CN1235950C - Method for preparing soft and elastic biodegradable polyhyoxyalkanmoate copolymer compositions andpolymer products comprising such compositions - Google Patents

Method for preparing soft and elastic biodegradable polyhyoxyalkanmoate copolymer compositions andpolymer products comprising such compositions Download PDF

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CN1235950C
CN1235950C CNB008150400A CN00815040A CN1235950C CN 1235950 C CN1235950 C CN 1235950C CN B008150400 A CNB008150400 A CN B008150400A CN 00815040 A CN00815040 A CN 00815040A CN 1235950 C CN1235950 C CN 1235950C
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CN1384851A (en
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D·H·梅利克
野田勇夫
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/62—Compostable, hydrosoluble or hydrodegradable materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

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Abstract

Soft and elastic polymer products are obtained by stretching a composition comprising a biodegradable polyhydroxyalkanoate copolymer comprising at least two randomly repeating monomer units. The first randomly repeating monomer unit has structure (I), wherein R<1> is H, or C1 or C2 alkyl, and n is 1 or 2. The second randomly repeating monomer unit is different from the first randomly repeating monomer unit and has structure (II), wherein m is 2 to about 9. At least about 70 mole % of the copolymer comprises randomly repeating monomer units having the structure of the first randomly repeating monomer unit (I). The products exhibit advantageous combinations of softness and elasticity while maintaining strength.

Description

The manufacture method that comprises the polymeric articles and this polymeric articles of biodegradable polyhydroxyalkanoatecopolymer copolymer compositions
FIELD OF THE INVENTION
The present invention relates to polymeric articles, it include, but are not limited to will comprise the composition drawn of biodegradable the polyhydroxy alkanoate copolymer film, fiber, supatex fabric and the sheet that obtain.This product has the desirable over-all properties that flexibility and elasticity keep intensity simultaneously concurrently.These products can be used for various biodegradable goods, comprise diaper topsheets, diaper tergite, refuse bag, food product pack, disposable external-cover etc.
The background of invention
Reduce the volume of the annual solid waste that produces by the human consumer from hope, biodegradable polymkeric substance and more and more seem important by the product that biodegradable polymers is made.
In the past, once studied the biological degradability and the physicals of various polyhydroxyalkanoatefroms.Polyhydroxyalkanoatefrom is the petchem by various microorganisms such as bacterium and algae generation.Although polyhydroxyalkanoatefrom is owing to its biodegradable obtains common attention, its as the practical application of plastics owing to its thermolability is hindered.For example, poly--3-butyric ester (PHB) is the product of the natural storage energy of a kind of bacterium and algae, it is present in the cytoplasmic individual particle.PHB is thermoplastic, and its degree of crystallinity is high and have a melt temperature of about 180 ℃ fine qualification.Unfortunately, it is unstable that PHB seems, it is degraded under the elevated temperature near its melt temperature.Because this thermolability, the commercial applications of PHB is very limited.
The polyhydroxyalkanoatefrom of also once studying other is as gathering (3-butyric ester-3-hydroxyl valerate) (PHBV).The example of PHB homopolymer and PHBV multipolymer is described in the United States Patent (USP) 4,393,167 and 4,880 of Holmes etc., and in 59, and the PHBV multipolymer is purchased from Monsanto with trade(brand)name BIOPOL.Unfortunately, polyhydroxyalkanoatefrom such as PHB and PHBV are difficult to be processed into the used film of various uses.As mentioned above, to make this processing almost be impossible to the thermolability of PHB.And the slow crystallization velocity of PHB and PHBV and flowability make the processing of film become difficult.The valerate content of the PHBV multipolymer that makes generally is about 5-24mol%.The raising of valerate content can reduce the melt temperature of polymkeric substance.Yet, because crystallinity change is smaller, so that the PHBV film remains concerning many application usually is hard and crisp.
Improved biodegradable multipolymer for example is disclosed in the United States Patent (USP) 5,498,692,5,536,564,5,602,227 and 5,685,756 of Noda.The biodegradable multipolymer of Noda comprises at least two kinds of random repeated monomer unit (RRMU), and wherein the structural formula of first kind of RRMU is [O-CH (R 1)-(CH 2) n-C (O)-], R wherein 1Be the alkyl of H or C1 or C2, n be 1 or the structural formula of 2, the second kind of RRMU be [O-CH (R 2)-CH 2-C (O)-], R wherein 2Be alkyl or the alkenyl of C4-C19, at least 50% RRMU has the structure of first kind of RRMU.The advantage of these multipolymers is that they are biodegradable and have the good comprehensive physicals that they can be processed film forming, sheet, fiber, foam materials, moulded parts, supatex fabric etc., thereby various useful goods are provided.Yet these multipolymers are not soft and resilient intensity when keeping their initial unstretched states simultaneously.
Known polyhydroxyalkanoatefrom (PHA) multipolymer of mainly being made up of the repeating unit of the longer side chain alkyl that comprises three to nine carbon atoms has soft and elastomeric elasticity as poly-Hydroxyoctanoic acid ester, the intensity that has some degree simultaneously is (for example referring to K.D.Gagnon, R.W.Lenz, the macromole of R.J.Farris and R.C.Fuller (Macromolecules), the 25th volume, pp.3723-3728,1992).Yet the softness of being made by this pha copolymer and the application of elastic product seriously are subjected to the restriction of about 60 ℃ disappointed low melting glass.Even can reach be higher than 80 ℃ summer the warehouse temperature under, the also dimensional stability of entail dangers to product.Like this, wish a kind of biodegradable softness and elastic product of making by the higher polymkeric substance of melt temperature.
