CN1521213A - Biodegradable material comprising polyhydroxy fotty acid ester blending polymer - Google Patents
Biodegradable material comprising polyhydroxy fotty acid ester blending polymer Download PDFInfo
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Abstract
One new kind of biodegradable material with low cost and high machining performance is mixture containing including 3-hydroxy butyrate homopolymer and copolymer of 3-hydroxy butyric acid and non-HB structure hydroxy fatty acid in the weight ratio of 1/9 to 9. The copolymer contains at least two random structural units I and II, with the structural unit I accounting for the molar ratio of 10-95 %. The plastic products made of the biodegradable material are also provided.
Description
Technical field
The present invention relates to Biodegradable material, especially relate to and comprise poly--3-butyric ester (Poly-3-hydroxybutyrate, below be abbreviated as PHB) and other polyhydroxyalkanoates (polyhydroxyalkanoates, below be abbreviated as PHA) Biodegradable material of the polymer blend that blend produced, and the plastics that utilize this class material to make for raw material.
Background technology
High molecular polymer can be used for making various plastics, comprises film, sheet material, fiber, foam, moulded parts, tackiness agent and many other special products.For packing, agricultural, household goods and personal care product's Application for Field, the use loop cycle of polymkeric substance very short (being less than 12 months).For example, in food product pack, polymkeric substance plays the protective medium effect, discards after inclusion is used up at once.Household product also discards after use as detergent bottle and diaper at once.
These plastic substances of great majority finally fall into solid waste, become " white pollution ", have increased expensive landfill space, have increased the weight of the burden of environment.Though people have done the effort of some recyclings, the mode that the character of polymkeric substance and they produced and be converted into product has limited the possibility that recycles.Also can make material degradation even very pure polymkeric substance repeats processing, the result obtains bad mechanical property.The mixed collection of the chemically similar plastics of different stage (as the polyethylene as the different molecular weight of milk jug and groceries bag) can cause processing problems, makes that the Recycled materials quality is bad maybe can not be used.
Polyhydroxyalkanoate is the polyester high molecular polymer of microorganisms.Polyhydroxyalkanoate is owing to its biodegradability and hot workability have caused people's interest, but its higher production cost has stoped its extensive use as plastics.For example, poly--the 3-butyric ester is bacterium storing energy and carbon source institute synthetic polyester, is present in the bacterial cytoplasm with discrete particulate form.Unlike other biosynthetic polymkeric substance such as protein and polysaccharide, PHB is degree of crystallinity height, the about 180 ℃ thermoplastic material of melt temperature, and biological degradability is good.But unfortunately, PHB is instability near its melt temperature the time, and thermal destruction easily takes place, and its mechanical property is relatively poor, therefore, though approaching traditional plastics such as polyethylene and the polypropylene of the production cost of PHB, its commercial application prospect is very limited.
The 3-hydroxybutyric acid of succeeding in developing in the eighties by Britain Imperial Chemical Industries (ICI) and multipolymer (the Copolyesters of 3-hydroxybutyrate and 3-hydroxyvalerate of 3-hydroxypentanoic acid, below be abbreviated as PHBV) enough thermostabilitys and other suitable chemistry and physical properties are arranged, overcome the PHB problem of difficult processing.Except good thermostability, the crystallization velocity of PHBV is slow, and good flowing properties makes thermoforming be processed into possibility.United States Patent (USP) 4,393,167 (Holmes etc., promulgations on July 12 nineteen eighty-three) and United States Patent (USP) 4,880,592 (promulgation on November 14th, 1989) have disclosed the various performances of PHB homopolymer and PHBV multipolymer.The PHBV multipolymer is produced by Britain ICI company, trade(brand)name BIOPOL.The PHBV multipolymer that can make at present, the about 5-24 mole of its 3-hydroxypentanoic acid content %.Increase the hardness that 3-hydroxypentanoic acid content can reduce melt temperature, degree of crystallinity and polymkeric substance.
