CN1436812A - Compound of polyhydroxy phytanate and polypropylene carbonate - Google Patents
Compound of polyhydroxy phytanate and polypropylene carbonate Download PDFInfo
- Publication number
- CN1436812A CN1436812A CN 03105020 CN03105020A CN1436812A CN 1436812 A CN1436812 A CN 1436812A CN 03105020 CN03105020 CN 03105020 CN 03105020 A CN03105020 A CN 03105020A CN 1436812 A CN1436812 A CN 1436812A
- Authority
- CN
- China
- Prior art keywords
- pha
- ester
- polypropylene carbonate
- work
- softening agent
- 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
Abstract
The present invention is one kind of compound of polyhydroxy alkanoate and polypropylene carbonate and its preparation process. Polyhydroxy alkanoate(s) in 100 weight portions, polypropylene carbonate in 10-100 weight portions, plasticizer in 10-100 weight portions, antioxidant in 1-3 weight portions and nucleator in 1-4 weight portions are pre-mixed and then mixed and pelletized at the melting temperature of polyhydroxyalkanoat to obtain the compound. The compound has the advantages of both polyhydroxy alkanoate and polypropylene carbonate, excellent comprehensive mechanical performance and no brittleness similar to that of polyhydroxy alkanoate.
Description
Technical field
The present invention relates to mixture of a kind of PHA and polypropylene carbonate and preparation method thereof.
Background technology
Along with science and technology development, the application of macromolecular material in people's life, work more and more widely.But the most macromolecular materials that use all are difficult to degraded in physical environment now, and the depleted superpolymer causes white pollution and black pollution, bring harm for people's live and work.Add the continuous enhancing of people's environmental consciousness, the scarcity of petroleum resources on the earth, Biodegradable Polymers just become many in recent years companies and researcher drops into the main direction that great effort is developed.
Polyhydroxycarboxyliacid acid fat (PHA) is a kind of biodegradable thermoplastic plastics, both can use biological fermentation process, also can prepare with chemical synthesis; Can make film, injection-molded item, foam article and extrusion moulding with traditional plastic working method; Can be in soil, seawater complete biodegradable, degrading in the presence of illumination and microorganism speeds up, free from environmental pollution; Having excellent biocompatibility simultaneously, is the ideal material of aspects such as medicament slow release controlled release, operating sutures, bone surgery be fixing.Because These characteristics, PHA is in agricultural, medicine, and the food product pack field has broad prospects.But most PHA products, particularly PHB, the PHBV that HV content is lower, its degree of crystallinity height, fragility big (Polymer, 1992,33 (15), 3295-3297), shock strength is low, thereby has limited being extensive use of of it.Although can reduce degree of crystallinity, thereby improve its toughness by improving the structure that the copolymerization second monomeric content changes molecular chain, the raising of copolymerization second monomer content can make the crystallization velocity of product become very slow, and the productive expense costliness.Another kind of more effective, more economical method is to come modification by carrying out blend with the lower polymkeric substance of suitable price or micromolecular compound.WO9428048A1 has reported a kind of working method of the PHA of raising performance, mainly is to realize by adding effective auxiliary agent.
Polypropylene carbonate is a kind of aliphatic polycarbonate, be aboveground auspicious flat (Makromol.Chem., 130,210 (1969)) that are synthesized the earliest by Japan, the thermo-mechanical analysis result shows that it is a kind of amorphous polymer (J.Appl.Polym.Sci., 18,1575 (1974)), second-order transition temperature is lower, about 35 ℃, than about only high 10 degree of common room temperature, therefore be difficult to use as plastics separately, generally a kind of properties-correcting agent as rubber or plastics uses.Chinese patent CN1176269 and CN1239110 have reported that polypropylene carbonate joins tangible reinforcing effect is arranged in the styrene-butadiene rubber(SBR).Chinese patent CN1058408, CN1239721, CN1232051 have reported the modified effect of polypropylene carbonate to nitrile rubber, terpolymer EP rubber, natural rubber respectively.These work all are the strengthening agent use of polypropylene carbonate as rubber.