Usually wish thermoplastic polymer is stretched, so that change its physicals.Unfortunately, PHB and PHBV can form the fragility product, even only it is carried out the stretching of not half, described product generally also can rupture.Once attempted the whole bag of tricks and improve the drawing process and the gained performance of stretching PHB and PHBV product, described method for example is disclosed in the United States Patent (USP) 4,427,614 of the United States Patent (USP) 4,537,738 of Holmes and Barham etc.Other method then is disclosed in Safta Europe reference EP 736,563 A1, physics and the Europe reference EP of chemical research institute 849, the pure applied chemistry of the WO reference 97/22459 of 311 A2, Waldock, Kusaka etc. (Pure Appl.Chem.) 834 (2): international polymer processing (Intern.Polymer Processing) XII of 319-335 (1998) and Yamamoto etc., among (1997) 1:29-37.Yet these methods are not successful especially on the method for the drawn products of some over-all properties that provides easy manufacturing to have desired physical properties.Especially, prior art does not provide and has the polymeric articles that flexibility and elasticity keep intensity simultaneously.
Therefore, advantageously will obtain such polymeric articles, it is biodegradable and has and can make the flexibility and the elastic required over-all properties of this product application in various uses.
The general introduction of invention
Therefore, an object of the present invention is to provide the product and the method for the novelty that overcomes the prior art shortcoming.A relevant purpose of the present invention provides the polymeric articles of being made by the composition that comprises biodegradable polymkeric substance.A further object of the present invention provides the polymeric articles with good comprehensive physicals.Of the present invention one more specifically purpose provide and have the biodegradable polymeric articles that flexibility and elasticity keep intensity simultaneously.Another object of the present invention provides the method for this product of easy manufacturing.Of the present invention also have a purpose to provide the goods that comprise this polymeric articles.
These are provided by product of the present invention and method with additional purpose and advantage.In one embodiment, the present invention relates to will comprise the composition of the biodegradable polyhydroxy alkanoate copolymer polymeric articles that stretches and obtain.Biodegradable polyhydroxy alkanoate copolymer comprises at least two kinds of random repeated monomer unit (RRMU).First kind of RRMU has structural formula (I):
Figure C0081504000071
R wherein 1Be H or C1 or C2 alkyl, n is 1 or 2.Second kind of RRMU is different from first kind of RRMU, and it has structural formula (II):
Wherein m is 2 to about 9.The RRMU that comprises (I) the first kind of RRMU structure that have formula at least about the multipolymer of 70mol%.The product that the suitable polymers product includes, but are not limited to film, sheet, fiber, supatex fabric and bondings such as many fibers such as non-woven sheets are got up to make.The advantage of polymeric articles of the present invention is that they have the over-all properties that flexibility and elasticity keep intensity simultaneously.
In another embodiment, the present invention relates to make the method for improved biodegradable polymeric articles.This method is included in the second-order transition temperature T that is higher than composition gBut be lower than the melt temperature T of composition mTemperature under will comprise biodegradable polyhydroxy alkanoate copolymer composition stretch.Biodegradable polyhydroxy alkanoate copolymer comprises at least two kinds of RRMU, wherein first kind of RRMU has the structure of formula (I), second kind of RRMU is different from first kind of RRMU, it has the structure of formula (II), these and comprise the RRMU of (I) the first kind of RRMU structure that have formula all as mentioned above at least about the multipolymer of 70mol%.Can adopt conventional solid state drawing easily.Like this, method of the present invention comprises the easy step of comparing with the cumbersome methods that many prior arts are made the strained polymer products, and method of the present invention can provide the product of the strained polymer with good comprehensive physicals.
From following detailed description, can understand these and additional purpose and advantage more completely.
Describe in detail
Although do not think bound by theoryly, think that the drawing process that reaches to a certain degree can make the copolymer chain of product of the present invention be orientated.Strained polymer product of the present invention unexpectedly has good comprehensive physicals, especially has flexibility and elasticity and keeps intensity simultaneously.Specifically, compare with the not drawn products of same composition, strained polymer product of the present invention has higher intensity (for example being recorded by higher tensile stress at break) and higher flexibility (for example being recorded by lower tensile modulus).This over-all properties is the very beyond thought result of drawing process.In general, drawing process can make product strength bigger and harder (not too soft), rather than intensity is bigger and more soft.For example, for fiber, M.S.M.Mark exists The polymer science dictionaryElsevier Applied Science, New York (1989), point out on the 295th page " stretch or the fiber of spinning intentionally along its length orientation; like this owing to uniaxial orientation improves in intensity and the rigidity that this side up " and L.E.Nielson and R.F.Landel exist The mechanical property of polymkeric substance and matrix material, the 2nd edition, Marcel Dekker, Inc., New York (1994) points out " many height-oriented Young's moduluss that fiber had are than a big approximately order of magnitude of non-oriented polymkeric substance " on the 116th page.For film, Nielson points out also that with Landel (the 116th page) " compare with non-oriented material, the film of the diaxial orientation that stretching makes on two orthogonal directions has the creep and the stress relaxation of decline.This result partly is because due to the modulus raising ".
This product has good elasticity, and promptly they can be replied fast when removing deformation force or pressure.In embodiment preferably, the elasticity that product of the present invention shows is springy, and promptly product is easy to respond the stress that is applied and it can return to its original shape apace after discharging deformation stress.Behavior this springy that the better product of the present invention shows and vulcanized rubber and the elastomeric elasticity of some synthetic thermoplastic are similar.Yet product of the present invention also has high intensity and creep resistance, and this product is in use with regard to the early deformation under the anti-low-stress of energy and anti-lax (sagging) like this.Product of the present invention also has good flexibility, and promptly they can be bent, twist or be folding, and can not rupture.In embodiment preferably, have flexible quality in the time of flexibility, this quality makes material be easy to bending, distortion or folding, and can not stay the vestige of any damage.Like this, product of the present invention only can have usually by high oriented material could be transcendental high strength when the gross distortion, have softness and resilient feature when small deformation simultaneously, this feature can provide the snappiness or the drape of raising, and promptly product is more easily fitted and more cosily coincide around object.In addition, this product does not have and the relevant viscosity of many conventional elastomericss, does not use powder or other anti that may influence performance or required application be produced negative effect.Importantly, product of the present invention is biodegradable.
