CN101735636A - Biodegradation time controlled plastic film and preparation method thereof - Google Patents
Biodegradation time controlled plastic film and preparation method thereof Download PDFInfo
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- CN101735636A CN101735636A CN200810072099A CN200810072099A CN101735636A CN 101735636 A CN101735636 A CN 101735636A CN 200810072099 A CN200810072099 A CN 200810072099A CN 200810072099 A CN200810072099 A CN 200810072099A CN 101735636 A CN101735636 A CN 101735636A
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Abstract
The invention discloses a biodegradation time controlled plastic film and a preparation method thereof. The biodegradation time controlled plastic film can be prepared through a blow molding method or a tape casting method; and the biodegradation time controlled plastic film mainly comprises a degradative resin and a time controlled soft antibacterial agent. The soft antibacterial agent is a long-chain quaternary ammonium compound consisting of three parts, namely long-chain alkyl, an easily-adjusted spacer and a terminal polar group (quaternary ammonium salt), and the inactivation half-life thereof at the temperature of 60 DEG C is at least more than 3h.
Description
Technical field
The present invention relates to biodegradation time controlled plastic film and preparation method thereof.
Background technology
Along with the development of country, the progressively raising of living standards of the people, the people's health perception and the consciousness of environment protection strengthened day by day.Create comfortable, cleaning, antibacterial and mouldproof, life, study and the Working environment of propagating that ward off disease be the pursuit that people make earnest efforts.But product abandonment thing automated biological degraded, free from environmental pollution also be an urgent demand of present international environmental protection cause.But, follow people when improving own living environment, also created favourable condition for the breeding growth of microorganism, bacterium.Because it is not biodegradable that major part derives from the plastics of oil, therefore so-called " white pollution " increases the weight of day by day, exerts heavy pressures on to the environment that we depend on for existence.
Biodegradable material (plastics) is an important component part of environmental engineering.The domestic degradation material of scale operation that can realize mainly contains at present: polyhydroxy acid ester (PHA), PBS (poly butylene succinate), PLA (poly(lactic acid)), PCL (polycaprolactone), PPC (polycarbonate), PVA (polyvinyl alcohol), TPS (thermoplastic starch), Ecoflex resin etc.These degredation plastic degraded products are carbonic acid gas and water, can not produce any detrimentally affect to environment, have excellent biological compatibility and Bioabsorbable in addition, have wide practical use in fields such as food product pack, fibrous woven, daily plastic, medical embedded material or tissue engineering materials.
But above-mentioned Biodegradable material is vulnerable to the influence of pathogenic bacterias such as bacterium and mould.Bacterium and mould are two kinds of main types of microorganism, have characteristics of a great variety, that distributed pole is wide, vitality is vigorous.When envrionment conditions be relative 65%, temperature between the 20-30 degree, the pH value is under the slightly acidic condition, will absorb the growth of nourishing and generating rapidly, cause material to go mouldy and destroy.The formed mycelium of bacterial growth is a conductor, and material insulation property is descended.The formed metabolite of mould-growth contains organic acid and mycin, can make that being clamminess appears in product surface, variable color, phenomenon such as become fragile, and can make that also the people of long-term these mould curd products of contact goes down with.
For fear of bacterium and mould to stating Biodegradable material and human influence, therefore research and development have antibiotic, " anti-biotic material " sterilizing function become one of focus of new and high technology, novel material research and development.The antiseptic-germicide that the antibacteria degradation material uses generally has: organic antibacterial agent, inorganic antiseptic and complex antimicrobials.Wherein organic antibacterial agent comprises: natural organic microbial inoculum (chitosan, chitosan derivatives), synthetic organic antibacterial agent (comprising low molecule organic antibacterial agent and polymer organic antibacterial agent), low molecule organic antibacterial agent (quaternary amine, diquaternary amine salt, season phosphonium salt, two season phosphonium salt, organotin, halogenated amine, Guanoctine etc.), polymer organic antibacterial agent (poly-quaternary ammonium salt, poly-diquaternary amine salt, poly-phosphonium salt, poly-double focusing phosphonium salt), inorganic antiseptic (nano-antibacterial metal powder, antibacterial metal ions and compound thereof), complex antimicrobials (organic antibacterial agent and inorganic resistance agent are compound).
