CN85100494A - The light-sensitive catalyst and the purposes that are used for photodegradative polyethylene film - Google Patents
The light-sensitive catalyst and the purposes that are used for photodegradative polyethylene film Download PDFInfo
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- CN85100494A CN85100494A CN85100494.6A CN85100494A CN85100494A CN 85100494 A CN85100494 A CN 85100494A CN 85100494 A CN85100494 A CN 85100494A CN 85100494 A CN85100494 A CN 85100494A
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- ferrocene
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- sensitive catalyst
- carboxylic acid
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Abstract
The invention belongs to the light-sensitive catalyst and the purposes of photodegradative polyethylene film.This light-sensitive catalyst is that the molecule formula is
Long-chain substituting group ferrocene deriv, R ' in the formula=H or R, R=C
7-C
11Alkyl, thiazolinyl, carboxylic acid group, carboxylic acid ester groups, or COR " and R " is C
6-C
10Alkyl, thiazolinyl, carboxylic acid group or carboxylic acid ester groups.This class light-sensitive catalyst with one or two or more kinds can be produced the controlled photodegradable polyethylene film, and the addition of catalyzer is 0.01-0.5% (weight).Film thickness is the 3-15 micron, and this photodegradation film can be used as the farm crop covering with plastic film.
Description
The invention relates to light-sensitive catalyst and the purposes of making the controlled photodegradable polyethylene film.Furtherly, the invention relates to long-chain substituting group ferrocene deriv light-sensitive catalyst and be used to produce the controlled photodegradable polyethylene film that contains this class light-sensitive catalyst.
The application of polyethylene film on agricultural proposed requirement opposite aspect two to it, promptly for topped as frame film or small area farm crop, wishes to prolong the work-ing life of film, to obtain bigger economic benefit; On the other hand, topped for the big area farm crop, or ground extensively lacks labour's area, then wishes to use controlled photodegradable film as thin as a wafer.Promptly use coverlay film in sowing or after transplanting.The short seedling growth of soil moisture conservation.Warm up when weather changes, plant growth is to the certain period, and film begins to break, and can further apply fertilizer accelerating growth.After results, film is all cracked, so that biological degradation, the soil assimilation.The fruitless labour of so not only having saved the very difficult of the useless film of big area cleaning and having taken a lot of work does not influence farming and following batch crop planting again.
(Kondrashkina, N.I., etal., Plast.Massy 1982(6) 11-12 such as Kant La Xijinna) having reported the degraded of polyethylene film under oxygen enrichment atmosphere uv irradiation that contains ferrocenylferrocene changes with its content inductive phase.When content was 0.50-1.0%, it played stabilizer function; And when content was 0.05-0.35%, it can the rapid photodegradation of catalytic film.Viscosity-average molecular weight drops to about 6,000 from initial 50,000.The light-sensitive catalyst of controlled photodegradable polyethylene film has ferrocene (Ger.Offen.2,331,676(1975) etc.), tertiary butyl ferrocene, cyclopentyl ferrocene (Brit.1,382061(1975)), two (the pivaloyl ferrocene (Brit.1,382,062(1975)), α-hydroxyethyl ferrocene, vinyl ferrocene, vinyl-1.1 '-diethyl ferrocene (Kalennikov, E.A., etal.U.S.S.R.823,395(1981); U.S.S.R, 840,069(1981) etc.), and ferrocenylferrocene (Trofimov, M.A., etal.Zh.Prikl.Khim.(Leningrad) 52 2767(1979)) etc.But the ferrocene that ferrocene and short carbon chain replace has the problem of easy distillation, migration in polyethylene, influence the quality control of film.Some solid derivative is had any problem in the processing film moulding, and synthetic difficulty such as ferrocenylferrocene, the cost height.So all there is certain problem in they in practicality.
The objective of the invention is to develop suitable ferrocene deriv light-sensitive catalyst and be used to produce the controlled photodegradable polyethylene film.The present invention is that a kind of molecular formula is
Long-chain substituting group ferrocene deriv light-sensitive catalyst, wherein, R '=H or R, R=C
7-C
11Alkyl, thiazolinyl, carboxylic acid group, carboxylic acid ester groups, or COR ", wherein R " is C
6-C
10Alkyl, thiazolinyl, carboxylic acid group, carboxylic acid ester groups; as positive capryloyl ferrocene, 1; 1 '-two positive capryloyl ferrocene, octyl ferrocene, β-ferrocene acyl propionic acid, γ-ferrocene acid, γ-ferrocene acid butyl ester, β-ferrocene acyl propionic acid butyl ester, β-ferrocene acyl propionic acid isopropyl ester, the isometric chain substituent ferrocene deriv of hendecene acyl Ferrocene light-sensitive catalyst.This class light-sensitive catalyst can be used for producing the controlled photodegradable polyethylene film.