Make the tensile polymeric articles by the composition that comprises the biodegradable polyhydroxy alkanoate copolymer that contains at least two kinds of RRMU.First kind of RRMU has structural formula (I):
Figure C0081504000091
R wherein 1Be H or C1 or C2 alkyl, n is 1 or 2.At one preferably in the embodiment, R 1Be methyl (CH 3), such first kind of RRMU has following structure:
Wherein n is 1 or 2.In another of first kind of RRMU preferably in the embodiment, R 1Be methyl, n is 1, and polyhydroxy alkanoate copolymer just comprises the 3-hydroxybutyrate units like this.
Second kind of contained in biodegradable polyhydroxy alkanoate copolymer RRMU is different from first kind of RRMU, and it has structural formula (II):
Figure C0081504000093
Wherein m is 2 to about 9.In general, in the RRMU of formula (II), (CH 2) mLength can influence the decline of multipolymer overall crystallinity to a certain extent.At one preferably in the embodiment, m is 2 to about 9, is more preferably to be about 2-5.In the better implement scheme, m is about 3.
In order to reach the biological degradability that good comprehensive physicals that strained polymer product of the present invention shows keeps polyhydroxy alkanoate copolymer simultaneously, comprise the RRMU of (I) the first kind of RRMU structure that have formula at least about the multipolymer of 70mol%.The mol ratio of first kind of RRMU and second kind of RRMU should be about 70 in the multipolymer: 30-98: 2.This mol ratio better is about 75: 25-95: 5, and this mol ratio is about 80 well again: 20-90: 10.As a result, the number-average molecular weight of polyhydroxy alkanoate copolymer should be greater than about 150,000g/mol.Although do not think bound by theoryly, think that the chain length of second kind of RRMU and the combination of specified molar weight can reduce by the degree of crystallinity of first kind of RRMU fully, thereby make multipolymer with desired physical properties.
In the other embodiment of the used polyhydroxy alkanoate copolymer of composition, can comprise one or more additional RRMU.Additional RRMU should have structural formula (III):
R wherein 3Be H or C1-C19 alkyl or alkenyl, p is 1 or 2, stipulates that additional RRMU and first kind or second kind of RRMU are inequality.
Biodegradable polyhydroxy alkanoate copolymer can be synthetic with the method for chemistry or bio-based, and described method for example is disclosed in the United States Patent (USP) 5,618 of Noda, 855 and the United States Patent (USP) 5 of Noda etc., in 942,597, the content of these two patents is quoted in this reference.
Composition better comprises the biodegradable polyhydroxy alkanoate copolymer greater than about 50 weight %, and described multipolymer better is present in the composition with the form of external phase.In one embodiment, composition can comprise polyhydroxy alkanoate copolymer as unique polymeric constituent, in other embodiment, can comprise one or more additional polymkeric substance or multipolymer and mix mutually with polyhydroxy alkanoate copolymer.For example, composition can comprise the combination of two or more this biodegradable polyhydroxy alkanoate copolymers, the combination of biodegradable polyhydroxy alkanoate copolymer described herein and other polyhydroxy alkanoate copolymer and/or additional polymeric constituent such as additional polyester components etc.In these embodiments, in composition, the content of biodegradable polyhydroxy alkanoate copolymer preferably at least about is 50 weight %, better is at least about 60 weight %, is at least about 75 weight % better.
Composition can also comprise various non-polymeric ingredients, comprises nucleator, anti, static inhibitor, surface slip agent, helps and add thermo-stabilizer (pro-heat stabilizers), antioxidant, help oxidation additive (pro-oxidant additives), pigment, filler etc.Although in general do not need these additives in composition, these additives can be measured routinely and use, to reach the excellent comprehensive performance of flexibility, elasticity and intensity.In addition, although similarly in general do not need softening agent, in composition, can use the softening agent of one or more convention amounts, to reach above-mentioned excellent comprehensive performance.
Have flexibility and elasticity and keep the upper limit of use temperature of biodegradable polymeric articles of the required over-all properties of intensity can be higher than room temperature significantly simultaneously, because the melt temperature of polymkeric substance that is used to make this product is than higher.The upper limit of the use temperature of product better can surpass more than 80 ℃, and can fusion or become undue soft, better is higher than 100 ℃, is higher than 120 ℃ well again.
Polymeric articles can be the form of any physics, the product that it generally comprises tensile film, sheet, fiber or supatex fabric or is made by stretched film, sheet, fiber or supatex fabric.For example, the tensile nonwoven products can make like this, be about to spunbond through comprising, melt and spray, non-woven structure that the ordinary method of the methods such as combination of air-laid, combing, Hydroentangled (hydroentangling) or aforesaid method makes stretches, wherein can adopt including, but not limited to the known any method bonded nonwoven fabric of prior art of heat, machinery, chemistry or adhesives.Perhaps, many oriented fibre can bond, and make the supatex fabric that has with similar flexibility, elasticity and the strength property of previous method.In addition, the tensile polymeric articles need not to be confined to the structure of one-component, for example unitary film or monfil.The tensile polymeric articles also can comprise various multi-component products, they comprise, but be not limited to fiber or supatex fabric that (1) has face-face, skin-core, many parts, fabric of island-in-sea type and matrix-fibrillar form, (2) by co-extruded films or sheet two-layer or that multilayer is formed, (3) matrix material of film/fiber, sheet/fiber, film/non-woven or sheet/supatex fabric, or the combination of (4) 1-3, as long as in composition, the content of pha copolymer is at least 50 weight %, better be at least about 60 weight %, be at least about 75 weight % better.And the technology skilful person of this area will understand is that the level of elasticity, intensity and flexibility that tensile multicomponent polymeric product shows is subjected to the specific form and the influence of structure, this case part be described in as The blend of polymkeric substance and alloy, M.J.Folkes and P.S.Hope (editor), Chapman ﹠amp; Hall, New York (1993) and Plastics film, the 2nd edition, J.H.Briston, Longman Inc. is among the New York (1983).