For example, CN100376626C discloses a kind of perfume antibacteria degradation polyolefin composition and manufacture method and purposes, wherein the biological degradation material is mixed the formation perfume antibacteria degradation polyolefin composition with antiseptic-germicide etc., prepare film article or bonded fabric product with said composition, be used for preservative film, freshness protection package, food pack and disposable absorbent article etc.Wherein antiseptic-germicide is selected from zeolite, imidazoles, pyridine etc.
For example, CN100410323C discloses a kind of anti-bacterium mildew-proof biodegradable polylactic acid foam plastic and preparation method thereof, wherein polylactic resin etc. is mixed then with antibacterial and mouldproof masterbatch etc. and extrudes and make with screw extrusion press.Wherein antiseptic-germicide is to adopt silver ions, zine ion, cupric ion, nano titanium oxide etc., and mould inhibitor adopts m-tetrachlorophthalodinitrile, derosal, thiabendazole etc.
It is the uncontrollable material of degradation time that but the defective of above-mentioned prior art is above-mentioned antibacterial biological degradable material, the degradation speed that is the antibacterial biological degradable material is difficult to control, before the time limit of service no show of antibacterial biological degradable material, just may degrade so, make the use properties of antibacterial biological degradable material descend, bacterium and mould can make that being clamminess appears in product surface, variable color, phenomenon such as become fragile, and the people who contacts these mould curd products for a long time has an aptitude to disease, thereby can cause detrimentally affect to the mankind.
Summary of the invention
For the uncontrollable problem of the degradation time that solves biodegradable material of the prior art the present invention is proposed.The present invention relates to biological degradation time controllable type degradation plastic film and preparation method thereof.The present invention reaches the controllability to the degradation plastic film degradation time by adjusting kind, the quantity that adds soft antiseptic-germicide.
The biological degradation time controllable type degradation plastic film that the present invention proposes can be by blow moulding or casting method preparation, this biological degradation time controllable type degradation plastic film mainly is made up of degradative resin and soft antiseptic-germicide and other auxiliary agents, and this biological degradation time controllable type degradation plastic film has following two kinds of preparation methods:
First kind of preparation method is: with PBS (poly butylene succinate), PLA (poly(lactic acid)), PCL (polycaprolactone), PHB (poly-beta-hydroxy-butanoic acid ester), PHBV (polyhydroxybutyrate valeric acid multipolymer), PPC (polycarbonate), PVA (polyvinyl alcohol), TPS (thermoplastic starch), at least a in the Ecoflex resin mixes in high-speed mixer according to certain ratio, adding a certain amount of auxiliary agent stirs, mix stirring with soft antiseptic-germicide again, then at single screw rod or twin screw extruder extruding pelletization, form the granulation particle, then the granulation particle is made film with blowing or casting technique.
Second kind of preparation method is: with at least a and other auxiliary agents in PBS (poly butylene succinate), PLA (poly(lactic acid)), PCL (polycaprolactone), PHB (poly-beta-hydroxy-butanoic acid ester), PHBV (polyhydroxybutyrate valeric acid multipolymer), PPC (polycarbonate), PVA (polyvinyl alcohol), TPS (thermoplastic starch), the Ecoflex resin according to certain mixed, mix with soft antiseptic-germicide again after the mixing, utilize blowing or casting technique to make film then.
The high-speed mixer rotating speed is 100-2500rpm, is preferably 300-1600rpm, and temperature is 125 ± 5 ℃, each churning time 10-30 minute;
Blowing or casting technique are the processes well known in this area.
Biological degradation time controllable type degradation plastic film of the present invention mainly is made up of degradative resin and soft antiseptic-germicide.Wherein in this biological degradation time controllable type degradation plastic film by weight percentage degradative resin account for 23-87%, soft antiseptic-germicide is 0.3-8%, other is an auxiliary agent.
Auxiliary agent comprises at least a in dispersion agent, coupling agent, weighting agent, softening agent, oxidation inhibitor, the lubricant.
Described dispersion agent comprises at least a in paraffin oil, polyethylene wax, oxidized polyethlene wax, stearate soap class, lipid acid lipid and the fatty acyl amide.
