CN1450120A - Complete biodegradable fatty polyester/starch composite material - Google Patents
Complete biodegradable fatty polyester/starch composite material Download PDFInfo
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Abstract
The present invention relates to completely bio-degradable aliphatic polyester/starch composite material. The composition of said composite material is formed from aliphatic polyester, starch and compatibilizer. It is characterized by that the aliphatic polyester is para-dioxocyclohexanone polymer, and the weight portion contents of all the components are: para-dioxocyclohexanone polymer 30-95 portions, starch 5-70 portions and compatibilizer 0.1-20 portions. Said composite material can be used for making disposable plastic articles of mulch film, shopping bag, refuse bag and package material, etc.
Description
One, technical field
The invention belongs to the biodegradable material technical field, be specifically related to a kind of aliphatic polyester/starch powder composite material of fully biodegradable.
Two, background technology
Plastic prod has caused global concern to the white pollution that environment causes.In order to reduce this pollution, all both had a plastics premium properties being devoted to exploitation both at home and abroad, simultaneously degradable again plastics of new generation.Now the biodegradable plastic on the domestic market mainly is the biological damage plastic, is to be matrix with general-purpose plastics such as polyethylene, polypropylene, carries out the biodegradable plastic that blend is made with degradable macromolecule such as starch.This class biodegradable plastic has just solved visual pollution, when it is embedded in the soil or directly under sunlight, microbial process, the high-molecular weight polyolefine is not degraded, only be that biological degradation has taken place the starch of sneaking into wherein, thereby what stay on plastics is cyclic cavity one by one.Therefore, in the biodegradable material technical field, people are from the angle of the protection eubiosis, and the main direction with exploitation turns to environment amenable fully biodegradable plastics.
Aliphatic polyester is a class superpolymer that develops the most soon fully biodegradable at present.The ester bond of facile hydrolysis makes it have favorable biological degradability in the main chain; Aliphatic structure makes it have the favorable mechanical performance again.But,, be only limited at present at field of medicaments and use because they cost an arm and a leg.If wide material sources such as starch, cheap material are added in the aliphatic polyester, this class intermingling material is expected to substitute general-purpose plastics such as polyethylene.The research of relevant this respect has many reports in recent years.The Mater-Bi series product of Italy Novamont company are exactly to gather (Bastioli, C.Polym.Degrad.Stab.1998,59 (1-3), the 263-272 that (6-caprolactone) and thermoplastic starch are the main raw material preparation; ).But because the fusing point of poly-(6-caprolactone) has only 60 ℃, thereby its range of application is restricted undoubtedly.Though and another kind of aliphatic polyester---polylactide is that fusing point is the highest in all aliphatic polyesters, but because its second-order transition temperature has only 54 ℃, elongation at break is very low, is a kind of material that is highly brittle.If starch is introduced in this very crisp base material, only meeting high-density weighting material fragility influences its use.Therefore the report about polylactide and starch blending just rests on conceptual phase (Wang, H.; Sun, X.Z.; Seib, P.J.Appl.Polym.Sci.2002,84,1257-1262.).
PPDO (PPDO) also is a kind of of aliphatic polyester, because of it has excellent biocompatibility and biodegradability, is successfully applied to and makes surgical sutures, hone lamella and tissue renovation material, as surgery devices such as screw, hook, sheet and pincers.Along with the biological degradability of PPDO in physical environment confirmed (Nishida, H. by the people; Konno, M.; A.; Tokiwa, Y.Polym.Degrad.Stab.2000,68,205-217), though there is the people to foretell, if can significantly reduce synthetic cost, PPDO is expected to be widely used in making materials such as film, expanded plastic, sheet material, tackiness agent, finishing agent and non-woven fabrics, and can satisfy environmental requirement.But because of its polymerization cost height, the forming process difficulty has not yet to see bibliographical information eventually.
Three, summary of the invention
The objective of the invention is existing problems, a kind of aliphatic polyester/starch powder composite material with fully biodegradable of actual application value is provided at prior art.
The aliphatic polyester/starch powder composite material of fully biodegradable provided by the invention, it consists of aliphatic polyester, starch and expanding material, it is characterized in that aliphatic polyester is to dioxy pimelinketone polymkeric substance, and the weight part content of each component is:
To 30～95 parts in dioxy pimelinketone polymkeric substance
5～70 parts of starch
0.1～20 part of expanding material
Wherein dioxy pimelinketone polymkeric substance is selected from the PPDO homopolymer or/and to the multipolymer of dioxy pimelinketone and 6-caprolactone, L-rac-Lactide, DL-rac-Lactide.