The tensile polymeric articles can adopt conventional solid state drawing method to make easily, wherein is being higher than the second-order transition temperature T of composition gBut be lower than the melt temperature T of composition mTemperature under composition is stretched.Better be to obtain product like this, promptly at the high at least 20 ℃ of (T of second-order transition temperature than composition g+ 20 ℃) but hang down 20 ℃ of (T at least than the melt temperature of composition m-20 ℃) temperature under composition is carried out solid state drawing.The second-order transition temperature of the polyhydroxy alkanoate copolymer that the present composition is used is usually less than room temperature, promptly is lower than about 25 ℃.The melt temperature of this multipolymer is usually above about 100 ℃.
The technology skilful person of this area will understand is that, the level of the elasticity that drawn products shows (comprising feature springy), intensity and the flexibility Temperature Influence that not only stretched, and be subjected to the influence of following factor, be tensile speed and degree, stretching is with constant or with variable velocity of displacement, strain or stress carry out, the tensile type, and concerning film, sheet or supatex fabric, stretching is to carry out with single shaft or with twin shaft, if carry out with twin shaft, then stretching step is according to the order of sequence, carries out simultaneously or in the mode of their certain combinations.Stretching can be carried out with constant or variable velocity of displacement, strain or stress by known method in the prior art, described method for example, for film, sheet and supatex fabric is tentering frame (tenter framing) method, and this method for example is described in J.H.Briston's Plastics film, the 2nd edition, Longman Inc., New York (1983) on the 83-85 page or leaf, is spinning operation or winding filament with the Godet roller for fiber product perhaps, this method for example is described in J.E.McIntyre and M.J.Denton The concise encyclopedia of polymer science and engineering, John Wiley ﹠amp; Sons, NewYork (1990) is on 390,391 and 395 pages.In addition, for film, sheet and supatex fabric, be stretching on the shaping thing and can carry out equably, for example in the tentering frame method, reached, perhaps on the shaping thing, can incrementally carry out, for example as United States Patent (USP) 4,116,892 and 5,296, annular roll operation (ring-rolling operation) described in 184, wherein tensile replaces parallel zone and in fact keeps not tensile zone coexistence.In addition, for the film and the sheet of blowing, stretching can be undertaken by two or tubular film bubble method, and this method for example is described in J.H.Briston's Plastics film, the 2nd edition, LongmanInc., New York (1983) is on 85 pages.And, look final purposes, the stretching of film, sheet and supatex fabric can be carried out in the mode of single shaft or twin shaft, as if the words of carrying out in the mode of twin shaft, by known method in the prior art, stretching step can be according to the order of sequence, carry out simultaneously or in the mode of their any combinations.The method of above-mentioned all stretched film, sheet and supatex fabric comprises that all even stretching method that increases progressively can use, and they all within the scope of the invention.
The tensile degree must surpass yield-point or the necking point (neckpoint) at least one direction of tensile, keeps below the breaking point on all draw directions simultaneously.Product better is to obtain by about 50% strained degree that stretching composition at least one direction reaches greater than its initial unstretched state, and being more preferably stretches to reach greater than about 100% strained degree of its initial unstretched state at least one direction obtains.In the better implement scheme, product is to obtain by about 200%-1500% strained degree that stretching composition at least one direction reaches its initial unstretched state, and being more preferably stretches at least one direction reaches about 300%-1000% strained degree of its initial unstretched state and obtain.In addition, what the technology skilful person of this area will further understand is that the process and the geometrical shape of distortion depended in the Effective strain on each draw direction.For example, in the even stretching method of like fibrous spinning, effectively strain by preliminary draft than determining, described preliminary draft than be the speed of fiber when leaving Godet or draw roll when entering Godet or draw roll divided by fiber speed and must ratio, it and sample length always be varied to direct ratio.By contrast, increasing progressively in the stretching method for example at similar annular roll, effectively strain by as at the United States Patent (USP) 4 of above-mentioned reference, 116, the stretch ratio in each stretching or metering zone (gaugesection) that discloses in 892 is determined, length localized variation in described stretch ratio and each drawing zone is in direct ratio, it usually not with sample length always be varied to direct ratio.
In general, finish in case stretch, the tensile polymeric articles can be cooled to and be lower than its second-order transition temperature, perhaps can carry out the thermal-setting step it, wherein at the second-order transition temperature that is higher than composition but be lower than under the temperature of melt temperature of composition, generally at about T g+ 20 ℃ to T mUnder strain, tensile shaping thing is annealed under-20 ℃ the temperature.
Can use in the prior art known any suitable device to carry out solid state drawing, for example as mentioned above.Following example has illustrated that use Instron uses trier more, is that miscellaneous equipment also can use but those of ordinary skill should understand.Used Instron or other stretcher better are equipped with environmental chamber, so that the drawing process of thermal control to be provided.The technology skilful person of this area will understand is that, for said given composition, can look required end-use and determine stretching condition and annealing conditions (if employing).
Drawn products of the present invention has the good comprehensive performances that good flexibility and elasticity keep intensity simultaneously.More particularly, strained polymer product of the present invention has (1) higher intensity, for example record by higher tensile stress at break, (2) higher flexibility, for example record by lower Young's modulus, (3) higher elasticity is for example compared with the not drawn products of same composition, is recorded by higher answer percentage ratio after discharging deformation stress.In embodiment preferably, press the examples measure of ASTM D882-97 to film, the tensile strength of strained polymer product is greater than about 15MPa, better greater than about 20Mpa.In addition, in embodiment preferably, press the examples measure of ASTM D882-97 to film, the Young's modulus of strained polymer product is less than about 400MPa, and is better less than about 300MPa, good again less than about 200MPa.
The elasticity of the elasticity of drawn products, especially product can be replied product basically when this drawn products extends in as use.Like this, in embodiment preferably, the tensile polymeric articles demonstrates following elastic behavior, i.e. measurement as film being carried out by ASTM D5459-95, when product elongation reaches approximately 50% the time, in the time that is less than about 15 seconds, product has the answer (recovery) greater than about 65%.Being more preferably the answer greater than about 75%, is well the answer that has greater than about 85% again.