But because crystallization velocity is slow, PHBV also can have problems in film process.Even the film of being made by PHBV itself also can bond together after cooling; The major portion of PHBV remains unbodied and heavy-gravity in long-time.In the casting film operation, the film of extruding from die head cools off at cooling roller at once, and fused PHBV usually adheres on the roller, has limited the speed of film processing, even film bonding itself is got up.When blown film, residual viscosity PHBV makes film piped film after cooling understand self bonding, breaks during coiling.
According to aforementioned content, people are sought after obtaining machinable biodegradable plastic raw material.The biodegradable goods of this class should make plastics " recycle " by composting, become harmless naturally product.In order to satisfy this demand, at first need easily to be processed into the biodegradable polymer of plastics.
The 3-hydroxybutyric acid of succeeding in developing recently and the multipolymer of 3-hydroxycaproic acid (Copolyesters of 3-hydroxybutyrate and 3-hydroxyhexanoate, abbreviate PHBHHx as, referring to " Chen GQ et al.Appl.Microbiol.Biotechnol.; 2001; 57:50 ") and multipolymer (the Copolyesters of3-hydroxybutyrate and 3-hydroxydecanoate of 3-hydroxybutyric acid and 3-hydroxydecanoic acid, abbreviate PHBD as, referring to " Abeet al.Int.J.Biol.Macromol; 1994,16:115 ") on mechanical property and hot workability, all further improvement has been arranged than PHBV.But the production cost of PHBHHx and PHBD is but far above PHB and PHBV.
Summary of the invention
An object of the present invention is to provide a kind of Biodegradable material of the novel polymer blend that comprises poly--3-butyric ester and other polyhydroxyalkanoates, this material can improve the processing and the mechanical property of polyhydroxyalkanoate, reduce production costs, make polyhydroxyalkanoate might become a kind of environment-friendly material that can use in a large number.
Another object of the present invention provides the excellent processing characteristics that utilizes above-mentioned Biodegradable material, produce the biodegradable plastic goods of various cheapnesss, these class plastics comprise film, sheet material, fiber, foam, moulded parts, nonwoven fabric, elastomerics and tackiness agent etc.
Particularly, the invention provides a kind of Biodegradable material, it is 1: 9～9: 1 the component A and the blend of B component that this Biodegradable material comprises weight ratio, wherein:
Component A is the homopolymer of poly--3-butyric ester (PHB), the polymerization degree greater than 100 less than 100,000;
B component is the multipolymer that is made of at least two kinds of random structure unit, the polymerization degree greater than 100 less than 100,000, wherein first kind of structural unit is shown in structural formula I, and its molar percentage that accounts for B component is 10-95%, is preferably 30-90%, second kind of structural unit is shown in structural formula II
Wherein, R
1Be hydrogen atom or replacement or unsubstituted C
1-C
12Alkyl or alkenyl, n=1 or 2, and, when n=1, R
1It is not methyl.
Preferably, described R
1Be hydrogen atom, C
1-C
7Alkyl, or the C that replaces by the phenyl of phenoxy group, halogen, phenyl or replacement
1-C
7Alkyl; Perhaps, R
1Be C
2-C
5Thiazolinyl.
In a preferred embodiment of the invention, the weight ratio of component A and B component is 1: 1～7: 1, and more preferably the weight ratio of component A and B component is 2: 1～4: 1.
Biodegradable material of the present invention can also contain the degradable material of other biological, as starch.In containing the Biodegradable material of the present invention of starch, the weight ratio of above-mentioned blend and starch is 1: 9～9: 1, is preferably 1: 3～3: 1.
The present invention also provides the plastics that utilize above-mentioned Biodegradable material to make.
In order to finish purpose of the present invention, the present inventor utilizes the cheap manufacturing cost of PHB, good machinery and hot workability in conjunction with PHBV, PHBHHx and PHBD etc., both are combined, both reduced cost, the suitable polymer blends of material such as the processability of getting back, mechanical property and PHBV, PHBHHx and PHBD.