Described coupling agent comprises one or more in butyleneglycol, tolylene diisocyanate, xylylene diisocyanate, diphenylmethanediisocyanate, the aluminium titanium composite coupler.
Described weighting agent comprises at least a in lime carbonate, talcum powder, the titanium dioxide.
Described softening agent is at least a in glycerine, mono-glycerides, sorbyl alcohol, the stearic acid.
Described antioxidant is (2, the 4-di-tert-butyl-phenyl) tris phosphite, 4-hydroxyl-2, at least a in 6-DI-tert-butylphenol compounds, four [methyl-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, orcin (BHT), Tyox B, pyrocatechol, the Resorcinol.
Described lubricant is at least a in polyethylene wax, calcium stearate, Zinic stearas, the naphthenic oil.
The Young's modulus of biodegradation time controlled plastic film of the present invention is 50-300Mpa, and tensile strength is 10-30Mpa, and elongation at break is 320-360%.Adding kind by regulating soft antiseptic-germicide, add the degradation time that quantity can the control degradation plastics film.
In the present invention, softening compound also is defined as biologically active substance, promptly biologically active and easily in vivo with environment in biological degradation be nontoxic, environment amenable material.The biodegradable quaternary ammonium compound that described soft antiseptic-germicide the is biologically active MIC＜10 μ g/mL of gram-positive microorganism (promptly to), above-mentioned quarternary ammonium salt compound is made up of spacer, terminal polar group three parts of long chain alkane base, easily adjusting, and the inactivation transformation period in the time of 60 ℃ is greater than 3h.The terminal polar group of described soft antiseptic-germicide is pyridine or part small molecules three alkanes quaternary ammonium salts, and described small molecules three alkanes quaternary ammonium salts are trimethylammonium, triethyl, three normal-butyl quaternary ammonium salts.Soft antiseptic-germicide inactivation just means that its anti-microbial effect lost efficacy, and the wherein soft antiseptic-germicide inactivation transformation period can be embodied its degradation time, and then degradable film just begins degraded, reaches the controlled purpose of degradation time.
Above-mentioned quarternary ammonium salt compound have degradable-CONH-and-COO-, easily degrade by enzyme effect or chemical action, product is nontoxic.This class antiseptic-germicide has enough chemical stabilities, thereby can guarantee its long lasting antibacterial effect.The long chain quaternary derivative that above-mentioned soft antiseptic-germicide is a series of structurally variables (so-called soft resemblance).The antibacterial effect of this class material is better, anti-microbial activity is stronger, chemical stability is good.Wherein, the selected structural unit of above-mentioned soft antiseptic-germicide partly derives from ocean ester class, and this ester compound has the spacer of polarity quaternary ammonium salt as end group and the adjusting of easy-to-use chemical process.
The biodegradable quaternary ammonium compound of the selected biologically active of the present invention is made up of different quaternary ammonium salt end groups, spacer, oleophylic alkyl chain.The major portion of this compounds is by natural structural unit synthetic, as: lipid acid, alcohols, amine.The end group of this compounds is the small molecules three alkanes quaternary ammonium salts (as: trimethylammonium, triethyl, three normal-butyls) of pyridine or part, spacer selects to contain the ester class or the amine of 1～3 carbon atom, and it is 12～18 long-chain (this class alkyl chain has best biological activity) that the oleophylic alkyl chain is mainly selected carbonatoms.And spacer groups is designed to mutability, so that the synthetic compound easily is degraded into nontoxic structural unit by chemical action and biological enzyme effect.Be the synthetic route and the degraded route of the soft antiseptic-germicide of quaternary ammonium salt below:
R＝CH
3?serie?1?X＝Br?or?Cl，n＝1-3，m＝0-16，Y＝NH、OH?or?COOH
R＝CH
2CH
3 2?Z＝COO?or?CONH
R＝Pyridine 3
R＝(CH
2)
3CH
3?4
Formula 1: the synthetic route of the soft antiseptic-germicide of quaternary ammonium salt and degraded route
The biodegradable quaternary ammonium compound that draws above-mentioned biologically active is to have passed through uncountable test to draw.The anti-microbial activity of above-mentioned quarternary ammonium salt compound is better than the anti-microbial activity of its parent sclerosis compound (ceepryn (3a) and chlorination alkyl dimethyl benzyl amine (5)), and more high temperature resistant than other general antiseptic-germicide.And in preparation and degradation process issuable all free fatty acidies, possible degraded product, synthesize in used solvent etc. can ignore to the influence of anti-microbial activity (MIC＞250 μ g/mL).Therefore, the anti-microbial activity of quarternary ammonium salt compound is relevant with the antimicrobial characteristic of compound itself as can be known, rather than by in the compound impurity or its degraded product produced.Above-mentioned quaternary ammonium salt compound shows very high antiviral activity, and to the Vero cell without any toxicity.