The tensile product can be used for various biodegradable goods, and they comprise disposable, the packing good to environment, housing material, absorbent article (comprises diaper/catemenial/ sanitary napkin top flat, nonwoven core and tergite), stretched film (comprising food and tray packing), plastic film for agricultural use, mulch film, balloon, the lagging packing, stretch package, bag (comprising food and refuse bag), contraceptive (comprising condom and barrier film), shrink package, synthetic paper, carpet, the fishing line, hospital's long gown, gloves, sticking plaster, wound dressings (wound dressings), disposable external-cover (comprising shirt and socks), disposable surgery cord, suture, mail package and agricultural purposes (comprise the capable coverture of seedling, the seedbed coverture, turf coverture and weeds barrier).
Further illustrate product of the present invention and method in the following embodiments.In embodiment and specification sheets of the present invention in the whole text, except as otherwise noted outside, umber and percentage number average are by weight.
Embodiment 1
The present embodiment explanation is carried out uniaxial extension by the present invention to the casting films that melt extrudes.Specifically, the multipolymer of 3-butyric ester and 11.1mol%6-hydroxycaproic ester (below be called the PHBHH multipolymer) is melt extruded to become to have from about 0.004 casting films to about 0.005 inch variable thickness.Cut about 1 * 4 inch rectangular strip from this film, the parallel longitudinal of length dimension and manufacturing.With each be placed on Instron use more trier (model 1122, Canton, MA) in, make length dimension on the tensile direction, the gauge length of test is 1 inch.This trier is equipped with Sintech ReNew TMThe 1122/R upgrade components, be used for the TestWorks of control test and analysis TMThe high/low wet of V3.02 software and 200lbf moves chuck (model S512.01), derive from MTS Systems Corp. all, Research TrianglePark, NC, described trier also is equipped with environmental chamber, and Series 3710, it derives from MTS Direct, EdenPrairie, MN, thus the uniaxial extension of thermal control is provided.For the draft temperature test different with envrionment temperature, allow the about 2-3 of test bar balance minute, begin drawing process afterwards.Adopt the initial strain rate of about 60 ℃ draft temperature He about 2in/in-min, the film bar of PHBHH casting films can be elongated before fracture and surpass 600% elongation.In addition, the tensile bar demonstrates elastic behavior, and when being about to draw back then between its thumb that is clipped in each hand of technician and the forefinger, film is easy to elongation and quickly recovers to its original length after release.This behavior shows that the PHBHH film composition is the height ductile, and tensile PHBHH film composition is resilient.
Embodiment 2
The present embodiment explanation is carried out uniaxial extension by the present invention to PHBHH multipolymer melt spun fibre.The PHBHH multipolymer that derives from embodiment 1 is melt-spun into the fiber that diameter is about 4mm.Be about 3 inches test tow (strands) from PHBHH fiber Cutting Length.According to embodiment 1 described stretching step, adopt the initial strain rate of about 60 ℃ draft temperature He about 2in/in-min, the tow of PHBHH fiber is extending before fracture to surpass 400%.In addition, the tensile fibre bundle demonstrates elastic behavior, and when being about to draw back then between its thumb that is clipped in each hand of technician and the forefinger, fiber is easy to elongation and quickly recovers to its original length after release.This behavior shows that the PHBHH fiber composition is the height ductile, and tensile PHBHH fiber is resilient.
Embodiment 3
The present embodiment explanation is carried out biaxial stretch-formed by the present invention to the casting films that PHBHH melt extrudes.At first the initial strain rate with about 60 ℃ temperature and about 4in/in-min stretches about 150% by the film bar that embodiment 1 described step will derive from the PHBHH multipolymer casting films of embodiment 1.In trier, such tensile sample revolved then and turn 90 degrees, make primary draw direction vertical with draw direction.Under the initial strain rate of about 60 ℃ temperature and about 4in/in-min, carry out elongation and be about 150% the stretching second time.The elastic performance of gained Biaxially oriented film can easily be found out by following method, promptly only uses the hand stretched film, and this film quickly recovers to its original length after discharging deformation strain.
Embodiment 4
Present embodiment relatively stretches and the tensile property of tensile PHBHH fusion extrusion casting film not.Specifically, adopt the method in ASTM D882-97, summarize, use and use trier more, determine to derive from the stretching of embodiment 1 and the tensile property of tensile PHBHH fusion extrusion casting film bar not as embodiment 1 described Instron.Under the initial strain rate of about 60 ℃ draft temperature and about 4.0in/in-min, preparation stretching sample.Compare with tensile object of reference not, confirm that by higher rupture stress stretched film intensity is bigger, confirm that by lower Young's modulus stretched film is than softish, but confirm that by lower breaking strain stretched film is not too tensile.
Embodiment 5
The elastic recovery of present embodiment explanation tensile PHBHH fusion extrusion casting film of the present invention.When stretching in how with trier as embodiment 1 described Instron, determine that the shown size of film replys, just can measure the elastic performance of the stretching PHBHH casting films that derives from embodiment 1.With the initial strain rate of 1.0in/in-min, at ambient temperature stretched film is elongated to predetermined elongation, remove the stress that is applied, measure strained after the time of relaxation of second at about 10-15 and descend.From reaching about 100% elongation, tensile PHBHH film bar demonstrates greater than about 85% short-term and replys.This behavior shows the secular mechanical elasticity of product of the present invention.
Embodiment 6
Elasticity, flexible sticking plaster that the present embodiment explanation makes from tensile PHBHH casting films of the present invention.Prepare stretched film from the PHBHH casting films of embodiment 1, wherein drawing process is to carry out under the initial strain rate of about 60 ℃ temperature and about 4.0in/in-min.Film bar from 0.75 * 3 inch of tensile PHBHH film cutting.0.75 * 1.0 inch absorption pad longitudinally is glued to the central authorities of bar, the Velcro sheet of autoadhesion is bonded to each end, make sticking plaster.On forefinger, use sticking plaster to show that this film is easy to bending, and can make forefinger bending motion back and forth, and can not relax.
