this invention: adopt with hydrogen peroxide oxidation Cyclohexanone Production caprolactone in polycaprolactone process for producing at present, oxidizing reaction is complicated violent, easily blast, and due to the existence of polycaprolactone five methylene radical, cause the wetting ability of polycaprolactone poor, biological degradation rate is low, the drawback that quality is heavy, provide one and obtain mould bacteria preparation with starch conversion, be raw material again with pimelinketone, with bivalent manganese and strong sulfuric acid response, again by bottom aeration, add starch and mould bacteria preparation again to carry out oxidizing reaction and obtain caprolactone, under stannous iso caprylate effect, polyreaction obtains the method for polycaprolactone plastic material, to reach the object solving in production process and easily blast with wetting ability difference.Safe preparation process of the present invention is good, and products obtained therefrom biological degradation rate is high.
For solving the problems of the technologies described above, the present invention adopts technical scheme as described below to be:
(1) get 1 ~ 2kg starch, put into fermentor tank, then respectively to adding the yeast of 4 ~ 6% and the water of 3 ~ 5% in fermentor tank, be uniformly mixed, 25 ~ 30 DEG C of lower seal fermentations 5 ~ 7 days, after fermentation completes, improving temperature is 35 ~ 45 DEG C, sealing and fermenting 7 ~ 9 days;
(2) after fermentation completes, in fermented product, add beef soup, add-on and fermented product mass ratio are 5:1, under rotating speed is 200 ~ 300r/min, stirs 30 ~ 40min and mix, and are then placed in darkness, moist place's preservation 8 ~ 10 days, make it naturally mouldy;
(3) mould self-sow to 3 ~ 5cm is treated, add 30 ~ 40mL distilled water wherein, be uniformly mixed under rotating speed is 300 ~ 500r/min, filter to obtain supernatant liquor, supernatant liquor is placed in the centrifugal 10 ~ 20min of whizzer of 3000 ~ 5000rpm, again collect supernatant liquor, obtain mould bacteria preparation for subsequent use;
(4) get 30 ~ 50mL pimelinketone and put into reaction vessel, add 15 ~ 20g manganous sulfate wherein, add strong sulfuric acid response 30 ~ 40min that 3 ~ 5mL massfraction is 98% wherein simultaneously, and then under sealed state, pass into air from reaction container bottom and carry out aeration 50 ~ 60min;
(5) after aeration completes, add 20 ~ 30g starch wherein, under rotating speed is 500 ~ 700r/min, stir 30 ~ 40min, drip the mould bacteria preparation of 30 ~ 40mL wherein with the speed of 2 ~ 3/s while stirring, after dropwising, continue stirring 5 ~ 10min and mix, and then pass into air continuation aeration 30 ~ 40min from reaction container bottom, obtain caprolactone;
(6) caprolactone of above-mentioned gained is put into polymerizing pipe, in polymerizing pipe, add the stannous iso caprylate of 0.05 ~ 0.07% and the toluene of 0.1 ~ 0.12% again, be then warming up to 88 ~ 90 DEG C with the speed program of 2 DEG C/min, stir 30 ~ 40min, mix, insulation 1 ~ 2h;
(7) after insulation completes, nitrogen is passed into after vacuumizing with oily vacuum diffusion pump, No. 3 ~ 4 tube sealings repeatedly, being placed in temperature is react 46 ~ 48h under 128 ~ 130 DEG C of oil baths, after question response completes, adds 5 ~ 7% sherwood oils, stir 30 ~ 40min to mix, by methanol wash 2 ~ 3 times after filtering, drier 40 ~ 48h under vacuo, obtain a kind of starch conversion polycaprolactone plastic material.
Application method of the present invention: at obtained starch conversion polycaprolactone plastic material is placed in 48 ~ 50 DEG C after drying, put into charger, plasticizing 1 ~ 2h, extrusion molding in 80 ~ 120 DEG C of temperature, through inflation, draw, batch after, be placed in cutting machine and be cut into test specimen, this test specimen good hydrophilic property, biological degradation rate is high.