The present invention relates to comprise the Biodegradable material of the biodegradable polyhydroxyalkanoate blend high molecular polymer of different structure, specifically, this material comprises poly--3-hydroxybutyric acid ester homopolymer (promptly above alleged component A) and contain 3-hydroxybutyric acid (3-hydroxybutyrate, be called for short HB) and the hydroxy fatty acid (hydroxyalkanoates of other non-HB structures, abbreviation HA) multipolymer, be referred to as the multipolymer of 3-hydroxybutyric acid and other hydroxy fatty acids, abbreviate P (HB-HA) (promptly above alleged B component) as.That is to say that P (HB-HA) multipolymer comprises at least two kinds of random structure unit, second kind of random structure unit of the first kind of random structure unit of structural formula I wherein as implied above and structural formula II as implied above.
Studies show that, in the blend PHB+P (HB-HA) that above-mentioned homopolymer PHB and copolymer p (HB-HA) blend obtain, the PHB homopolymer accounts for more than 10%, HB structural unit among the P (HB-HA) accounts for P (HB-HA) overall texture unitary 10% when above, and polymer blend PHB+P (HB-HA) has good consistency.Blend reduces the PHB processing temperature, and mechanical property improves, and snappiness strengthens, and hot-work is easier to carry out.
Polymer blend involved in the present invention has good workability.Compare with P (HB-HA), its production cost reduces greatly, and shock strength strengthens, and it is big that crystallization velocity becomes; Compare with the PHB homopolymer, its elasticity strengthens, and fusing point reduces, and therefore is more suitable for processing.
Above-mentioned blend high molecular polymer also can with starch blending, starch content can account for more than 10%.By can further reducing the cost of above-mentioned macromolecular material, do not influence its biological degradability simultaneously with starch blending.
Biodegradable material of the present invention can be any type of material, and as master batch, also further plastics are made in hot-work, comprise film, sheet material, fiber, foam, moulded parts, nonwoven fabric, elastomerics and tackiness agent etc.
" comprising " used herein expression can add other step and other component that can not influence net result.This term contain term " by ... form " and " basically by ... composition ".
Hydroxy fatty acid homopolymer or multipolymer except that poly--3-butyric ester that " PHA " used herein expression is involved in the present invention.
The hydroxy aliphatic acid mono of the non-3-hydroxybutyric acid of " HA " used herein expression.
The multipolymer of the hydroxy fatty acid of " P (HB-HA) " used herein expression 3-hydroxybutyric acid and other non-3-hydroxybutyric acids.
The blend that " PHB+P (HB-HA) " used herein expression homopolymer PHB and copolymer p (HB-HA) blend obtain.
" biodegradable " used herein expression polymkeric substance resolves into CO fully by microorganism and/or natural surroundings factor
2Character with water.
" blend " described in the present invention is meant the method for various blend well known to those of ordinary skill in the art to comprise mechanical blending, solution blending, melt blending etc.
The ratio of polymer blend moiety as herein described unless otherwise indicated, refers generally to mass ratio.The ratio of multipolymer moiety as herein described unless otherwise indicated, refers generally to mol ratio.
" plastics " used herein comprise goods such as film, sheet material, fiber, foam materials, moulded parts, nonwoven fabric, elastomerics or tackiness agent.
In embodiments of the invention, R
1Be C
2Alkyl, n are 1, thereby have formed repeating unit 3-hydroxypentanoic acid; R
1Be C
3Alkyl, n are 1, and repeating unit is the 3-hydroxycaproic acid; R
1Be C
7Alkyl, n are 1, and repeating unit is the 3-hydroxydecanoic acid; Work as n=2, R
1During=H, repeating unit is a 4 hydroxybutyric acid; R
1Be C
3Thiazolinyl, n are 1, and repeating unit is 3-hydroxyl-5-thiazolinyl caproic acid; R
1Be the C that phenoxy group replaces on the carbon endways
3Alkyl, n are 1, and repeating unit is 3-hydroxyl-6-phenoxy group caproic acid.