Embodiment 7
The present embodiment explanation has elastic force, softish non-woven sheets from tensile PHBHH fiber of the present invention manufacturing.Make non-woven sheets from tensile PHBHH fiber.Under the initial strain rate of about 60 ℃ temperature and about 3.0in/in-min, press embodiment 2 described stretching melt-spun PHBHH fibers.Some tensile tow are cut into 3 inches long, they are placed on randomly that two 10mm are thick, between 6 * 6 inches tetrafluoroethylene (Teflon ) sheet, whole object are placed between the pressing plate of Carver  hydraulic test constant pressure machine.Top board is preheating to the high about 15 ℃ temperature of the fusing point of measuring than the calorimetry of PHBHH, and making it that 25 bonding diameters be arranged on per square inch is the spot gluing pattern of the equidistant arrangement of 1.0mm.Apply enough pressure, make the softening and fusing of bonding point.Relief pressure allows non-woven sheets be cooled to room temperature, removes the teflon plate of outside afterwards.The elastic performance of non-woven sheets can easily be found out by following method, promptly only uses the hand drawing sheet, and this sheet quickly recovers to its original size after discharging the strain that is applied.
Embodiment 8
The casting films that the present embodiment explanation melt extrudes routine is carried out uniaxial extension and its tensile property.Make the casting films that melt extrudes from some biodegradable polymkeric substance, described biodegradable polymkeric substance comprises polycaprolactone (Tone  P787, Union Carbide,), Bionolle 1001 and 3001 (ShowaHighpolymer Co., LTD., Tokyo, JP), Eastar 14766 (Eastman Chemical Company, Kingsport, TN) and BAK 1095 (Bayer Corporation, Pittsburgh, PA), and make the casting films that melt extrudes from some nondegradable polymkeric substance, described nondegradable polymkeric substance comprises that (kind is 7300KF to polypropylene, Millennium Petrochemicals, Cincinnati, OH), (kind is LTPR059 to high density polyethylene(HDPE) (HDPE), Millennium Petrochemicals, Cincinnati, OH) and 50: 50 (weight) new LDPE (film grade)s (LDPE): (kind is respectively NA940000 and GA5010110 to the blend of LLDPE (LLDPE), MillenniumPetrochemicals, Cincinnati, OH).According to embodiment 1 described preparation sample and stretching step, adopt the initial strain rate of about 25 ℃ draft temperature He about 1.0in/in-min, the film bar of various casting films can elongate before fracture and surpass 300% elongation.This behavior is consistent with the ductile film composition.
Use and use trier more,, determine the tensile property of tensile fusion extrusion casting film bar by the method for summarizing among the ASTM 882-97 as embodiment 1 described Instron.Compare with tensile object of reference not, for typical case's representative of drawing process, promptly various stretched film confirm that by higher rupture stress it is that intensity is bigger, but confirm that by higher Young's modulus it is harder, and confirm that by lower rupture stress it is not too tensile.
The tensile property that derives from the stretching PHBHH film of embodiment 4 is made comparisons as can be seen with the tensile property that derives from the stretched film of present embodiment, compare with the stretched film of making from conventional composition, the PHBHH film is than softish.In fact, drawing process can improve the flexibility of PHBHH film, and this can be descended by Young's modulus and be confirmed, and the rigidity of conventional composition all improves, and this can be confirmed by the Young's modulus raising.In all cases, stretched film all demonstrates the answer of some degree to the distortion of little elongation; Yet, compare with stretched film of the present invention, elongating the stretched film made by conventional composition, to surpass less elongation much more difficult.For example, the drawing force of 10lb or the stress that is equivalent to 35MPA for 1 inch wide, 0.002 inch thick film bar can cause 45% elongation immediately concerning tensile PHBHH film, and demonstrate 8% elongation immediately at most for the stretched film of being made by conventional composition.
Embodiment 9
The present embodiment explanation adopts meltblown to make non-woven sheets.Specifically, the PHBHH multipolymer that derives from embodiment 1 is sent in the forcing machine, described forcing machine makes its fusion gradually when polymkeric substance is sent into meltblown beam.Die head is metered into polymkeric substance in the weighing road, described material road linear orientation on transverse and longitudinal, and the spinning nozzle direction in the some holes on every linear inch narrows down.In the exit, polymkeric substance tow under the effect of the high-speed air of heat, attenuate (attentuate).The fiber that forms is continuous and very thin, and it is online that it is sprayed onto mobile collector, forms the structure of supatex fabric.Allow fabric pile up roller by 2-roller stainless steel, fabric is carried out thermal caking, on a described roller, the diameter that bonds of having an appointment on per square inch 25 is the spot gluing pattern of 1.0mm.To pile up roller and be preheating to the high about 15 ℃ temperature of the fusing point of measuring than the calorimetry of PHBHH composition, it be applied enough pressure when piling up roller, make the softening and fusing of spot gluing at fabric.Lack flexibility and can easily find out by following method, promptly only stretch supatex fabric with pulling, this fabric is difficult for elongation and it can not return to its original size after discharging the strain that is applied.
Embodiment 10
The present embodiment explanation is made resilient non-woven sheets from the melt-blown non-woven fabric.Cut about 1 * 4 inch rectangular strip, the parallel longitudinal of length dimension and manufacturing from embodiment 9 described agglutinating PHBHH fabrics.According to embodiment 1 described stretching step, adopt the initial strain rate of about 60 ℃ draft temperature He about 1.0in/in-min, can make the elongation bar of PHBHH supatex fabric.The elastic performance of draw nonwoven sheet can easily find out by following method, promptly only uses hand drawing sheet, this sheet to be easy to extend and it can quickly recover to its original size after discharging the strain that is applied.With making comparisons as can be seen of this behavior and embodiment 7, the non-woven sheets that is made by ordinary method by stretching or make non-woven sheets from the tensile fiber can make the similar nonwoven products of elasticity.
