CN103183938A - Polycaprolactone/poly butylene succinate/eggshell powder composite material and preparation method thereof - Google Patents
Polycaprolactone/poly butylene succinate/eggshell powder composite material and preparation method thereof Download PDFInfo
- Publication number
- CN103183938A CN103183938A CN2013100908958A CN201310090895A CN103183938A CN 103183938 A CN103183938 A CN 103183938A CN 2013100908958 A CN2013100908958 A CN 2013100908958A CN 201310090895 A CN201310090895 A CN 201310090895A CN 103183938 A CN103183938 A CN 103183938A
- Authority
- CN
- China
- Prior art keywords
- egg
- polycaprolactone
- shell meal
- poly butylene
- butylene succinate
- 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.)
- Granted
Links
Images
Classifications
-
- 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
- B29C48/92—Measuring, controlling or regulating
-
- 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
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92923—Calibration, after-treatment or cooling zone
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to a polycaprolactone/poly butylene succinate/eggshell powder composite material and a preparation method thereof. The composite material comprises the following components in percentage by weight: 50-85 percent of polycaprolactone, 10-40 percent of poly butylene succinate, 0.5-1.0 percent of eggshell powder and 2-6 percent of coupling agent. The method comprises the following steps: melt-blending a uniform mixture of all the components by using a double-screw rod extruder or an internal mixer at a temperature of 120-190 DEG C, and enabling a macromolecular conjugate formed by the polycaprolactone and the poly butylene succinate through the chemical coupling of the conjugate to form a blend with the eggshell powder. The polycaprolactone/poly butylene succinate/eggshell powder composite material and the preparation method thereof have the benefits that a molecular chain is excellently combined, the eggshell powder plays an enhancing role, the tensile modulus of the composite material is increased compared with that of the polycaprolactone, the elongation at break is improved, and the tensile strength is also improved. The polycaprolactone/poly butylene succinate/eggshell powder composite material can be widely applied to the industries of toys, package, electronic products and the like.
Description
Technical field
The invention belongs to the polymer composite field, specifically the preparation method of a kind of polycaprolactone/poly butylene succinate/egg-shell meal matrix material and this matrix material.
Background technology
General purpose material mainly concentrates on the petroleum derivation material at present, and its " white " garbage problem grows with each passing day, and has caused very important energy dilemma and environmental pollution.Develop potential new packaging material and become academic and industry member study hotspot.Aliphatic polyester, as polycaprolactone (PCL), polyglycolic acid (PGA) etc. has good biocompatibility and degradability and is widely used in the numerous areas of biologic medical.
Polycaprolactone (PCL) is a kind of good biodegradable material and medical material, is all the focus that people study all the time.In recent years along with the reinforcement of people's environmental protection consciousness; biodegradable material becomes a research direction very active in materialogy especially; polycaprolactone is very similar to general-purpose plastics on a lot of physicalies; and and a lot of superpolymer has consistency preferably; PCL has unique biocompatibility with it; biological degradability, and medicine is had through release property and is widely used in biomaterial.Therefore huge potential using value is arranged in the biodegradable material field.Be usually used in medical molding material, industry, art modelling material, toy, organic colorant, hot copying ink adhesive agent, hot melt adhesive mixture.
It is main raw material that poly butylene succinate (PBS) be take aliphatic dibasic acid, dibasic alcohol, both can satisfy the demands by petrochemicals, also can pass through the renewable farm crop products of nature such as Mierocrystalline cellulose, milk industry by product, glucose, fructose, lactose through biological fermentation production, the PBS of high molecular has excellent over-all properties.Mechanical property approaches polypropylene (iPP) and acrylonitrile-butadiene-styrene (ABS) (ABS) plastics, resistance toheat is good, heat-drawn wire approaches 100oC, PBS only just degrades under the contact specified microorganisms conditions such as compost, water body, highly stable in normal storage and use procedure performance.Rely on excellent over-all properties, PBS becomes rapidly one of the universal Biodegradable Materials that can extensively promote the use of.Itself have good cost performance, exploitation energy-conserving and environment-protective high-performance biological degradation matrix material has major application and is worth.