All kinds of biodegradable PHAs that comprise among the present invention can synthesize by biological method, referring to international patent application 9302187, and Somerville, Poirier and Dennis, on February 4th, 1993 is open; United States Patent (USP) 5,650,555, Dennis etc., promulgation on July 22nd, 1997, and United States Patent (USP) 5,610,041, Nawrath etc., promulgation on March 11st, 1997.
Blend PHB+P used herein (HB-HA) and can be processed into various plastics with the further blend of starch includes but not limited to film, sheet material, fiber, foam materials, moulded parts, nonwoven fabric, elastomerics and tackiness agent.Complete processing can be joined following United States Patent (USP): US 5,653,930; US 5,747, and 584; US 5,780, and 368; US 5,502, and 116; US 5,498, and 692; US 5,536, and 564; US 5,618, and 855; US 5,685, and 756; US5,780,368; US 5,990, and 271; US 6,013, and 590; US 6,174,990 B; US 5,489, and 470; US5,489,692; US 5,536, and 564; US 5,685, and 756; US 5,780, and 368; US 6,027, and 787; US6,143,947; US 6,160, and 199; US 6,174, and 990; And following Chinese patent: CN 90107256.7; CN90103240.9; CN 90103071.6; CN 93111901.4; CN 95101808.6; CN 93114821.9; CN95103871.0; CN 95111358.5.
Below in conjunction with specific embodiments the present invention is further described.Should be pointed out that these embodiments only are several in the various embodiments of the present invention, be not used for limiting the present invention.
Embodiment
Embodiment 1
The blend of PHB+3-hydroxybutyric acid and 3-hydroxyl pentanoate copolymer (PHBV)
PHB and PHBV adopt " Chen et al.Biotechnol.Techniques, 1997,11:347 " and " Chen et al.Antonie van Leewenhoek, 1991,60:61 " reported method synthetic respectively.Take by weighing 20 pulverous PHB of gram and 20 gram 3-hydroxypentanoic acid content and be 20% PHBV, abbreviate P (HB-20%HV) as, fully mixing.Adopt the small capacity double screw extrusion press to carry out granulation.Blend PHB+P (HB-20%HV) relatively sees Table 1 with the performance of homopolymer PHB and multipolymer.
Table 1 PHB, the performance of 3-hydroxybutyric acid and 3-hydroxyl pentanoate copolymer (PHBV) and blend thereof relatively
| Sample | Fusing point (℃) | Stretch (MPa) | Elongation at break (%) |
| ????PHB | ????177 | ????43 | ????5 |
| ????P(HB-20％HV) | ????135 | ????20 | ????100 |
| ????PHB+P(HB-20％HV) | ????163 | ????35 | ????53 |
Embodiment 2
The blend of PHB+3-hydroxybutyric acid and 3-hydroxycaproic acid multipolymer (PHBHHx)
PHB and PHBHHx adopt " Chen et al.Biotechnol.Techniques, 1997,11:347 " and " Chen GQ et al.Appl.Microbiol.Biotechnol., 2001,57:50 " reported method synthetic respectively.Take by weighing 20 pulverous PHB of gram and 10 gram 3-hydroxycaproic acid content and be 15% PHBHHx, abbreviate P (HB-15%HHx) as, fully mixing.Adopt the small capacity double screw extrusion press to carry out granulation.Blend PHB+P (HB-15%HHx) relatively sees Table 2 with the performance of homopolymer PHB and copolymer p HBHHx.