Summary of the invention
The mixture that the purpose of this invention is to provide a kind of PHA and polypropylene carbonate;
Another object of the present invention provides the preparation method of the mixture of a kind of PHA and polypropylene carbonate.
Cause the big shortcoming of fragility at PHA because of the degree of crystallinity height, select the polypropylene carbonate of amorphous for use, cooperate softening agent, oxidation inhibitor and nucleator, carry out compound with PHA again, improve PHA degree of crystallinity, thereby obtain the mixture that comprehensive mechanical property is better, have higher toughness.
The mixture of a kind of PHA provided by the invention and polypropylene carbonate specifically consists of: be made up of one or more PHAs of 100 parts of parts by weight, the polypropylene carbonate of 10-100 part, the softening agent of 5-50 part, the oxidation inhibitor of 1-3 part and the nucleator of 1-4 part.
Wherein the structure of PHA (PHA) is:
Work as m=1, when R was methyl, PHA was the poly butyric ester PHB that uses always; Work as m=1, when R was methyl and ethyl, PHA was butyric ester and hydroxypentanoic acid resin copolymer (PHBV); Work as m=1, when R was ethyl, PHA was the poly-hydroxyl valerate PHV that uses always; PHA is by biological fermentation process or chemosynthesis preparation; Softening agent is phthalic ester, citrate, certain herbaceous plants with big flowers two acid esters, adipic acid ester, phosphoric acid ester, contains the oligopolymer or 1, the 2 propylene glycol carbonic ether of the ethylene glycol of 2-10 carbon atom that wherein ester group is C
1-C
12Alkyl; Oxidation inhibitor be four [3-(3 ', 5 '-di-t-butyl) propionic acid] pentaerythritol ester (antioxidant 1010), three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (oxidation inhibitor 168) or two (octadecyl) pentaerythritol diphosphites (oxidation inhibitor 618); Nucleator is potter's clay, wilkinite or Sodium Benzoate.
Technological process is as follows:
Cooperate polypropylene carbonate, softening agent, oxidation inhibitor, nucleator in high-speed mixer, to carry out earlier pre-mixing PHA, then materials mixed is joined in the Banbury mixer, under 120-170 ℃, 50 conditions of changeing, mixed 5 minutes, pull out sheet material rapidly in 120-170 ℃ mill again, cooled sheet material is cut into pellet with the shear force machine again.Perhaps directly carry out extruding pelletization after the pre-mixing and obtain mixture with twin screw extruder or single screw extrusion machine.The temperature of forcing machine is set at: feeding section 50-120 ℃, the mixing section temperature is 100-150 ℃, and the fluxing zone temperature is 120-170 ℃, and extrusion temperature is 100-160 ℃.
The present invention has utilized the amorphism characteristics of polypropylene carbonate, cooperate softening agent, improve the toughness of PHA, mixture has good comprehensive mechanical property, has overcome PHA and has caused the big shortcoming of fragility because of the degree of crystallinity height, polypropylene carbonate is used as toughner, widened its range of application, the raw material of processing aid is easy to get, and complete processing is simple, utilize compounding technology, reduced the cost of product.