Diphenylmethanediisocyanate (MDI) is properties-correcting agent commonly used in the macromolecular material blend, in order to improve the consistency of poly butylene succinate and matrix.Usually need two components to add other auxiliary agent, the method for processing mainly adds softening agent, coupling agent, trifunctional organic modifiers etc.By to the coupling agent coupling processing, can significantly improve mechanical property, crystal property of polycaprolactone/poly butylene succinate matrix material etc.Have no relevant report about this type of coupling agent and the research of poly butylene succinate modification polycaprolactone.
Egg-shell meal is the epidermis shell of birds, beasts and eggs, generally do not there is larger economic worth, after edible, often pass into disuse, its main component is carbonate, carbonate is toughener commonly used in polymer modification, have a large amount of eggshells to become refuse treatment every year and fall, this patent takes full advantage of the asepsis environment-protecting safety of agricultural-food eggshell resource and the enhancement characteristics of material, prepares the matrix material of environmental protection by utilization of waste material.
Summary of the invention
The shortcoming that modulus is low, tensile property is poor in view of existing polycaprolactone existence, the invention provides the preparation method of a kind of high-performance poly caprolactone/poly butylene succinate/egg-shell meal matrix material and this matrix material, can access the matrix material of high extensibility, better tensile strength, tensile modulus and the tough sexual balance of rigidity.To achieve these goals, the present invention by the following technical solutions.
A kind of polycaprolactone/poly butylene succinate/egg-shell meal matrix material, it is characterized in that, described matrix material is the macromole conjugate that formed by the coupling agent chemical coupling by polycaprolactone, poly butylene succinate and the blend of egg-shell meal, described egg-shell meal is dispersed between described macromole conjugate, wherein, described coupling agent is diphenylmethanediisocyanate, and described macromole conjugate chemical structural formula is:
Further, the component concentration of described matrix material is: polycaprolactone 50-85wt%, poly butylene succinate 10-40wt%, egg-shell meal 0.5-10wt%, coupling agent 2-6wt%.
Further, the content of described egg-shell meal is 0.5-5wt%.
Further, the component concentration of described matrix material is: polycaprolactone 62-68wt%, poly butylene succinate 25-30wt%, egg-shell meal 0.5-5wt%, coupling agent 2.5-5 wt%.
Further, described egg-shell meal is 100-1000 purpose egg-shell meal.The tensile strength of the above-mentioned matrix material that described egg-shell meal content is 0.5-5wt% is 34.5 Mpa-47 Mpa
.
The present invention also provides the preparation method of a kind of polycaprolactone/poly butylene succinate/egg-shell meal matrix material, comprises step:
According to said components content batching, at first polycaprolactone, poly butylene succinate and egg-shell meal are sent in stirrer, with the 20-80rpm rotating speed, stir, mix to obtain the mixture of three components;
Sneak into the diphenylmethanediisocyanate coupling agent in described mixture, then with twin screw extruder or Banbury mixer, carry out melt blending, form matrix material.
Further, described twin screw extruder to the material melt blending, is then extruded Cast Strip, granulating and forming at 120-190 ℃ of temperature, with 20-80rpm.
Further, described Banbury mixer time to the material melt blending at 120-190 ℃ of temperature is 10-15 minute.
Further, described polycaprolactone, poly butylene succinate and shell powder carry out drying and processing before pre-mixing, and bake out temperature is 60-80 ℃.
The present invention by twin screw extruder or Banbury mixer by polycaprolactone, poly butylene succinate and egg-shell meal blend, under action of coupling agents, make poly butylene succinate and polycaprolactone coupling form the macromole conjugate, and form blend with egg-shell meal, molecular chain is in conjunction with excellence, work the egg-shell meal that strengthens toughening effect and be dispersed between described macromole conjugate, further improve composite materials property.The tensile modulus of the polycaprolactone/poly butylene succinate of gained/egg-shell meal matrix material increases to some extent than polycaprolactone, and elongation at break improves, and tensile strength also is improved, and can be widely used in the industries such as toy, packing, electronic product.