Table 2 PHB, the performance of 3-hydroxybutyric acid and 3-hydroxycaproic acid multipolymer (PHBHHx) and blend thereof relatively
| Sample | Fusing point (℃) | Stretch (MPa) | Elongation at break (%) |
| ????PHB | ????177 | ????43 | ????5 |
| ????P(HB-15％HHx) | ????125 | ????20 | ????620 |
| ????PHB+P(HB-15％HHx) | ????162 | ????32 | ????280 |
Embodiment 3
The blend of PHB+3-hydroxybutyric acid and 3-hydroxydecanoic acid multipolymer (PHBD)
PHB and PHBD adopt " Chen et al.Biotechnol.Techniques, 1997,11:347 " and " Abeet al.Int.J.Biol.Macromol, 1994,16:115 " reported method to synthesize respectively.Take by weighing 20 pulverous PHB of gram and 10 gram 3-hydroxydecanoic acid content and be 8% PHBD, abbreviate P (HB-8%HD) as, fully mixing.Adopt the small capacity double screw extrusion press to carry out granulation.Blend PHB+P (HB-8%HD) relatively sees Table 3 with the performance of homopolymer PHB and copolymer p HBD.
Table 3 PHB, the performance of 3-hydroxybutyric acid and 3-hydroxydecanoic acid multipolymer (PHBD) and blend thereof relatively
| Sample | Fusing point (℃) | Stretch (MPa) | Elongation at break (%) |
| ????PHB | ????177 | ????43 | ????5 |
| ????P(HB-8％HD) | ????122 | ????22 | ????580 |
| ????PHB+P(HB-8％HD) | ????166 | ????37 | ????230 |
Embodiment 4
PHB+P (HB-4-HB) blend
PHB and P (HB-4-HB) adopt " Chen et al.Biotechnol.Techniques, 1997,11:347 " and " Kunioka et al.Int.J.Biol.Macromol, 1989,30:569 " reported method synthetic respectively.Take by weighing 20 pulverous PHB of gram and 5 gram 4 hydroxybutyric acid content and be 16% P (HB-4-HB), abbreviate P (HB-16%4-HB) as, fully mixing.Adopt the small capacity double screw extrusion press to carry out granulation.Blend PHB+P (HB-16%4-HB) relatively sees Table 4 with the performance of homopolymer PHB and copolymer p (HB-16%4-HB).
Table 4 PHB, 3-hydroxybutyric acid and 4 hydroxybutyric acid copolymer p (HB-16%4-HB)
And the performance of blend relatively
| Sample | Fusing point (℃) | Stretch (MPa) | Elongation at break (%) |
| ????P(HB-20％HV) | ????135 | ????20 | ????100 |
| ????P(HB-16％4-HB) | ????142 | ????33 | ????290 |
| ????PHB+P(HB-16％4-HB) | ????160 | ????39 | ????120 |
Embodiment 5
The blend of PHB+3-hydroxybutyric acid and 3-hydroxyl-5-thiazolinyl caproic acid copolymer p (HB-5-HHe)
PHB adopts " Chen et al.Biotechnol.Techniques, 1997,11:347 " reported method synthetic; P (HB-5-HHe) adopts " Preusting et al.Macromolecules, 1990,23:4220 " reported method synthetic, but different be that except that original carbon source, the butyric acid that has also added 8 grams per liters is as common carbon source in the substratum of microorganism.Hydroxyl-5-thiazolinyl caproic acid content is 56% P (HB-5-HHe), abbreviates P (HB-56%5-HHe) as to take by weighing 20 pulverous PHB of gram and 5 gram 3-, fully mixing.Adopt the small capacity double screw extrusion press to carry out granulation.Blend PHB+P (HB-56%5-HHe) relatively sees Table 5 with the performance of homopolymer PHB and copolymer p (HB-56%5-HHe).