Embodiment 11
United States Patent (USP) 4,116 is pressed in the present embodiment explanation, and 892 modes with annular roll operation increase progressively stretching PHBHH film and make resilient film product.By a pair of fluted roller that is preheating to about 60 ℃ of temperature make vertically on introduce the PHBHH casting films that melt extrudes that derives from embodiment 1.Groove is vertical vertical with film, and described groove has dark for 3mm, at a distance of the shape of sinusoidal haply of 3mm, and stretch ratio reaches about 2.When the shape that film stretched with the applying groove, the top film of inserting simultaneously of 8 grooves.Film is added in the roll gap of the intermeshing fluted roller that rotates with the speed of about 2RPM, feed rate reaches about 2 feet per minute clocks, and reels with the speed of about 4 feet per minute clocks.Film contain with the corresponding 3mm of point of contact more transparent line at interval, or tensile zone is tensile opaque section not between them.With the direction of parallel longitudinal on the elastic performance through the PHBHH film of annular roll operation can easily find out by following method, promptly only use hand drawing sheet, this sheet to be easy to extend and after discharging the strain that is applied, can quickly recover to its original size.By contrast, with vertical vertical direction on the stretched film product do not demonstrate elastic force or elasticity significantly arranged, promptly this sheet is difficult for elongation and also can not returns to its original size after discharging the strain that is applied.Present embodiment illustrates that annular roll operation can make preferred film product have single shaft or directive elastic behavior.This method also is applicable to preferred sheet and nonwoven products.
Embodiment 12
(Tokyo JP) increases progressively stretching and makes the stretched film product mode that the present embodiment explanation is operated with annular roll for ShowaHighpolymer Co., LTD. to Bionolle 3001 films.Specifically, adopt temperature to be about 25 ℃ fluted roller, the fusion extrusion casting film that thickness is about 0.002 inch Bionolle 3001 is carried out annular roll operation by embodiment 11 described steps.Lack flexibility and easily to find out by following method, promptly with parallel longitudinal of making and vertical direction on only with pulling the film product of stretching through annular roll operation, this film is difficult for elongation and it can not return to its original size after discharging the strain that is applied.In fact, annular roll operation makes the distortion for good and all in the vertical of Bionolle 3001 films.
Embodiment 13
The mode that the present embodiment explanation is operated with annular roll increases progressively stretch multi-layer and makes shrinkability film product.Specifically, the PHBHH multipolymer that derives from embodiment 1 is coextruded into two-layer casting films product with the Bionolle3001 resin that derives from embodiment 12, wherein the thickness of PHBHH layer is about 0.002 inch, and the thickness that Bionolle is 3001 layers is about 0.001 inch.Adopt temperature to be about 60 ℃ fluted roller then, this PHBHH/Bionolle film is carried out annular roll operation by embodiment 11 described steps.The result of annular roll operation has made shrinkability film product; wherein the PHBHH layer is described resilient as embodiment 11; and 3001 layers of Bionolle do not have elasticity and a tension set as embodiment 12 is described; and when the PHBHH layer shrank after discharging the strain that is applied, the Bionolle layer formed and draws in or pleat.In addition, the Bionolle layer limits the degree that makes the product elastic stretching at least and reaches the incipient extension point at most.
Embodiment 14
Present embodiment has illustrated manufacturing disposable infant diaper, and wherein listed size is the children that are used for 6-10 kilogram magnitude range.For the children of different sizes, or for the incontinence briefs of being grown up, these sizes can be by standard practices correct pro rata.
1. tergite: the film of the 0.020-0.038mm that forms by the PHBHH multipolymer that derives from embodiment 1; The width of top and bottom is 33cm; The center width of otch is 28.5cm in both sides are oriented; Length is 50.2cm.
2. top flat: the polypropylene fibre of the staple length of combing and thermal caking (Hercules type 151 polypropylene); The width of top and bottom is 33cm; The center width of otch is 28.5cm in both sides are oriented; Length is 50.2cm.
3. absorbent core: 28.6g Mierocrystalline cellulose wood pulp and 4.9g absorption agent gel-like material particle (available from the commodity polyacrylic ester of NipponShokubai); Thickness is 8.4mm, calendering; The width of top and bottom is 28.6cm; The center width of otch is 10.2cm in both sides are oriented; Length is 44.5cm.
4. the elastic bottom bands of trouser legs: four independent string rubbers (every side has 2); Width is 4.77cm; Length is 37cm; Thickness is 0.178mm (top all sizes all are the sizes under relaxation state).
To be placed on the tergite gummed then with the core material that top flat covers, prepare diaper in the mode of standard.
Flexible tie (be designated as " interior band " and " in addition ", they are respectively with the most close and the most corresponding away from being with of core) is stretched to about 50.2cm, its each vertical side along core (2 bands of every side) is placed between top flat/tergite.Be placed on the about 55mm of the narrowest width (counting) along the interior band of each side from the preglabellar field of flexible tie apart from core.So just can between the core edge of interior flexible tie and bending, provide the parts of spacing along each side that comprises the diaper of pliable and tough top flat/backsheet material.Along its length, under the tensile state, band in the gummed.Be placed in addition apart from the about 13mm of interior band place, and, under the tensile state, glue together it along its length.Top flat/tergite subassembly is flexible, and the gummed band shrink, make each side high resilience of diaper.
Embodiment 15
Replace the elasticity bottom bands of trouser legs with embodiment 1 described resilient PHBHH film product, improve the diaper of embodiment 14.
Embodiment 16
Replace the elasticity bottom bands of trouser legs with embodiment 13 described shrinkability film products, improve the diaper of embodiment 14.
The described specific embodiment and the embodiment that provide above are only presented for purposes of illustration, and they are not limited to the scope of following claims.Other embodiments of the present invention and the advantage that gets therefrom are conspicuous to those skilled in the art, and they are all in the scope of claims.