The present invention is compared with additive method, and Advantageous Effects is:
(1) with bivalent manganese and the vitriol oil, then generating caprolactone by being oxidized with starch and mould bacteria preparation after the aeration of bottom, solving the drawback that production process is easily blasted;
(2) safe preparation process of the present invention is good, and products obtained therefrom good hydrophilic property, biological degradation rate is high.
Embodiment
First get 1 ~ 2kg starch, put into fermentor tank, then respectively to adding the yeast of 4 ~ 6% and the water of 3 ~ 5% in fermentor tank, be uniformly mixed, 25 ~ 30 DEG C of lower seal fermentations 5 ~ 7 days, after fermentation completes, improving temperature is 35 ~ 45 DEG C, sealing and fermenting 7 ~ 9 days; After fermentation completes, in fermented product, add beef soup, add-on and fermented product mass ratio are 5:1, under rotating speed is 200 ~ 300r/min, stirs 30 ~ 40min and mix, and are then placed in darkness, moist place's preservation 8 ~ 10 days, make it naturally mouldy; Then mould self-sow to 3 ~ 5cm is treated, add 30 ~ 40mL distilled water wherein, be uniformly mixed under rotating speed is 300 ~ 500r/min, filter to obtain supernatant liquor, supernatant liquor is placed in the centrifugal 10 ~ 20min of whizzer of 3000 ~ 5000rpm, again collect supernatant liquor, obtain mould bacteria preparation for subsequent use; Get 30 ~ 50mL pimelinketone again and put into reaction vessel, add 15 ~ 20g manganous sulfate wherein, add strong sulfuric acid response 30 ~ 40min that 3 ~ 5mL massfraction is 98% wherein simultaneously, and then under sealed state, pass into air from reaction container bottom and carry out aeration 50 ~ 60min; After aeration completes, add 20 ~ 30g starch wherein, under rotating speed is 500 ~ 700r/min, stir 30 ~ 40min, drip the mould bacteria preparation of 30 ~ 40mL wherein with the speed of 2 ~ 3/s while stirring, after dropwising, continue stirring 5 ~ 10min and mix, and then pass into air continuation aeration 30 ~ 40min from reaction container bottom, obtain caprolactone; Again the caprolactone of above-mentioned gained is put into polymerizing pipe, in polymerizing pipe, add the stannous iso caprylate of 0.05 ~ 0.07% and the toluene of 0.1 ~ 0.12% again, be then warming up to 88 ~ 90 DEG C with the speed program of 2 DEG C/min, stir 30 ~ 40min, mix, insulation 1 ~ 2h; Finally after insulation completes, nitrogen is passed into after vacuumizing with oily vacuum diffusion pump, No. 3 ~ 4 tube sealings repeatedly, being placed in temperature is react 46 ~ 48h under 128 ~ 130 DEG C of oil baths, after question response completes, adds 5 ~ 7% sherwood oils, stir 30 ~ 40min to mix, by methanol wash 2 ~ 3 times after filtering, drier 40 ~ 48h under vacuo, obtain a kind of starch conversion polycaprolactone plastic material.
