CN101974136A - Method for preparing high-toughness degradable material by using melt-grafting blending method - Google Patents
Method for preparing high-toughness degradable material by using melt-grafting blending method Download PDFInfo
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- CN101974136A CN101974136A CN2010105105266A CN201010510526A CN101974136A CN 101974136 A CN101974136 A CN 101974136A CN 2010105105266 A CN2010105105266 A CN 2010105105266A CN 201010510526 A CN201010510526 A CN 201010510526A CN 101974136 A CN101974136 A CN 101974136A
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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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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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
- B29C48/92—Measuring, controlling or regulating
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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
- 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
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- 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
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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
- 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
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to a method for preparing a high-toughness degradable material by using a melt-grafting blending method, which comprises the following steps: (1) carrying out melt-grafting on polycaprolactone PCL, anhydride and an initiator, and then obtaining modified polycaprolactone by way of extrusion granulation, wherein the mass ratio of the polycaprolactone PCL to the anhydride to the initiator is 100: (1 to 10): 0.5; and (2) carrying out melt-grafting blending on poly (3-hydroxybutyrate-3-hydroxyvalerate) PHBV, the modified polycaprolactone, methyl acrylate and an initiator, and then obtaining the high-toughness PHBV-class degradable material by way of extrusion granulation, wherein the mass ratio of the poly (3-hydroxybutyrate-3-hydroxyvalerate) PHBV to the modified polycaprolactone to the methyl acrylate to the initiator is 100: (5 to 50): (0.5 to 10):0.5, the processing temperature is 100 to 170 DEG C, and the screw speed is 50-80 R.P.M. The method is simple in process, low in cost, and suitable for industrialization, and the elongation at break of the produced PHBV-class degradable material can reach 560 percent; therefore, the method of the invention has good application prospect.
Description
Technical field
The invention belongs to toughness reinforcing biodegradable plastic field, particularly relate to a kind of method that adopts the fusion-grafting blending method to prepare the high tenacity degradation material.
Background technology
Along with the progress of science and technology and the development of Green Chemistry, various degradable macromolecular materials have caused people's very big concern, and environment-degradable plastic mainly contains biodegradable plastic, photodegradable plastics and light/biodegradable plastic at present.PHB in the biodegradable plastic family (poly-(3-butyric ester)) and PHBV (poly-(3-butyric ester-3-hydroxyl valerate)) are that a class is passed through microorganism synthetic aliphatic polyester, have caused people's very big concern because of its performance with a lot of excellences.The repeating unit HB of PHB and PHBV and the structural formula of HV are as follows:
HB：-[O-CH(CH
3)-CH
2-CO-]
HV：-[O-CH(C
2H
5)-CH
2-CO-]
Excellent biodegradability and biocompatibility make in fields such as articles for daily use, medical science and agricultural and demonstrate great potential and business opportunity, can be used for daily plastics, pharmaceutical carrier, surgical stapling, agricultural mulching etc.But PHB is extremely unstable under the high temperature, and process window is narrow, just easily is degraded into the low product of relative molecular mass during the several years being higher than fusing point, has reduced its mechanical property; PHB and PHBV fragility are very high in addition, and is easily cracked, and when HV content was 1.14%, its elongation at break only was 0.98%.With the increase of HV content, the toughness of PHBV has the content that improves HV slightly to be lower than at 20% o'clock, and PHBV still shows as more crisp and behavior easy fracture.Have only HV content greater than 20%, PHBV just has good toughness.But the PHBV that will obtain high-content HV also has certain limitation technically.
At the high fragility of PHB and PHBV material, unmanageable shortcoming, processing modifiedly mainly concentrate on toughness reinforcing and two aspects of plasticising.Parulekar etc. utilize renewable resources natural rubber and epoxy natural rubber as toughner to carrying out blending and modifying, improve its toughness.In the phenolic compound phenolic hydroxyl group easily with PHB or PHBV in the hydroxyl oxygen atom form hydrogen bond, thereby the special interaction of generation in phenol.Chinese patent 02156420.5 has been applied for relevant PHB and the toughness reinforcing patent of PHBV, employing contains in the matrix that the phenolic hydroxyl group component is filled into PHB and PHBV, by phenolic hydroxyl group and and carbonylic oxygen atom between hydrogen bond action destroyed the crystallization of PHB and PHBV, thereby improved the mechanical property of PHB and PHBV.The PHB and the PHBV that obtain having excellent toughness by solution blending and melt blending are material modified.But the elongation at break of material is only to improve about 200%.