The accompanying drawing explanation
The elongation at break of polycaprolactone/poly butylene succinate that Fig. 1 is the embodiment of the present invention 1,2,6 gained/egg-shell meal matrix material is with the variation diagram of egg-shell meal content;
The tensile strength that Fig. 2 is the embodiment of the present invention 1,2,6 gained polycaprolactone/poly butylene succinates/egg-shell meal matrix material is with the variation diagram of egg-shell meal content;
The composite tensile modulus of polycaprolactone/poly butylene succinate that Fig. 3 is the embodiment of the present invention 1,2,6 gained/egg-shell meal is with the variation diagram of egg-shell meal content.
Embodiment
The realization of the object of the invention, functional characteristics and advantage, below in conjunction with embodiment, are described in further detail with reference to accompanying drawing.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
In following examples, the egg-shell meal preparation method is: at first eggshell is cleaned and removed the egg film, dry at 50-70 ℃ of temperature, send in pulverizer and be ground into powder, cross 300 mesh sieve, obtain 100-1000 order egg-shell meal.The speed of pulverizer is selected in the 70-150rpm scope.
By polycaprolactone and poly butylene succinate pellet, egg-shell meal in 70 ℃ of dryings three hours;
In weight part, 70 parts of polycaprolactones and 30 parts of poly butylene succinates, 1 part of egg-shell meal are sent in stirrer, be uniformly mixed and obtain ternary mixture with 70 rpm; Add again 5 parts of MDI, then with twin screw extruder at 120 ℃ of temperature, with the 60rpm rotating speed, carry out melt blending, extrude Cast Strip, granulation, obtain polycaprolactone/poly butylene succinate/egg-shell meal matrix material.
By polycaprolactone and poly butylene succinate, egg-shell meal in 70 ℃ of dryings three hours;
In weight part, 70 parts of polycaprolactones and 30 parts of poly butylene succinates, 2 parts of egg-shell meals are sent in stirrer, be uniformly mixed and obtain ternary mixture with 40 rpm; Add 5 parts of MDI, then with Banbury mixer temperature be under 130 ℃ to material melt blending 10 minutes, obtain polycaprolactone/poly butylene succinate/egg-shell meal matrix material.
By polycaprolactone and poly butylene succinate, egg-shell meal in 80 ℃ of dryings three hours;
In weight part, 60 parts of polycaprolactones and 40 parts of poly butylene succinates, 1 part of egg-shell meal are sent in stirrer, be uniformly mixed and obtain ternary mixture with 30 rpm; Add 3 parts of MDI, then with twin screw extruder at 190 ℃ of temperature, with the 80rpm rotating speed, carry out melt blending, extrude Cast Strip, granulation, obtain polycaprolactone/poly butylene succinate/egg-shell meal matrix material.
By polycaprolactone/poly butylene succinate, egg-shell meal in 60 ℃ of dryings three hours;
In weight part, 60 parts of polycaprolactones and 40 parts of poly butylene succinates, 2 parts of egg-shell meals are sent in stirrer, be uniformly mixed and obtain ternary mixture with 50 rpm; Add 3 parts of MDI, then with Banbury mixer temperature be under 120 ℃ to material melt blending 15 minutes, obtain polycaprolactone/poly butylene succinate/egg-shell meal matrix material.
By polycaprolactone and poly butylene succinate, egg-shell meal in 70 ℃ of dryings three hours;
In weight part, 60 parts of polycaprolactones and 40 parts of poly butylene succinates, 2 parts of egg-shell meals are sent in stirrer, be uniformly mixed and obtain ternary mixture with 55 rpm; Add 5 parts of MDI, then with twin screw extruder at 160 ℃ of temperature, with the 60rpm rotating speed, carry out melt blending, extrude Cast Strip, granulation, obtain polycaprolactone/poly butylene succinate/egg-shell meal matrix material.