The production method of above-mentioned ferrocene deriv light-sensitive catalyst of the present invention can be reacted by the step in the reactions such as his reduction of the paying of ferrocene-Ke acylations, Clemmensen reduction or base and catalytic esterification or a few step and made.This method requires not harsh to the reagent solvent, adopt general unit organic reaction equipment and operation.Productive rate is higher.
Above-mentioned light-sensitive catalyst of the present invention can be used for the production of controlled photodegradable polyethylene film.Adding above-mentioned molecular formula in the prescription is
The weight percentage of light-sensitive catalyst be 0.01-0.50%, wherein R and R ' can contain the above-mentioned light-sensitive catalyst of one or two or more kinds with aforementioned in the prescription, also can add light activating agent or other auxiliary agents of trace, all the other are polyethylene.This film can adopt common melt-blown film-forming process production, and film thickness is the 3-15 micron, and optimum thickness is the 5-10 micron.
Ferrocene deriv light-sensitive catalyst of the present invention is high boiling liquid or low melting point solid.Their volatility is very low, no sublimation, thereby transport property is seldom, and the processing performance that they add in the polyethylene film is good, and quality product is easy to control, has good storage stability.The polyethylene film that contains light-sensitive catalyst of the present invention has and the same good mechanical performance of former film.
The controlled photodegradable polyethylene film that contains ferrocene deriv light-sensitive catalyst of the present invention can be used as farm crop such as cotton, vegetables, potato, corn, grape ... Deng topped mulch film.Generally under sun exposure, film is controlled, and all degraded was cracked in 1 to 5 months.Controlled photodegradable polyethylene film of the present invention uses in the farmland can save a large amount of labor forces; do not influence farming and fertilising; be specially adapted to extensive mechanized agriculture production, photodegradation film of the present invention also can be used as the wrapping material of specific end use, and useless film is easy to digestion process.
Example 1 positive capryloyl ferrocene
Take by weighing 0.515 mol aluminum trichloride (anhydrous) and the positive capryl(yl)chloride of 0.515 mol, be mixed with the dichloromethane solution of complex compound, contain in reinforced dropping funnel.In 1000 milliliters of three-necked flasks, add 0.50 mol ferrocene and methylene dichloride.Drip above-mentioned complex solution at logical nitrogen with under stirring, in room temperature to 34 ℃ continuation reaction down, its degree that reacts completely is judged with thin layer chromatography again.Reaction mixture through hydrolysis, extraction, operation such as wash and desolventize, obtain thick product 137 grams of positive capryloyl ferrocene, again through vacuum fractionation, collect 170-176 ℃/0.17-0.30mm fraction, just obtain highly finished product 111 grams, productive rate 73.1%.
Example 21,1 '-two positive capryloyl ferrocene
Adopt aluminum chloride: positive capryl(yl)chloride: ferrocene=1.3: 1.3: the feed ratio 0.5(mol), operation by example 1, the first dichloromethane solution of preparation positive capryl(yl)chloride-aluminum chloride complex compound slowly is added drop-wise to the dichloromethane solution of the ferrocene of preparation in the complex solution and reacts.And is by the post-processing operation of example 1, and thick product just can obtain 1,1 '-two positive capryloyl ferrocene again through recrystallizing methanol, productive rate 57.1%, and it is a kind of orange red solid, fusing point 57-58 ℃ (not proofreading and correct).
Example 3 octyl ferrocenes
Prepare zinc amalgam earlier, the positive capryloyl ferrocene that again example 1 is made adds wherein, carries out the Clemmensen reduction reaction in benzene-water-hydrochloric acid under the stirring and refluxing.The degree that reacts completely monitors with thin layer chromatography, and after reduction was finished, operations such as filtering, wash and desolventize after vacuum fractionation, collection boiling range are 154-162 ℃/0.8-1.0mm fraction, can make orange liquid.The octyl ferrocene highly finished product, overall yield 68.8%.