Example 1
First get 1kg starch, put into fermentor tank, then respectively to adding the yeast of 4% and the water of 3% in fermentor tank, be uniformly mixed, ferment 5 days at 25 DEG C of lower seals, after fermentation completes, improving temperature is 35 DEG C, sealing and fermenting 7 days; After fermentation completes, in fermented product, add beef soup, add-on and fermented product mass ratio are 5:1, under rotating speed is 200r/min, stirs 30min and mix, and are then placed in darkness, moist place's preservation 8 days, make it naturally mouldy; Then treat that mould self-sow is to 3cm, add 30mL distilled water wherein, be uniformly mixed under rotating speed is 300r/min, filter to obtain supernatant liquor, supernatant liquor is placed in the centrifugal 10min of whizzer of 3000rpm, again collects supernatant liquor, obtain mould bacteria preparation for subsequent use; Get 30mL pimelinketone again and put into reaction vessel, add 15g manganous sulfate wherein, add the strong sulfuric acid response 30min that 3mL massfraction is 98% wherein simultaneously, and then under sealed state, pass into air from reaction container bottom and carry out aeration 50min; After aeration completes, add 20g starch wherein, under rotating speed is 500r/min, stir 30min, drip the mould bacteria preparation of 30mL wherein with the speed of 2/s while stirring, after dropwising, continue to stir 5min and mix, and then pass into air continuation aeration 30min from reaction container bottom, obtain caprolactone; Again the caprolactone of above-mentioned gained is put into polymerizing pipe, then in polymerizing pipe, add the stannous iso caprylate of 0.05% and the toluene of 0.1%, be then warming up to 88 DEG C with the speed program of 2 DEG C/min, stir 30min, mix, insulation 1h; Finally after insulation completes, nitrogen is passed into after vacuumizing with oily vacuum diffusion pump, No. 3 tube sealings repeatedly, being placed in temperature is react 46h under 128 DEG C of oil baths, after question response completes, adds 5% sherwood oil, stir 30min to mix, by methanol wash 2 times after filtering, drier 40h under vacuo, obtain a kind of starch conversion polycaprolactone plastic material.
At obtained starch conversion polycaprolactone plastic material is placed in 48 DEG C after drying, put into charger, plasticizing 1h, extrusion molding in 80 DEG C of temperature, through inflation, draw, batch after, be placed in cutting machine and be cut into test specimen, this test specimen good hydrophilic property, biological degradation rate is high.
Example 2
First get 1.5kg starch, put into fermentor tank, then respectively to adding the yeast of 5% and the water of 4% in fermentor tank, be uniformly mixed, ferment 6 days at 28 DEG C of lower seals, after fermentation completes, improving temperature is 40 DEG C, sealing and fermenting 8 days; After fermentation completes, in fermented product, add beef soup, add-on and fermented product mass ratio are 5:1, under rotating speed is 250r/min, stirs 35min and mix, and are then placed in darkness, moist place's preservation 9 days, make it naturally mouldy; Then treat that mould self-sow is to 4cm, add 35mL distilled water wherein, be uniformly mixed under rotating speed is 400r/min, filter to obtain supernatant liquor, supernatant liquor is placed in the centrifugal 15min of whizzer of 4000rpm, again collects supernatant liquor, obtain mould bacteria preparation for subsequent use; Get 40mL pimelinketone again and put into reaction vessel, add 18g manganous sulfate wherein, add the strong sulfuric acid response 35min that 4mL massfraction is 98% wherein simultaneously, and then under sealed state, pass into air from reaction container bottom and carry out aeration 55min; After aeration completes, add 25g starch wherein, under rotating speed is 600r/min, stir 35min, drip the mould bacteria preparation of 35mL wherein with the speed of 3/s while stirring, after dropwising, continue to stir 8min and mix, and then pass into air continuation aeration 35min from reaction container bottom, obtain caprolactone; Again the caprolactone of above-mentioned gained is put into polymerizing pipe, then in polymerizing pipe, add the stannous iso caprylate of 0.06% and the toluene of 0.11%, be then warming up to 89 DEG C with the speed program of 2 DEG C/min, stir 35min, mix, insulation 1.5h; Finally after insulation completes, nitrogen is passed into after vacuumizing with oily vacuum diffusion pump, No. 4 tube sealings repeatedly, being placed in temperature is react 47h under 129 DEG C of oil baths, after question response completes, adds 6% sherwood oil, stir 35min to mix, by methanol wash 3 times after filtering, drier 44h under vacuo, obtain a kind of starch conversion polycaprolactone plastic material.
