CN1091120C - Controllable optic biological degradation vistanex mother material and preparation method thereof - Google Patents
Controllable optic biological degradation vistanex mother material and preparation method thereof Download PDFInfo
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- CN1091120C CN1091120C CN96109080A CN96109080A CN1091120C CN 1091120 C CN1091120 C CN 1091120C CN 96109080 A CN96109080 A CN 96109080A CN 96109080 A CN96109080 A CN 96109080A CN 1091120 C CN1091120 C CN 1091120C
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- vistanex
- nickel
- biological degradation
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Abstract
The present invention relates to a controllable optic biological degradation polyolefine resin mother material and a preparation method thereof. The controllable optic biological degradation polyolefine resin mother material comprises polyolefine resin, a photosensitizer, a light stabilizing agent, other compounding agents and a starch base degradation mother material. The present invention has the other aim for providing the preparation method of the controllable optic biological degradation polyolefine resin mother material. The degradation polyolefine resin mother material of the present invention is suitable for producing a degradable plastic product and is particularly suitable for producing a degradable plastic film and a packing material.
Description
What the present invention relates to is controllable optic biological degradation vistanex mother material and preparation method thereof, is applicable to produce the degradability plastics, is particularly useful for producing degradability plastics film and wrapping material.
In recent years, along with the development of petrochemical complex, synthesized polymer material was because of the performance of its various excellences and cheap price, not only replacing natural materials in a large number and widely, but also, become the requisite in people's daily life constantly seeking new Application Areas, particularly plastics.Wherein again with agricultural film and wrapping material consumption maximum.On the other hand, the raising of living standards of the people and the increase of consumption, the waste in the life is also increasing, and the discarded amount of synthetic macromolecule all increased with year.The only partially recycled utilization of these increasing wastes.What have carries out burning disposal, produces a large amount of toxic gases; What have carries out landfill disposal, and the landfill place is a big problem, and the waste behind the landfill can not decompose, and also brings harm to soil; What have then abandons in river, ocean, hill, the park consciously or unconsciously, and city, rural area and the Nature are caused severe contamination, thereby causes the very big concern of society.
In addition, this this waste itself also is the significant wastage to natural resources, makes because the overwhelming majority in these macromolecular materials is raw material with the oil.
As everyone knows; the main component of plastics is resins; if in resin, add special Synergist S-421 95; become the degradability resin; the plastics made from such resin use discarded after; having under light or the biological condition that exists and to become atoxic carbonaceous soil by natural degradation; final generate carbonic acid gas and water and return in the Nature; therefore, for the public hazards that prevent that high molecular waste material from causing, seek its natural reduction decomposition; it is died of old age with finishing; so just can solve the problem of environmental pollution that waste causes, protect the Nature, for the mankind dedicate a love to.
As in resin, adding photosensitizers, photosensitizers particle in the resin then can absorb the ultraviolet ray in the sunlight consumingly, the energy of its absorption and release is enough to cut off high molecular molecular chain, and cause the photodegradation reaction, degrade under field conditions (factors) to reach the nature reduction by the product that such degradative resin is made.
The research of degradative resin is from the seventies, its degradation pathway is to make photosensitizers with the ferrocene organism, but because the cost height of ferrocene photosensitizers, the product of making is poisonous, in use simultaneously, be difficult to control the inductive phase of product, thereby the new photosensitizers that can overcome the above-mentioned shortcoming of ferrocene is provided in the present invention.
The object of the present invention is to provide a kind of controllable optic biological degradation vistanex mother material and preparation method; this masterbatch uses a kind of new photosensitizers; this photosensitizers can be an inorganic metal compound; also use a kind of organic nickel compound to do photostabilizer in addition; the mixture of these two kinds of compounds can be made controllable biologically degraded masterbatch with polyolefin resin and other Synergist S-421 95s; its end article; as film degradation product in use farm crop are had no side effect; control product inductive phase effectively; can preserve the ecological environment; improve crop yield, and can solve the oil crisis that faces.
