CN101205356A - Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid - Google Patents

Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid Download PDF

Info

Publication number
CN101205356A
CN101205356A CNA2006101579892A CN200610157989A CN101205356A CN 101205356 A CN101205356 A CN 101205356A CN A2006101579892 A CNA2006101579892 A CN A2006101579892A CN 200610157989 A CN200610157989 A CN 200610157989A CN 101205356 A CN101205356 A CN 101205356A
Authority
CN
China
Prior art keywords
phas
pla
blend
multipolymer
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.)
Withdrawn
Application number
CNA2006101579892A
Other languages
Chinese (zh)
Inventor
曾方
夏帮富
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHENZHEN O'BIOER TECHNOLOGY Co Ltd
Original Assignee
SHENZHEN O'BIOER TECHNOLOGY Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by SHENZHEN O'BIOER TECHNOLOGY Co Ltd filed Critical SHENZHEN O'BIOER TECHNOLOGY Co Ltd
Priority to CNA2006101579892A priority Critical patent/CN101205356A/en
Publication of CN101205356A publication Critical patent/CN101205356A/en
Withdrawn legal-status Critical Current

Links

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
    • B29C48/03—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
    • 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
    • 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
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
    • B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
    • 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
    • B29C48/94—Lubricating
    • B29C48/95—Lubricating by adding lubricant to the moulding material
    • 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
    • B29C2948/92895—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
    • B29C2948/92857—Extrusion unit
    • B29C2948/92904—Die; Nozzle zone

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The invention discloses a PHBV with good performance and a copolymer of PHBV and PLA and the preparation technique method. The invention is characterized in that 1 per cent to 99 per cent of PHAs, 1 per cent to 99 per cent of PLA1 and other additives 0-40 per cent are put in a mixer for 1 to 30 minutes, and then put in an electricity hot blast drying oven a temperature ranging from 40 to 100 DEG C for 2 to 48 hours after being mixed equally. The dried compound is plastified in a double screw extruder, the highest temperature of the double screw extruder is between 90 and 180 DEG C according to the the different content of PHAs and the temperature of the mouth mold is between110 to 170 DEG C. The material extruded from a die head is cooled, stretched and grained to form the complete biodegradation aggregate. The resin consisting of PHBV and copolymer of PHBV and PLA is able to be used for producing the thin films, plates and sheet materials and injected mold to plastic materials. The compound has biological degradability and good machining performance. The target product of the compound has excellent mechanical properties and can be used for replacing the petroleum base plastic to be widely used for packing, agriculture, medical material, electron, chemical industry concerning products for daily use, etc.