At obtained starch conversion polycaprolactone plastic material is placed in 49 DEG C after drying, put into charger, plasticizing 1.5h, extrusion molding in 100 DEG C of temperature, through inflation, draw, batch after, be placed in cutting machine and be cut into test specimen, this test specimen good hydrophilic property, biological degradation rate is high.
Example 3
First get 2kg starch, put into fermentor tank, then respectively to adding the yeast of 6% and the water of 5% in fermentor tank, be uniformly mixed, ferment 7 days at 30 DEG C of lower seals, after fermentation completes, improving temperature is 45 DEG C, sealing and fermenting 9 days; After fermentation completes, in fermented product, add beef soup, add-on and fermented product mass ratio are 5:1, under rotating speed is 300r/min, stirs 40min and mix, and are then placed in darkness, moist place's preservation 10 days, make it naturally mouldy; Then treat that mould self-sow is to 5cm, add 40mL distilled water wherein, be uniformly mixed under rotating speed is 500r/min, filter to obtain supernatant liquor, supernatant liquor is placed in the centrifugal 20min of whizzer of 5000rpm, again collects supernatant liquor, obtain mould bacteria preparation for subsequent use; Get 50mL pimelinketone again and put into reaction vessel, add 20g manganous sulfate wherein, add the strong sulfuric acid response 40min that 5mL massfraction is 98% wherein simultaneously, and then under sealed state, pass into air from reaction container bottom and carry out aeration 60min; After aeration completes, add 30g starch wherein, under rotating speed is 700r/min, stir 40min, drip the mould bacteria preparation of 40mL wherein with the speed of 3/s while stirring, after dropwising, continue to stir 10min and mix, and then pass into air continuation aeration 40min from reaction container bottom, obtain caprolactone; Again the caprolactone of above-mentioned gained is put into polymerizing pipe, then in polymerizing pipe, add the stannous iso caprylate of 0.07% and the toluene of 0.12%, be then warming up to 90 DEG C with the speed program of 2 DEG C/min, stir 40min, mix, insulation 2h; Finally after insulation completes, nitrogen is passed into after vacuumizing with oily vacuum diffusion pump, No. 4 tube sealings repeatedly, being placed in temperature is react 48h under 130 DEG C of oil baths, after question response completes, adds 7% sherwood oil, stir 40min to mix, by methanol wash 3 times after filtering, drier 48h under vacuo, obtain a kind of starch conversion polycaprolactone plastic material.
At obtained starch conversion polycaprolactone plastic material is placed in 50 DEG C after drying, put into charger, plasticizing 2h, extrusion molding in 120 DEG C of temperature, through inflation, draw, batch after, be placed in cutting machine and be cut into test specimen, this test specimen good hydrophilic property, biological degradation rate is high.
Claims (1)
1. a preparation method for starch conversion polycaprolactone plastic material, is characterized in that concrete preparation process is:
(1) get 1 ~ 2kg starch, put into fermentor tank, then respectively to adding the yeast of 4 ~ 6% and the water of 3 ~ 5% in fermentor tank, be uniformly mixed, 25 ~ 30 DEG C of lower seal fermentations 5 ~ 7 days, after fermentation completes, improving temperature is 35 ~ 45 DEG C, sealing and fermenting 7 ~ 9 days;
(2) after fermentation completes, in fermented product, add beef soup, add-on and fermented product mass ratio are 5:1, under rotating speed is 200 ~ 300r/min, stirs 30 ~ 40min and mix, and are then placed in darkness, moist place's preservation 8 ~ 10 days, make it naturally mouldy;