Embodiment embodiment 1: take by weighing each component PHB 100 polypropylene carbonates 10 tributyl phosphates 5 antioxidant 1010s 1.0 potter's clay 1.0 by following prescription (weight part) and earlier each component is carried out pre-mixing 5 minutes in high-speed mixer then, materials mixed is joined extruding pelletization in the forcing machine again.The temperature setting of forcing machine is: 120 ℃ of feeding sections, and 150 ℃ of mixing sections, 170 ℃ of fluxing zones, 160 ℃ of heads, screw speed are 50 rev/mins.The tensile strength of gained material is 30MPa, and notched Izod impact strength is 51J/m.Embodiment 2: take by weighing each component PHB 100 polypropylene carbonates 100 dimethyl phthalates 40 oxidation inhibitor 618 3.0 wilkinite 4.0 by following prescription (weight part) and earlier each component is carried out pre-mixing 5 minutes in high-speed mixer, again materials mixed is joined in the Banbury mixer, at 170 ℃, mixed 5 minutes under 50 conditions of changeing, pull out sheet material rapidly in 170 ℃ mill again, cooled sheet material is cut into pellet with the shear force machine again.The tensile strength of material is 12MP
aNotched Izod impact strength is 160J/m embodiment 3: take by weighing each component PHB 80PHBV (8V%) 20 polypropylene carbonates 60 tributyl citrates 20 oxidation inhibitor 168 3.0 Sodium Benzoate 1.5 by following prescription (weight part) and obtain matrix material by the mixing expressing technique granulation of embodiment 1, being set to of forcing machine: 80 ℃ of feeding sections, 130 ℃ of mixing sections, 170 ℃ of fluxing zones, 160 ℃ of heads, screw speed are 50 rev/mins.The tensile strength of gained material is 20MP
a, notched Izod impact strength is 180J/m.Embodiment 4: take by weighing each component PHV 100 polypropylene carbonates 100 ethylene glycol 50 antioxidant 1010s 2.0 wilkinite 2.0 by following prescription (weight part) and obtain matrix material by the mixed granulation process of embodiment 2, mix with the temperature of opening the refining pulling-on piece being 120 ℃.The tensile strength of gained material is 16MP
a, notched Izod impact strength is 140J/m.Embodiment 5: take by weighing each component PHBV (20V%) 100 polypropylene carbonate 601 by following prescription (weight part), 2 propylene glycol carbonic ethers, 30 antioxidant 1010s, 3.0 potter's clay 4.0 obtain matrix material by the mixed granulation process of embodiment 2, mix with the temperature of opening the refining pulling-on piece to be 140 ℃.The tensile strength of gained material is 11MP
a, notched Izod impact strength is 280J/m.
Embodiment 6PHV 100 polypropylene carbonates 60 hexanodioic acids two different certain herbaceous plants with big flowers ester 20 antioxidant 1010s 1.5 wilkinites 2.0 obtain matrix material by the mixing expressing technique granulation of embodiment 1, being set to of forcing machine: 50 ℃ of feeding sections, 100 ℃ of mixing sections, 115 ℃ of fluxing zones, 110 ℃ of heads, screw speed are 50 rev/mins.The tensile strength of gained material is 15MP
a, notched Izod impact strength is 110J/m.Embodiment 7: take by weighing each component PHBV (8V%) 100 polypropylene carbonates 70 certain herbaceous plants with big flowers two dibutyl phthalates 30 antioxidant 1010s 3.0 potter's clay 1.5 by following prescription (weight part) and obtain matrix material by the mixed granulation process of embodiment 2, mix with the temperature of opening the refining pulling-on piece being 165 ℃.The tensile strength of gained material is 18MP
a, notched Izod impact strength is 170J/m.Embodiment 8: take by weighing each component PHB 60PHBV (20V%) 40 polypropylene carbonates 50 BLP butyl lauryl phthalates 10 antioxidant 1010s 3.0 potter's clay 3.5 by following prescription (weight part) and obtain matrix material by the mixing expressing technique granulation of embodiment 1, being set to of forcing machine: 110 ℃ of feeding sections, 130 ℃ of mixing sections, 170 ℃ of fluxing zones, 160 ℃ of heads, screw speed are 50 rev/mins.The tensile strength of gained material is 22MP
a, notched Izod impact strength is 150J/m.