Embodiment 6
By polycaprolactone and poly butylene succinate, egg-shell meal in 70 ℃ of dryings three hours;
In weight part, 70 parts of polycaprolactones and 30 parts of poly butylene succinates, 5 parts of egg-shell meals are sent in stirrer, be uniformly mixed and obtain ternary mixture with 35 rpm; Add 3 parts of MDI, then with twin screw extruder at 145 ℃ of temperature, with the 25rpm rotating speed, carry out melt blending, extrude Cast Strip, granulation, obtain polycaprolactone/poly butylene succinate/egg-shell meal matrix material.
Embodiment 7
By polycaprolactone and poly butylene succinate, egg-shell meal in 70 ℃ of dryings three hours;
In weight part, 60 parts of polycaprolactones and 40 parts of poly butylene succinates, 5 parts of egg-shell meals are sent in stirrer, be uniformly mixed and obtain ternary mixture with 75 rpm; Add 5 parts of MDI, then with Banbury mixer temperature be under 155 ℃ to material melt blending 13 minutes, obtain polycaprolactone/poly butylene succinate/egg-shell meal matrix material.
Embodiment 8
By polycaprolactone and poly butylene succinate, egg-shell meal in 70 ℃ of dryings three hours;
In weight part, 88 parts of polycaprolactones and 12 parts of poly butylene succinates, 1 part of egg-shell meal are sent in stirrer, be uniformly mixed and obtain ternary mixture with 45 rpm; Add 5 parts of MDI, then with twin screw extruder at 160 ℃ of temperature, with the 30rpm rotating speed, carry out melt blending, extrude Cast Strip, granulation, obtain polycaprolactone/poly butylene succinate/egg-shell meal matrix material.
Illustrate that below in conjunction with accompanying drawing egg-shell meal adds fashionable, the variation of the composite property of polycaprolactone/poly butylene succinate, wherein, in parts by weight, the matrix material (calling comparative composite in the following text) of contrast polycaprolactone/poly butylene succinate comprises 70 parts of polycaprolactones, 30 parts of poly butylene succinates, coupling agent 3-5 part.
The elongation at break of the polycaprolactone/poly butylene succinate of above-described embodiment 1,2,6 gained/egg-shell meal matrix material with the variation of egg-shell meal content as shown in Figure 1.During egg-shell meal content in Fig. 1 (being powdered egg content) 0 wt % (corresponding comparative composite), elongation at break is 948.5%, when egg-shell meal content is 1 wt %, the fracture extensibility of gained polycaprolactone/poly butylene succinate/egg-shell meal matrix material has a small increase, and is reached for 1071%; When egg-shell meal content surpasses 5%, elongation at break reaches 1218%, and visible elongation at break increases and increases along with egg-shell meal content generally, improves its processing characteristics, can meet the matrix material plastic uptake processing request of polycaprolactone/poly butylene succinate.
The tensile strength of the polycaprolactone/poly butylene succinate of above-described embodiment 1,2,6 gained/egg-shell meal matrix material with the variation of egg-shell meal content as shown in Figure 2.The corresponding comparative composite of egg-shell meal content 0%(in Fig. 2), tensile strength is 21.2Mpa, with comparative composite, compare, considerable change appears in the matrix material tensile strength of gained polycaprolactone/poly butylene succinate, during egg-shell meal content 0.5 wt%, the matrix material tensile strength is 34.5 Mpa; During egg-shell meal content 1wt%, the matrix material tensile strength obviously is increased to 47 Mpa, then reduce, but during content 2 wt% still higher than 34.5 Mpa, between content 2 wt%-5wt%, slowly increase, be increased to 42.2Mpa during 5wt%.When egg-shell meal content is 0.5-5wt% in a word, tensile strength is 34.5 Mpa-47 Mpa, introduces egg-shell meal and makes the tensile strength of matrix material be improved.