Starch is selected from any of native starch, treated starch, thermoplastic starch, and native starch specifically is selected from least a of W-Gum, potato starch, wheat starch, tapioca (flour) and cereal starch; Treated starch specifically is selected from least a of starch acetate, hydroxymethyl starch, hydroxyethylamyle; Thermoplastic starch then is made up of native starch and softening agent, wherein the weight percent content of softening agent is 10-30%, specifically be selected from water, glycerine, ethylene glycol, propylene glycol, polyoxyethylene glycol, polypropylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, the acetate sorbitol ester, the mannitol monoacetate, mannitol monosubstituted ethoxy thing, carboxymethyl Sorbitol Powder sodium salt, urea, amine at least a, native starch specifically is selected from W-Gum, potato starch, wheat starch, any of tapioca (flour) and cereal starch.
Expanding material (SGP) is selected from by native starch and PPDO polymeric graft copolymer, its grafting degree (NG) contains 10～100 grafted aliphatic polyester chains for per 100 glucose units, the mean polymerisation degree of grafted chain (DGP) is 1～20, and concrete graft polymerization procedure sees that application number is 02113539.8 Chinese patent.
The preparation method of the aliphatic polyester/starch powder composite material of relevant fully biodegradable of the present invention does not have special restriction.Just when starch adopts native starch or treated starch, the various components that directly will fill a prescription added the high-speed mixer premix after 5～10 minutes, in single screw extrusion machine, twin screw extruder, Banbury mixer or Haake mixing roll, carry out melt blending again, the temperature of melt blending should be higher than the melt temperature to dioxy pimelinketone polymkeric substance, be preferably in 80～120 ℃ of scopes, then extruding pelletization.But then must before above-mentioned operation, increase a starch plasticizing operation when starch adopts thermoplastic starch, promptly first with native starch and softening agent high-speed mixer premix 5～10 minutes, and then compound added extruding pelletization in the forcing machine.
The present invention has the following advantages:
1, because matrix material provided by the invention is to have added starch in dioxy pimelinketone polymkeric substance, thereby not only can reduce cost greatly, also can improve the crystallization rate and the biodegradation rate of dioxy pimelinketone polymkeric substance, help the machine-shaping of dioxy pimelinketone polymkeric substance and the requirement of adaptation compost biodegrade.
2, the biological degradability of film under the discarded heap environment of simcity made from matrix material provided by the invention, discovery has just been degraded fully less than 20 days films, its rate of weight loss is a kind of aliphatic polyester/starch powder composite material of genuine fully biodegradable greater than 90%.
3, the aliphatic polyester/starch powder composite material of fully biodegradable provided by the invention can be widely used in and make agricultural mulching, shopping bag, refuse bag, wrapping material etc., is a kind of aliphatic polyester/starch powder composite material with fully biodegradable of actual application value.
Four, embodiment
Provide embodiment below so that the invention will be further described; but what deserves to be explained is that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field still belongs to protection scope of the present invention according to the content of the invention described above to some nonessential improvement and the adjustment that the present invention makes.
Embodiment 1
At first (NG=30 DGP=8) with high-speed mixer pre-mixing 5 minutes, is added to the mixture behind the premix that extruding pelletization gets final product in the single screw extrusion machine then to dioxy pimelinketone homopolymer, 5 parts of W-Gums, 1 part of expanding material with 95 parts.The temperature setting of forcing machine is: 70 ℃ of feeding sections, and 95 ℃ of mixing sections, fluxing zone are 100 ℃, 95 ℃ of heads, screw speed are 9rpm.The tensile strength of the material that obtains is 30MPa.
Embodiment 2
(1) at first 100 portions of wheat starches and 30 parts of softening agent (wherein the ratio of water and glycerine is 2: 1) are used high-speed mixer pre-mixing 5 minutes, then the mixture behind the premix is added to that extruding pelletization promptly gets thermoplastic starch in the single screw extrusion machine, standby, the temperature setting of forcing machine is: 60 ℃ of feeding sections, 115 ℃ of mixing sections, 110 ℃ of heads, screw speed are 7rpm;
(2) at first (NG=62 DGP=12) with high-speed mixer pre-mixing 8 minutes, is added to the mixture behind the premix that extruding pelletization gets final product in the single screw extrusion machine then to dioxy pimelinketone homopolymer, 20 parts of thermoplastic starchs, 5 parts of expanding materials with 80 parts.The temperature setting of forcing machine is: (70 ℃ of feeding sections, 95 ℃ of mixing sections, fluxing zone are 100 ℃, 95 ℃ of heads, screw speed are 9rpm.The tensile strength of the material that obtains is 32MPa.