Table 5 PHB, 3-hydroxybutyric acid and 3-hydroxyl-5-thiazolinyl caproic acid copolymer p (HB-5-HHe)
And the performance of blend relatively
| Sample | Fusing point (℃) | Stretch (MPa) | Elongation at break (%) |
| ????PHB | ????177 | ????43 | ????5 |
| ????P(HB-56％5-HHe) | ????73 | ????12 | ????900 |
| ?PHB+P(HB-12％5-HHe) | ????150 | ????30 | ????490 |
Embodiment 6
The blend of PHB+3-hydroxybutyric acid and 3-hydroxyl-6-phenoxy group caproic acid copolymer p (HB-6-HBOHx)
PHB adopts " Chen et al.Biotechnol.Techniques, 1997,11:347 " reported method synthetic; P (HB-6-HBOHx) adopts " Song et al.Appl.Environ.Microbiol; 1996,62:536 " reported method synthetic, but different is, except that original carbon source, the butyric acid that has also added 5 grams per liters is as being total to carbon source in the substratum of microorganism.Hydroxyl-6-phenoxy group caproic acid content is 68% P (HB-6-HBOHx), abbreviates P (HB-68%6-HBOHx) as to take by weighing 20 pulverous PHB of gram and 3 gram 3-, fully mixing.Adopt the small capacity double screw extrusion press to carry out granulation.Blend PHB+P (HB-68%6-HBOHx) relatively sees Table 6 with the performance of homopolymer PHB and copolymer p (HB-68%6-HBOHx).
Table 6 PHB, 3-hydroxybutyric acid and 3-hydroxyl-6-phenoxy group caproic acid copolymer p (HB-6-HBOHx)
And the performance of blend relatively
| Sample | Fusing point (℃) | Stretch (MPa) | Elongation at break (%) |
| ????PHB | ????177 | ????43 | ????5 |
| ?P(HB-68％6-HBOHx) | ????69 | ????11 | ????1200 |
| ?PHB+P(HB-68％6-HBOHx) | ????150 | ????38 | ????390 |
Embodiment 7
PHB+3-hydroxybutyric acid and 3-hydroxycaproic acid multipolymer (PHBHHx) blend further with starch blending
Taking by weighing 200 gram water content is that about 12% W-Gum joins 500 milliliters of reaction flasks that place in the oil bath pan, add 200 milliliters of white oils while stirring, add 4 gram anion surfactants stop starch in dehydration, to gather and starch in moisture make starch pasting.Intensification is also opened vacuum system, and to 0.095 MPa, temperature raises system pressure gradually by 0.05 MPa, and top temperature must not be above 180 ℃.Treat that moisture is lower than at 0.5% o'clock, stop to vacuumize, cooling.With the slurry after the dehydration, be put into and carry out sanded in the sand mill or carry out miniaturization through clarifixator, clarifixator pressure is the 400-800 kilogram, starch fineness after the refinement reaches below 10 microns, its refinement purpose is to increase starch surface active area, and helping starch, to cover hydroxyl modification and production thinness be 0.008 millimeter ultrathin film.Select for use tripod pendulum type batch centrifugal to dry, with starch and oil phase liquid separation.Isolated starch filter cake is put into reaction flask, add and cover hydroxyl properties-correcting agent aluminic acid compound 4 grams, cover the hydroxyl modification, purpose is the blend that improves between blend PHB+P (HB-15%HHx) and ultra-fine starch, improve the dispersiveness of starch in base-material, guarantee that starch is compatible with blend PHB+P (HB-15%HHx).Add lubricant white oil 10 grams and mixed 10-20 minute, 150 ℃ of temperature, discharging becomes modified starch SMA.Above-mentioned modified starch SMA is put into the cold mixed bottle of low speed to be mixed with blend PHB+P (HB-15%HHx) resin (according to embodiment 2 described method preparations) of 130 grams, blend PHB+P (HB-15%HHx) resin can be selected the PHB/PHBHHx of different ratios for use according to performance requriements, add 1 gram softening agent Octyl adipate, purpose is the plasticity that increases goods, gives the goods snappiness.Select for use the small capacity double screw extrusion press to carry out granulation, can obtain starch content and reach complete biodegradable plastics masterbatch more than 60%.Present embodiment mainly is to replace polythene PE or polypropylene PP with blend PHB+P (HB-15%HHx), and the PE starch plastic that part is degraded becomes the biological plastics of Wholly-degradable.By blend, starch+PHB+P (HB-15%HHx) application performance is better than starch+30%PE (table 9).
Performance after table 9 starch and PHB+P (HB-15%HHx) blend relatively
| Sample | Fusing point (℃) | Stretch (MPa) | Elongation at break (%) |
| Starch+50%PE | ????180 | ????14 | ????150 |
| ????PHB+P(HB-15％HHx) | ????162 | ????32 | ????280 |
| Starch+PHB+P (HB-15%HHx) * | ????170 | ????29 | ????220 |
*The mass percent that starch accounts for [starch+PHB+P (HB-15%HHx)] blend is 50%
Should be understood that embodiment that this paper discloses and embodiment only for setting forth usefulness, present technique field personnel can make various changes to it, but they all are included in the scope of the application's spirit and claims.
Claims (10)
1. Biodegradable material, comprising weight ratio is 1: 9～9: 1 the component A and the blend of B component, wherein:
Component A is the homopolymer of poly--3-butyric ester, the polymerization degree greater than 100 less than 100,000;
B component is the multipolymer that is made of at least two kinds of random structure unit, and the polymerization degree is greater than 100 less than 100,000, and wherein first kind of structural unit is shown in structural formula I, and its molar percentage that accounts for B component is 10-95%, second kind of structural unit shown in structural formula II,
Wherein, R
1Be hydrogen atom or replacement or unsubstituted C
1-C
12Alkyl or alkenyl, n=1 or 2, and, when n=1, R
1It is not methyl.
2. according to the Biodegradable material of claim 1, it is characterized in that described R
1Be hydrogen atom, C
1-C
7Alkyl, or the C that replaces by the phenyl of phenoxy group, halogen, phenyl or replacement
1-C
7Alkyl.
3. according to the Biodegradable material of claim 1, it is characterized in that described R
1Be C
2-C
5Thiazolinyl.
4. according to the Biodegradable material of claim 1, the weight ratio that it is characterized in that component A and B component is 1: 1～7: 1.
5. according to the Biodegradable material of claim 4, the weight ratio that it is characterized in that component A and B component is 2: 1～4: 1.
6. according to the Biodegradable material of claim 1, the molar percentage that the first kind of structural unit that it is characterized in that B component accounts for B component is 30-90%.
7. according to the Biodegradable material of claim 1, it is characterized in that described Biodegradable material comprises one of following blend:
(A) B component is the multipolymer of 3-hydroxybutyric acid and 3-hydroxypentanoic acid, and the molar percentage that the 3-hydroxypentanoic acid accounts for this multipolymer is 20%; The weight ratio of component A and B component is 1: 1;
(B) B component is the multipolymer of 3-hydroxybutyric acid and 3-hydroxycaproic acid, and the molar percentage that the 3-hydroxycaproic acid accounts for this multipolymer is 15%; The weight ratio of component A and B component is 2: 1;
(C) B component is the multipolymer of 3-hydroxybutyric acid and 3-hydroxydecanoic acid, and the molar percentage that the 3-hydroxydecanoic acid accounts for this multipolymer is 8%; The weight ratio of component A and B component is 2: 1;
(D) B component is the multipolymer of 3-hydroxybutyric acid and 4 hydroxybutyric acid, and the molar percentage that 4 hydroxybutyric acid accounts for this multipolymer is 16%; The weight ratio of component A and B component is 4: 1;
(E) B component is the multipolymer of 3-hydroxybutyric acid and 3-hydroxyl-5-thiazolinyl caproic acid, and the molar percentage that 3-hydroxyl-5-thiazolinyl caproic acid accounts for this multipolymer is 56%; The weight ratio of component A and B component is 4: 1;
(F) B component is the multipolymer of 3-hydroxybutyric acid and 3-hydroxyl-6-phenoxy group caproic acid, and the molar percentage that 3-hydroxyl-6-phenoxy group caproic acid accounts for this multipolymer is 68%; The weight ratio of component A and B component is 20: 3.