(3) mould self-sow to 3 ~ 5cm is treated, add 30 ~ 40mL distilled water wherein, be uniformly mixed under rotating speed is 300 ~ 500r/min, filter to obtain supernatant liquor, supernatant liquor is placed in the centrifugal 10 ~ 20min of whizzer of 3000 ~ 5000rpm, again collect supernatant liquor, obtain mould bacteria preparation for subsequent use;
(4) get 30 ~ 50mL pimelinketone and put into reaction vessel, add 15 ~ 20g manganous sulfate wherein, add strong sulfuric acid response 30 ~ 40min that 3 ~ 5mL massfraction is 98% wherein simultaneously, and then under sealed state, pass into air from reaction container bottom and carry out aeration 50 ~ 60min;
(5) after aeration completes, add 20 ~ 30g starch wherein, under rotating speed is 500 ~ 700r/min, stir 30 ~ 40min, drip the mould bacteria preparation of 30 ~ 40mL wherein with the speed of 2 ~ 3/s while stirring, after dropwising, continue stirring 5 ~ 10min and mix, and then pass into air continuation aeration 30 ~ 40min from reaction container bottom, obtain caprolactone;
(6) caprolactone of above-mentioned gained is put into polymerizing pipe, in polymerizing pipe, add the stannous iso caprylate of 0.05 ~ 0.07% and the toluene of 0.1 ~ 0.12% again, be then warming up to 88 ~ 90 DEG C with the speed program of 2 DEG C/min, stir 30 ~ 40min, mix, insulation 1 ~ 2h;
(7) after insulation completes, nitrogen is passed into after vacuumizing with oily vacuum diffusion pump, No. 3 ~ 4 tube sealings repeatedly, being placed in temperature is react 46 ~ 48h under 128 ~ 130 DEG C of oil baths, after question response completes, adds 5 ~ 7% sherwood oils, stir 30 ~ 40min to mix, by methanol wash 2 ~ 3 times after filtering, drier 40 ~ 48h under vacuo, obtain a kind of starch conversion polycaprolactone plastic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510865121.7A CN105315442A (en) | 2015-12-01 | 2015-12-01 | Preparation method of starch modified polycaprolactone plastic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510865121.7A CN105315442A (en) | 2015-12-01 | 2015-12-01 | Preparation method of starch modified polycaprolactone plastic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105315442A true CN105315442A (en) | 2016-02-10 |
Family
ID=55243823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510865121.7A Pending CN105315442A (en) | 2015-12-01 | 2015-12-01 | Preparation method of starch modified polycaprolactone plastic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105315442A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5250707A (en) * | 1990-04-25 | 1993-10-05 | Ube Industries, Ltd. | Process for preparing ε-caprolactone |
| CN1371897A (en) * | 2001-02-23 | 2002-10-02 | 南京理工大学 | Process for synthesizing orthophenylphenol from cyclohexanone |
| CN101285047A (en) * | 2008-05-16 | 2008-10-15 | 南京工业大学 | High-optical-purity D-lactic acid producing strain and process for producing D-lactic acid by fermentation of same |
| CN101307045A (en) * | 2008-07-11 | 2008-11-19 | 湖南大学 | Method for preparing caprolactone from cyclohexanone by catalytic oxidation |
| CN102344433A (en) * | 2011-08-30 | 2012-02-08 | 江苏傲伦达科技实业股份有限公司 | Preparation method of epsilon-caprolactone |
| CN102978134A (en) * | 2012-11-21 | 2013-03-20 | 华南理工大学 | Lactobacillus and method for producing D-lactic acid by fermenting using lactobacillus |
| CN104130234A (en) * | 2014-07-25 | 2014-11-05 | 南京红太阳新材料有限公司 | Preparation method for caprolactone |
| CN104211675A (en) * | 2014-09-22 | 2014-12-17 | 四川大学 | One-step method for preparing epsilon-caprolactone from cyclohexanone |
-
2015
- 2015-12-01 CN CN201510865121.7A patent/CN105315442A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5250707A (en) * | 1990-04-25 | 1993-10-05 | Ube Industries, Ltd. | Process for preparing ε-caprolactone |