Controllable optic biological degradation vistanex mother material provided by the present invention comprises polyolefin resin, photosensitizers, photostabilizer.
Controllable optic biological degradation vistanex mother material provided by the present invention also comprises other Synergist S-421 95.Described Synergist S-421 95 comprises oxidation inhibitor and UV light absorber.
Controllable optic biological degradation vistanex mother material provided by the present invention can also comprise the starch-based degrading masterbatch again.
In the controllable optic biological degradation vistanex mother material provided by the present invention, described photosensitizers comprises the compound of metallic iron, nickel, cobalt, manganese, zirconium, cerium or osmium.Described metallic compound is metal oxide or salt.
In the controllable optic biological degradation vistanex mother material provided by the present invention, described photostabilizer is the organic nickel compound.
In the controllable optic biological degradation vistanex mother material provided by the present invention, described 0.36-0.52 weight part photosensitizers, the photostabilizer of the ratio of each component is: 100 weight part polyolefin resines.The weight ratio of described photosensitizers, photostabilizer is 1-1.4: 1.
In the controllable optic biological degradation vistanex mother material provided by the present invention, described starch-based degrading masterbatch accounts for 2/3rds of weight part.In the described starch-based degrading masterbatch, add the starch of 5-40 weight part in the polyolefin resin of 100 weight parts.
In the controllable optic biological degradation vistanex mother material provided by the present invention, the consumption of described oxidation inhibitor is in the polyolefin resin of 100 weight parts 1-5 weight part oxidation inhibitor to be arranged; The consumption of described UV light absorber is a 0.02-1.6 weight part UV light absorber: 100 weight part polyolefin resines.
Polyolefin resin in the controllable optic biological degradation vistanex mother material of the present invention can be base-materials such as polyethylene, polypropylene.
Photosensitizers in the controllable optic biological degradation vistanex mother material of the present invention is the compound of some metal, these metals are iron (Fe), manganese (Mn), cobalt (Co), copper (Cu), zirconium (Zr), cerium (Ce), osmium (Os), their compound can be oxide compound or salt, as Fe
2O
3, MnO
2, MnO
3, Co
2O
3, CoO
3, CuO, Zr
2O
3, Ce
2O
3, Ce
2O
4, Os
2O
3, OsO
2, OsO
3, OsO
4, KMnO
4, Mn (SO
4)
2, Co (SO
4)
2, CoMnO
4And Co (ClO
4)
2Deng, and be best to use water-fast metallic compound.
Photostabilizer in the controllable optic biological degradation vistanex mother material of the present invention is the organic nickel compound, and they are: C
1-80Alkyl sulfenyl nickel, C
1-80The organic salt of alkyl oxy nickel and nickel, wherein C
1-80Have in the alkyl and do not contain or contain one or more heteroatomss, for example oxygen, sulphur, nitrogen, phosphorus etc., preferred organic nickel compound is: N, the amino tetracosane oxygen of the two octadecyls of N-base nickel, N, the amino tetracosane sulfenyl of the two octadecyls of N-nickel, two (3,5-di-t-butyl-4-hydroxyl monoethyl phosphate) nickel, 2,2 '-thiobis (uncle's 4-octyl phenol oxygen base) nickel-2 ethyl hexylamine complex compound, 2,2 '-thiobis (uncle's 4-octadecyl phenol oxygen base) nickel, N, N ,-two C
1-80Alkyl dithiocarbamic acid nickel (C wherein
1-80Alkyl can not contain or contain one or more heteroatomss, as oxygen, sulphur, nitrogen, phosphorus etc.) and resinous acid nickel and nickel naphthenate etc.
For controlling the photodegradation process of plastics more accurately, can regulate the consumption of metallic compound and organic nickel compound on request, with the degradation time of decision plastics.For 100 weight part polyolefin resines, the gross weight of the two is the 3-12 weight part.The weight ratio of metallic compound and organic nickel compound is 1-1.4: 1.