This paper has carried out the research of accelerated degradation in pH is 6.0 and 60 ℃ water buffered soln, the structure of spacer and lipophilicity are very big to following quarternary ammonium salt compound influence as can be known, be that this compounds depends on how variable spacer couples together alkane chain and tri alkyl quaternary ammonium salt group, then influence not quite by the quarternary ammonium salt compound that changes alkane chain length.With two types agar the stability of quarternary ammonium salt compound is studied, the result is as broad as long.Is 6.0 o'clock at 60 ℃ with pH, and its apparent degradation rate and relative rate just are equivalent to the transformation period of quarternary ammonium salt compound.Wherein, the selected active quarternary ammonium salt compound transformation period (t1/2) is at least 3h in the time of 60 ℃, and that have is 7h, and the transformation period of the active quarternary ammonium salt compound that has in the time of 37 ℃ is up to 36h.Therefore can select having the quarternary ammonium salt compound that said structure forms, thereby decide the degradation time of its controllability according to its transformation period.Even selected quarternary ammonium salt compound has enough lipophilicities, still, compound has only better chemical stability, and the enough antibiotic time just can be arranged, and its antibacterial effect is only fully like this.Therefore, the lipophilicity that further improves compound can not improve its anti-microbial activity.And when the carbonatoms in the long alkyl chain surpasses 18, the anti-microbial activity of compound will reduce.
This paper studies alkyl chain with different lengths, different quaternary ammonium salt terminal polar group and the quarternary ammonium salt compound of different interval base.Wherein, selected to have the quarternary ammonium salt compound of following characteristics, be that sterilization effect is very good, and, the antiseptic-germicide that the synthetic activity the is the strongest MIC＜10 μ g/mL of gram-positive microorganism (promptly to), it generally has following characteristics: the carbonatoms in the alkyl chain is 12～18, the inactivation transformation period in the terminal polar group (end group is the small molecules quaternary ammonium salt preferably), 60 ℃ of aqueous solution is not less than 3h.The result shows, these quarternary ammonium salt compounds can substitute the antiseptic-germicide that uses at present, not only environmentally friendly, and multifunctional usages such as infection with inhibition bacterium and virus, and the most important thing is that under microbial process these quarternary ammonium salt compounds are that soft antiseptic-germicide is degraded in the regular hour, the degraded of degradative plastics material just can take place after the above-mentioned soft antiseptic-germicide degraded, can in the time limit of service of material, just not degrade, thereby reach controlled purpose of the time of being degraded to.Having the quarternary ammonium salt compound of stating on the dedicated half-life according to the desirable degradation time of biological degradation time controllable type film and selection, to reach degradation of plastic film be controlled purpose of time.
Time controllability degradative plastics material of the present invention is under microbial process, in the controlled soft antiseptic-germicide degraded of inner control time regular hour, the above-mentioned time, the degraded of controllability degradative plastics material just can take place afterwards in controlled soft antiseptic-germicide degraded, can in the time limit of service of material, just not degrade, thereby reach controlled purpose of the time of being degraded to.This time controllability degradative plastics material produce technology is simple, and hygienic safety meets national standard and industry standard, can pass through the ISO14855 standard detection, degradation time is controlled, and complete biodegradable, environment is not worked the mischief after the degraded, compliance with environmental protection requirements, market outlook are wide.
Embodiment
Below will further describe the present invention by embodiment.In an embodiment, mark and per-cent is all by weight except as otherwise noted.But the present invention is not limited to these examples.Those skilled in the art can content according to the present invention do some unsubstantialities improvement and adjustment to the present invention.But the technical scheme after above-mentioned improvement and the adjustment still falls within the scope of protection of the present invention.