8. according to the Biodegradable material of claim 1, it is characterized in that described Biodegradable material has further comprised starch, and the weight ratio of described blend and starch is 1: 9～9: 1.
9. Biodegradable material according to Claim 8, the weight ratio that it is characterized in that described blend and starch is 1: 3～3: 1.
10. plastics of making according to the Biodegradable material of one of claim 1-9.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250453A (en) * | 2011-05-29 | 2011-11-23 | 江苏华信塑业发展有限公司 | Polyhydroxyalkanoate (PHA) and poly(ethylene terephthalate)glycol (PETG) blend film and preparation method thereof |
| CN102850741A (en) * | 2012-09-06 | 2013-01-02 | 江苏兆鋆新材料科技有限公司 | Polyhydroxyalkanoate full-degradation composite material, preparation method and applications thereof |
| CN104140522A (en) * | 2014-06-27 | 2014-11-12 | 江南大学 | Degradable polyhydroxyalkanoate |
| CN104861210A (en) * | 2015-04-30 | 2015-08-26 | 亿帆鑫富药业股份有限公司 | Starch-base fully biodegradable resin with steady hydrophobic property and preparation method thereof |
| CN106147161A (en) * | 2015-04-16 | 2016-11-23 | 深圳市联创科技集团有限公司 | A kind of biodegradable plastic and preparation method thereof |
| CN108026440A (en) * | 2015-09-18 | 2018-05-11 | 通用电气(Ge)贝克休斯有限责任公司 | The method for carrying out steering and Inter-zonal packing in subsurface formations using biodegradable polymer |
-
2003
- 2003-01-31 CN CN 03103621 patent/CN1244634C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250453A (en) * | 2011-05-29 | 2011-11-23 | 江苏华信塑业发展有限公司 | Polyhydroxyalkanoate (PHA) and poly(ethylene terephthalate)glycol (PETG) blend film and preparation method thereof |
| CN102250453B (en) * | 2011-05-29 | 2013-02-27 | 江苏华信塑业发展有限公司 | Polyhydroxyalkanoate (PHA) and poly(ethylene terephthalate)glycol (PETG) blend film and preparation method thereof |
| CN102850741A (en) * | 2012-09-06 | 2013-01-02 | 江苏兆鋆新材料科技有限公司 | Polyhydroxyalkanoate full-degradation composite material, preparation method and applications thereof |
| CN104140522A (en) * | 2014-06-27 | 2014-11-12 | 江南大学 | Degradable polyhydroxyalkanoate |
| CN104140522B (en) * | 2014-06-27 | 2016-02-10 | 江南大学 | A kind of degradable polyhydroxyalkanoate |
| CN106147161A (en) * | 2015-04-16 | 2016-11-23 | 深圳市联创科技集团有限公司 | A kind of biodegradable plastic and preparation method thereof |
| CN106147161B (en) * | 2015-04-16 | 2018-05-22 | 深圳市联创科技集团有限公司 | A kind of biodegradable plastic and preparation method thereof |
| CN104861210A (en) * | 2015-04-30 | 2015-08-26 | 亿帆鑫富药业股份有限公司 | Starch-base fully biodegradable resin with steady hydrophobic property and preparation method thereof |
| CN108026440A (en) * | 2015-09-18 | 2018-05-11 | 通用电气(Ge)贝克休斯有限责任公司 | The method for carrying out steering and Inter-zonal packing in subsurface formations using biodegradable polymer |
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| CN1244634C (en) | 2006-03-08 |
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