Claims (33)

1. polymeric articles, it obtains by a kind of composition that stretches, described composition comprises and contains at least two kinds of unitary biodegradable polyhydroxy alkanoate copolymers of random repeated monomer, and wherein first kind of random repeated monomer unit has structural formula (I):
Figure C008150400002C1
R wherein 1Be H or C1 or C2 alkyl, n is 1 or 2; Second kind of random repeated monomer unit is different from first kind of random repeated monomer unit, and it has structural formula (II):
Figure C008150400002C2
Wherein m is 2 to 9, wherein the multipolymer of 70mol% comprises the random repeated monomer unit with first kind of random repeated monomer unit (I) structure at least, and first kind of random repeated monomer unit and second kind of unitary mol ratio of random repeated monomer are 70 in the multipolymer: 30-98: 2; Described polymeric articles is to obtain by the 50% strained degree that the described composition that stretches reaches greater than its initial unstretched state; And the described composition that stretches is at the second-order transition temperature T than composition gAt least high 20 ℃ but than the melt temperature T of composition mAt least carry out under low 20 ℃ the temperature.
2. polymeric articles as claimed in claim 1, wherein product is to obtain by the 200%-1500% strained degree that the stretching composition reaches its initial unstretched state.
3. polymeric articles as claimed in claim 2, wherein product is to obtain by the 300%-1000% strained degree that the stretching composition reaches its initial unstretched state.
4. polymeric articles as claimed in claim 1, wherein first kind of random repeated monomer unit has following structure:
Figure C008150400002C3
Wherein n is 1 or 2.
5. polymeric articles as claimed in claim 4, wherein n is 1.
6. polymeric articles as claimed in claim 5, wherein m is 2-5.
7. polymeric articles as claimed in claim 6, wherein m is 3.
8. polymeric articles as claimed in claim 1, wherein first kind of random repeated monomer unit and second kind of unitary mol ratio of random repeated monomer are 75 in the multipolymer: 25-95: 5.
9. polymeric articles as claimed in claim 1, wherein the number-average molecular weight of biodegradable polyhydroxy alkanoate copolymer is greater than 150,000g/mol.
10. polymeric articles as claimed in claim 1, wherein composition comprises the biodegradable polyhydroxy alkanoate copolymer of at least 50 weight %.
11. polymeric articles as claimed in claim 10, wherein composition also comprises at least a additional polymeric constituent.
12. polymeric articles as claimed in claim 10, wherein composition also comprises softening agent.
13. polymeric articles as claimed in claim 1, wherein product is the form of film.
14. polymeric articles as claimed in claim 13 wherein carries out uniaxial extension to film.
15. polymeric articles as claimed in claim 13 wherein carries out biaxial stretch-formed to film.
16. polymeric articles as claimed in claim 13 wherein comes stretched film by annular roll.
17. polymeric articles as claimed in claim 1, wherein product is the form of fiber.
18. polymeric articles as claimed in claim 1, wherein product is the form of non-woven sheets.
19. polymeric articles as claimed in claim 1 is wherein compared with the not drawn products of the composition that comprises biodegradable polyhydroxy alkanoate copolymer, this product has higher breaking tenacity tensile stress and lower Young's modulus.
20. polymeric articles as claimed in claim 1, wherein product demonstrates following elastic behavior, and promptly when the product elongation reached 50%, product had at least 65% answer.
21. polymeric articles as claimed in claim 20, wherein product demonstrates following elastic behavior, and promptly when the product elongation reached 50%, product had at least 85% answer.
22. make the method for polymeric articles according to claim 1 for one kind, it is included in the second-order transition temperature T than composition gAt least high 20 ℃ but than the melt temperature T of composition mAt least the composition that comprises biodegradable polyhydroxy alkanoate copolymer of stretching under low 20 ℃ the temperature reaches 50% strained degree greater than its initial unstretched state, wherein biodegradable polyhydroxy alkanoate copolymer comprises at least two kinds of random repeated monomer unit, and wherein first kind of random repeated monomer unit has structural formula (I):
Figure C008150400003C1
R wherein 1Be H or C1 or C2 alkyl, n be 1 or 2, the second kind of random repeated monomer unit be different from first kind of random repeated monomer unit, it has structural formula (II):
Figure C008150400004C1
Wherein m is 2 to 9, wherein the multipolymer of 70mol% comprises the random repeated monomer unit with first kind of random repeated monomer unit (I) structure at least, and first kind of random repeated monomer unit and second kind of unitary mol ratio of random repeated monomer are 70 in the multipolymer: 30-98: 2.
23. method as claimed in claim 22, wherein product is to obtain by the 200%-1500% strained degree that the stretching composition reaches its initial unstretched state.
24. method as claimed in claim 23, wherein product is to obtain by the 300%-1000% strained degree that the stretching composition reaches its initial unstretched state.
25. method as claimed in claim 22, wherein product is the form of film, and stretching is to carry out equably on film.
26. method as claimed in claim 25 is wherein carried out uniaxial extension to film.
27. method as claimed in claim 25 is wherein carried out biaxial stretch-formed to film.
28. method as claimed in claim 22, wherein product is the form of film, and stretching is incrementally to carry out on film.
29. method as claimed in claim 27 is wherein come stretched film by annular roll.
30. method as claimed in claim 22, wherein product is the form of fiber.
31. method as claimed in claim 29, it comprises that also the oriented fibre with many gained is bonded to non-woven sheets.
32. method as claimed in claim 22, wherein product is the form of non-woven sheets.
33. method as claimed in claim 22, it also comprises the thermal-setting step, wherein is being higher than the second-order transition temperature T of composition gBut be lower than the melt temperature T of composition mTemperature under, under strain, the tensile product is annealed.
CNB008150400A 1999-10-28 2000-10-27 Method for preparing soft and elastic biodegradable polyhyoxyalkanmoate copolymer compositions andpolymer products comprising such compositions Expired - Fee Related CN1235950C (en)

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