Description

The blending and modifying of PHA and multipolymer thereof and poly(lactic acid)
Technical field
The present invention relates to a kind of method of modifying of fully biodegradable macromolecular material, in particular, relate to a kind ofly, improve the processing characteristics and the use properties of these two kinds of degradation materials by PHAs and PLA blending and modifying.
Background technology
Along with the mankind to the continuous growth of energy demand, to the pay attention to day by day of environment protection, a large amount of petroleum-based energy of conventional plastic industry consumption and " white pollution " that brings receive increasing concern on the one hand in addition.Since last century 6, the seventies, people have begun the research and development to degradative plastics.Still under constantly making great efforts, along with technology is constantly progressive, existing now multiple biodegradable material (Biodegradable materials) comes out numerous at home and abroad scientists, and further perfect.Become water and carbonic acid gas after the biodegradable plastic degraded, therefore can not produce harm environment.Simultaneously, it can also carry out compost, and as fertilizer sources or soil improvement agent go back to nature.The research and development of biodegradable plastic and industrialization process have become the focus of attracting attention in the whole world.Many, the reasonable biodegradable plastic of performance of research both at home and abroad at present mainly contain PHA (PHAs) and poly(lactic acid) (PLA).
PHA (PHAs) be a class by microorganism synthetic macromolecule polyester, its molecular weight generally several ten thousand between millions of, extensively is present in the natural multiple microbe.The molecular structure diversity of PHAs is strong, therefore its performance also has very strong mutability and controllability, the polymkeric substance compositing monomer of having found at present is above 150 kinds, various monomeric different structures will bring many functions and application for biological polyester material, and new monomer will constantly be found.Its some physical properties and traditional petroleum-based plastics polypropylene-base are seemingly, and be synthetic by the reproducible energy, and can complete biodegradable.Because the difference of the polymerization single polymerization monomer and the polymerization degree, PHAs can realize changing to elasticity to softness from hard, its fusing point can change in 40 ℃～180 ℃ scopes, can produce molecular weight now 1,000～1,000, PHAs between 000, the elongation at break of these products is from 5%～1, and 000% does not wait, and degree of crystallinity is between 10% to 80%.
Wherein, be that poly 3-hydroxy butyrate PHB that monomer is formed is the most common a kind of among the PHAs with the 3-hydroxybutyric acid, be a kind of polymkeric substance of crystal type, because of its physical properties more crisp, similar and be not suitable for industrial applications with PLA.And the rerum natura of some multipolymers of PHB can be become soft tough by original hard embrittlement, as PHBV, becomes a kind of polymkeric substance of half hitch crystal formation, and its melt viscosity increases, thereby can improve hot workability, improves mechanical mechanics property simultaneously.Other multipolymers such as P3HB4HB, owing to introduce the flexible monomer 4HB of linear aliphatic, toughness improves, ductility increases substantially, can be near the character of rubber.Along with the increase of flexible unit, multipolymer to whippy rubbery state transition, and has good thermostability concurrently by crystalline duroplasts, can be processed into the very high fiber of clear films and intensity.Show according to the study, can change the physical and mechanical properties of polymkeric substance in the PHAs multipolymer by the content that changes flexible molecule in the polymkeric substance, to obtain to have the material that different rigidity, crystallinity, fusing point and second-order transition temperature are applicable to different purposes.
Though the performance of copolymer of PHAs is very good, but be to use the method processing of conventional melt-processed to have great difficulty, because this polymkeric substance has kept great viscosity after melted state cools down, up to enough degree of crystallinity occurring, for higher especially true of the flexible composition of multipolymer.After-tack can make goods itself bondings (adhered to one another as the film that blowing is come out) that process or be bonded on the processing units (as injection mold, casting roller etc.), both of these case perhaps takes place simultaneously, and this has limited speed, molding mode and rolling speed of product processing or the like greatly.Wanting to produce this product with suitability for industrialized production speed on the processing units of routine must make improvements, and because the cooling of PHAs multipolymer needs long time, inside also may be soft after the placement several hrs, can not realize the pipeline system operation with traditional granulation mode, this large-scale application to the PHAs multipolymer has also caused very big inconvenience.
The polymkeric substance that U.S. Pat 6191203 provides a kind of P3HB4HB of comprising and nucleator to carry out blend improves its processing characteristics and extension property, and with this blend extrude, injection moulding, coating, melt-spinning or the like, but its processing characteristics is not changed.
Chinese patent CN 02808028.9 provides a kind of fiber that comprises polyhydroxy alkanoate copolymer/polylactic acid polymer or copolymer mixture, though it mentions PHAs and PLA is the polymkeric substance that belongs to compatible substantially, but it does not clearly propose to use PLA and copolymer blended its physical and mechanical properties and the processing characteristics each other that change of PHAs, and only be the skin-cored structure degradable conjugated fibre in environment that proposes, PHAs is put in the core, the PLA polymkeric substance is placed in the skin, help to prevent the viscosity relevant usually with polyhydroxyalkanoatecopolymers copolymers, avoid processing problems such as the bonding or contraction of fiber, and be limited to the purposes aspect melt-spinning.And for come modification PLA with some character of PHAs multipolymer, remedy the inherent defective mutually, make both form a kind of excellent property, the blend that processability is good, can be used to comprise the novel plastic of multiple processing modes such as fibers melt spinning, injection moulding, film blowing, bottle blowing, curtain coating, this patent does not relate to.Therefore this patent clearly proposes PLA and the copolymer blended modification of PHAs, improve the toughness of PLA, performance such as tear-resistant, improve the adhesion problem of PHAs multipolymer in the courses of processing such as injection moulding, blowing, curtain coating, two-way stretch, thereby this novel blend relies on its excellent characteristic can bring into play the unique advantage of degradable material in aspect large-scale application such as packing, daily disposable products.
Chinese patent 200510017207 proposes a kind of lactic acid composite material that carries out the quaternary built fully biodegradable with poly(lactic acid), polypropylene carbonate, poly-own interior alcohol, poly 3-hydroxy butyrate, purpose is intended to improve the fragility in the PLA blowing process, but poly 3-hydroxy butyrate (P3HB) itself is quite crisp a kind of polymkeric substance, degree of crystallinity is also very big, use P3HB that PLA is carried out the effect that modification can not be played expectation, in particular for film-blowing process, the processibility of its product, tear strength and elongation at break are difficult to reach the requirement of use.