The report of the reactive toughness reinforcing aspect of PHB and PHBV is less at present.Therefore all have active hydrogen atom (tertiary carbon hydrogen atom) among PHB and the PHBV, under the situation that initiator exists, the tertiary carbon at this active hydrogen atom place easily forms cross-linking set, thereby makes or chemically crosslinked takes place, and forms the gel in the similar vulcanized rubber.It is crosslinked that Dong etc. by linking agent dicumyl peroxide (DCP) PHBV have taken place, and studied the crosslinked parameter (gel quality affects content, swelling ratio etc.) of cross-linking products.And having confirmed the position of cross-linking set by solid-state nuclear magnetic resonance spectrum, PHBV tensile strength of material and elongation at break after crosslinked all increase.
Among the U.S. Pat Patent 4427614 (1984), people such as Holmes P.A. and Barham P.J. propose " cold rolling " method (cold-rolling), have controlled the crackle in the PHB spherocrystal, and the mechanical property of PHB is improved.It is very difficult that but this working method implements, and can not be pushed wide application.
By different polymers (wherein a certain component also can the be low molecule) blend with two or more, thereby polymer being carried out modification, is a kind of simple and easy to do, comparatively economic method of modifying.The main purpose of PHBV blending and modifying is the reduction material price, widens the process window of material, improves the mechanical property of material crystal property, processing characteristics and final material etc.The main research contents of blending and modifying is: the thermal behavior of all kinds of co-mixing systems, crystallization behavior, consistency, morphological structure and material mechanical performance, biodegradability etc.By research, can sum up related law, thereby be that screening, the material for preparing desired properties lay the foundation all kinds of co-mixing systems.
(PCL Polycaprolacton) with its superior biodegradable and memory, begins to obtain extensive concern to polycaprolactone, and its relevant research is also developed rapidly.But the PCL fusing point is lower, has only about 60 ℃, and the heat-resistant deforming performance is relatively poor.So adopt PHBV and PHB grafting PCL method to prepare the biological degradation blend, can improve PHBV and PHB toughness, also can improve the thermotolerance of PCL.
Graft modification is to introduce suitable polar side chain on molecular chain, utilizes the polarity and the reactivity of side chain, improves the deficiency on the superpolymer performance, increases new character simultaneously.The grafted method mainly contains solution grafting, fusion-grafting method, solid phase grafting method and suspension grafting method etc.Wherein fusion-grafting is more than melting point polymer, with grafted monomer and polymkeric substance fusion together, and carries out graft reaction under the initiator effect.
It is that the plasticizing extrusion system formed with screw rod and barrel is as flow reactor that reactivity is extruded, various feed composition with the desire reaction, as monomer, initiator, polymkeric substance, auxiliary agent etc. once or gradation join in the screw rod by identical or different charging openings, under screw rod rotates, realize mixing, conveying, plasticizing, reaction between each raw material and the process of extruding from die orifice.The tradition extrusion generally is raw material with the polymkeric substance, by add impose on material in heat and the screw rod rotation process shearing friction heat with its fusion and mix, extrude, obtain goods behind the die modeling, demoulding cooling through die orifice then.Its extrusion is the process based on physical change of material by solid-state (crystal form or vitreous state)-liquid (viscous state)-solid-state (crystal form or vitreous state).And reactivity exists chemical transformation in extruding, as the polyreaction of the polycondensation between the monomer, addition, open loop formation superpolymer, the graft reaction between polymkeric substance and the monomer, the crosslinking reaction between the polymkeric substance.
According to above basic technology as can be known: the defective of prior art is in the PHBV toughening modifying, good toughening effect is arranged chemical modification but complex process is difficult to form suitability for industrialized production, and technology physically modified simple to operation can not get comparatively ideal toughening effect.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method that adopts the fusion-grafting blending method to prepare the high tenacity degradation material, present method technology is simple, cost is low, be fit to industrialization, and the PHBV class degradable plastics elongation at break that makes can reach 560%, has a good application prospect.
A kind of method that adopts the fusion-grafting blending method to prepare the high tenacity degradation material of the present invention comprises:
(1) polycaprolactone (PCL), acid anhydrides and initiator were carried out fusion-grafting in 100: 1～10: 0.5 by mass ratio, make the modification polycaprolactone through extruding pelletization;
(2) will gather (3-butyric ester-3-hydroxyl valerate) PHBV, modification polycaprolactone, methacrylic ester and initiator and carry out the fusion-grafting blend in 100: 5～50: 0.5～10: 0.5 by mass ratio, processing temperature is 100～170 ℃, screw speed is 50-80 rev/min, makes the PHBV class degradable plastics of high tenacity through extruding pelletization.