Claims (2)
1. the mixture of PHA and polypropylene carbonate, it consists of: the softening agent of one or more PHAs that parts by weight are 100 parts, the polypropylene carbonate of 10-100 part, 5-50 part, the oxidation inhibitor of 1-3 part and the nucleator of 1-4 part;
Wherein the structure of PHA is:
Work as m=1, when R was methyl, PHA was a poly butyric ester; Work as m=1, when R was methyl and ethyl, PHA was butyric ester and hydroxypentanoic acid resin copolymer; Work as m=1, when R was ethyl, PHA was poly-hydroxyl valerate; Softening agent is phthalic ester, citrate, certain herbaceous plants with big flowers two acid esters, adipic acid ester, phosphoric acid ester, contain the oligopolymer or 1 of the ethylene glycol of 2-10 carbon atom, 2 propylene glycol carbonic ethers, oxidation inhibitor be four [3-(3 ', 5 '-di-t-butyl) propionic acid] pentaerythritol ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester or two (octadecyl) pentaerythritol diphosphites; Nucleator is potter's clay, wilkinite or Sodium Benzoate.
2. the mixture of PHA as claimed in claim 1 and polypropylene carbonate is characterized in that softening agent is that ester group in phthalic ester, citrate, certain herbaceous plants with big flowers two acid esters, adipic acid ester or the phosphoric acid ester is C
1-C
12Alkyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03105020 CN1436812A (en) | 2003-03-03 | 2003-03-03 | Compound of polyhydroxy phytanate and polypropylene carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03105020 CN1436812A (en) | 2003-03-03 | 2003-03-03 | Compound of polyhydroxy phytanate and polypropylene carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1436812A true CN1436812A (en) | 2003-08-20 |
Family
ID=27634046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03105020 Pending CN1436812A (en) | 2003-03-03 | 2003-03-03 | Compound of polyhydroxy phytanate and polypropylene carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1436812A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007125039A1 (en) * | 2006-04-27 | 2007-11-08 | Basf Se | Transparent blends of polypropylene carbonate |
| US7825179B2 (en) | 2005-10-05 | 2010-11-02 | Unitika Ltd. | Biodegradable resin composition, production method therefor, and product molded or formed therefrom |
| CN101827889B (en) * | 2007-10-16 | 2012-01-04 | 帝人化成株式会社 | Aromatic polycarbonate resin composition |
| CN103951960A (en) * | 2014-05-23 | 2014-07-30 | 中国科学院长春应用化学研究所 | Modified polypropylene carbonate and preparation method thereof |
| CN104130562A (en) * | 2014-07-28 | 2014-11-05 | 江苏嘉铂新材料有限公司 | Nano-bentonite composite flame-retardant polyhydroxybutyrate bioplastic and preparation method thereof |
| EP2933283A1 (en) | 2014-04-17 | 2015-10-21 | Changchun Institute Of Applied Chemistry Chinese Academy Of Sciences | Chlorinated poly(propylene carbonate) and preparation method thereof |
| CN106521688A (en) * | 2016-09-22 | 2017-03-22 | 江南大学 | High strength coarse denier (3-hydroxybutryate-co-3-hydroxylpentanoate) filament and preparation method thereof |
| CN109486129A (en) * | 2018-11-01 | 2019-03-19 | 南京五瑞生物降解新材料研究院有限公司 | PHA modified PPC/PBAT biodegradable resin and preparation method thereof |
-
2003
- 2003-03-03 CN CN 03105020 patent/CN1436812A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7825179B2 (en) | 2005-10-05 | 2010-11-02 | Unitika Ltd. | Biodegradable resin composition, production method therefor, and product molded or formed therefrom |
| CN101223239B (en) * | 2005-10-05 | 2011-11-16 | 尤尼吉可株式会社 | Biodegradable resin composition, process for production of the same, and molded article using the same |
| WO2007125039A1 (en) * | 2006-04-27 | 2007-11-08 | Basf Se | Transparent blends of polypropylene carbonate |
| CN101827889B (en) * | 2007-10-16 | 2012-01-04 | 帝人化成株式会社 | Aromatic polycarbonate resin composition |
| EP2933283A1 (en) | 2014-04-17 | 2015-10-21 | Changchun Institute Of Applied Chemistry Chinese Academy Of Sciences | Chlorinated poly(propylene carbonate) and preparation method thereof |