Poly(lactic acid) (PLA) is by artificial semisynthetic thermoplasticity aliphatic polyester, and synthetic its monomer lactic acid is by fermentations such as reproducible corn, cereal, and being also referred to as is " corn plastics ".PLA is the degradable material of a kind of fusing point higher (175 degrees centigrade), its degraded product is water and carbonic acid gas, its physical properties is between PET and PA-6, degree of crystallinity is big, excellent transparency, and good good solubility-resistence, protection against the tide, grease resistance, ventilation property are arranged, and also has certain fungus resistance, flame retardant resistance and ultraviolet-resistent property, has good biocompatibility in addition, nontoxic, biodegradable, degraded product can not assembled at vitals, so purposes is very extensive.
But poly(lactic acid) is a kind of typical linear polymer, compares with polyolefine, and its melt elasticity is poor, makes also to have some difficulties in actual application.Poly(lactic acid) easily absorbs water, and water-content is remarkable to the influence of its processing characteristics.And pure poly(lactic acid) is very crisp, low elongation at break (pure PLA elongation at break only is 6%) and higher modulus have hindered its application aspect a lot, if be processed into this class purposes of plastics film the most widely the non-returnable container material can only carry out moulding by the method for two-way stretch, and will use the method for conventional blowing must add suitable plasticizing system, and the Plasticising system that adds can not influence biodegradable performance.Because fragility is too big, PLA also is difficult in the goods that inject quality excellent in shape complexity in the common injection moulding.
Generally speaking, PLA can degrade, but processing characteristics is relatively poor, is difficult to process the product that meets service requirements by the working method of routine on the conventional polymer processing units.In order to enlarge its Application Areas, great majority improve its processing characteristics by the method for modification at present.Mainly comprise: (1) modification by copolymerization, with other hydrophilic substance copolymerization, complex process.(2) blending and modifying, with other Biodegradable material blend, technology is simple, and is easy to operate.(3) composite modified, be the compound fragility of improving PLA of matrix and other materials with PLA, can moulding complicated shape, but mostly can not be by traditional plastic processing machinery moulding, range of application is restricted.
It is a kind of hard brittle material that Chinese patent CN200510030546.2 mentions pure poly(lactic acid), this character has a strong impact on its workability and range of application, therefore propose PLA and rubber copolymerized method and carry out modification, can improve the fragility of PLA, the broadened application scope, but the method complex process of this copolymerization, needing earlier acid by dehydrating lactic polycondensation and terminal groups modification are made as molecular weight is 1000～60000 hydroxyl-terminated polylactic acid, be 400～10000 rubber copolymerized reaction of isocyanate terminated base and chain extension effect then with molecular weight, but the bad control of its technology, and the material after the copolymerization can not complete biodegradable, can not solve existing contradiction.
Chinese patent CN1367189A mentions Penise.C, employing free radical grafting methods such as Ejuibura.JL are used for polydactyl acid with polyvinyl alcohol, vinylformic acid, unsaturated cyclic acid anhydrides or unsaturated cyclic imide, on side chain introducing-OH ,-COOH or inferior amide group, improved the wetting ability situation of poly(lactic acid); Veenstra.H, Breitenbach.A etc. adopt rac-Lactide and copolymerization such as glycollide, phosphorous acid ester, polyoxyethylene glycol or polyvalent alcohol, and poly(lactic acid) is introduced main chain because of comonomer has increased the kindliness of chain, and has improved wetting ability and degradation property to a certain extent.But method, the complex process of chemical modification are adopted in these researchs, and cost is higher.
Chinese patent 03150485.X points out that PLA is used as bone material and has that initial strength is low, the characteristics of poor toughness; therefore use chitin fiber to strengthen PLA; can obtain the acylation modification chitin fiber by the wet-spinning moulding process; compression molding after preimpregnation is cut out again; but the moulding process of this wet-spinning is very complicated; controllability is bad, and this forming method only is applicable to the preparation of medical framework material.
Because PLA can only degrade under greater than 60 ℃ of situations in the condition of compost or temperature, it is still slower that Chinese patent 03135999.x points out to compare with the refuse accumulation rate degradation rate of PLA, propose a kind of starch powder and PLA to be obtained a kind of mixture by the method for using coupling symbasis group machinery to mix, improve degradation speed by increasing starch content, but this blend wet tenacity is poor, and lacking toughness.
Summary of the invention
The preparation technology's method that the purpose of this invention is to provide a kind of well behaved PHA and multipolymer and polylactic acid blend, PLA is played the effect of softening agent, solve existing P LA toughness and tear resistance deficiency, elongation at break is low, deficiencies such as the more crisp lacking toughness of film, improve the PHAs processing characteristics, make it can use legacy equipment to produce according to industrialization speed, just with PHAs and PLA blending and modifying, by content and the toughness of the PHAs physical and mechanical properties and the processing characteristics that change blend of control PHAs in blend, the use properties of the goods that the while blend is made also changes, make this blend on conventional plastic processing machinery, to be used for injection moulding with suitability for industrialized production speed, blowing, extrude, curtain coating, various conventional plastic complete processings such as two-way stretch and melt-spinning, product performance can satisfy service requirements, and the introducing of fully biodegradable PHAs has increased the biological degradability of PLA, finally obtains a kind of fully biodegradable polymkeric substance of performance brilliance.
PHAs among the present invention and the blend of PLA, its component that relates to mainly comprises:
Poly hydroxyalkanoate (PHAs)
Poly(lactic acid) (PLA)
Various auxiliary agents
PHAs in this patent should include but not limited to the multipolymer of PHB and PHAs, as the mixture of P3HB4HB, PHBV, PHBH etc. and these multipolymers or homopolymer.
The auxiliary agent of this patent middle finger should include but not limited to that softening agent, slip(ping)agent, nucleator, opening agent, linking agent, tensio-active agent, white dyes, tinting material, lubricant, heat-resisting stabilizing agent, antioxidant, fire retardant, wax, tackifying resin, supplement, the fast agent of anti-caking, static inhibitor or other are inorganic, organic filler and their mixture.
When forming process is carried out in poly(lactic acid) (PLA) conduct, poor heat stability, fragility is big, and tear strength is poor, and range of application is restricted.Use PHAs that it is carried out modification among the present invention, change its toughness, change the performance of blend, and, add necessary assistant, to obtain high performance matrix material according to the difference of processing mode by composition and the multipolymer content that changes PHAs.Change the processing characteristics of PHAs simultaneously, make it can use legacy equipment to produce, finally obtain a kind of fully biodegradable polymkeric substance of performance brilliance according to industrialization speed.
The fully biodegradable plastics that contain PHAs and PLA that the present invention proposes, its weight percent is:
(A) PHA (PHAs) 99～1
(B) poly(lactic acid) (PLA) 1～99
(C) various auxiliary agents 0～40
It is to PHAs and the mutual modification of PLA that the present invention only proposes, and its subsequent applications also comprises the blend of this mixture and other polymkeric substance, mineral filler, and this patent is not listed as space is limited one by one.
The present invention also proposes a kind of preparation process and method of mixture, may further comprise the steps:
1) weighing: according to the end-use of product, select the ratio of PHAs/PLA, and the content of multipolymer among the PHAs, take by weighing the polymkeric substance of corresponding weight;
2) blend: prepare PHAs and PLA or a little auxiliary according to the above ratio and be placed in the high-speed mixer and stir;
3) drying: the above-mentioned blend that will stir is placed in the electric heating blast dry oven dries;
4) plasticizing: use the twin screw extruder blend that drying is good to plastify, finish blending and modifying, form a kind of new degradation material;
5) granulation: will be after the tank cooling through blend that twin screw extruder is extruded, traction becomes pellet by common dicing machine.
Above-mentioned steps 2) PHAs and PLA churning time in mixing machine are 1～30 minute in, are preferably 5～10 minutes.
Above-mentioned steps 3) temperature of electric heating blast dry oven is 40～100 ℃ in, is preferably 50～80 ℃; Be 2～48 hours time of drying, is preferably 6～12 hours;
Above-mentioned steps 4) blend composition in plastifies in twin screw extruder, the feeding section of whole twin screw extruder, compression section and homogenizing zone temperature range are between 90～180 ℃, be preferably 110～165 ℃, keeping die temperature is 110～170 ℃, is preferably 120～165 ℃.
Embodiment
Below by description, describe the present invention in detail to preferred embodiment of the present invention.Below describe and do not limit the present invention.
Embodiment 1
Take by weighing industrial 10kgPHBV (15%HV) and PLA90kg, stirring at normal temperature 8min obtains the starting material compound of fully biodegradable plastics in stirrer.The compound that stirs was placed in the electric drying oven with forced convection 70 ℃ of dryings 10 hours, 65 twin screw extruders that with the good compound length-to-diameter ratio of above-mentioned drying are 40: 1 are then extruded, die temperature is 150 ℃, and direct granulation obtains the fully biodegradable plastic matrix after extruding.The performance of intermingling material is as shown in table 1.
This blend composition can directly be processed moulding on the traditional injection moulding machine, can produce by industrialization speed, and the goods workability is good, has intensity and certain toughness preferably, can satisfy service requirements.
Embodiment 2
Take by weighing industrial 10kg P3HB4HB (16%4HB) and 5kgPHBV (15%HV) and PLA85kg, stirring at normal temperature 8min obtains the starting material compound of fully biodegradable plastics in stirrer.The compound that stirs was placed in the electric drying oven with forced convection 70 ℃ of dryings 10 hours, 65 twin screw extruders that with the good compound length-to-diameter ratio of above-mentioned drying are 40: 1 are then extruded, die temperature is 145 ℃, and direct granulation obtains the fully biodegradable plastic matrix after extruding.The performance of intermingling material is as shown in table 1.
This blend composition can directly be produced thickness and be lower than fully biodegradable sheet material for 0.7mm on traditional casting apparatus, sheet material can be produced and rolling by industrialization speed, can satisfy service requirements, and can further carry out processing such as plastic uptake.
Embodiment 3
Take by weighing industrial 20kgP3HB4HB (16%4HB) and PLA80kg, stirring at normal temperature 8min obtains the starting material compound of fully biodegradable plastics in stirrer.The compound that stirs was placed in the electric drying oven with forced convection 70 ℃ of dryings 10 hours, 65 twin screw extruders that with the good compound length-to-diameter ratio of above-mentioned drying are 40: 1 are then extruded, die temperature is 140 ℃, and direct granulation obtains the fully biodegradable plastic matrix after extruding.The performance of intermingling material is as shown in table 1.
This blend composition can directly carry out bottle blowing on traditional bottle blowing equipment, formed product is effective, and the surface has glossiness preferably, can be used for the packing and the drinking water container of cosmetics of everyday use.
Embodiment 4
Take by weighing industrial 30kg P3HB4HB (16%4HB), PLA70kg and 0.5kg tributyl citrate, stirring at normal temperature 8min obtains the starting material compound of fully biodegradable plastics in stirrer.The compound that stirs was placed in the electric drying oven with forced convection 70 ℃ of dryings 10 hours, 65 twin screw extruders that with the good compound length-to-diameter ratio of above-mentioned drying are 40: 1 are then extruded, die temperature is 130 ℃, and direct granulation obtains the fully biodegradable plastic matrix after extruding.The performance of intermingling material is as shown in table 1.
This blend composition can directly be produced fully-biodegradable film on traditional blow moulding equipment, the product processing characteristics is good, has toughness and heat sealability preferably preferably, can be used for daily wrapping material.
Embodiment 5
Take by weighing industrial 40kg P3HB4HB (30%4HB), PLA60kg, 0.6kg tributyl citrate, 0.3kgEBS (ethylene bis stearic acid amide) and 0.1kgBN (hexagonal boron nitride), stirring at normal temperature 8min obtains the starting material compound of fully biodegradable plastics in stirrer.The compound that stirs was placed in the electric drying oven with forced convection 70 ℃ of dryings 10 hours, 65 twin screw extruders that with the good compound length-to-diameter ratio of above-mentioned drying are 40: 1 are then extruded, die temperature is 120 ℃, and direct granulation obtains the fully biodegradable plastic matrix after extruding.The performance of intermingling material is as shown in table 1.
This blend composition can directly be produced fully-biodegradable film on traditional blow moulding equipment, the product processing characteristics is good, and toughness is good, can be made into the flexible packing material of thinner thickness.
Embodiment 6
Take by weighing industrial 25kg P3HB4HB (30%4HB), 25kgPHB, PLA50kg, 0.6kg tributyl citrate, 0.3kgEBS (ethylene bis stearic acid amide) and 0.1kgBN (hexagonal boron nitride), stirring at normal temperature 8min obtains the starting material compound of fully biodegradable plastics in stirrer.The compound that stirs was placed in the electric drying oven with forced convection 70 ℃ of dryings 10 hours, 65 twin screw extruders that with the good compound length-to-diameter ratio of above-mentioned drying are 40: 1 are then extruded, die temperature is 120 ℃, and direct granulation obtains the fully biodegradable plastic matrix after extruding.The performance of intermingling material is as shown in table 1.
This blend composition can directly be produced fully-biodegradable film on traditional blow moulding equipment, the product processing characteristics is good, and toughness is good, can be made into wrapping material.
The composition and the performance of table 1PHAs and PLA intermingling material
Embodiment PHAs (percentage composition, %) PLA (percentage composition, %) Tensile strength (MPa) Elongation at break (%)
PLA 0 100 36.2 6
1 10 90 37.1 8
2 15 85 39.6 18
3 20 80 42.8 21
4 30 70 43.4 30
5 40 60 46.3 68
6 50 50 40.9 33
PHAs(P3HB4HB，16％4HB) 100 0 48.2 300

Claims (9)

1. the blend of a PHA and multipolymer and poly(lactic acid) is characterized in that the component of this blend mainly comprises:
1) PHA (PHAs)
2) poly(lactic acid) (PLA)
3) various auxiliary agents.
2. multipolymer according to claim 1 is characterized in that described PHA includes but not limited to the multipolymer of PHB and PHB, as the mixture of P3HB4HB, PHBV, PHBH etc. and these multipolymers or homopolymer.
3. multipolymer according to claim 2, it is characterized in that, in the multipolymer (as P3HB4HB, PHBV, PHBH etc.) of PHB, the content of comonomer (as 4HB, HV, HH) is 1～99% in the described PHA (PHAs), and wherein preferred content is 1～30%.
4. multipolymer according to claim 1, it is characterized in that described auxiliary agent includes but not limited to that softening agent, slip(ping)agent, nucleator, opening agent, linking agent, tensio-active agent, white dyes, tinting material, lubricant, heat-resisting stabilizing agent, antioxidant, fire retardant, wax, tackifying resin, supplement, the fast agent of anti-caking, static inhibitor or other are inorganic, organic filler and their mixture.
5. multipolymer according to claim 1 is characterized in that, the component of described blend, and its weight percent is:
1) PHA (PHAs) 99～1
2) poly(lactic acid) (PLA) 1～99
3) various auxiliary agents 0～40
6. method for preparing the described blend of claim 1 may further comprise the steps:
1) weighing: according to the end-use of product, select the ratio of PHAs/PLA, and the content of multipolymer among the PHAs, take by weighing the polymkeric substance of corresponding weight;
2) blend: prepare PHAs and PLA or a little auxiliary according to the above ratio and be placed in the high-speed mixer and stir;
3) drying: the above-mentioned blend that will stir is placed in the electric heating blast dry oven dries;
4) plasticizing: use the twin screw extruder blend that drying is good to plastify, finish blending and modifying, form a kind of new degradation material;
5) granulation: will be after the tank cooling through blend that twin screw extruder is extruded, traction becomes pellet by common dicing machine.
7. method according to claim 6 is characterized in that step 2) in PHAs and PLA churning time in mixing machine be 1～30 minute, be preferably 5～10 minutes.
8. method according to claim 6 is characterized in that the temperature of electric heating blast dry oven is 40～100 ℃ in the step 3), is preferably 50～80 ℃; Be 2～48 hours time of drying, is preferably 6～12 hours.
9. method according to claim 6, it is characterized in that, blend composition in the step 4) plastifies in twin screw extruder, the feeding section of whole twin screw extruder, compression section and homogenizing zone temperature are 90～180 ℃, be preferably 110～165 ℃, keeping die temperature is 110～170 ℃, is preferably 120～165 ℃.
CNA2006101579892A 2006-12-22 2006-12-22 Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid Withdrawn CN101205356A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNA2006101579892A CN101205356A (en) 2006-12-22 2006-12-22 Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNA2006101579892A CN101205356A (en) 2006-12-22 2006-12-22 Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid

Publications (1)

Publication Number Publication Date
CN101205356A true CN101205356A (en) 2008-06-25

Family

ID=39565845

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2006101579892A Withdrawn CN101205356A (en) 2006-12-22 2006-12-22 Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid

Country Status (1)

Country Link
CN (1) CN101205356A (en)