Embodiment 1
The PLA (poly(lactic acid)) of PBS (poly butylene succinate), the 26wt% of 70wt% and dispersion agent, the 1wt% coupling agent of 1wt% are placed high-speed mixer (rotating speed 1600rpm, 125 ℃ of temperature) stir after 10 minutes, the soft antiseptic-germicide, the 0.5wt% oxidation inhibitor that add 1.5wt% again mix and stirred 5 minutes.And then evenly back feeding twin screw extruder extrude, pelletizing, drying, packing.
The particle that to make is made film by blowing or casting technique then.
Embodiment 2
TPS (thermoplastic starch), the 7wt%PLA (poly(lactic acid)) of Ecoflex, the 25wt% of the BASF of 50wt% and the softening agent of 15wt% are placed high-speed mixer (rotating speed 1800rpm, 130 ℃ of temperature) stir after 10 minutes, the soft antiseptic-germicide, the 0.5wt% oxidation inhibitor that add 2.5wt% again, high-speed mixing stirred 5 minutes.And then evenly back feeding twin screw extruder extrude, pelletizing, drying, packing.
The particle that to make is made film by blowing or casting technique then.
Embodiment 3
The dispersion agent of PBS (poly butylene succinate), 15%PCL, 15wt%PHBV (polyhydroxybutyrate valeric acid multipolymer) and the 1wt% of 65wt% is placed high-speed mixer (rotating speed 1800rpm, 130 ℃ of temperature) stir after 10 minutes, add soft antiseptic-germicide, the 0.5wt% oxidation inhibitor high-speed stirring 5 minutes of 3.5wt% again.And then behind the uniform mixing feeding twin screw extruder extrude, pelletizing, drying, packing.
The particle that to make is made film by blowing or casting technique then.
Embodiment 4
In the weighting agent of PBS (poly butylene succinate), the 42wt% of 50wt%, 1wt% dispersion agent, the 5wt% lubricant one or more are placed high-speed mixer (rotating speed 1800rpm, 130 ℃ of temperature) stir after 10 minutes, the soft antiseptic-germicide and the 0.5wt% oxidation inhibitor that add 1.5wt% again mixed high-speed stirring 5 minutes, and then behind the uniform mixing feeding twin screw extruder extrude, pelletizing, drying, packing.
The particle that to make is made film by blowing or casting technique then.
The present invention reaches the controllability to the degradable film degradation time by adjusting kind, the quantity that adds soft antiseptic-germicide, guarantees the use properties of film product in time limit of service.Simple in production process operation of the present invention, production unit is less demanding, and the film market outlook are wide.Overcome in the prior art defective of Biodegradable film in the past: it is the uncontrollable film of degradation time, film degradation speed is difficult to control, film may be degraded in time limit of service and be made the use properties of film descend, and the use properties of film is caused very big loss.This time controllability degradable film can be used for holder in food product pack, Industrial products, the electronic product, medical treatment and sanitary product and other disposable materials used.To those skilled in the art; the foregoing description only is exemplary; and be not determinate; those skilled in the art are after reading content of the present invention; can carry out various changes and modification to the present invention, but the technical scheme of various changes of above-mentioned process and modification falls within the scope of protection of the present invention still.Protection scope of the present invention is limited by claim.
Claims (14)
1. biodegradation time controlled plastic film, it is characterized in that biodegradation time controlled plastic film mainly is made up of degradative resin and soft antiseptic-germicide, wherein in this biodegradation time controlled plastic film by weight percentage degradative resin account for 23-87%, soft antiseptic-germicide is 0.3-8%, and other is an auxiliary agent.
2. biodegradation time controlled plastic film according to claim 1 is characterized in that described soft antiseptic-germicide is by long chain alkane base, the spacer of easily regulating, the long chain quaternary compound that terminal polar group three parts are formed.
3. biodegradation time controlled plastic film according to claim 2 is characterized in that the carbonatoms in the alkyl chain of described soft antiseptic-germicide is 12-18.
4. biodegradation time controlled plastic film according to claim 2, the terminal polar group that it is characterized in that described soft antiseptic-germicide are pyridine or part small molecules three alkanes quaternary ammonium salts.
5. according to claim 2,3 or 4 described biodegradation time controlled plastic films, it is characterized in that the inactivation transformation period of described soft antiseptic-germicide in 60 ℃ of aqueous solution is not less than 3h.