The composite tensile modulus of the polycaprolactone/poly butylene succinate of above-described embodiment 1,2,6 gained/egg-shell meal with the variation of egg-shell meal content as shown in Figure 3.The corresponding comparative composite of egg-shell meal content 0%(in Fig. 3), tensile modulus is 57MPa, and the tensile modulus of this matrix material of introducing of egg-shell meal is compared and first reduced then to increase to some extent with comparative composite.
Abovely by several specific embodiments, the present invention has been done to detailed explanation, these concrete descriptions can not think that the present invention only only limits to the content of these embodiment.Those skilled in the art conceive according to the present invention, these descriptions any improvement of making in conjunction with general knowledge known in this field, be equal to replacement scheme, all should be included in the protection domain of the claims in the present invention.
Claims (10)
1. polycaprolactone/poly butylene succinate/egg-shell meal matrix material, it is characterized in that, described matrix material is the macromole conjugate that formed by the coupling agent chemical coupling by polycaprolactone, poly butylene succinate and the blend of egg-shell meal, described egg-shell meal is dispersed between described macromole conjugate, wherein, described coupling agent is diphenylmethanediisocyanate, and described macromole conjugate chemical structural formula is:
2. matrix material according to claim 1, is characterized in that, the component concentration of described matrix material is: polycaprolactone 50-85wt%, poly butylene succinate 10-40wt%, egg-shell meal 0.5-10wt%, coupling agent 2-6wt%.
3. matrix material according to claim 2, is characterized in that, the content of described egg-shell meal is 0.5-5wt%.
4. matrix material according to claim 1, is characterized in that, the component concentration of described matrix material is: polycaprolactone 62-68wt%, and poly butylene succinate 25-30wt%,, egg-shell meal 0.5-5wt%, coupling agent 2.5-5 wt%.
5. according to the described matrix material of claim 3 or 4, it is characterized in that, described egg-shell meal is 100-1000 purpose egg-shell meal, and the tensile strength that contains the described matrix material of described egg-shell meal 0.5-5wt% is 34.5 Mpa-47 Mpa.
6. the preparation method as polycaprolactone/poly butylene succinate/egg-shell meal matrix material as described in claim 1-4 any one is characterized in that comprising step:
Described polycaprolactone, poly butylene succinate and egg-shell meal are sent in stirrer, stirred with the 20-80rpm rotating speed, mix to obtain ternary mixture;
Sneak into described coupling agent in described mixture, with twin screw extruder or Banbury mixer, carry out melt blending, form matrix material.
7. preparation method according to claim 6, is characterized in that, described twin screw extruder to the material melt blending, is then extruded Cast Strip, granulating and forming at 120-190 ℃ of temperature, with 20-80rpm.
8. preparation method according to claim 6, is characterized in that, described Banbury mixer time to the material melt blending at 120-190 ℃ of temperature is 10-15 minute.
9. preparation method according to claim 6, is characterized in that, described polycaprolactone, poly butylene succinate and egg-shell meal three components are carried out drying and processing before mixing, and bake out temperature is 60-80 ℃.