The oxidation inhibitor component that is contained in the controllable optic biological degradation vistanex mother material of the present invention is a phenolic compound, and they are: 1-hydroxy-3-methyl-4-isopropyl benzene, 2,6 ditertiary butyl p cresol etc.In the polyolefin resin of 100 weight parts, the consumption of oxidation inhibitor is the 1-5 weight part.
The preferred salicylate of UV light absorber component, benzophenone, the benzotriazole compound that are contained in the controllable optic biological degradation vistanex mother material of the present invention.For 100 weight part polyolefin resines, the consumption of UV light absorber is the 0.02-1.6 weight part, and the 0.1-1.5 weight part is best.The UV light absorber that masterbatch of the present invention uses in dosing resin after, in the usage period, can absorb ultraviolet ray, suppress or weaken the photodegradation except that having, and after the usage period, gene wherein can become again the effective photosensitizers of high-molecular optical DeR, helps biological degradation.
In order to reach degraded fully, controllable optic biological degradation vistanex mother material of the present invention can also mix with the starch-based degrading masterbatch, and its ratio of mixture is 1: 2 (weight ratio).In the starch-based degrading mother liquor, the polyolefin resin of 100 weight parts adds the starch of 5-40 weight part.
Polyolefin resin of the present invention, photosensitizers, photostabilizer, oxidation inhibitor, UV light absorber are mixed with mixture in proportion, and processing to become controllable optic biological degradation vistanex mother material of the present invention again.
Controllable optic biological degradation vistanex mother material of the present invention is said polyolefins resin concentrates mixture to be opened refining by Banbury mixer banburying, mill and tablets press carries out granulation and forms.
Specifically will add by the masterbatch mixture that prescription prepares in the Banbury mixer; the plasticating temperature of close machine remains in 140 ℃ of-160 ℃ of scopes; pressure-controlling is at 6-9Pa; discharging after 10-20 minute; and send into through conveying belt between two rollers of mill; 100 ℃-130 ℃ of the blanket roller temperature of mill; back roller temperature is controlled at 105 ℃-135 ℃; play the triangle bag repeatedly, following sheet after 20 minutes, the width of tablet is controlled at 9-10cm; be cooled to 20 ℃-30 ℃; send into again and carry out granulation in the tablets press, air-cooled pelletizing, it is good to make inner quality at last; outward appearance is good; the controllable optic biological degradation vistanex mother material of the present invention of color and luster.
In the preparation processing of controllable optic biological degradation vistanex mother material of the present invention, the effect characteristics of Banbury mixer are: masterbatch mixture is carried out thermoplastication, make the material uniform mixing; The processing of mill is that to carry out secondary plasticizing mixing, and discharges moisture content and volatile gases in the material, in case during the major structure grain, produce bubble; Carry out granulation by tablets press, in granulator, the rotating speed of screw rod is slow as best one can, to avoid destroying granulation because of shearing knife up.
For the effect of controllable optic biological degradation vistanex mother material of the present invention is described, with the masterbatch of different ingredients with after polyolefin base material mixes, again through extruding, blown film, batching and make the controllable optic biological degradation vistanex film.
Embodiment 1
In the polyvinyl resin base-material of 100 weight parts, add the 1# photosensitizers of 0.4 weight part, the 7# photosensitizers (Fe of 3.5 weight parts
2O
3, MnO
2, MnO
3, Co
2O
3, CoO
3, CuO, Zr
2O
3, ZrO
2, Ce
2O
3, Ce
2O
4, Os
2O
3, OsO
2, OsO
3, OsO
4, KMnO
4, Mn (SO
4)
2, Co (SO
4)
2, CoMnO
4And Co (ClO
4)
2Form), the N of 3.5 weight parts, the amino tetracosane oxygen of the two octadecyls of N-base nickel, the benzophenone of 1 weight part, the 2,6 ditertiary butyl p cresol of 1 weight part is made controllable optic biological degradation vistanex mother material mixture of the present invention.