6. according to claim 2,3 or 4 described biodegradation time controlled plastic films, it is characterized in that the inactivation transformation period of described soft antiseptic-germicide in 37 ℃ of aqueous solution is 36h.
7. biodegradation time controlled plastic film according to claim 1 is characterized in that described degradative resin is: at least a in poly butylene succinate (PBS), poly(lactic acid) (PLA), polycaprolactone (PCL), poly-beta-hydroxy-butanoic acid ester (PHB), polyhydroxybutyrate valeric acid multipolymer (PHBV), polycarbonate (PPC), polyvinyl alcohol (PVA), thermoplastic starch (TPS), the Ecoflex resin.
8. biodegradation time controlled plastic film according to claim 1 is characterized in that described auxiliary agent comprises at least a in dispersion agent, coupling agent, weighting agent, softening agent, oxidation inhibitor, the lubricant.
9. biodegradation time controlled plastic film according to claim 7 is characterized in that described dispersion agent comprises one or more in paraffin oil, polyethylene wax, oxidized polyethlene wax, stearate soap class, lipid acid lipid and the fatty acyl amide; Described coupling agent comprises at least a in butyleneglycol, tolylene diisocyanate, xylylene diisocyanate, diphenylmethanediisocyanate, the aluminium titanium composite coupler; Described weighting agent comprises at least a in lime carbonate, talcum powder, the titanium dioxide; Described softening agent is one or more in glycerine, mono-glycerides, sorbyl alcohol, the stearic acid; Described antioxidant is (2, the 4-di-tert-butyl-phenyl) tris phosphite, 4-hydroxyl-2, in 6-DI-tert-butylphenol compounds, four [methyl-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, orcin (BHT), Tyox B, pyrocatechol, the Resorcinol one or more; Described lubricant is at least a in polyethylene wax, calcium stearate, the Zinic stearas.
10. biodegradation time controlled plastic film according to claim 1, the Young's modulus that it is characterized in that described biodegradation time controlled plastic film is 50-300Mpa, tensile strength is 10-30Mpa, and elongation at break is 320-360%.
11. preparation method as the described biodegradation time controlled plastic film of each claim of claim 1-10, it is characterized in that: with poly butylene succinate (PBS), poly(lactic acid) (PLA), polycaprolactone (PCL), poly-beta-hydroxy-butanoic acid ester (PHB), polyhydroxybutyrate valeric acid multipolymer (PHBV), polycarbonate (PPC), polyvinyl alcohol (PVA), thermoplastic starch (TPS), the at least a of Ecoflex resin mixes in high-speed mixer according to certain ratio, adding a certain amount of auxiliary agent stirs, mix stirring with soft antiseptic-germicide again, then at single screw rod or twin screw extruder extruding pelletization, form the granulation particle, then the granulation particle is made film with blowing or casting technique, wherein in mixture by weight percentage degradative resin account for 23-87%, time, controlled soft antiseptic-germicide was 0.3-8%, and other is an auxiliary agent.
12. preparation method as each claim of claim 1-10 controllability degradation plastic film of described time, it is characterized in that: with poly butylene succinate (PBS), poly(lactic acid) (PLA), polycaprolactone (PCL), poly-beta-hydroxy-butanoic acid ester (PHB), polyhydroxybutyrate valeric acid multipolymer (PHBV), polycarbonate (PPC), polyvinyl alcohol (PVA), thermoplastic starch (TPS), at least a in the Ecoflex resin mixes in high-speed mixer according to certain ratio according to certain mixed, adding a certain amount of auxiliary agent stirs, mix stirring with controlled soft antiseptic-germicide of time again, utilize blowing or casting technique to make film then, wherein in mixture by weight percentage degradative resin account for 23-87%, soft antiseptic-germicide is 0.3-8%, and other is an auxiliary agent.
13. preparation method according to claim 11 is characterized in that the high-speed mixer rotating speed is 100-2500rpm, temperature is 125 ± 5 ℃, and each churning time is 10-30 minute.
14. preparation method according to claim 12 is characterized in that the high-speed mixer rotating speed is 100-2500rpm, temperature is 125 ± 5 ℃, and each churning time is 10-30 minute.
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