10. preparation method according to claim 6, is characterized in that, described egg-shell meal adopts 100-1000 purpose egg-shell meal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310090895.8A CN103183938B (en) | 2013-03-21 | 2013-03-21 | Polycaprolactone/poly butylene succinate/egg-shell meal matrix material and method for making thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310090895.8A CN103183938B (en) | 2013-03-21 | 2013-03-21 | Polycaprolactone/poly butylene succinate/egg-shell meal matrix material and method for making thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103183938A true CN103183938A (en) | 2013-07-03 |
| CN103183938B CN103183938B (en) | 2015-08-26 |
Family
ID=48675397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310090895.8A Expired - Fee Related CN103183938B (en) | 2013-03-21 | 2013-03-21 | Polycaprolactone/poly butylene succinate/egg-shell meal matrix material and method for making thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103183938B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674615A (en) * | 2016-11-22 | 2017-05-17 | 汪逸凡 | Preparation method of enhanced type polycaprolactone biodegradable plastics |
| GB2596154A (en) * | 2020-06-11 | 2021-12-22 | Listen Green Tech Co Ltd | Disposable eggshell eco-friendly material and manufacturing method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735626A (en) * | 2009-12-25 | 2010-06-16 | 李国涛 | Specific modified cold-mixed asphalt for heat-area normal-temperature blending asphalt concrete |
-
2013
- 2013-03-21 CN CN201310090895.8A patent/CN103183938B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735626A (en) * | 2009-12-25 | 2010-06-16 | 李国涛 | Specific modified cold-mixed asphalt for heat-area normal-temperature blending asphalt concrete |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674615A (en) * | 2016-11-22 | 2017-05-17 | 汪逸凡 | Preparation method of enhanced type polycaprolactone biodegradable plastics |
| GB2596154A (en) * | 2020-06-11 | 2021-12-22 | Listen Green Tech Co Ltd | Disposable eggshell eco-friendly material and manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103183938B (en) | 2015-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109401225B (en) | Biodegradable preservative film and preparation method thereof | |
| Makhijani et al. | Biodegradability of blended polymers: A comparison of various properties | |
| CN109777048B (en) | Biomass composite material for toothbrush handle and preparation method thereof | |
| CN102796286A (en) | Full-biodegradable material and preparation method thereof | |
| CN103992518B (en) | Biodegradable packaging material | |
| CN102604164A (en) | Master batch capable of fully and biologically degrading plastic film and preparation method thereof | |
| CN102585464B (en) | Polylactic acid (PLA)/polybutylene succinate (PBS)/bamboo powder composite material and preparation method thereof | |
| CN102643523B (en) | Modified polylactic acid/polycaprolactone composite material and preparation method thereof | |
| CN113354929A (en) | Low-precipitation biodegradable PLA alloy, preparation method thereof and straw material | |
| CN106336531A (en) | Modified corn straw granule enhanced PBAT [poly(butyleneadipate-co-terephthalate)] starch composite material and preparation method thereof | |
| CN103183937B (en) | A kind of modified polylactic acid composite material and preparation method thereof | |
| WO2021017031A1 (en) | Nanoscale plant fiber modified biodegradable composite material, preparation method therefor, and application thereof | |
| CN109825045A (en) | Graphene composite biomass reinforced PBS/PBAT biodegradable composite material and preparation method thereof | |
| CN106916421A (en) | One kind enhancing is poly-（Terephthalic acid (TPA) butanediol co adipic acid butanediols）Ester degradable material | |
| CN102134380B (en) | Completely biodegradable composite material and preparation method thereof | |
| CN112094487A (en) | Easily-cleaned high-temperature-resistant polylactic acid composite material for environment-friendly tableware | |
| CN103183938B (en) | Polycaprolactone/poly butylene succinate/egg-shell meal matrix material and method for making thereof | |
| CN102250389A (en) | Biodegradable polymer material compatibilized and blended by lignocellulose and preparation method thereof | |
| Osman et al. | Effects of durian seed flour on processing torque, tensile, thermal and biodegradation properties of polypropylene and high density polyethylene composites | |
| CN102604344B (en) | Polycaprolactone/poly (butylene succinate) composite material and preparation method thereof | |
| CN102424719A (en) | Straw powder-containing modified poly lactic acid composite material and preparation method thereof | |
| CN102558795A (en) | Polylactic acid-starch blended material and preparation method thereof | |
| CN113234305A (en) | Degradable composite material and preparation method and application thereof | |
| WO2019019443A1 (en) | Chlorinated poly(propylene carbonate)/biomass composite material and preparation method therefor | |
| CN111560159A (en) | Bamboo powder poly (butylene succinate) starch biodegradable plastic and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150826 Termination date: 20200321 |