Method is to add in this mixture in the Banbury mixer; the banburying temperature is 160 ℃; pressure is 8Pa; discharging after 15 minutes; send into mill through conveying belt; the preceding roll temperature of mill is 110 ℃; back roll temperature is 125 ℃; sheet under after 20 minutes is cooled to 20-30 ℃, sends into tablets press; the tablets press temperature is respectively 140 ℃, 170 ℃, 170 ℃, 150 ℃, 150 ℃ from hopper to heading; screw speed is 40 rev/mins, through air-cooled pelletizing, then obtains controllable optic biological degradation vistanex mother material of the present invention.
With this master batch material of 5 weight parts, the end article film that the polyvinyl resin of 95 weight parts is made, be 60-70 days its outdoor inductive phase, and be 360 days indoor inductive phase.
Embodiment 2
In the polyvinyl resin base-material of 100 weight parts, the 2# photosensitizers (identical) that adds 4.5 weight parts with embodiment 1,3.5 two (3 of weight part, 5-di-t-butyl-4-hydroxyl monoethyl phosphate) nickel, 2.5 the 1-of weight part hydroxy-3-methyl-4-isopropyl benzene is made controllable optic biological degradation vistanex mother material mixture of the present invention.Its close material, open refining, granulation process is identical with embodiment 1, thereby make masterbatch of the present invention.
With this masterbatch of 5 weight parts, the final product film that the polyvinyl resin of 95 weight parts is made, be 65-75 days its outdoor inductive phase, be 360 days indoor inductive phase.
Embodiment 3
The prescription of masterbatch and preparation method be with embodiment 1, and with the film that the polyvinyl resin of the starch-based degrading masterbatch of this masterbatch of 5 weight parts and 10 weight parts, 85 weight parts is made, be 55-60 days its outdoor inductive phase, and be 360 days indoor inductive phase.
Can find out that by embodiment the film that controllable optic biological degradation vistanex mother material of the present invention is made not only has reliable and stable degraded inductive phase, resolves into carbonic acid gas and water after the use, has reduced the pollution to environment.
Claims (7)
1, a kind of controllable optic biological degradation vistanex mother material is characterized in that comprising polyolefin resin, photosensitizers, photostabilizer;
Wherein said 0.36-0.52 weight part photosensitizers, the photostabilizer of the ratio of each component is: 100 weight part polyolefin resines;
The weight ratio of described photosensitizers, photostabilizer is 1-1.4: 1, and described photosensitizers comprises the metal oxide or the salt of metallic iron, nickel, cobalt, manganese, zirconium, cerium or osmium, described photostabilizer is the organic nickel compound;
Described polyolefin resin comprises polyethylene or polypropylene.
2, controllable optic biological degradation vistanex mother material according to claim 1 is characterized in that also comprising oxidation inhibitor and UV light absorber.
3, controllable optic biological degradation vistanex mother material according to claim 2, it is characterized in that described oxidation inhibitor is 1-hydroxy-3-methyl-4-isopropyl benzene, 2,6-ditertbutylparacresol, consumption are in the polyolefin resin of 100 weight parts 1-5 weight part oxidation inhibitor to be arranged; Described UV light absorber is salicylate, benzophenone, benzotriazole compound, and consumption is a 0.02-1.6 weight part UV light absorber: 100 weight part polyolefin resines.
4, according to the controllable optic biological degradation vistanex mother material described in claim 1 or 2, it is characterized in that also comprising the starch-based degrading masterbatch, account for 2/3rds of total weight parts; In the described starch-based degrading masterbatch, add the starch of 5-40 weight part in the polyolefin resin of 100 weight parts.