| CN1371897A (en) * | 2001-02-23 | 2002-10-02 | 南京理工大学 | Process for synthesizing orthophenylphenol from cyclohexanone |
| CN101285047A (en) * | 2008-05-16 | 2008-10-15 | 南京工业大学 | High-optical-purity D-lactic acid producing strain and process for producing D-lactic acid by fermentation of same |
| CN101307045A (en) * | 2008-07-11 | 2008-11-19 | 湖南大学 | Method for preparing caprolactone from cyclohexanone by catalytic oxidation |
| CN102344433A (en) * | 2011-08-30 | 2012-02-08 | 江苏傲伦达科技实业股份有限公司 | Preparation method of epsilon-caprolactone |
| CN102978134A (en) * | 2012-11-21 | 2013-03-20 | 华南理工大学 | Lactobacillus and method for producing D-lactic acid by fermenting using lactobacillus |
| CN104130234A (en) * | 2014-07-25 | 2014-11-05 | 南京红太阳新材料有限公司 | Preparation method for caprolactone |
| CN104211675A (en) * | 2014-09-22 | 2014-12-17 | 四川大学 | One-step method for preparing epsilon-caprolactone from cyclohexanone |
Non-Patent Citations (3)
| Title |
|---|
| 章亚东: "环己酮Baver-Villiger氧化反应制备己内酯的研究进展", 《河南化工》 * |
| 郑爱芳: "《南京工业大学硕士毕业论文》", 31 December 2006 * |
| 郑爱芳: "由环己酮生物合成己内酯的研究", 《天然产物研究与开发》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102604347B (en) | Preparation method of chitosan modified polylactic acid material by gamma-ray irradiation | |
| CN106957514B (en) | PBAT base biodegradation composite material with high water vapor barrier property | |
| CN102675113A (en) | Method for preparing diglycol phthalate by performing alcoholysis on polyester (PET) | |
| CN105885112A (en) | Environment-friendly plastic bag | |
| CN102504331A (en) | Degrading method for recovering polyurethane | |
| CN107298835A (en) | One kind can degradable biomass-based composite material and preparation method thereof | |
| CN107033565A (en) | A kind of preparation method of strong―binding interface type bamboo fibre/polylactic acid degradable material | |
| CN109867819A (en) | Polylactic acid-starch-PVA composite degradable packaging film and preparation method thereof | |
| CN109796733A (en) | A kind of preparation method of poly-lactic acid material | |
| CN106349669A (en) | Bagasse biodegradable plastic and preparation method thereof | |
| CN102701985A (en) | Method for preparing epoxy resin curing agent by performing alcoholysis on PET (Polyethylene Terephthalate) polyester | |
| CN101508786A (en) | Method for dissolution of bacteria cellulose | |
| CN104231175B (en) | A kind of preparation method of etherification oxidation graft polyol converted starch | |
| CN101864184B (en) | Thermoplastic vegetable fiber/starch blending material and preparation method thereof | |
| CN105418900B (en) | The preparation method of poly butylene succinate and polylactic-acid block copolymer | |
| CN105315442A (en) | Preparation method of starch modified polycaprolactone plastic material | |
| CN107043524B (en) | A kind of disposable plastic product composite polylactic acid resin | |
| CN106397725B (en) | Utilize recycling waste hard polyurethane foam production insulating tube material, insulating tube and production method | |
| CN107793719B (en) | Polydactyl acid-Rosinpolyether polylol composite material preparation process | |
| CN101319034A (en) | Method for preparing crosslinked poly-succinic butanediol ester | |
| CN108164660B (en) | Polyvinyl alcohol material and preparation method thereof | |
| CN102443269A (en) | Radiation modified soybean isolated protein/starch plastic and preparation method thereof | |
| CN105462200A (en) | Method for preparing environment-friendly plastic | |
| CN111875854A (en) | Environment-friendly easily-degradable plastic and preparation method thereof | |
| CN105462199A (en) | Environment-friendly plastic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160210 |
|
| RJ01 | Rejection of invention patent application after publication |