Embodiment 3
At first with 80 parts of multipolymers, 5 parts of potato starches, 15 parts of W-Gums, 10 parts of expanding material (NG=50 to dioxy pimelinketone and 6-caprolactone, DGP=20), then the mixture behind the premix is added to that extruding pelletization gets final product in the single screw extrusion machine with high-speed mixer pre-mixing 6 minutes.The temperature setting of forcing machine is: (70 ℃ of feeding sections, 95 ℃ of mixing sections, fluxing zone are 100 ℃, 95 ℃ of heads, screw speed are 7rpm.The tensile strength of the material that obtains is 25MPa.
Embodiment 4
(1) at first 100 parts of W-Gums and 10 parts of softening agent (ratio of glycerine, polyoxyethylene glycol is 3: 1) are used high-speed mixer pre-mixing 10 minutes, then the mixture behind the premix is added to that extruding pelletization promptly gets thermoplastic starch in the single screw extrusion machine, standby, the temperature setting of forcing machine is: 60 ℃ of feeding sections, 105 ℃ of mixing sections, 95 ℃ of heads, screw speed are 9rpm;
(2) at first (NG=25 DGP=9) with high-speed mixer pre-mixing 8 minutes, is added to the mixture behind the premix that extruding pelletization gets final product in the single screw extrusion machine then to dioxy pimelinketone homopolymer, 30 parts of thermoplastic starchs, 10 parts of expanding materials with 70 parts.The temperature setting of forcing machine is: 50 ℃ of feeding sections, and 95 ℃ of mixing sections, fluxing zone are 108 ℃, 100 ℃ of heads, screw speed are 9rpm.The tensile strength of the material that obtains is 20MPa.
Embodiment 5
(1) at first 100 parts of carboxymethyl starch and 25 parts of softening agent (water and propylene glycol ratio are 1: 1) are used high-speed mixer pre-mixing 8 minutes, then the mixture behind the premix is added to that extruding pelletization promptly gets thermoplastic starch in the single screw extrusion machine, standby, the temperature setting of forcing machine is: 60 ℃ of feeding sections, 120 ℃ of mixing sections, 105 ℃ of heads, screw speed are 9rpm;
(2) at first (NG=80 DGP=20) with high-speed mixer pre-mixing 8 minutes, is added to the mixture behind the premix that extruding pelletization gets final product in the single screw extrusion machine then to dioxy pimelinketone homopolymer, 50 parts of thermoplastic starchs, 20 parts of expanding materials with 50 parts.The temperature setting of forcing machine is: 70 ℃ of feeding sections, and 105 ℃ of mixing sections, fluxing zone are 120 ℃, 110 ℃ of heads, screw speed are 9rpm.The tensile strength of the material that obtains is 30MPa.
Embodiment 6
At first (NG=90 DGP=5) with high-speed mixer pre-mixing 6 minutes, is added to the mixture behind the premix that extruding pelletization gets final product in list or the twin screw extruder then to dioxy pimelinketone homopolymer, 20 parts of starch acetates, 10 parts of expanding materials with 80 parts.The temperature setting of forcing machine is: 70 ℃ of feeding sections, and 105 ℃ of mixing sections, fluxing zone are 110 ℃, 105 ℃ of heads, screw speed are 7rpm.The tensile strength of the material that obtains is 20MPa.
Embodiment 7
At first (NG=50 DGP=15) with high-speed mixer pre-mixing 6 minutes, is added to the mixture behind the premix that extruding pelletization gets final product in list or the twin screw extruder then to dioxy pimelinketone homopolymer, 10 parts of carboxymethyl starch, 5 parts of expanding materials with 90 parts.The temperature setting of forcing machine is: 70 ℃ of feeding sections, and 105 ℃ of mixing sections, fluxing zone are 105 ℃, 100 ℃ of heads, screw speed are 9rpm.The tensile strength of the material that obtains is 32MPa.
Embodiment 8
(1) at first 100 portions of tapioca (flour)s and 30 parts of softening agent (water and acetate sorbitol ester ratio are 3: 1) are used high-speed mixer pre-mixing 10 minutes, then the mixture behind the premix is added to that extruding pelletization promptly gets thermoplastic starch in the single screw extrusion machine, standby, the temperature setting of forcing machine is: 60 ℃ of feeding sections, 104 ℃ of mixing sections, 110 ℃ of heads, screw speed are 9rpm;
(2) at first (NG=95 DGP=5) with high-speed mixer pre-mixing 10 minutes, is added to the mixture behind the premix that extruding pelletization gets final product in the single screw extrusion machine then to dioxy pimelinketone homopolymer, 70 parts of thermoplastic starchs, 20 parts of expanding materials with 30 parts.The temperature setting of forcing machine is: 40 ℃ of feeding sections, and 95 ℃ of mixing sections, fluxing zone are 100 ℃, 95 ℃ of heads, screw speed are 9rpm.The tensile strength of the material that obtains is 18MPa.
Embodiment 9
(1) at first 100 parts of W-Gums and 25 parts of softening agent (ratio of water and glycerine is 2: 1) are used high-speed mixer pre-mixing 10 minutes, then the mixture behind the premix is added to that extruding pelletization promptly gets thermoplastic starch in the single screw extrusion machine, standby, the temperature setting of forcing machine is: 60 ℃ of feeding sections, 110 ℃ of mixing sections, 100 ℃ of heads, screw speed are 9rpm;
(2) at first with 75 parts of multipolymers, 25 parts of thermoplastic starchs, 10 parts of expanding material (NG=62 to dioxy pimelinketone and L rac-Lactide, DGP=12), then the mixture behind the premix is added to that extruding pelletization gets final product in the single screw extrusion machine with high-speed mixer pre-mixing 10 minutes.The temperature setting of forcing machine is: 40 ℃ of feeding sections, and 95 ℃ of mixing sections, fluxing zone are 100 ℃, 95 ℃ of heads, screw speed are 9rpm.The tensile strength of the material that obtains is 20MPa.
Embodiment 10
At first with 40 parts to dioxy pimelinketone homopolymer, 30 parts of multipolymers, 30 portions of wheat starches, 20 parts of expanding material (NG=15 to dioxy pimelinketone and DL-rac-Lactide, DGP=20), then the mixture behind the premix is added to that extruding pelletization gets final product in list or the twin screw extruder with high-speed mixer pre-mixing 10 minutes.The temperature setting of forcing machine is: 70 ℃ of feeding sections, and 100 ℃ of mixing sections, fluxing zone are 105 ℃, 98 ℃ of heads, screw speed are 9rpm.The tensile strength of the material that obtains is 35MPa.
Claims (10)
1, a kind of aliphatic polyester/starch powder composite material of fully biodegradable, this matrix material consists of aliphatic polyester, starch and expanding material, it is characterized in that aliphatic polyester is to dioxy pimelinketone polymkeric substance, and the weight part content of each component is:
To 30～95 parts in dioxy pimelinketone polymkeric substance
5～70 parts of starch
0.1～20 part of expanding material.
2, the aliphatic polyester/starch powder composite material of fully biodegradable according to claim 1 is characterized in that dioxy pimelinketone polymkeric substance is selected from the PPDO homopolymer or/and to the multipolymer of dioxy pimelinketone and 6-caprolactone, L-rac-Lactide, DL-rac-Lactide.
3, the aliphatic polyester/starch powder composite material of fully biodegradable according to claim 1 and 2 is characterized in that starch is selected from any of native starch, treated starch, thermoplastic starch.
4, the aliphatic polyester/starch powder composite material of fully biodegradable according to claim 3 is characterized in that native starch is selected from least a of W-Gum, potato starch, wheat starch, tapioca (flour) and cereal starch.
5, the aliphatic polyester/starch powder composite material of fully biodegradable according to claim 3 is characterized in that treated starch is selected from least a of starch acetate, hydroxymethyl starch, hydroxyethylamyle.
6, the aliphatic polyester/starch powder composite material of fully biodegradable according to claim 3 is characterized in that thermoplastic starch is made up of native starch and softening agent, and wherein the weight percent content of softening agent is 10-30%.
7, the aliphatic polyester/starch powder composite material of fully biodegradable according to claim 6 is characterized in that native starch is selected from any of W-Gum, potato starch, wheat starch, tapioca (flour) and cereal starch.
8, the aliphatic polyester/starch powder composite material of fully biodegradable according to claim 6, it is characterized in that softening agent is selected from water, glycerine, ethylene glycol, propylene glycol, polyoxyethylene glycol, polypropylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, acetate sorbitol ester, mannitol monoacetate, mannitol monosubstituted ethoxy thing, carboxymethyl Sorbitol Powder sodium salt, urea, amine at least a.