Cited By (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011071666A1 (en) * 2009-12-08 2011-06-16 International Paper Company Thermoformed articles made from reactive extrusion products of biobased materials
WO2011079492A1 (en) * 2009-12-28 2011-07-07 天津国韵生物材料有限公司 Fully biodegradable multi-component film material and preparing method thereof
CN102143766A (en) * 2008-08-06 2011-08-03 麦德托尼克公司 Medical devices and methods including blends of biodegradable polymers
CN102219988A (en) * 2010-04-14 2011-10-19 美亚无纺布工业有限公司 Biodegradable recycling material
CN102295830A (en) * 2010-06-23 2011-12-28 深圳市意可曼生物科技有限公司 Completely biodegradable material for cards
CN102295831A (en) * 2010-06-23 2011-12-28 深圳市意可曼生物科技有限公司 Special material for fully biodegradable rigid sheet and preparation method thereof
CN102321353A (en) * 2011-07-26 2012-01-18 成都市新津事丰医疗器械有限公司 Degradable material for preparing outside sleeve of disposable injector
CN102392318A (en) * 2011-04-22 2012-03-28 中国科学院宁波材料技术与工程研究所 Biobased biodegradable fiber and preparation method thereof
CN102675839A (en) * 2011-03-14 2012-09-19 美亚无纺布工业有限公司 Biological degradable film and laminated material
CN102906193A (en) * 2010-05-17 2013-01-30 梅塔玻利克斯公司 Toughening polylactic acid with polyhydroxyalkanoates
CN102924890A (en) * 2012-10-09 2013-02-13 山东省意可曼科技有限公司 Fully-biodegradable heat shrinkage film and preparation method thereof
CN102977563A (en) * 2012-11-15 2013-03-20 江苏天仁生物材料有限公司 Heat resistant polylactic acid and polyhydroxyalkanoates copolymer thin film and preparation method thereof
CN103044870A (en) * 2011-10-12 2013-04-17 富士施乐株式会社 Resin composition and resin molded article
CN103087484A (en) * 2013-01-11 2013-05-08 北京工商大学 Biodegradable composite film material of controllable degradation rate and preparation method thereof
CN103459498A (en) * 2011-04-11 2013-12-18 斯洛伐克科学院聚合物研究所 Biologically degradable polymeric composition with high deformability
CN103819884A (en) * 2012-11-16 2014-05-28 上海载和实业投资有限公司 Novel heat-resistant high-toughness polylactic acid composite material and preparation method thereof
CN103992627A (en) * 2014-05-20 2014-08-20 中国科学院宁波材料技术与工程研究所 Environment-friendly bio-based polymer hemodialyzer casing material
CN104194551A (en) * 2014-09-28 2014-12-10 芜湖县双宝建材有限公司 Impact-resistant flame retardant coating
CN104231836A (en) * 2014-09-28 2014-12-24 芜湖县双宝建材有限公司 Degradable modified flame-retardant coating
CN104293071A (en) * 2014-09-28 2015-01-21 芜湖县双宝建材有限公司 Degradable corrosion-resistant paint
CN104293072A (en) * 2014-09-28 2015-01-21 芜湖县双宝建材有限公司 Flame-retardant and corrosion-resistant modified coating
CN104788754A (en) * 2015-04-29 2015-07-22 中国热带农业科学院农产品加工研究所 Presulfurized natural latex/polyhydroxybutyrate blend material and preparation method thereof
CN105220264A (en) * 2015-09-13 2016-01-06 天津工业大学 A kind of modified polylactic acid fiber and preparation method thereof
CN105440617A (en) * 2015-12-23 2016-03-30 江苏道勤新材料科技有限公司 Environment-friendly plastic material
CN105504727A (en) * 2016-02-03 2016-04-20 黑龙江鑫达企业集团有限公司 High-tenacity full-degradable polylactic acid based composite and preparation method thereof
US9353258B2 (en) 2012-06-05 2016-05-31 Metabolix, Inc. Low glass transition polyhydroxyalkanoates for modification of biodegradable polymers
CN105802159A (en) * 2014-12-29 2016-07-27 江苏华信新材料股份有限公司 Degradable PHA/PLA mixture film and preparation method thereof
CN106046730A (en) * 2016-08-22 2016-10-26 广西南宁智翠科技咨询有限公司 Novel plastic
CN106046728A (en) * 2016-08-22 2016-10-26 广西南宁智翠科技咨询有限公司 Degradable environmental protection plastic
CN106046729A (en) * 2016-08-22 2016-10-26 广西南宁智翠科技咨询有限公司 Novel environment-friendly plastic
CN106189130A (en) * 2016-07-11 2016-12-07 董晓 A kind of Microbial Synthesis of Polyhydroxyalkanoates prepares the method for composite package film
CN106280331A (en) * 2016-08-22 2017-01-04 广西南宁智翠科技咨询有限公司 A kind of environmentally-friendly plastic
CN106317813A (en) * 2016-08-22 2017-01-11 广西南宁智翠科技咨询有限公司 Novel degradable plastic
CN106366569A (en) * 2016-08-29 2017-02-01 芜湖众力部件有限公司 Degradable modified plastic with good low temperature resistance and preparation method thereof
CN106398144A (en) * 2016-08-29 2017-02-15 安徽奥斯博医疗仪器设备有限公司 PLA-based degradable 3D printing consumable and preparation method thereof
CN107759988A (en) * 2016-08-22 2018-03-06 广西南宁智翠科技咨询有限公司 A kind of degradable plastics
CN108752887A (en) * 2018-06-20 2018-11-06 瞿向东 A kind of environment-friendly type degradable composite material for disposable vaginal dilator
CN109370178A (en) * 2018-09-05 2019-02-22 安徽新翔包装材料有限公司 A kind of degradable polyethylene plastic bag of environmental protection
CN110016214A (en) * 2019-04-11 2019-07-16 林元钦 A kind of PLA blending modified material and preparation method thereof for 3D printing
CN110564121A (en) * 2019-09-18 2019-12-13 广东省化学纤维研究所 preparation method of high-toughness heat-resistant fully-degradable straw
CN111621127A (en) * 2020-05-25 2020-09-04 南京金凯木纳米材料有限公司 Polyethylene glycol modified PHA composite material and preparation method thereof
US11007758B2 (en) * 2013-10-27 2021-05-18 Tipa Corp. Ltd Biodegradable sheet
CN112920571A (en) * 2021-01-28 2021-06-08 重庆和泰润佳股份有限公司 Modified PLA (polylactic acid) and PHA (polyhydroxyalkanoate) blending material and preparation method thereof
KR20210095003A (en) * 2020-01-22 2021-07-30 산수음료(주) Biodegradable pla bottle having improved transparency, gas-barrier and impact-resistance, and method of manufacturing the same
KR20210095005A (en) * 2020-01-22 2021-07-30 산수음료(주) Biodegradable pla label and film having improved transparency and heat-shrinkable, and method of manufacturing the same
KR20210095004A (en) * 2020-01-22 2021-07-30 산수음료(주) Biodegradable pla screw cap having improved translucency, gas-barrier, impact-resistance and sealing performance, and method of manufacturing the same
US11091632B2 (en) 2015-11-17 2021-08-17 Cj Cheiljedang Corporation Polymer blends with controllable biodegradation rates
CN114133718A (en) * 2021-12-09 2022-03-04 宏全食品包装(清新)有限公司 Full-degradable plastic bottle based on polyhydroxyalkanoate
CN114456564A (en) * 2022-03-18 2022-05-10 湖南工程学院 PLA-PHB blended biodegradable film filled with modified calcium carbonate and preparation method thereof

Cited By (70)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102143766A (en) * 2008-08-06 2011-08-03 麦德托尼克公司 Medical devices and methods including blends of biodegradable polymers
CN102143766B (en) * 2008-08-06 2014-04-23 麦德托尼克公司 Medical devices and methods including blends of biodegradable polymers
US8231954B2 (en) 2009-12-08 2012-07-31 International Paper Co. Thermoformed articles made from reactive extrusion products of biobased materials
WO2011071666A1 (en) * 2009-12-08 2011-06-16 International Paper Company Thermoformed articles made from reactive extrusion products of biobased materials
WO2011079492A1 (en) * 2009-12-28 2011-07-07 天津国韵生物材料有限公司 Fully biodegradable multi-component film material and preparing method thereof
CN102219988A (en) * 2010-04-14 2011-10-19 美亚无纺布工业有限公司 Biodegradable recycling material
CN102906193A (en) * 2010-05-17 2013-01-30 梅塔玻利克斯公司 Toughening polylactic acid with polyhydroxyalkanoates
CN104910599A (en) * 2010-05-17 2015-09-16 梅塔玻利克斯公司 Toughening polylactic acid with polyhydroxyalkanoates
CN102906193B (en) * 2010-05-17 2015-07-01 梅塔玻利克斯公司 Toughening polylactic acid with polyhydroxyalkanoates
US9328239B2 (en) 2010-05-17 2016-05-03 Metabolix, Inc. Toughening polylactic acid with polyhydroxyalkanoates
CN104910599B (en) * 2010-05-17 2018-02-09 梅塔玻利克斯公司 Plasticizing polylactic acid containing PHA
CN102295831A (en) * 2010-06-23 2011-12-28 深圳市意可曼生物科技有限公司 Special material for fully biodegradable rigid sheet and preparation method thereof
CN102295830A (en) * 2010-06-23 2011-12-28 深圳市意可曼生物科技有限公司 Completely biodegradable material for cards
CN102675839A (en) * 2011-03-14 2012-09-19 美亚无纺布工业有限公司 Biological degradable film and laminated material
CN103459498B (en) * 2011-04-11 2017-03-01 斯洛伐克科学院聚合物研究所 The high biodegradable polymer compositionss of deformability
CN103459498A (en) * 2011-04-11 2013-12-18 斯洛伐克科学院聚合物研究所 Biologically degradable polymeric composition with high deformability
CN102392318B (en) * 2011-04-22 2013-11-27 中国科学院宁波材料技术与工程研究所 Biobased biodegradable fiber and preparation method thereof
CN102392318A (en) * 2011-04-22 2012-03-28 中国科学院宁波材料技术与工程研究所 Biobased biodegradable fiber and preparation method thereof
CN102321353B (en) * 2011-07-26 2012-10-03 成都市新津事丰医疗器械有限公司 Degradable material for preparing outside sleeve of disposable injector
CN102321353A (en) * 2011-07-26 2012-01-18 成都市新津事丰医疗器械有限公司 Degradable material for preparing outside sleeve of disposable injector
CN103044870A (en) * 2011-10-12 2013-04-17 富士施乐株式会社 Resin composition and resin molded article
CN103044870B (en) * 2011-10-12 2015-12-02 富士施乐株式会社 Resin combination and resin-formed body
US9353258B2 (en) 2012-06-05 2016-05-31 Metabolix, Inc. Low glass transition polyhydroxyalkanoates for modification of biodegradable polymers
US10113060B2 (en) 2012-06-05 2018-10-30 Cj Cheiljedang Corporation Biobased rubber modified biodegradable polymer blends
CN102924890A (en) * 2012-10-09 2013-02-13 山东省意可曼科技有限公司 Fully-biodegradable heat shrinkage film and preparation method thereof
CN102977563A (en) * 2012-11-15 2013-03-20 江苏天仁生物材料有限公司 Heat resistant polylactic acid and polyhydroxyalkanoates copolymer thin film and preparation method thereof
CN103819884A (en) * 2012-11-16 2014-05-28 上海载和实业投资有限公司 Novel heat-resistant high-toughness polylactic acid composite material and preparation method thereof
CN103087484A (en) * 2013-01-11 2013-05-08 北京工商大学 Biodegradable composite film material of controllable degradation rate and preparation method thereof
CN103087484B (en) * 2013-01-11 2016-03-02 北京工商大学 Biodegradable composite film material that degradation rate is controlled and preparation method thereof
US11007758B2 (en) * 2013-10-27 2021-05-18 Tipa Corp. Ltd Biodegradable sheet
CN103992627A (en) * 2014-05-20 2014-08-20 中国科学院宁波材料技术与工程研究所 Environment-friendly bio-based polymer hemodialyzer casing material
CN104231836B (en) * 2014-09-28 2016-08-24 芜湖县双宝建材有限公司 A kind of degradable modified flame-retardant coating
CN104194551A (en) * 2014-09-28 2014-12-10 芜湖县双宝建材有限公司 Impact-resistant flame retardant coating
CN104293071A (en) * 2014-09-28 2015-01-21 芜湖县双宝建材有限公司 Degradable corrosion-resistant paint
CN104293072A (en) * 2014-09-28 2015-01-21 芜湖县双宝建材有限公司 Flame-retardant and corrosion-resistant modified coating
CN104231836A (en) * 2014-09-28 2014-12-24 芜湖县双宝建材有限公司 Degradable modified flame-retardant coating
CN104293071B (en) * 2014-09-28 2016-06-08 芜湖县双宝建材有限公司 A kind of degradable corrosion resistant coating
CN104293072B (en) * 2014-09-28 2016-07-27 芜湖县双宝建材有限公司 A kind of fire-retardant corrosion-resistant modified coating
CN105802159A (en) * 2014-12-29 2016-07-27 江苏华信新材料股份有限公司 Degradable PHA/PLA mixture film and preparation method thereof
CN104788754B (en) * 2015-04-29 2017-02-01 中国热带农业科学院农产品加工研究所 Presulfurized natural latex/polyhydroxybutyrate blend material and preparation method thereof
CN104788754A (en) * 2015-04-29 2015-07-22 中国热带农业科学院农产品加工研究所 Presulfurized natural latex/polyhydroxybutyrate blend material and preparation method thereof
CN105220264A (en) * 2015-09-13 2016-01-06 天津工业大学 A kind of modified polylactic acid fiber and preparation method thereof
CN105220264B (en) * 2015-09-13 2017-10-13 天津工业大学 A kind of modified polylactic acid fiber and preparation method thereof
US11091632B2 (en) 2015-11-17 2021-08-17 Cj Cheiljedang Corporation Polymer blends with controllable biodegradation rates
CN105440617A (en) * 2015-12-23 2016-03-30 江苏道勤新材料科技有限公司 Environment-friendly plastic material
CN105504727A (en) * 2016-02-03 2016-04-20 黑龙江鑫达企业集团有限公司 High-tenacity full-degradable polylactic acid based composite and preparation method thereof
CN105504727B (en) * 2016-02-03 2018-05-18 黑龙江鑫达企业集团有限公司 A kind of high tenacity fully-degradable polylactic acid based composites and preparation method thereof
CN106189130A (en) * 2016-07-11 2016-12-07 董晓 A kind of Microbial Synthesis of Polyhydroxyalkanoates prepares the method for composite package film
CN106046730A (en) * 2016-08-22 2016-10-26 广西南宁智翠科技咨询有限公司 Novel plastic
CN106317813A (en) * 2016-08-22 2017-01-11 广西南宁智翠科技咨询有限公司 Novel degradable plastic
CN106280331A (en) * 2016-08-22 2017-01-04 广西南宁智翠科技咨询有限公司 A kind of environmentally-friendly plastic
CN106046729A (en) * 2016-08-22 2016-10-26 广西南宁智翠科技咨询有限公司 Novel environment-friendly plastic
CN107759988A (en) * 2016-08-22 2018-03-06 广西南宁智翠科技咨询有限公司 A kind of degradable plastics
CN106046728A (en) * 2016-08-22 2016-10-26 广西南宁智翠科技咨询有限公司 Degradable environmental protection plastic
CN106366569A (en) * 2016-08-29 2017-02-01 芜湖众力部件有限公司 Degradable modified plastic with good low temperature resistance and preparation method thereof
CN106398144A (en) * 2016-08-29 2017-02-15 安徽奥斯博医疗仪器设备有限公司 PLA-based degradable 3D printing consumable and preparation method thereof
CN108752887A (en) * 2018-06-20 2018-11-06 瞿向东 A kind of environment-friendly type degradable composite material for disposable vaginal dilator
CN109370178A (en) * 2018-09-05 2019-02-22 安徽新翔包装材料有限公司 A kind of degradable polyethylene plastic bag of environmental protection
CN110016214A (en) * 2019-04-11 2019-07-16 林元钦 A kind of PLA blending modified material and preparation method thereof for 3D printing
CN110564121A (en) * 2019-09-18 2019-12-13 广东省化学纤维研究所 preparation method of high-toughness heat-resistant fully-degradable straw
KR20210095003A (en) * 2020-01-22 2021-07-30 산수음료(주) Biodegradable pla bottle having improved transparency, gas-barrier and impact-resistance, and method of manufacturing the same
KR20210095005A (en) * 2020-01-22 2021-07-30 산수음료(주) Biodegradable pla label and film having improved transparency and heat-shrinkable, and method of manufacturing the same
KR20210095004A (en) * 2020-01-22 2021-07-30 산수음료(주) Biodegradable pla screw cap having improved translucency, gas-barrier, impact-resistance and sealing performance, and method of manufacturing the same
KR102317488B1 (en) * 2020-01-22 2021-10-26 산수음료(주) Biodegradable pla screw cap having improved translucency, gas-barrier, impact-resistance and sealing performance, and method of manufacturing the same
KR102317491B1 (en) * 2020-01-22 2021-10-26 산수음료(주) Biodegradable pla label and film having improved transparency and heat-shrinkable, and method of manufacturing the same
KR102342537B1 (en) * 2020-01-22 2021-12-23 산수음료(주) Biodegradable pla bottle having improved transparency, gas-barrier and impact-resistance, and method of manufacturing the same
CN111621127A (en) * 2020-05-25 2020-09-04 南京金凯木纳米材料有限公司 Polyethylene glycol modified PHA composite material and preparation method thereof
CN112920571A (en) * 2021-01-28 2021-06-08 重庆和泰润佳股份有限公司 Modified PLA (polylactic acid) and PHA (polyhydroxyalkanoate) blending material and preparation method thereof
CN114133718A (en) * 2021-12-09 2022-03-04 宏全食品包装(清新)有限公司 Full-degradable plastic bottle based on polyhydroxyalkanoate
CN114456564A (en) * 2022-03-18 2022-05-10 湖南工程学院 PLA-PHB blended biodegradable film filled with modified calcium carbonate and preparation method thereof

Similar Documents

Publication Publication Date Title
CN101205356A (en) Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid
CN101475735B (en) Completely biodegradable polyhydroxyalkanote / poly(butylene succinate) blending alloy
CN111995848A (en) Degradable plastic composition and preparation method and application thereof
CN108822514B (en) Completely biodegradable polylactic acid based blown film and preparation method thereof
CN103265798B (en) Poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and moulded products thereof
CN1216101C (en) Preparation method of toughness enhanced and reinforced polybutanediol terephthalate nanometer composition
WO2022252266A1 (en) Composite toughened and high-temperature-resistant polylactic acid modified material and preparation method therefor
CN101525487B (en) Composite material degraded by environment and preparation method thereof
CN101280095A (en) Glass fiber reinforced polyethylene glycol terephthalate composite material and preparation thereof
CN111040400A (en) Full-biodegradable sheet and preparation method thereof
CN102070880A (en) Biodegradable resin composition and product thereof
CN106916424A (en) A kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material and preparation method thereof
CN104387732A (en) Transparent, tear-resistant and biodegradable polylactic acid thin film and preparation method thereof
CN101775199B (en) High-rigidity PHAs/PLA blending alloy and preparation method thereof
CN106467657A (en) High heat-resisting PLA/PHA composite and preparation method thereof
CN101983986B (en) Transparent and toughening polylactic acid resin and method for preparing the same
CN113956640B (en) Biodegradable PLA film and preparation method thereof
CN114213817B (en) Preparation method of PBAT/PLA/CaCO3 full-biodegradable composite material
CN113956630A (en) Completely biodegradable film and preparation method thereof
CN110317406A (en) A kind of biodegradable polypropene composition and preparation method thereof
CN110066502A (en) A kind of modified polylactic acid material and the preparation method and application thereof with low-temperature flexibility
CN102690506B (en) Polylactic acid/long carbon chain nylon blend and preparation method thereof
CN102408689A (en) PHA/PLA blended alloy and its preparation method
CN101475734B (en) Completely biodegradable polyhydroxyalkanote / polycarbonate blending alloy and preparation thereof
CN113429762A (en) Starch/polylactic acid/PBAT nano composite material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C57 Notification of unclear or unknown address
DD01 Delivery of document by public notice

Addressee: Zeng Fang

Document name: Notification of Publication of the Application for Invention

C04 Withdrawal of patent application after publication (patent law 2001)
WW01 Invention patent application withdrawn after publication