PCL molecular weight in the described step (1) is 10,000～500,000.
Acid anhydrides in the described step (1) is maleic anhydride MAH or Tetra hydro Phthalic anhydride.
Fusion-grafting in the described step (1) carries out in twin screw or Banbury mixer, and the twin screw processing parameter is 50～130 ℃ of processing temperatures, rotating speed 30-50rad/s; The Banbury mixer processing parameter is processing temperature 70-140 ℃, screw speed 40-60rad/s.
Initiator in described step (1) or (2) is dibenzoyl peroxide BPO, Potassium Persulphate, cumyl hydroperoxide DCP, ditertiary butyl peroxide DTBP, tertbutyl peroxide TBH, Diisopropyl azodicarboxylate AIBN, 2,2'-Azobis(2,4-dimethylvaleronitrile) ABVN or di-isopropyl peroxydicarbonate IPP.
HV content is 0～40% among the PHBV in the described step (2).
Methacrylic ester in the described step (2) is glyceral methacrylate GMA, Propenoic acid, 2-methyl, isobutyl ester IBMA or hydroxyethyl methylacrylate HEMA.
Beneficial effect
Present method technology is simple, and cost is low, is fit to industrialization, and the PHBV class degradable plastics elongation at break that makes can reach 560%, has a good application prospect.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1:
PCL powder: molecular weight 10,000; Acid anhydrides: MAH; Initiator: BPO;
(1) PCL, MAH and BPO (PCL, MAH and BPO are 100: 1: 0.5 by mass percentage) are carried out the fusion-grafting mixing at twin screw, wherein extruder temperature is an intake zone: 50 ℃, and the preheating zone: 75 ℃, dissolve area: 120 ℃, the compression zone: 125 ℃, discharge port: 130 ℃; Screw speed: 30 rev/mins, the laggard dicing machine of blend makes modification PCL pellet; (2) (HV content is 0 among the PHBV with PHBV, modification PCL pellet, GMA and DCP; PHBV, modification PCL, GMA and DCP are 100: 5: 0.5 by mass percentage: 0.5) carry out fusion-grafting at twin screw and mix melt blending grafting temperature, intake zone: 100 ℃, preheating zone: 135 ℃, melting zone: 170 ℃, the compression zone: 165 ℃, discharge port: 160 ℃; Screw speed: 50 rev/mins, detect to such an extent that elongation at break is 120% through mechanics.
Embodiment 2:
PCL powder: molecular weight 30,000; Acid anhydrides: MAH; Initiator: AIBN;
(1) PCL, Tetra hydro Phthalic anhydride and BPO (PCL, Tetra hydro Phthalic anhydride and AIBN are 100: 10: 0.5 by mass percentage) are carried out blend graft, melting temperature: 70 ℃ in Banbury mixer; Screw speed: 40rad/s makes modification PCL pellet after the blend;
(2) (HV content is 40% among the PHBV with PHBV, modification PCL pellet, IBMA and DIBP; PHBV, modification PCL pellet, IBMA and DIBP are 100: 10: 10 by mass percentage: 0.5) carry out fusion-grafting at twin screw and mix melt blending grafting temperature, intake zone: 100 ℃, preheating zone: 135 ℃, melting zone: 150 ℃, the compression zone: 170 ℃, discharge port: 150 ℃; Screw speed: 50 rev/mins, detect to such an extent that elongation at break is 318% through mechanics.
Embodiment 3:
PCL powder: molecular weight 80,000, median size 10 μ m; Acid anhydrides: MAH; Initiator: DCP;
(1) PCL, MAH and isopropyl benzene hydroperoxide (PCL, MAH and DCP are 100: 3: 0.5 by mass percentage) are carried out the fusion-grafting mixing at twin screw, wherein extruder temperature is an intake zone: 50 ℃, and the preheating zone: 75 ℃, dissolve area: 120 ℃, the compression zone: 125 ℃, discharge port: 130 ℃; Screw speed: 12 rev/mins, the laggard dicing machine of blend makes modification PCL pellet;
(2) (HV content is 10% among the PHBV with PHBV, modification PCL pellet, HEMA and TBH; PHBV, modification PCL, HEMA and TBH are 100: 30: 3 by mass percentage: 0.5) carry out fusion-grafting at twin screw and mix screw rod melt blending temperature, intake zone: 140 ℃, preheating zone: 165 ℃, melting zone: 170 ℃, the compression zone: 160 ℃, discharge port: 160 ℃; Screw speed: 30 rev/mins, detect to such an extent that elongation at break is 355% through mechanics.
Embodiment 4:
PCL powder: molecular weight 500,000; Acid anhydrides: MAH; Initiator: Potassium Persulphate;
(1) PCL, MAH and Potassium Persulphate (PCL, MAH and Potassium Persulphate are 100: 2: 0.5 by mass percentage) are carried out blend graft, melting temperature: 140 ℃ in Banbury mixer; Screw speed: 60rad/s makes modification PCL pellet after the blend;
(2) (HV content is 15% among the PHBV with PHBV, modification PCL pellet, GMA and AIBN; PHBV, modification PCL, GMA and AIBN are 100: 50: 2 by mass percentage: 0.5) carry out fusion-grafting at twin screw and mix melt blending grafting temperature, intake zone: 100 ℃, the preheating zone: 135 ℃, melting zone: 170 ℃, the compression zone: 165 ℃, discharge port: 160 ℃; Screw speed: 50 rev/mins, detect to such an extent that elongation at break is 560% through mechanics.
Embodiment 5:
PCL powder: molecular weight 100,000; Acid anhydrides: MAH; Initiator: ABVN;
(1) PCL, MAH and Potassium Persulphate (PCL, MAH and ABVN are 100: 2: 0.5 by mass percentage) are carried out blend graft, melting temperature: 140 ℃ in Banbury mixer; Screw speed: 60rad/s makes modification PCL pellet after the blend;
(2) (HV content is 15% among the PHBV with PHBV, modification PCL pellet, GMA and IPP; PHBV, modification PCL, GMA and IPP are 100: 40: 2 by mass percentage: 0.5) carry out fusion-grafting at twin screw and mix melt blending grafting temperature, intake zone: 100 ℃, the preheating zone: 135 ℃, melting zone: 170 ℃, the compression zone: 165 ℃, discharge port: 160 ℃; Screw speed: 50 rev/mins, detect to such an extent that elongation at break is 540% through mechanics.
Claims (7)
1. method that adopts the fusion-grafting blending method to prepare the high tenacity degradation material comprises:
(1) polycaprolactone (PCL), acid anhydrides and initiator were carried out fusion-grafting in 100: 1～10: 0.5 by mass ratio, make the modification polycaprolactone through extruding pelletization;
(2) will gather (3-butyric ester-3-hydroxyl valerate) PHBV, modification polycaprolactone, methacrylic ester and initiator and carry out the fusion-grafting blend in 100: 5～50: 0.5～10: 0.5 by mass ratio, processing temperature is 100～170 ℃, screw speed is 50-80 rev/min, makes the PHBV class degradable plastics of high tenacity through extruding pelletization.
2. a kind of method that adopts the fusion-grafting blending method to prepare the high tenacity degradation material according to claim 1 is characterized in that: the PCL molecular weight in the described step (1) is 10,000～500,000.
3. a kind of method that adopts the fusion-grafting blending method to prepare the high tenacity degradation material according to claim 1 is characterized in that: the acid anhydrides in the described step (1) is maleic anhydride MAH or Tetra hydro Phthalic anhydride.
4. a kind of method that adopts the fusion-grafting blending method to prepare the high tenacity degradation material according to claim 1, it is characterized in that: the fusion-grafting in the described step (1) carries out in twin screw or Banbury mixer, the twin screw processing parameter is 50～130 ℃ of processing temperatures, rotating speed 30-50rad/s; The Banbury mixer processing parameter is processing temperature 70-140 ℃, screw speed 40-60rad/s.
5. a kind of method that adopts the fusion-grafting blending method to prepare the high tenacity degradation material according to claim 1 is characterized in that: the initiator in described step (1) or (2) is dibenzoyl peroxide BPO, Potassium Persulphate, cumyl hydroperoxide DCP, ditertiary butyl peroxide DTBP, tertbutyl peroxide TBH, Diisopropyl azodicarboxylate AIBN, 2,2'-Azobis(2,4-dimethylvaleronitrile) ABVN or di-isopropyl peroxydicarbonate IPP.
6. a kind of method that adopts the fusion-grafting blending method to prepare the high tenacity degradation material according to claim 1 is characterized in that: HV content is 0～40% among the PHBV in the described step (2).
7. a kind of method that adopts the fusion-grafting blending method to prepare the high tenacity degradation material according to claim 1 is characterized in that: the methacrylic ester in the described step (2) is glyceral methacrylate GMA, Propenoic acid, 2-methyl, isobutyl ester IBMA or hydroxyethyl methylacrylate HEMA.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224697A (en) * | 2013-05-21 | 2013-07-31 | 上海交通大学 | Completely-biodegradable PHA (polyhydroxyalkanoate)/PCL (polycaprolactone) blend and preparation method thereof |
| CN105061687A (en) * | 2015-08-09 | 2015-11-18 | 罗卫华 | Compatibilizer concurrently flexibilizer made from polylactic acid compound materials and preparation method of compatibilizer concurrently flexibilizer |
| CN106084690A (en) * | 2016-06-08 | 2016-11-09 | 绍兴文理学院 | A kind of preparation method of PHBV/PP g MAH intermingling material |
| CN107936187A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | The thermoplastic cellulose of graft modification and Microbe synthesis polyester blend and preparation method |
| CN107936445A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | Thermoplastic film and preparation method thereof |
| CN107936501A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | Injection-molded item and preparation method thereof |
| CN107936442A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | 3D printing silk material and preparation method thereof |
| CN109749381A (en) * | 2019-01-08 | 2019-05-14 | 福建师范大学 | A kind of biomass-based masterbatch and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6191203B1 (en) * | 1997-10-31 | 2001-02-20 | Monsanto Company | Polymer blends containing polyhydroxyalkanoates and compositions with good retention of elongation |
| CN101516998A (en) * | 2006-09-19 | 2009-08-26 | 纳幕尔杜邦公司 | Toughened poly(hydroxyalkanoic acid) compositions |
| CN101679731A (en) * | 2007-05-14 | 2010-03-24 | 阿克马法国公司 | Coextrusion binders on a renewable/biodegradable basis |
-
2010
- 2010-10-18 CN CN2010105105266A patent/CN101974136B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6191203B1 (en) * | 1997-10-31 | 2001-02-20 | Monsanto Company | Polymer blends containing polyhydroxyalkanoates and compositions with good retention of elongation |
| CN101516998A (en) * | 2006-09-19 | 2009-08-26 | 纳幕尔杜邦公司 | Toughened poly(hydroxyalkanoic acid) compositions |
| CN101679731A (en) * | 2007-05-14 | 2010-03-24 | 阿克马法国公司 | Coextrusion binders on a renewable/biodegradable basis |
Non-Patent Citations (1)
| Title |
|---|
| 《材料导报》 20010515 胡芸等 PCL改性途径研究 第52页第3－5段 1 第15卷, 第5期 2 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224697A (en) * | 2013-05-21 | 2013-07-31 | 上海交通大学 | Completely-biodegradable PHA (polyhydroxyalkanoate)/PCL (polycaprolactone) blend and preparation method thereof |
| CN103224697B (en) * | 2013-05-21 | 2015-12-02 | 上海交通大学 | PHA/PCL blend of a kind of fully biodegradable and preparation method thereof |
| CN105061687A (en) * | 2015-08-09 | 2015-11-18 | 罗卫华 | Compatibilizer concurrently flexibilizer made from polylactic acid compound materials and preparation method of compatibilizer concurrently flexibilizer |
| CN106084690A (en) * | 2016-06-08 | 2016-11-09 | 绍兴文理学院 | A kind of preparation method of PHBV/PP g MAH intermingling material |
| CN107936187A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | The thermoplastic cellulose of graft modification and Microbe synthesis polyester blend and preparation method |
| CN107936445A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | Thermoplastic film and preparation method thereof |
| CN107936501A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | Injection-molded item and preparation method thereof |
| CN107936442A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | 3D printing silk material and preparation method thereof |
| CN107936442B (en) * | 2016-10-13 | 2020-12-29 | 中国石油化工股份有限公司 | 3D printing wire and preparation method thereof |
| CN107936187B (en) * | 2016-10-13 | 2021-03-26 | 中国石油化工股份有限公司 | Graft modified thermoplastic cellulose and microbial synthetic polyester blend and preparation method thereof |
| CN107936445B (en) * | 2016-10-13 | 2021-03-30 | 中国石油化工股份有限公司 | Thermoplastic film and method for producing the same |
| CN109749381A (en) * | 2019-01-08 | 2019-05-14 | 福建师范大学 | A kind of biomass-based masterbatch and preparation method thereof |
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