9, according to the aliphatic polyester/starch powder composite material of claim 1 or 2 or 4 or 5 or 6 or 7 or 8 described fully biodegradables, it is characterized in that expanding material is selected from by native starch and PPDO polymeric graft copolymer, its grafting degree is that per 100 glucose units contain 10～100 grafted aliphatic polyester chains, and the mean polymerisation degree of grafted chain is 1～20.
10, the aliphatic polyester/starch powder composite material of fully biodegradable according to claim 3, it is characterized in that expanding material is selected from by native starch and PPDO polymeric graft copolymer, its grafting degree is that per 100 glucose units contain 10～100 grafted aliphatic polyester chains, and the mean polymerisation degree of grafted chain is 1～20.
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| CN 03117788 CN1226345C (en) | 2003-04-30 | 2003-04-30 | Complete biodegradable fatty polyester/starch composite material |
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| CN 03117788 CN1226345C (en) | 2003-04-30 | 2003-04-30 | Complete biodegradable fatty polyester/starch composite material |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007012142A1 (en) * | 2005-07-28 | 2007-02-01 | Biograde (Hong Kong) Pty Ltd | Biodegradable polymer composition |
| CN1300231C (en) * | 2004-12-30 | 2007-02-14 | 四川大学 | Polypara dioxocyclohexanone / montmorillonite nano-composite material and its preparation method |
| CN101516996B (en) * | 2006-07-28 | 2011-10-12 | 比澳格（香港）有限公司 | Masterbatch and polymer composition |
| CN107236153A (en) * | 2017-06-29 | 2017-10-10 | 苏州凌科特新材料有限公司 | A kind of high-strength biodegradable starch-resin and preparation method thereof |
| CN112341766A (en) * | 2020-10-30 | 2021-02-09 | 辽宁幸福人科技有限公司 | Fully-degradable bio-based composite material product and preparation method thereof |
| CN112358710A (en) * | 2020-11-16 | 2021-02-12 | 深圳市正旺环保新材料有限公司 | Biodegradable plastic bag and preparation method thereof |
| CN112694728A (en) * | 2020-12-31 | 2021-04-23 | 通源塑料包装(苏州)有限公司 | Plastic bag with poly (p-dioxanone) as substrate and preparation method thereof |
| CN113462136A (en) * | 2021-07-27 | 2021-10-01 | 武汉欣宏创塑料印刷包装有限公司 | Degradable cup cover film |
| CN113698637A (en) * | 2021-08-11 | 2021-11-26 | 兰州鑫银环橡塑制品有限公司 | Full-biodegradable mulching film material for tobacco planting and preparation method thereof |
-
2003
- 2003-04-30 CN CN 03117788 patent/CN1226345C/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300231C (en) * | 2004-12-30 | 2007-02-14 | 四川大学 | Polypara dioxocyclohexanone / montmorillonite nano-composite material and its preparation method |
| WO2007012142A1 (en) * | 2005-07-28 | 2007-02-01 | Biograde (Hong Kong) Pty Ltd | Biodegradable polymer composition |
| CN101516996B (en) * | 2006-07-28 | 2011-10-12 | 比澳格（香港）有限公司 | Masterbatch and polymer composition |
| CN107236153A (en) * | 2017-06-29 | 2017-10-10 | 苏州凌科特新材料有限公司 | A kind of high-strength biodegradable starch-resin and preparation method thereof |
| CN112341766A (en) * | 2020-10-30 | 2021-02-09 | 辽宁幸福人科技有限公司 | Fully-degradable bio-based composite material product and preparation method thereof |
| CN112341766B (en) * | 2020-10-30 | 2023-08-25 | 辽宁幸福人科技有限公司 | Fully-degradable bio-based composite material product and preparation method thereof |
| CN112358710A (en) * | 2020-11-16 | 2021-02-12 | 深圳市正旺环保新材料有限公司 | Biodegradable plastic bag and preparation method thereof |
| CN112694728A (en) * | 2020-12-31 | 2021-04-23 | 通源塑料包装(苏州)有限公司 | Plastic bag with poly (p-dioxanone) as substrate and preparation method thereof |
| CN113462136A (en) * | 2021-07-27 | 2021-10-01 | 武汉欣宏创塑料印刷包装有限公司 | Degradable cup cover film |
| CN113698637A (en) * | 2021-08-11 | 2021-11-26 | 兰州鑫银环橡塑制品有限公司 | Full-biodegradable mulching film material for tobacco planting and preparation method thereof |
| CN113698637B (en) * | 2021-08-11 | 2023-08-22 | 兰州鑫银环橡塑制品有限公司 | Full-biodegradable mulching film material for tobacco planting and preparation method thereof |
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