5, controllable optic biological degradation vistanex mother material according to claim 1 is characterized in that described oxide compound or salt are Fe
2O
3, MnO
2, MnO
3, Co
2O
3, CoO
3, Zr
2O
3, Ce
2O
3, Ce
2O
4, Os
2O
3, OsO
2, OsO
3, OsO
4, KMnO
4, Mn (SO
4)
2, Co (SO
4)
2, CoMnO
4And Co (ClO
4)
2
6, controllable optic biological degradation vistanex mother material according to claim 1, it is characterized in that described organic nickel compound is: N, the amino tetracosane oxygen of the two octadecyls of N-base nickel, N, the amino tetracosane sulfenyl of the two octadecyls of N-nickel, two (3,5-di-t-butyl-4-hydroxyl monoethyl phosphate) nickel, 2,2 '-thiobis (uncle's 4-octyl phenol oxygen base) nickel-2 ethyl hexylamine complex compound, 2,2 '-thiobis (uncle's 4-octadecyl phenol oxygen base) nickel, N, N ,-two C
1-80Alkyl dithiocarbamic acid nickel and resinous acid nickel and nickel naphthenate; C wherein
1-80Alkyl does not contain or contains the one or more heteroatomss in aerobic, sulphur, nitrogen, the phosphorus.
7; a kind of method for preparing the described controllable optic biological degradation vistanex mother material of claim 1; it is characterized in that: will add by the masterbatch mixture that prescription prepares in the Banbury mixer; the plasticating temperature of Banbury mixer remains in the 140-160 ℃ of scope; pressure-controlling is at 6-9Pa; discharging after 10-20 minute; and send into through conveying belt between two rollers of mill; 100-130 ℃ of the blanket roller temperature of mill, back roller temperature are controlled at 105-135 ℃, play the triangle bag repeatedly; sheet under after 20 minutes; the width of tablet is controlled at 9-10cm, is cooled to 20-30 ℃, sends into and carries out granulation in the tablets press; the degradation polyolefin resin concentrates is made in air-cooled pelletizing at last.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109080A CN1091120C (en) | 1996-08-22 | 1996-08-22 | Controllable optic biological degradation vistanex mother material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109080A CN1091120C (en) | 1996-08-22 | 1996-08-22 | Controllable optic biological degradation vistanex mother material and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1174856A CN1174856A (en) | 1998-03-04 |
| CN1091120C true CN1091120C (en) | 2002-09-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109080A Expired - Fee Related CN1091120C (en) | 1996-08-22 | 1996-08-22 | Controllable optic biological degradation vistanex mother material and preparation method thereof |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062573C (en) * | 1998-04-14 | 2001-02-28 | 陈锡隆 | Light degradable polypropylene as food package material |
| CN103642110B (en) * | 2013-11-18 | 2015-12-09 | 西南科技大学 | A kind of photo-thermal works in coordination with controlled degradation mulch film and preparation method thereof |
| CN103642109B (en) * | 2013-11-18 | 2015-12-02 | 西南科技大学 | Photo-thermal works in coordination with controlled degradation polymer composite master batch and preparation method thereof |
| CN106905583A (en) * | 2017-03-07 | 2017-06-30 | 王育钦 | A kind of use agricultural by-products are close degradable synthetic resin of ambient time regulation type of raw material and preparation method thereof |
| CN112646231A (en) * | 2020-12-28 | 2021-04-13 | 惠州市冠展实业有限公司 | Photooxidation biodegradation modifier |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090300A (en) * | 1993-12-27 | 1994-08-03 | 中国科学院上海有机化学研究所 | A kind of controllably graded polyolefine plastics, manufacturing and application that contains aminoalkyl ferrocene derivative |
-
1996
- 1996-08-22 CN CN96109080A patent/CN1091120C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090300A (en) * | 1993-12-27 | 1994-08-03 | 中国科学院上海有机化学研究所 | A kind of controllably graded polyolefine plastics, manufacturing and application that contains aminoalkyl ferrocene derivative |
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| Publication number | Publication date |
|---|---|
| CN1174856A (en) | 1998-03-04 |
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