CN104140660A - Full degradation PHA modified material - Google Patents
Full degradation PHA modified material Download PDFInfo
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- CN104140660A CN104140660A CN201410376328.3A CN201410376328A CN104140660A CN 104140660 A CN104140660 A CN 104140660A CN 201410376328 A CN201410376328 A CN 201410376328A CN 104140660 A CN104140660 A CN 104140660A
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- pha
- fatty acid
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- maleic anhydride
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Abstract
The invention discloses a full degradation PHA modified material. The full degradation PHA modified material comprises, by weight, 86% of PHA, 3-4% of PIB, 3-5% of EEA, 1% of maleic anhydride graft compatibilizer, 4-6% of LDHS and 1% of disperse lubricant. In the application of the full degradation PHA modified material in mulching films, the technical requirements of the thickness of 0.008 mm and 0.01 mm, the elongation at break larger than 300% and the tensile strength larger than 25 Mpa are met.
Description
Technical field
The present invention relates to the preparation field of plastics, especially a kind of Fully-degradable hydroxy fatty acid is material modified.
Background technology
Agricultural mulching is widely used in recent years, has effectively controlled the temperature and humidity of soil, has reduced moisture and nutraceutical loss, has promoted high yield and the stable yields of farm crop, thereby has increased agriculture production benefit.But meanwhile,, due to the disposable use of mulch film, all can there is a large amount of residual films to stay in soil every year.It is tens thousand of to hundreds thousand of polyethylene that plastic film mostly is molecular weight, and they are difficult to degraded at occurring in nature.These mulch film fragments can form barrier layer in soil, make the constricted flow such as water in soil, gas, fertilizer, cause Soil structure to harden, and serious harm ecotope, causes white pollution.Therefore, solve the task of top priority that residual film contaminated soil problem has become plastic mulching cultivation technology.Two during the last ten years a person of noble aspirations both domestic and external be devoted to the research to degradable material.To the environmental pollution causing because plastics are discarded to be solved, researchist is doing a large amount of effort and is winning initial success aspect theoretical investigation, investigation of materials, product development and application, publicity popularization and the standard formulation in degradative plastics field, the whole society has generally accepted and has approved this concept of degradative plastics, and large quantities of degradable plastic products are applied.Most of degradable material can meet service requirements in the situation that dimensional thickness is greater than 1mm and do not need extension and regular tenacity, but in products thickness, be less than in the sheet material of 1mm or the production of film, because its thermoplasticity is too poor, make range of application be subject to obvious restriction.According to the requirement of agricultural mulching standard GB/T 13735-92, ground film thickness is 0.02mm to the maximum, and minimum is 0.008mm.The material of likely producing for degradative plastic film is at present that structure-type production degradable material can be divided into natural macromolecular material, microorganism synthesized polymer material and chemosynthesis degradable material by its source.Natural macromolecular material has completely biodegradable, but its calorifics, poor mechanical property, the contentedly requirement of mould material.Chemosynthesis type degradable material is as PLA, PCL, PBS etc., still needs research how by its chemical structure, to make it possess different qualities and purposes at present, and this class material because of its cost too high, on mulch film, apply and there is no practical significance.The synthetic macromolecular material of microorganism has higher Biodegradable as this class material of PHA, and thermoplasticity is better, easy-formation processing, but its mechanical property is not good, and its popularization in mulch film application is restricted.
Summary of the invention
Object of the present invention is exactly to overcome the deficiency that prior art exists and provide Fully-degradable hydroxy fatty acid material modified preparation method.
For achieving the above object, technical scheme of the present invention is as follows:
This Fully-degradable hydroxy fatty acid is material modified, and the weight percent of each component is: polyhydroxyalkanoates 86%, polyisobutene PIB3-4%, ethylene ethyl acrylate EEA3-5%, maleic anhydride graft compatilizer 1%, magnalium hydrotalcite LDHS4-6%, dispersed lubricant 1%.