| US9546245B2 (en) | 2014-04-17 | 2017-01-17 | Changchun Institute Of Applied Chemistry, Chinese Academy Of Sciences | Chlorinated poly(propylene carbonate) and preparation method thereof |
| US9908969B2 (en) | 2014-04-17 | 2018-03-06 | Changchun Institute Of Applied Chemistry, Chinese Academy Of Sciences | Chlorinated poly(propylene carbonate) and preparation method thereof |
| CN103951960A (en) * | 2014-05-23 | 2014-07-30 | 中国科学院长春应用化学研究所 | Modified polypropylene carbonate and preparation method thereof |
| CN103951960B (en) * | 2014-05-23 | 2016-04-20 | 中国科学院长春应用化学研究所 | A kind of modification polypropylene carbonate and preparation method thereof |
| CN104130562A (en) * | 2014-07-28 | 2014-11-05 | 江苏嘉铂新材料有限公司 | Nano-bentonite composite flame-retardant polyhydroxybutyrate bioplastic and preparation method thereof |
| CN106521688A (en) * | 2016-09-22 | 2017-03-22 | 江南大学 | High strength coarse denier (3-hydroxybutryate-co-3-hydroxylpentanoate) filament and preparation method thereof |
| CN109486129A (en) * | 2018-11-01 | 2019-03-19 | 南京五瑞生物降解新材料研究院有限公司 | PHA modified PPC/PBAT biodegradable resin and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111995848B (en) | Degradable plastic composition and preparation method and application thereof | |
| US6841603B1 (en) | Polymer blends containing polyhydroxyalkanoates and compositions with good retention of elongation | |
| JP5736091B2 (en) | Thermoplastic starch and biodegradable polyester / starch composites and their preparation | |
| EP2480589B1 (en) | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof | |
| CN101475735B (en) | Completely biodegradable polyhydroxyalkanote / poly(butylene succinate) blending alloy | |
| CN104072957B (en) | A kind of food grade biodegradable polylactic acid based composites and application thereof | |
| EP1789488B1 (en) | Nucleating agents for polyhydroxyalkanoates | |
| US8691913B2 (en) | Polylactic acid compositions, polylactic acid materials and methods of preparing the same | |
| CA1339026C (en) | Degradable thermoplastics from lactides | |
| CN101280095A (en) | Glass fiber reinforced polyethylene glycol terephthalate composite material and preparation thereof | |
| WO2008028344A1 (en) | The composition containing polyhydroxyalkanoate copolymer and polylactic acid used for foam | |
| JP2009527594A (en) | Environmentally degradable polymer composition and method for obtaining an environmentally degradable polymer composition | |
| CN108822514A (en) | A kind of completely biological degradation polylactic acid base inflation film and preparation method thereof | |
| CN106674923B (en) | A kind of controllable PBAT/PLA composite membranes and preparation method thereof of degrading | |
| CN112552654B (en) | PBAT/PHA/wood flour composition suitable for preparing film and preparation and application thereof | |
| CN112920567A (en) | Wheat straw filled modified PLA fully-degradable plastic and preparation method thereof | |
| WO2007095708A1 (en) | Environmentally degradable polymeric blend and process for obtaining an environmentally degradable polymeric blend | |
| JP6666328B2 (en) | Method for producing polyester resin composition and molded article, and polyester resin composition and molded article | |
| CN1436812A (en) | Compound of polyhydroxy phytanate and polypropylene carbonate | |
| KR101322600B1 (en) | Biodegradable plastic composition | |
| CN112961479A (en) | Coffee-flavored completely biodegradable plant-based material and preparation method and application thereof | |
| CN1215122C (en) | Biodegradable aliphatic polyester composite material | |
| EP3246361B1 (en) | Polyester resin composition and polyester resin formed article | |
| CN111961321A (en) | Biodegradable poly (4-hydroxybutyrate) agricultural mulching film and preparation method thereof | |
| CN115627057B (en) | Straw 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 | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |