CN1503824A - Processing of polyhydroxyalkanoates using a nucleant and a plasticizer - Google Patents
Processing of polyhydroxyalkanoates using a nucleant and a plasticizer Download PDFInfo
- Publication number
- CN1503824A CN1503824A CNA028085825A CN02808582A CN1503824A CN 1503824 A CN1503824 A CN 1503824A CN A028085825 A CNA028085825 A CN A028085825A CN 02808582 A CN02808582 A CN 02808582A CN 1503824 A CN1503824 A CN 1503824A
- Authority
- CN
- China
- Prior art keywords
- extrusion molding
- phb
- copolymers composition
- polyhydroxyalkanoatecopolymers
- film
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention is directed to a polyhydroxyalkanoate copolymer composition that can be readily and quickly processed into extruded and molded articles and film-based products. More specifically, the invention pertains to melt processing of polyhydroxyalkanoates which contain a novel combination of nucleant and plasticizer for enhancing crystallization rates thus causing improved processibility.
Description
Technical field
The present invention relates to polyhydroxyalkanoatecopolymers copolymers, with the field of the article and the melt processing method of its making.More particularly, the present invention relates to contain be useful on and improve chain-mobility, crystallization velocity melt and cast-film extrusion in the hope of the polyhydroxyalkanoatefrom that improves novel combination workability in the usual melt technology, nucleator and softening agent.
Background technology
Polyhydroxyalkanoatefrom (PHA) and other thermoplastic polyester are represented the potential starting material of countless useful products.Example comprise melt spun fibre, compost grocery bag and the refuse bag that can be used for the nonwoven products that production medical gown and face shield use with inflation film and cast film, healthy and personal care product with injection moulding bottle and biodegradable/compost snack food product container with the extruding coating on paper/cardboard.Produce in the technology of PHA product, importantly reach economically ideal linear velocity, cycling time, and other machined parameters.
Polyhydroxy alkanoate copolymer is at least in part because the extreme slowly crystallization velocity on its crystallization phases farmland is extremely sticking when melt.This viscosity or " being stained with sticking " behavior cause and can not process this polymkeric substance via any melt process equipment, comprise extrusion molding, compounding, film and fiber operation.Unmodified polymer has the strong tendency that adheres on all mechanical parts, and irrelevant with building material.This polymkeric substance also has self-adhesion and the strong tendency that adheres on the human body skin when contact.About several minutes to a few hours, this viscosity or be stained with and sticking just fade away.Yet this time frame is significantly long for any usual processing technology, and these these polymkeric substance of technology general requirement became not sticking at several seconds in the scope.
Work in the past shows, adding the crystallization nucleating agent in the some compositions of polyhydroxy alkanoate copolymer, can to make crystallization velocity bring up to melt processability be acceptable degree.In addition, such nucleating agent improves the physicals and the mechanical property of the article of processing sometimes.Usual nucleating agent comprises, for example, and talcum, micronization mica, lime carbonate, boron nitride (seeing for example EP 0291024) and ammonium chloride (seeing for example WO 9119759).
US 5,296, and 521 have described the polymer blend that increases crystallization velocity is arranged, and the formula RO[P (O) that comprises thermoplastic polyester and 0.5～about 5wt% is (CH (Ph)
2)
mO] the nH nucleating agent, R is a kind of basic metal or alkaline-earth metal in the formula; M is 1,2 or 3; N gets the mean value in 1～5 scope.This nucleating agent can randomly mix with its acid or ester-formin, as long as the 50mol% at least of this nucleating agent is salt form.This nucleating agent better is sodium-salt form (for example, hydroxymethyl phenyl phosphonic acids sodium salt or oligomeric methylene radical phenyl Alendronate salt).
US 4,536,531 have described the purposes of the carboxylate salt of periodic table of elements I family and II family metal as the nucleating agent of polyester, and have enumerated for example metal-salt of acetate, propionic acid, caproic acid, palmitinic acid, stearic acid, oleic acid, docosoic and montanic acid of aliphatic monocarboxylic acid.The metal that is suitable for is sodium, potassium, lithium, magnesium, calcium, barium and zinc.In these carboxylate salts, there is no need to make carboxyl all to change into salt form, all the other groups can be free acid or ester-formin but the part of this carboxyl can be salt form.
Some reference disclose the purposes of organo phosphorous compounds as nucleating agent.US5,061,743 discloses by making cyclohexyl phosphonic acids and Zinic stearas and polyhydroxybutyrate a kind of nucleating agent of polyhydroxyalkanoatefrom preferably of the dried blend manufacturing of valerate altogether.This nucleating agent is as being particularly conducive to the altogether coring of valerate and disclosed of the high polyhydroxybutyrate of hydroxypentanoic acid ester content.WO 9905208 discloses has at least two segmental organo phosphorous compoundss of phosphonic acids can be used as the nucleating agent of polyhydroxyalkanoatefrom and other thermoplastic polyester.
Although thereby many validity that demonstrated aspect the coring density raising crystallization velocity of raising polyhydroxyalkanoatefrom in these compounds have had some shortcoming and its use to interrelate.For example, the dispersion of particulate state nucleating agent is problematic, because during the processing agglomeration often takes place, this can produce stress concentration and uneven zone in molding.In addition, have been found that as the boron nitride nucleating agent in some cases, especially in film and injection molded product, play the pigment effect, thereby under general situation of wishing to obtain opaque products, produce opaque product.And then, some nucleating agent systems comprise may be on the environment and toxicology on undesirable composition.
And then it is the sort of amorphous feature that can increase this polymkeric substance effectively or the multipolymer that reduces the comonomer of its crystallization velocity of not containing that the polymkeric substance of former reference tends to.Resulting polymkeric substance crisp often and cause undesirable performance.What contain the amorphous phase that can cause remarkable quantity has more the better often polymkeric substance of the monomeric polyhydroxy alkanoate copolymer of modified copolymer, because they demonstrate high-caliber toughness and rebound resilience.Yet, contain in these polymkeric substance that a large amount of amorphous phases are unfavorable for that good crystallization forms or crystallization velocity fast.And then the interpolation of nucleating agent generally can not make crystallization quantity or crystallization velocity increase to such an extent that be enough to make the melt of these polymkeric substance to become feasible in these polymkeric substance.Therefore, need optimum at present and the effective nucleating agent system of cost, make to produce the polyhydroxyalkanoateresin resin of appropriateness to mouldability, physical strength and the dimensional stability of highly crystalline, excellence.
Therefore, the problem that solve provide a kind of can the generation can be easily and promptly to be processed into film be the tough of product and the polymer composition of deflection polyhydroxyalkanoatefrom.Another object of the present invention provides a kind of continuous melt extrusion process of these polyhydroxyalkanoatefroms.Another purpose again of the present invention provides a kind of continuous curtain coating film production method of using these polyhydroxyalkanoatefroms.
Summary of the invention
The invention provides and a kind ofly can be processed into the polyhydroxyalkanoatecopolymer copolymer compositions that film is product, extrusion molding product and moulded work and coating, comprise; (a) a kind of polyhydroxy alkanoate copolymer, (b) a kind of nucleating agent and (c) a kind of softening agent; And the making method of said composition.
In a kind of embodiment preferably, the unique combination of poly--the 3-hydroxyl (butyric ester is octanoate altogether) poly--the 3-hydroxyl (butyric ester is capronate altogether) is with poly butyric ester (nucleating agent) and Laurate methyl or dibutyl maleinate (softening agent) polymerization.
Embodiment
Applicant etc. are by providing the combination of nucleating agent and softening agent to solve this problem for polyhydroxyalkanoatefrom (" PHA ") multipolymer.The interpolation of this nucleating agent and softening agent makes crystallisation process to take place in that actual melt is become in the possible time frame in the pha copolymer.The present invention is applicable to any situation of wishing to accelerate crystallization velocity.Specifically, this nucleating agent and softening agent are to be used for improving the production of PHA and other thermoplastic polyester product by reducing film, extrusion molding product and moulded work and coating material production common needed cycle time (cycle time).
In disclosure book, many terms and shortenings have been used.Following definition is provided.
" poly-(the 3-butyric ester is 3-Hydroxyoctanoic acid ester altogether) " is also referred to as " poly--the 3-hydroxyl (butyric ester is octanoate altogether) ", and breviary is P3HBO.
" poly-(the 3-butyric ester is the 3-hydroxycaproic ester altogether) " is also referred to as " poly--the 3-hydroxyl (butyric ester is capronate altogether) ", and breviary is P3HBH.
" polyhydroxyalkanoatefrom " breviary is PHA.
" poly butyric ester " breviary is PHB.
Polyhydroxyalkanoatefrom
Polyhydroxyalkanoatefrom of the present invention (" PHA ") comprises natural derived polymers, and poly butyric ester (PHB) for example comprises the homopolymer of 3-butyric ester and 4 hydroxybutyric acid ester.They also comprise the multipolymer of PHB and alcohol acid, for example, and PHB and 3-hydroxycaproic ester, 3-Hydroxyoctanoic acid ester or long-chain alcohol acid (C for example more
9-C
12Alcohol acid) multipolymer, and multipolymer.PHA of the present invention also can be from the synthetic deutero-of hydroxycarboxylic acid.And then this PHA can also mainly have R (-) configuration, mainly has S (+) configuration, perhaps random, the block of R (-) and S (+) configuration or other combination.Will be understood that as the insider R (-) and S (+) isomer refer to that respectively respectively this repeating unit of this polymkeric substance makes plane polarized light in the counterclockwise direction or the ability of rotating on the clockwise direction.The racemize multipolymer is made up of R (-) in this polymkeric substance and S (+) repeating unit, and these unit can comprise random or the arrangement of block configuration by any combination.
The better example of the polyhydroxy alkanoate copolymer that uses among the present invention is poly--3-hydroxyl (butyric ester is octanoate altogether) (y=3) (P3HBO)
R=CH
3(CH
2)
yY=0-11 and poly--3-hydroxyl (butyric ester is capronate altogether) (y=1) (P3HBH) in the formula.These segmented copolymers have generalization structure shown below.
M=0.7-0.97 and n=0.3-0.03, m+n=1.0 in the formula
Generally speaking, can prepare segmented copolymer with various different structures.For example, the A-B Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock has a polymer A segmental block to be coupled on the block of a B polymer segment.The A-B-A triblock copolymer have a B segmental block on its each end with the coupling of an A segmental block.-(A-B)
n-segmented copolymer has A and B segmental alternate sequence, and n is the positive integer greater than 1 in the formula.The statistic copolymer of good especially is 85～about 95wt% that the PHB segment accounts for this multipolymer.In order to be used for the present invention, the weight-average molecular weight of PHA is about 600,000～1, more than 000,000; The number-average molecular weight scope is about 280,000～500,000g/mol.
PHA generally is difficult to have with usual melt processes one-tenth film, fiber, monofilament, bar, tubing or other form of physical integrity.Usual melt technology comprises continuous melt extrusion technology, cast film expressing technique, inflation film expressing technique, melt-spinning process and other method that the insider generally knows." polymkeric substance that is difficult to melt " means that this polymkeric substance demonstrates effective melt strength and/or set time, is formed with the ability of the product of physical integrity by usual melt extrusion technology thereby detracted.
" effectively melt strength " means that a kind of molten polymer drawdown is to the desired yardstick resistance of thickness (under the situation of film) or diameter or dawn value (under the situation of fiber or monofilament) for example.Effectively the low polymkeric substance of melt strength can not tolerate and make this polymer melt be stretched to the needed bottom line strain of desired yardstick.For example, this polymer materials may demonstrate that unstable for example ruptures, molten hanging down or draw resonance.The physical integrity height is uneven often for resulting product.
" set time " means that this melt polymer material reaches a kind of in fact sticking or needed period of inviscid physical condition under the given processing condition of a cover.Be important set time, may not take place because if solidify then adhesion in one section appropriate time of this polymkeric substance during processing.Therefore, have residual tack polymer materials may in addition cool to room temperature or following after also can self-adhesion and/or adhere on the processing units.Such residual tack may limit the speed that this product can process or hinder this product to collect with the form of suitable quality.
Be subjected to polymer materials and processing units and condition influence set time.In general, under usual processing condition, set time should be on the magnitude of second.Such condition typically comprises scope from such as known chill roll temperature is to the temperature of the melt temperature of institute's work material in the industry, and the latter can be up to about 150 ℃ (better 120～135 ℃).In general, the long process cycle time (for example, putting collection from melt extrusion batches a little) is tended to hold long set time.
" glue " or " viscosity " is that the insider is known, mean viscosity or viscosity quantity.Sticking generally is a kind of subjective measurement that carries out with the finger touch film surface.If this surface be " gluing " or be stained with stickingly, then it has " gluing " property.Sticking can subjectively the measurement by means of a lot of yardsticks, but, can think that flypaper is the high point of this yardstick for this notion is described, and Teflon
(available from E.I.du Pont de Nemours and Company, Wilmington DE) does not have viscosity to sheet material (tetrafluoroethylene).For the present invention's purpose, viscosity is to be coated with Teflon at the film with a kind of suitable blend polymer at two by an a single operation person
The aluminium foil sheet material between press subjective measurement after 5 times.After pressing the 5th, make sample thin film at room temperature cool off for 10 seconds, and note making at first this film and Teflon
Sheet material breaks away from needed relative power.In addition, also subjectively monitored this film after himself is folding from himself peeling off needed power, and peel off the needed power of this polymkeric substance from operator's gloves.When from this Teflon
When on the sheet material or folding back need not apparent additional force from himself removing this film, just write down the result of " sticking ".The subjective classification yardstick of " little sticking " to " in glue " shows needs bigger power just can make this film from Teflon in each classification respectively
Draw back in sheet material and himself." glue " this classification and show, when cooling off under the standard times in 10 seconds, this film utmost point is difficult to from Teflon
Remove on the sheet material, and after folding, in fact can not separate with himself.
Nucleating agent
" nucleating agent " (nucleants or nucleating agents) is used for being the compound of polyhydroxyalkanoatefrom from molten state crystalline process artificially importing nucleation site.In U.S. Patent No. 5,534, provided a kind of description in 616 (the 36th row beginnings of the 1st hurdle).This article is classified this paper reference as.Nucleating agent helps to compensate a lot of PHA because the low crystallization velocity that its low coring density causes.The better quantity of nucleating agent in the said composition is benchmark with the gross weight of said composition, is about 1%～about 10%.Nucleating agent in this better composition is a poly butyric ester, and is benchmark with the gross weight of said composition, be with scope be about 0.005%～about 20%, more preferably about 0.05%～about 10%, be preferably about quantity of 0.5%～about 5% and use.
Softening agent
In the present composition, softening agent be used for improveing the mechanical performance of products that forms and improve the workability of said composition.In general, softening agent tends to reduce the modulus and the tensile strength of this polymeric articles and increases its elongation limit, shock strength and tear strength.Thereby also can being used for reducing the fusing point of said composition, this softening agent can carry out melt at a lower temperature.In the present invention, this softening agent is used for reducing second-order transition temperature, thereby becomes the auxiliary agent that a kind of raising reaches the speed of non-stick product.
Known in the industry external plasticizer comprises glycerine, ethylene glycol and low molecular poly.The better softening agent of the PHA that is investigated comprises two (2-ethylhexyl) dioctyl maleate; paraffin; dodecanol; sweet oil; soybean oil; polytetramethylene glycol; Witconol 2301; n propyl oleate; tetrahydrofurfuryl oleate; epoxy linseed oil; epoxy acid 2-ethylhexyl; triacetin; methyl linoleate; dibutyl fumarate; ethanoyl ricinolic acid methyl esters; the ethanoyl tri-n-butyl citrate; CitroflexA-2; tri-n-butyl citrate; triethyl citrate; dimer acids two (2-hydroxy methacrylate); the ricinolic acid butyl ester; glycerine three (ethanoyl ricinoleate ester); the ricinolic acid methyl esters; the positive butyl ester of ethanoyl ricinolic acid; the propylene glycol ricinoleate ester; ethyl succinate; diisobutyl adipate; dimethyl azelate; nonane diacid two (just own ester) and tributyl phosphate.The best softening agent of the PHA that is investigated comprises Laurate methyl and n-butyl maleate.The better quantity of softening agent in the said composition is benchmark with the weight of said composition, be about 5%～about 35%, be more preferably about 12%～about 20%.
The melt extrusion process
Use usual melt extrusion process to produce extrusion molding product of the present invention and moulded work.Such melt extrusion process comprises each component of polymer blend, subsequently this blend extrusion molding.In a kind of embodiment preferably, the wire rod of PHA polymkeric substance be about 120～160 ℃, better 130～145 ℃, be extruded onto via die plate in the water-bath of 30～40 ℃ of temperature of having an appointment.
In a kind of better melt extrusion process of the present invention, at first prepare the pellet of each component of polymer.PHA nucleating agent and softening agent can be done blend, melting mixing in film extruder itself then earlier.Substituting, if in this melt extruding machine insufficient mixing has taken place, then each component can be done blend earlier, mixes in a pre-compounded extruding machine then, make pellet subsequently before film melt extrusion molding.
PHA film of the present invention can be processed with conventional method, and is used for producing individual layer or multilayer film on usual film making equipment.Be used for making the curtain coating of PHA film of the present invention or the U.S. Patent No. 6 that the blown-film extrusion method is being classified this paper reference as, 027, more abundant description is arranged in 787, in Allan A.Griff work Plastics Extrusion Technology-2ndEd. (Van Nostrand Reinhold, 1976), description is arranged also.In a kind of embodiment preferably, this PHA polymkeric substance continuous film is to be extruded onto on have an appointment 30～45 ℃, the roller of better about 40 ℃ of temperature at about 120～160 ℃, better 120～140 ℃.
" film " mean one have high length/thickness rate and height wide/the continuous extruded material of thickness rate.Although the accurate upper limit or lower limit to thickness have no requirement, better film thickness of the present invention is about 0.05～about 50 mils, and better film thickness is about 0.5～about 15 mils.Film of the present invention can comprise one deck, two-layer or more multi-layered.
PHA composition of the present invention also can manufacture the molding of some selection with usual injection molding technology.
Embodiment
The present invention further defines with following embodiment.Should be understood that, only provide in illustrational mode though these embodiment have pointed out better embodiment of the present invention.From above discussion and these embodiment, the insider can confirm essential characteristic of the present invention, and can do various variation of the present invention and improvement so that it adapts to various uses and condition under the situation that does not deviate from its spirit and scope.
The implication of shortenings is as follows: " h " refers to hour, and " min " refers to minute, and " sec " refers to second, and " d " refers to the sky, and " mL " refers to milliliter, and " L " refers to rise, and " ft " refers to foot, and " lb " refers to that pound and " g " refer to gram.
General method
Poly--the 3-hydroxyl (butyric ester is octanoate altogether) is (P3HBO) available from P﹠G (Ohio, USA Cincinnati).Poly--the 3-hydroxyl (butyric ester is capronate altogether) is (P3HBH) available from P﹠G (Ohio, USA Cincinnati), biotechnology development centre, Jiangmen and Tsing-Hua University (China).PHB is that (St.Louis MO) supplies in Aldrich chemical company.
Embodiment 1
The identification of " activity " nucleating agent and plasticizer combinations
The screening of nucleating agent and plasticizer combinations is carried out as follows: nucleating agent PHB and a kind of PHA especially mixture of melts of P3HBO P3HBH are PHB and the P3HBO by making the proper amt earlier or powder bucket of P3HBH mixes preparation.In general, 1wt%PHB (0.75g) is added in P3HBO (74.25g) polymkeric substance, and 3wt%PHB (2.25g) is added in P3HBH (72.75g) polymkeric substance.(it is to be determined by the anti-stick performance in preliminary experiment that nucleating agent adds percentage.) after suitably the component bucket mixed, it was in 155 ℃ the little 16mm PRISM Bitruder that this powder feed to one is set to top temperature.This polymkeric substance is with via a water-cooled in 3/16 inch die head melt extrusion to a water-bath of a single hole " not sticking ".This polymkeric substance tends to adhere to this and is with, and cuts into 2～3ft length and hangs down pleat on a toothed rack, makes crystallization takes place if having time.Behind 20min～1hr, this polymkeric substance wire rod crystallization is to being enough to produce little (2～8mm is long) pellet with the scissors manual cut or by blade cut-off machine.Then, this pellet is pressed into film under following condition: press temperature (140 ℃); Pressure (1000psi); Time in the press (2min); Cooling temperature (25 ℃).Then, resulting film is cut into the wide strip of the 2～5mm that will use in this screening technology.
Owing to do not have the good mixing facility to can be used for very small amount of polymkeric substance of blending and softening agent, thereby develop and screen the mixture of melts of polymkeric substance, nucleating agent and softening agent in accordance with following methodology.In a small test tube, add the desirable softening agent of 0.4g.The test tube that contains this softening agent is put one into and is heated in 160 ℃ the Wood ' s metal bath and keeps 10min therein.After this softening agent preheating, in this test tube, add the suitable PHA film strip that 1.6g contains this PHB nucleating agent (by the above preparation).Then, the entire content of this test tube is at 160 ℃ of 50min that heating is other.Then, this test tube takes out from heating bath, and makes it at room temperature to cool off 1h at least.Resulting polymkeric substance is taken out (in case of necessity test tube being broken) from this test tube.Resulting polymkeric substance and any liquid contents be put into scribble Teflon
The aluminium foil sheet material (can be available from E.I.du Pont de Nemours and Company, Wilmington DE) goes up and is pressed into film.Then, with film from this sheet material take off, self is folding, be pressed into film again.This film pressing process repeats 5 times with the good blend of guaranteeing these three kinds of components and the validity of assessing this nucleating agent-plasticizer combinations.The processing film condition is generally as follows: press temperature (140 ℃); Press pressure (1000psi); The press time (2min); Cooling temperature (room temperature); Cooling pressure (51b plate); And cooling time (10sec).After final film compacting and the cooling 10sec immediately with this sample from being coated with Teflon
Sheet material on peel off, and assess it this be coated with Teflon
Sheet material, to self with to the viscosity of operator's gloves.If any surface that this sample demonstrates being exposed does not have defined viscosity herein, then give it with " inviscid " grade.All other grades are all pointed out a certain levels of adhesion.Then, this sample is wiped any residue softening agent away, is weighed.By final polymer weight is determined that with theoretical weight comparison and inverse plasticizer loading softening agent combines percentage, suppose to have only losses of plasticizer.A sample is calculated as follows:
The component of being added:
1.6g (nucleating agent+polymkeric substance) is form of film
0.4g softening agent
Component total amount=the 1.60g+0.40g=2.00g of processing
The theoretical %=(0.40g/2.00g) of softening agent * 100%=20%
General example:
Actual final weight=the Xg of film
Hypothesis final weight=the Xg-1.60g=Yg of softening agent
The actual %=(Yg/Xg) * 100% of softening agent
Particular case:
Actual final weight=the 1.86g of film
Hypothesis final weight=the 1.86g-1 of softening agent, 60g=0.26g
The film that actual %=(0.26g/1.86g) * 100%=14% should be noted that under any circumstance and produced of existing softening agent all is not less than 1.60g, and showing all has some softening agent to be attached in this polymkeric substance in all cases.
Table 1 (embodiment 1～44) has gathered nucleating agent and the softening agent screening of carrying out respectively with P3HBO and P3HBH, show inviscid result.Table 2 (embodiment 45～60) has gathered the comparative example that demonstrates viscosity.The shortenings Tg that uses in table 1 and the table 2 represent second-order transition temperature (℃).
In general,, held back the sample of more softening agent, compared, tended to show better (demonstrating even lower viscosity) with the sample of having held back less softening agent for the sample of those generations " inviscid " grade.Once in a while, viscosity is still obvious when some films at room temperature cool off.To have some then to demonstrate in them during 65 ℃ of coolings inviscid when same these films.These films are assessed as inviscid grade; Yet they are considered to be inferior to those and at room temperature cool off and demonstrate noncohesive film after 10 seconds.Demonstrate sample that viscosity eliminates rapidly and be considered to candidate via the melt of injection molded, film extrusion and fiber extrusion molding.
Embodiment 2
Poly--the 3-hydroxyl (butyric ester is capronate altogether) melt continuously is extruded into wire rod and online pelletizing
Demonstration
Each component blend (dibutyl maleinate softening agent): in one 35 a gallons fiber sprinning assembly, add Powdered P3HBH of 15088.6g and the Powdered PHB of 588.5g.In this powdered mixture,, add the 3923.0g dibutyl maleinate slowly can make the speed in this powder of liquid plasticizer inspiration immediately.Then, this fiber sprinning assembly is put into the mixed 6h of bucket on the polishing drum, to guarantee well blend.
The extrusion molding of polymkeric substance wire rod and pelletizing (n-butyl maleate softening agent): after aforesaid polymeric constituent bucket mixed, resulting mixture was fed in the 30mm Bitruder with the speed of about 10lb/h.The extruding machine temperature is set to such an extent that can keep 120 ℃～160 ℃ gradient barrel zone temperature.Screw rod RPM remains on 100.Resulting molten polymer is extruded onto in 12 feet long tanks that remain on 34 ℃～38 ℃ of temperature via 3/16 inch die head.This polymkeric substance cuts and is fed in the Conair polymer cutting machine with the speed of 6～8ft/min, collects to add up to the 40.9lb pellet.
Resulting polymkeric substance wire rod demonstrates certain viscous behavior in 6 feet scopes of this quench tank.In this tank this wire rod become inviscid after, this polymkeric substance is all showing inviscid behavior between this processing operational period or in processing operation subsequently any time.
Embodiment 3
Poly--the 3-hydroxyl (butyric ester is capronate altogether) melt continuously is extruded into wire rod and online pelletizing
Demonstration
The blend of polymkeric substance wire rod and extrusion molding and pelletizing (Laurate methyl softening agent): one be similar among the embodiment 2 for described that a kind of technology of the polymkeric substance of n-butyl maleate blend in, blend following component: 11,793g P3HBH, 459.5g PHB and 3063g Laurate methyl.Then, resulting mixture be fed to one set can keep 120 ℃～160 ℃ the gradient barrel zone temperature, in the foregoing 30mm extruding machine.Screw rod RPM remains on 100, and polymkeric substance is extruded onto one via 3/16 inch die head and remains in 12 feet tanks of 34 ℃～38 ℃.This polymkeric substance cuts with the speed of about 12ft/min with a Conair polymer cutting machine.Polymkeric substance quenching time (observing the time of no further viscosity) is about 25sec.Collected and added up to the inviscid pellet of about 32lb.Be noted that Laurate methyl has promoted quenching time faster, thereby allow cutting speed in feet per minute faster.
Embodiment 4
Use the continuous of poly--3-hydroxyl (butyric ester is capronate altogether) and Laurate methyl softening agent
The demonstration that cast film is produced
Prepare among the embodiment of front, with Laurate methyl plasticising and with the P3HBH pellet of PHB coring, be fed to 14 inches sheeting dies of outfit and set to such an extent that can keep in single multiple screw extruder of gradient machine barrel/die head temperature of 140 ℃～120 ℃.Resulting polymer-extruded logistics is prolonged to the stainless steel rider of 12 inch diameters that is set in 40 ℃ of temperature.The film rolling of extruding is got on the chill roll, batched then on the packing roller, and its velocity range is 2ft/min～13ft/min, is the film of 1 mil～10 mils to produce thickness range.This film demonstrates performance listed in inviscid and the following table 3 (standard method of test according to ASTM D 882-95a-thin plastic sheet material tensile property is measured):
Table 3
| Direction | Thickness (mil) | Young's modulus (MPa) | Breaking strain (%) | Rupture stress (MPa) | Toughness (J/in 3) |
| Vertically | ???1.7 | ????187 | ????562 | ????10.3 | ????745 |
| Laterally | ???1.7 | ????147 | ????524 | ????8.2 | ????623 |
Table 1
| Embodiment number | Form (+nucleating agent) | Softening agent | The WT% softening agent | Membrane quality |
| ????1 | ?PHBO/PHB(99∶1) | Two (2-ethylhexyl) dioctyl maleate | ????12 | Inviscid |
| ????2 | ?PHBO/PHB(99∶1) | Paraffin | ????3.6 | Inviscid |
| ????3 | ?PHBO/PHB(99∶1) | Dodecanol | ????7 | Inviscid |
| ????4 | ?PHBO/PHB(99∶1) | Polyethylene Glycol-600 | ????7 | Inviscid |
| ????5 | ?PHBO/PHB(99∶1) | Polyoxyethylene glycol 8000 | ????11 | Inviscid |
| ????6 | ?PHBO/PHB(99∶1) | Sweet oil | ????2.4 | Inviscid |
| ????7 | ?PHBO/PHB(99∶1) | Soybean oil | ????4.8 | Inviscid |
| ????8 | ?PHBO/PHB(99∶1) | TERETHANE?650 | ????14 | Inviscid |
| ????9 | ?PHBO/PHB(99∶1) | Witconol 2301 | ????14 | Inviscid |
| ????10 | ?PHBO/PHB(99∶1) | N propyl oleate | ????12 | Inviscid |
| ????11 | ?PHBO/PHB(99∶1) | Tetrahydrofurfuryl oleate | ????13 | Inviscid |
| ????12 | ?PHBO/PHB(99∶1) | Epoxy linseed oil | ????9 | Inviscid |
| ????13 | ?PHBO/PHB(99∶1) | Epoxy acid 2-ethylhexyl | ????11 | Inviscid |
| ????14 | ?PHBO/PHB(99∶1) | Dibutyl fumarate | ????20 | Inviscid |
| ????15 | ?PHBO/PHB(99∶1) | Triacetin | ????18 | Inviscid |
| ????16 | ?PHBO/PHB(99∶1) | Laurate methyl | ????12 | Inviscid |
| Embodiment number | Form (+nucleating agent) | Softening agent | The WT% softening agent | Membrane quality |
| ????17 | ?PHBO/PHB(99∶1) | Methyl linoleate, 75% | ????9 | Inviscid |
| ????18 | ?PHBO/PHB(99∶1) | N-butyl maleate | ????17 | Inviscid |
| ????19 | ?PHBO/PHB(99∶1) | Ethanoyl ricinolic acid methyl esters | ????11 | Fine |
| ????20 | ?PHBO/PHB(99∶1) | Ethanoyl citric acid three (positive butyl ester) | ????19 | Viscosity is very little |
| ????21 | ?PHBO/PHB(99∶1) | CitroflexA-2 | ????20 | Viscosity is very little |
| ????22 | ?PHBO/PHB(99∶1) | Tri-n-butyl citrate | ????20 | Viscosity is very little |
| ????23 | ?PHBO/PHB(99∶1) | Triethyl citrate | ????20 | Viscosity is very little |
| ????24 | ?PHBO/PHB(99∶1) | Dimer acids two (2-ethylhexyl) | ????7 | Viscosity is very little |
| ????25 | ?PHBO/PHB(99∶1) | The ricinolic acid butyl ester | ????19 | Qualified |
| ????26 | ?PHBO/PHB(99∶1) | Glycerine three (ethanoyl ricinoleate ester) | ????6 | Qualified |
| ????27 | ?PHBO/PHB(99∶1) | The ricinolic acid methyl esters | ????18 | Qualified |
| ????28 | ?PHBO/PHB(99∶1) | The positive butyl ester of ethanoyl ricinolic acid | ????13 | Qualified |
| ????29 | ?PHBO/PHB(99∶1) | The ricinolic acid propylene glycol ester | ????17 | Qualified |
| 30 (contrasts) | ?PHBO/PHB(99∶1) | The viscosity height | ||
| ????31 | ?PHBH/PHB(97∶3) | Paraffin | ????2.4 | Inviscid |
| ????32 | ?PHBH/PHB(97∶3) | Dodecanol | ????8 | Inviscid |
| ????33 | ?PHBH/PHB(97∶3) | Dibutyl fumarate | ????17 | Not sticking |
| ????34 | ?PHBH/PHB(97∶3) | Laurate methyl | ????18 | Not sticking |
| Embodiment number | Form (+nucleating agent) | Softening agent | The WT% softening agent | Membrane quality |
| ????35 | ?PHBH/PHB(97∶3) | Methyl linoleate | ????17 | Not sticking |
| ????36 | ?PHBH/PHB(97∶3) | N-butyl maleate | ????19 | Not sticking |
| ????37 | ?PHBH/PHB(97∶3) | The ricinolic acid methyl esters | ????18 | Not sticking |
| ????38 | ?PHBH/PHB(97∶3) | Ethyl succinate | ????17 | Not sticking |
| ????39 | ?PHBH/PHB(97∶3) | Diisobutyl adipate | ????19 | Not sticking |
| ????40 | ?PHBH/PHB(97∶3) | Dimethyl azelate | ????19 | Not sticking |
| ????41 | ?PHBH/PHB(97∶3) | Di n hexyl azelate | ????17 | Not sticking |
| ????42 | ?PHBH/PHB(97∶3) | Tributyl phosphate | ????20 | Not sticking |
| ????43 | ?PHBH/PHB(97∶3) | Two (2-ethylhexyl) dioctyl maleate | ????17 | Qualified |
| ????44 | ?PHBH/PHB(97∶3) | TERETHANE?650 | ????15 | Qualified |
Table 2
| Embodiment number | Form (+nucleating agent) | Softening agent | The WT% softening agent | Membrane quality |
| ??45 | The PHBO-contrast | Sticking | ||
| ??46 | The PHBH-contrast | Sticking | ||
| ??47 | ?PHBH/PHB(97∶3) | Sticking | ||
| ??48 | ?PHBO/PHB(97∶3) | Sticking |
| Embodiment number | Form (+nucleating agent) | Softening agent | The WT% softening agent | Membrane quality |
| ????49 | PHBO/ Microcrystalline Cellulose (97: 3) | Sticking-during Re easily from Teflon On take off, along with cooling becomes sticky | ||
| ????50 | ?PHBO/NUCREL?1214(95∶5) | Sticking | ||
| ????51 | PHBO/ paraffin (95: 5) | Than control group difference | ||
| ????52 | ?PHBO/PO2G(95∶5) | Sticking | ||
| ????53 | PHBO/ polyoxyethylene glycol 8000 (97: 3) | Little sticking | ||
| ????54 | PHBO/ poly(lactic acid) (97: 3) | Sticking | ||
| ????55 | ?PHBO/SURLYN?8020(95∶5) | Sticking | ||
| ????56 | ?PHBH/PHB(97∶3) | Butyl oleate | ????8 | Sticking |
| ????57 | ?PHBH/PHB(97∶3) | Hexanodioic acid two (tridecane ester) | ????15 | Little sticking |
| ????58 | ?PHBH/PHB(97∶3) | Dodecanol | ????8 | Little sticking |
| ????59 | ?PHBH/PHB(97∶3) | Epoxy linseed oil | ????13 | Little sticking |
| ????60 | ?PHBH/PHB(97∶3) | Sweet oil | ????2 | Little sticking |
| ????61 | ?PHBH/PHB(97∶3) | Soybean oil | ????3 | Sticking |
| ????62 | ?PHBH/PHB(97∶3) | Triethyl citrate | ????18 | Sticking |
| ????63 | ?PHBO/PHB(99∶1) | Chloroparaffin 50%Cl | ????9 | Sticking |
| ????64 | ?PHBO/PHB(99∶1) | N-butyl stearate | ????6 | A bit sticking |
Claims (25)
1. a polyhydroxyalkanoatecopolymers copolymers composition that has reduced viscosity comprises
(a) a kind of polyhydroxy alkanoate copolymer,
(b) a kind of nucleating agent and
(c) a kind of softening agent.
2. a polyhydroxyalkanoatecopolymers copolymers composition that has reduced viscosity comprises
(a) 55～94% polyhydroxy alkanoate copolymers,
(b) 1～10% nucleating agent and
(c) 5～35% softening agent.
3. the polyhydroxyalkanoatecopolymers copolymers composition of claim 1,
Formula I
R=CH
3(CH
2)
yY=0-11 in the formula
Wherein, this polyhydroxy alkanoate copolymer is selected from compound shown in the formula I, m=0.7 in the formula～0.97, n=0.3～0.03, and m+n=1.0 in the formula.
4. the polyhydroxyalkanoatecopolymers copolymers composition of claim 1, wherein, a group of forming of this polyhydroxy alkanoate copolymer is selected from poly--3-hydroxyl (butyric ester is octanoate altogether) and poly--3-hydroxyl (butyric ester is capronate altogether).
5. the polyhydroxyalkanoatecopolymers copolymers composition of claim 1, wherein, this nucleating agent is a poly butyric ester.
6. the polyhydroxyalkanoatecopolymers copolymers composition of claim 1, wherein, this nucleating agent is selected from a group that the carboxylate salt of talcum, micronization mica, lime carbonate, boron nitride, ammonium chloride, sodium salt and periodic table of elements I family and II family metal is formed.
7. the polyhydroxyalkanoatecopolymers copolymers composition of claim 1; wherein, this softening agent is selected from a group of following composition: n-butyl maleate; Laurate methyl; dibutyl fumarate; two (2-ethylhexyl) dioctyl maleate; paraffin; dodecanol; sweet oil; soybean oil; polytetramethylene glycol; Witconol 2301; n propyl oleate; tetrahydrofurfuryl oleate; epoxy linseed oil; epoxy acid 2-ethylhexyl; triacetin; methyl linoleate; dibutyl fumarate; ethanoyl ricinolic acid methyl esters; the ethanoyl tri-n-butyl citrate; CitroflexA-2; tri-n-butyl citrate; triethyl citrate; dimer acids two (2-hydroxy methacrylate); the ricinolic acid butyl ester; glycerine three (ethanoyl ricinoleate ester); the ricinolic acid methyl esters; the positive butyl ester of ethanoyl ricinolic acid; the ricinolic acid propylene glycol ester; ethyl succinate; diisobutyl adipate; dimethyl azelate; di n hexyl azelate and tributyl phosphate.
8. improve the method for the workability of polyhydroxyalkanoatecopolymers copolymers composition by reducing viscosity, this method comprises makes polyhydroxyalkanoatecopolymers copolymers and a kind of nucleating agent contact the step that forms a kind of polyhydroxyalkanoatecopolymers copolymers composition with a kind of softening agent.
9. according to the method for claim 8, further comprise the step of extrusion molding polyhydroxyalkanoatecopolymers copolymers composition.
10. according to the method for claim 9, further comprise step with the polyhydroxyalkanoatecopolymers copolymers composition pelletizing of extrusion molding.
11., further comprise the step of the polyhydroxyalkanoatecopolymers copolymers composition of extrusion molding pelletizing according to the method for claim 10.
12. according to the method for claim 10, wherein, the polyhydroxyalkanoatecopolymers copolymers composition is by compounding extruding machine extrusion molding.
13. extrusion molding product comprise the polyhydroxyalkanoatecopolymers copolymers composition of claim 1.
14. the extrusion molding product of claim 13 are the form of fiber, monofilament, bar, tubing or cast film.
15. the cast film of claim 14, the film thickness of 0.05～about 50 mils of having an appointment.
16. the cast film of claim 14, the film thickness of 0.10～about 15 mils of having an appointment.
17. the extrusion molding product of producing with the method for claim 8.
18. the extrusion molding product of producing with the method for claim 9.
19. the extrusion molding product of producing with the method for claim 11.
20. the extrusion molding product of producing with the method for claim 12.
21. extrusion molding product with the method for claim 8 form that produce, that be fiber, monofilament, bar, tubing or cast film.
22. extrusion molding product with the method for claim 9 form that produce, that be fiber, monofilament, bar, tubing or cast film.
23. extrusion molding product with the method for claim 11 form that produce, that be fiber, monofilament, bar, tubing or cast film.
24. extrusion molding product with the method for claim 12 form that produce, that be fiber, monofilament, bar, tubing or cast film.
25. injection molded product comprise the polyhydroxyalkanoatecopolymers copolymers composition of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28556001P | 2001-04-20 | 2001-04-20 | |
| US60/285,560 | 2001-04-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1503824A true CN1503824A (en) | 2004-06-09 |
Family
ID=23094770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA028085825A Pending CN1503824A (en) | 2001-04-20 | 2002-04-19 | Processing of polyhydroxyalkanoates using a nucleant and a plasticizer |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1379590A1 (en) |
| JP (1) | JP2005501927A (en) |
| KR (1) | KR20030096324A (en) |
| CN (1) | CN1503824A (en) |
| BR (1) | BR0209118A (en) |
| CA (1) | CA2441781A1 (en) |
| MX (1) | MXPA03009554A (en) |
| WO (1) | WO2002085983A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102492274A (en) * | 2011-12-14 | 2012-06-13 | 王长青 | Process for preparing degradable polyhydroxyalkanoate (PHA) calendering film |
| CN108484356A (en) * | 2018-03-23 | 2018-09-04 | 世界家庭用具制品厂有限公司 | A kind of purification process of crude glycerine and application thereof obtained from kitchen garbage |
| CN115028978A (en) * | 2022-08-11 | 2022-09-09 | 北京蓝晶微生物科技有限公司 | Polyhydroxyalkanoate composition and molded article thereof |
| CN115613155A (en) * | 2022-11-18 | 2023-01-17 | 北京微构工场生物技术有限公司 | Filament or staple fiber and preparation method thereof |
| CN116277593A (en) * | 2023-05-23 | 2023-06-23 | 北京微构工场生物技术有限公司 | Method for granulating and molding polyhydroxyalkanoate and molded body thereof |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602004009764T2 (en) * | 2003-02-21 | 2008-08-28 | Metabolix, Inc., Cambridge | PHA KLEBSTOFFE |
| US6706942B1 (en) | 2003-05-08 | 2004-03-16 | The Procter & Gamble Company | Molded or extruded articles comprising polyhydroxyalkanoate copolymer compositions having short annealing cycle times |
| US7098292B2 (en) | 2003-05-08 | 2006-08-29 | The Procter & Gamble Company | Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer |
| US8034270B2 (en) | 2003-05-08 | 2011-10-11 | Tepha, Inc. | Polyhydroxyalkanoate medical textiles and fibers |
| DE602004016563D1 (en) | 2003-12-30 | 2008-10-23 | Metabolix Inc | nucleating |
| PT1778305E (en) * | 2004-08-03 | 2010-07-27 | Tepha Inc | Non-curling polyhydroxyalkanoate sutures |
| CN101035902B (en) * | 2004-08-06 | 2012-07-04 | Phb工业股份有限公司 | Use of fatty alcohols as plasticizer to improve the physical-mechanical properties and processability of PHB and its co-polymers |
| US7301000B2 (en) * | 2004-09-15 | 2007-11-27 | The Procter & Gamble Company | Nucleating agents for polyhydroxyalkanoates |
| BRPI0600783A (en) * | 2006-02-24 | 2007-11-20 | Phb Ind Sa | biodegradable polymer composition and method for producing a biodegradable polymer composition |
| WO2008018567A1 (en) | 2006-08-10 | 2008-02-14 | Kaneka Corporation | Biodegradable resin composition and molded body thereof |
| KR100885143B1 (en) * | 2007-02-06 | 2009-02-23 | 피에이치비 인더스트리얼 에스/에이 | Use of fatty alcohols as plasticizer to improve the physical-mechanical properties and processability of phb and its co-polymers |
| US20100041835A1 (en) * | 2007-03-01 | 2010-02-18 | BASF SE Patents, Trademarks and Lincense | Polyester mixture comprising biodiesel |
| JP5207274B2 (en) * | 2007-10-15 | 2013-06-12 | 国立大学法人東京工業大学 | Biodegradable resin composition |
| FR2965814B1 (en) | 2010-10-08 | 2012-11-16 | Roquette Freres | PLASTIFICATION OF ALIPHATIC POLYESTERS BY ALKYLIC ESTERS OF DIANHYDROHEXITOLS |
| US9475930B2 (en) | 2012-08-17 | 2016-10-25 | Metabolix, Inc. | Biobased rubber modifiers for polymer blends |
| EP3004225A1 (en) | 2013-05-30 | 2016-04-13 | Metabolix, Inc. | Recyclate blends |
| US9339580B2 (en) | 2013-11-27 | 2016-05-17 | Kimberly-Clark Worldwide, Inc. | Flushable tampon applicator |
| US9456931B2 (en) | 2013-11-27 | 2016-10-04 | Kimberly-Clark Worldwide, Inc. | Thermoplastic and water-dispersible injection moldable materials and articles |
| US9320656B2 (en) | 2013-11-27 | 2016-04-26 | Kimberly-Clark Worldwide, Inc. | Water-dispersible thermoplastic injection molded composition |
| CN106459544B (en) | 2014-03-27 | 2021-10-01 | Cj 第一制糖株式会社 | Highly filled polymer systems |
| EP3180040B1 (en) | 2014-08-15 | 2020-05-13 | Tepha, Inc. | Self-retaining sutures of poly-4-hydroxybutyrate and copolymers thereof |
| EP3230500A1 (en) | 2014-12-11 | 2017-10-18 | Tepha, Inc. | Methods of orienting multifilament yarn and monofilaments of poly-4-hydroxybutyrate and copolymers thereof |
| US10626521B2 (en) | 2014-12-11 | 2020-04-21 | Tepha, Inc. | Methods of manufacturing mesh sutures from poly-4-hydroxybutyrate and copolymers thereof |
| EP3529296A1 (en) * | 2016-10-18 | 2019-08-28 | Meredian Bioplastics, Inc. | Crystal nucleating agents for polyhydroxyalkanoates |
| JP7481879B2 (en) * | 2020-03-30 | 2024-05-13 | 大阪瓦斯株式会社 | Crystallization promoter and its uses |
| JPWO2024029491A1 (en) * | 2022-08-01 | 2024-02-08 | ||
| KR20240061572A (en) * | 2022-10-31 | 2024-05-08 | 씨제이제일제당 (주) | Composition for biodegradable multifilament fiber, biodegradable multifilament fiber and preparation method thereof |
| WO2024117006A1 (en) * | 2022-11-28 | 2024-06-06 | 株式会社カネカ | Resin composition and molded body |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4900299A (en) * | 1987-05-11 | 1990-02-13 | Mcneil-Ppc, Inc. | Biodegradable tampon application comprising poly(3-hydroxybutyric acid) |
| ATA258390A (en) * | 1990-12-19 | 1997-08-15 | Danubia Petrochem Polymere | MIXTURE PRESENTLY FROM A POLYHYDROXYALKANOATE AND A COMPOUND THAT CONTAINS AT LEAST TWO REACTIVE GROUPS LIKE ACID AND / OR ALCOHOL GROUPS AND A POLYMERIZED PRODUCTION BY MELTING THE MIXTURE |
| AU676191B2 (en) * | 1992-08-13 | 1997-03-06 | Metabolix, Inc. | Polymer compositions |
| GB9223350D0 (en) * | 1992-11-06 | 1992-12-23 | Ici Plc | Polymer composition |
| GB9310712D0 (en) * | 1993-05-24 | 1993-07-07 | Zeneca Ltd | Polymer composition |
| GB9311402D0 (en) * | 1993-06-02 | 1993-07-21 | Zeneca Ltd | Processing of polyesters |
| ZA95627B (en) * | 1994-01-28 | 1995-10-05 | Procter & Gamble | Biodegradable copolymers and plastic articles comprising biodegradable copolymers |
| AU8758498A (en) * | 1997-07-25 | 1999-02-16 | Monsanto Company | Nucleating agents for polyhydroxyalkanoates and other thermoplastic polyesters and methods for their production and use |
| JPH1160917A (en) * | 1997-08-25 | 1999-03-05 | Mitsubishi Gas Chem Co Inc | Biodegradable resin composition and its production |
| EP1025152A1 (en) * | 1997-10-31 | 2000-08-09 | Monsanto Company | Plasticized polyhydroxyalkanoate compositions and methods for their use in the production of shaped polymeric articles |
| EP1027384B1 (en) * | 1997-10-31 | 2005-07-27 | Metabolix, Inc. | Polymer blends containing polyhydroxyalkanoates and compositions with good retention of elongation |
| EP1345984B1 (en) * | 2000-12-21 | 2006-05-03 | The Procter & Gamble Company | Method for making biodegradable polyhydroxyalkanoate copolymers having improved crystallization properties |
-
2002
- 2002-04-19 WO PCT/US2002/012541 patent/WO2002085983A1/en active Search and Examination
- 2002-04-19 JP JP2002583506A patent/JP2005501927A/en active Pending
- 2002-04-19 KR KR10-2003-7013614A patent/KR20030096324A/en not_active Application Discontinuation
- 2002-04-19 CA CA002441781A patent/CA2441781A1/en not_active Abandoned
- 2002-04-19 MX MXPA03009554A patent/MXPA03009554A/en not_active Application Discontinuation
- 2002-04-19 EP EP02723928A patent/EP1379590A1/en not_active Withdrawn
- 2002-04-19 CN CNA028085825A patent/CN1503824A/en active Pending
- 2002-04-19 BR BR0209118-6A patent/BR0209118A/en not_active IP Right Cessation
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN102492274A (en) * | 2011-12-14 | 2012-06-13 | 王长青 | Process for preparing degradable polyhydroxyalkanoate (PHA) calendering film |
| CN108484356A (en) * | 2018-03-23 | 2018-09-04 | 世界家庭用具制品厂有限公司 | A kind of purification process of crude glycerine and application thereof obtained from kitchen garbage |
| CN115028978A (en) * | 2022-08-11 | 2022-09-09 | 北京蓝晶微生物科技有限公司 | Polyhydroxyalkanoate composition and molded article thereof |
| CN115613155A (en) * | 2022-11-18 | 2023-01-17 | 北京微构工场生物技术有限公司 | Filament or staple fiber and preparation method thereof |
| CN116277593A (en) * | 2023-05-23 | 2023-06-23 | 北京微构工场生物技术有限公司 | Method for granulating and molding polyhydroxyalkanoate and molded body thereof |
| CN116277593B (en) * | 2023-05-23 | 2023-10-20 | 北京微构工场生物技术有限公司 | Method for granulating and molding polyhydroxyalkanoate and molded body thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20030096324A (en) | 2003-12-24 |
| JP2005501927A (en) | 2005-01-20 |
| WO2002085983A1 (en) | 2002-10-31 |
| BR0209118A (en) | 2004-07-27 |
| EP1379590A1 (en) | 2004-01-14 |
| MXPA03009554A (en) | 2004-02-12 |
| CA2441781A1 (en) | 2002-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1503824A (en) | Processing of polyhydroxyalkanoates using a nucleant and a plasticizer | |
| CN1225494C (en) | Biodegradable compositions comprising starch and polysaccharide esters | |
| KR100893840B1 (en) | Ternary mixtures of biodegradable polyesters and products manufactured from them | |
| CN103154112B (en) | With the alkyl esters of two dewatering hexitol, plasticising is carried out to aliphatic polyester series | |
| CA1339026C (en) | Degradable thermoplastics from lactides | |
| JP2010507006A (en) | Impact improved polylactide resin | |
| JP2018162428A (en) | Resin composition and resin molding molded therewith | |
| JP6612785B2 (en) | Composition comprising a polymer based on polylactide | |
| US6774158B2 (en) | Processing of polyhydroxyalkanoates using a nucleant and a plasticizer | |
| JP3359744B2 (en) | Porous film and method for producing the same | |
| JP2011168716A (en) | Impact resistance-imparting agent for polylactic acid resin and polylactic acid resin composition containing the same agent | |
| EP3452546B1 (en) | 3d-printed pla articles | |
| AU2010200315A1 (en) | Biodegradable resin composition, method for production thereof and biodegradable film therefrom | |
| CN114702799A (en) | Biodegradable polylactic acid plastic uptake sheet | |
| JP5145531B2 (en) | Polylactic acid composition and polylactic acid molded article | |
| JP4246523B2 (en) | Lactic acid resin composition | |
| JPWO2013141126A1 (en) | Polylactic acid resin composition and polylactic acid film formed by molding the same | |
| JP5688150B2 (en) | Impact resistance agent for polylactic acid resin | |
| JP2012077254A (en) | Polylactic acid-based resin composition and molding | |
| AU634723B2 (en) | Degradable thermoplastic from lactides | |
| JP4315698B2 (en) | L-lactic acid polymer composition | |
| CN114316524A (en) | High-strength PBAT/starch biodegradable masterbatch and preparation method thereof | |
| EP3696232A1 (en) | Injection moulded item | |
| Burns | Mechanical properties and compostability of injection-moulded biodegradable compositions |
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 |