Polyhydroxyalkanoate (PHA) is polyester natural macromolecular material in the synthetic a kind of cell of a lot of microorganisms, it is the linear polyester that a class 3-hydroxy fatty acid forms, molecular weight is 50000-2000000 dalton, and the hydroxyl of monomer and the hydroxyl of adjacent monomer form ester bond.Monomer is all R-configuration, and the different PHA key distinctions are side-chain radicals different on C-3 position, the medium chain length PHA that the monomer that the present invention uses is C6-C14.Compare with biomaterials such as poly(lactic acid) (PLA), PGA, PHA structural diversification, has formed the performance variation that structure diversity brings and has made it in application, have obvious advantage.Therefore PHA be a kind of have polymer essential property can thermoplastic machine-shaping polyester.It has the not available biological degradability of synthetic plastics, biocompatibility, optical activity, piezoelectricity and can utilize the excellent properties such as reclaimed materials in biosynthetic process.Because PHA is the linear degradable polyester with optically active monomer composition, its physicals mainly forms decision by monomer whose, homopolymer P (3HB) mechanical property forming due to 3 (HB) and processing characteristics are with respect to olefines macromolecular material or poor, in order to increase the range of application of P (3HB), the monomer that must insert non-3 (HB) between monomer whose carries out modification blend.
Polyisobutene (PIB) is to take the liquid that iso-butylene forms as a small amount of n-butene copolymerization of advocating peace, and its structure is nearly all long-chain, and has the monoolefine of two keys.Polybutene and low molecular polyisobutylene in use do not have strict difference, because preparation method is basic identical, are therefore difficult for strict differentiation.But polyisobutene is to take mixed butene as raw material, from structure, is the multipolymer of iso-butylene and n-butene, and molecular weight is lower, is a kind of thick liquid, is mainly used in the multiple industries such as lubricating oil, tackiness agent, makeup.In general, the material of molecular weight between 350 to 3500 claims low-molecular-weight polyisobutylene, and molecular weight is middle molecular weight products between 10,000 to 100,000, and molecular weight is high molecular weight products between 100,000 to 10,000,000.Molecular weight is in a liquid state conventionally at the product below 30,000, and the material that molecular weight is higher is solid-state, and what the present invention selected is that molecule is 3500 liquid polyisobutene, can improve plasticity-and the ductility of polyester material.
Ethylene ethyl acrylate (EEA) is by radical polymerization, to be produced in the high-pressure polyethylene reactor of reequiping specially.When the content of ethyl propenoate increases, it is more tough and tensile, more soft, more flexible that multipolymer will become.Improving ethyl propenoate content can increase the polarity of resin, can increase the ability of resin surface absorption ink simultaneously and have bond property.
Maleic anhydride graft compatilizer is that a kind of macromolecule interfacial coupling agent, compatilizer, dispersion are facilitated agent.It,, by introducing strong polar reaction group, makes material have very high polarity and reactivity, makes intermolecular combination become the combination of molecular chain, and the material mechanical performance of the multicomponent system of mixing is improved greatly.The compatilizer that the present invention selects is maleic anhydride grafted ethene acrylate copolymer.
The chemical formula of magnalium hydrotalcite (LDHS) is [Mg
6a
l2(OH)
16cO
3] 4H
2o.Be the negatively charged ion stratiform functional inorganic materials that a class has laminate structure, its special structure is being applied to when mulch film is produced to make it under the prerequisite that does not affect printing opacity, possess certain heat insulation function.The hydrotalcite median size that the present invention selects is that 15 μ m, whiteness are greater than 90 degree, oil-absorption(number) is 0.31ml/g, content of magnesia 32-40%, alumina content 14-18%.
Dispersed lubricant is pure polyethylene wax, relative molecular weight between 1500-9500, relative density 0.9-0.93g/cm
3, softening temperature 101-115 ℃, angle few from usage quantity, that dispersion effect is good considers to select kind that molecular weight is little for well.
The Fully-degradable hydroxy fatty acid of the present invention research is material modified is that to take polyhydroxyalkanoate, polyisobutene, ethylene, propylene ethyl ester be blending and modifying main body, adding maleic anhydride graft compatilizer, magnalium hydrotalcite is function modified material, by shearing in extruding continuously twin screw equipment with blend to reach the performance of improving PHA.During blending extrusion, must meet the following conditions: extrusion temperature, between 120-140 ℃, and can not surpass 140 ℃, and molten state is produced constant pressure continuously, and the residence time is no more than 2 minutes.To the requirement of temperature, pressure, the residence time, be that structural performance based on material of main part PHA is considered, be greater than 140 ℃ or compared with long residence time situation under, between P (3HB) monomer, link easily disconnects early, accelerated the degraded of this natural macromolecular material and aging, and physicals extreme difference.For obtaining the product with higher price-performance ratio, make it in mulch film application, meet 0.008mm and 0.01mm thickness elongation at break is greater than 300%, tensile strength is greater than the technical requirements of 25MPa, and various components will be optimized and coordinate, by repetition test and comparative analysis, definite formula is: polyhydroxyalkanoates 86%, polyisobutene PIB3%, ethylene ethyl acrylate EEA4%, maleic anhydride graft compatilizer 1%, magnalium hydrotalcite LDHS 5%, dispersed lubricant 1%.
Embodiment
Below in conjunction with specific embodiment, the present invention is carried out to detailed analysis;
Embodiment 1:
Fully-degradable hydroxy fatty acid is material modified, and the weight percent of each component is: polyhydroxyalkanoates 86%, polyisobutene PIB3%, ethylene ethyl acrylate EEA3%, maleic anhydride graft compatilizer 1%, magnalium hydrotalcite LDHS 6%, dispersed lubricant 1%.
Preparation method: first each compositions in weight percentage is accurately weighed good standby, polyhydroxyalkanoate, polyisobutene, ethylene, propylene ethyl ester are blending and modifying main body, adding maleic anhydride graft compatilizer, magnalium hydrotalcite is function modified material, by shearing in extruding continuously twin screw equipment with blend to reach the performance of improving PHA.During blending extrusion, must meet the following conditions: extrusion temperature is between 120-140 ℃, and can not surpass 140 ℃, molten state is produced constant pressure continuously, and the residence time is no more than 2 minutes, then by forcing machine, extruded, through fervent, air-cooled, make required masterbatch.
Embodiment 2:
Fully-degradable hydroxy fatty acid is material modified, and the weight percent of each component is: polyhydroxyalkanoates 86%, polyisobutene PIB3%, ethylene ethyl acrylate EEA5%, maleic anhydride graft compatilizer 1%, magnalium hydrotalcite LDHS 4%, dispersed lubricant 1%.
Preparation method is with embodiment 1.
Embodiment 3:
Fully-degradable hydroxy fatty acid is material modified, and the weight percent of component is: polyhydroxyalkanoates 86%, polyisobutene PIB4%, ethylene ethyl acrylate EEA4%, maleic anhydride graft compatilizer 1%, magnalium hydrotalcite LDHS 4%, dispersed lubricant 1%.
Preparation method is with embodiment 1.
Embodiment 3:
Fully-degradable hydroxy fatty acid is material modified, and the weight percent of component is: polyhydroxyalkanoates 86%, polyisobutene PIB3.5%, ethylene ethyl acrylate EEA4.5%, maleic anhydride graft compatilizer 1%, magnalium hydrotalcite LDHS 4%, dispersed lubricant 1%.
Preparation method is with embodiment 1.
Claims (4)
1. Fully-degradable hydroxy fatty acid is material modified, it is characterized in that the weight percent of each component is: polyhydroxyalkanoates 86%, polyisobutene PIB3-4%, ethylene ethyl acrylate EEA3-5%, maleic anhydride graft compatilizer 1%, magnalium hydrotalcite LDHS4-6%, dispersed lubricant 1%.
2. Fully-degradable hydroxy fatty acid according to claim 1 is material modified, it is characterized in that: described polyhydroxyalkanoates adopts the medium chain length PHA that monomer is C6-C14.
3. Fully-degradable hydroxy fatty acid according to claim 1 is material modified, it is characterized in that: described polyisobutene PIB adopts the liquid polyisobutene that molecular weight is 3500.
4. Fully-degradable hydroxy fatty acid according to claim 1 is material modified, it is characterized in that: described maleic anhydride graft compatilizer is maleic anhydride grafted ethene acrylate copolymer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410376328.3A CN104140660A (en) | 2014-08-03 | 2014-08-03 | Full degradation PHA modified material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410376328.3A CN104140660A (en) | 2014-08-03 | 2014-08-03 | Full degradation PHA modified material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075373A (en) * | 2020-08-19 | 2022-02-22 | 国家能源投资集团有限责任公司 | Modified polyglycolic acid composition, and preparation method and application thereof |
-
2014
- 2014-08-03 CN CN201410376328.3A patent/CN104140660A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075373A (en) * | 2020-08-19 | 2022-02-22 | 国家能源投资集团有限责任公司 | Modified polyglycolic acid composition, and preparation method and application thereof |
| CN114075373B (en) * | 2020-08-19 | 2023-07-11 | 国家能源投资集团有限责任公司 | Modified polyglycolic acid composition, preparation method and application thereof |
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141112 |
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| WD01 | Invention patent application deemed withdrawn after publication |