Example 4 β-ferrocene acyl propionic acid
In the dichloromethane solution of 1 mol Succinic anhydried, add the aluminum trichloride (anhydrous) of pulverizing, under agitation drip the dichloromethane solution of 1 mol ferrocene then.Temperature rising reflux 2 to 3 hours stops only to overflow up to hydrogen chloride gas.By reactant slowly is hydrolyzed, operations such as separation, pickling, alkali are molten, acidifying; when PH=7～8; just there are a large amount of orange solids to separate out; washing more after filtration,, drying, recrystallization (dehydrated alcohol) just obtain β-ferrocene acyl propionic acid, fusing point 165-167 ℃ (proofreading and correct).
Example 5 γ-ferrocene acid
β-the ferrocene acyl propionic acid that example 4 is made with freshly prepd zinc amalgam stirs in benzene-water-methanol-hydrochloric acid soln, refluxes, and carries out the gloomy reduction reaction of Ke Caimen.And monitor the degree that reacts completely with thin layer chromatography.There is considerable part γ-ferrocene acid methyl esters to generate in the reaction.Handle through saponification again.Use the dilute hydrochloric acid acidifying at last.Get light orange solids.After filtration, washing, drying, just obtain γ-ferrocene acid.Productive rate 70-81%.Fusing point 114-116 ℃ (not proofreading and correct).
Example 6 γ-ferrocene acid butyl ester
γ-ferrocene acid that example 5 is made is dissolved in the benzene.Add propyl carbinol and BF
3Et
2O carries out catalytic esterification under stirring and refluxing.Monitor the degree that reacts completely with thin layer chromatography.Add NaHCO after the cooling
3The aqueous solution is neutralized to PH=7.Through separate, washing, dry, operation such as desolventize, carry out underpressure distillation at last, just obtain orange liquid γ-ferrocene acid butyl ester, 194 ℃/4mm of boiling point.Thick product yield about 95%; The elaboration rate is generally at 80-84%, if the vacuum tightness height still can bring up to 94%
Example 7 β-ferrocene acyl propionic acid butyl ester
β-ferrocene acyl propionic acid that example 4 is made carries out catalytic esterification by the operation of example 6.Thick product normal hexane recrystallization.Just can make β-ferrocenyl butyl propionate.Fusing point 45-46 ℃.Productive rate reaches more than 85%.
Example 8 β-ferrocene acyl propionic acid isopropyl ester
β-ferrocene acyl propionic acid that example 4 is made is by the operation of example 6, and replaces propyl carbinol with Virahol, carries out catalytic esterification.Thick product normal hexane recrystallization.Just can make β-ferrocene acyl propionic acid isopropyl ester, productive rate is more than 80%.
Example 9 controlled photodegradable polyethylene films
The polyethylene film that contains the light-sensitive catalyst of the present invention of 0.01-0.5% with the preparation of melt-blown film-forming process.Thickness is the 3-15 micron.Its mechanical property is identical with the control sample that does not add photosensitizers.The mechanical property of wherein adding the photodegradative polyethylene film (2,3,4,5, No. 6) of 0.1% light-sensitive catalyst of the present invention sees Table 1.
By table 1 as seen, the controlled photodegradable polyethylene film that adds light-sensitive catalyst of the present invention has the good mechanical performance, and it can't reduce the performance of former film.
The topped film light degraded test of example 10 cotton fields
Respectively with No. 1 film (not having photosensitive catalyzer) of example 9 with to contain the photodegradative polyethylene film of light-sensitive catalyst for 2,3,4,5 and No. 6 topped on the mould field that is implanted with seedling.Carry out field observation.The result shows that cotton branches and leaves growing way is luxuriant.Behind 1 first quarter moon, the film that contains light-sensitive catalyst all breaks.After 2 months, 2,3, No. 4 film seriously breaks, and No. 1 pleurodiaphragmatic in terspace sample does not split.Through three months, 2,3, No. 4 film was all cracked, and 5, No. 6 film seriously breaks, and No. 1 film does not still split.
Claims (17)
1, the light-sensitive catalyst of a class two luxuriant derivatives is characterized in that molecular formula is
Long-chain substituting group ferrocene deriv, wherein, R '=H or R, R=C
7-C
11Alkyl, thiazolinyl, carboxylic acid group, carboxylic acid ester groups, or COR ", and R " is C
6-C
10Alkyl, thiazolinyl, carboxylic acid group or carboxylic acid ester groups.
2, according to the light-sensitive catalyst of claim 1, it is characterized in that octyl ferrocene.
3,, it is characterized in that γ-ferrocene acid butyl ester according to the light-sensitive catalyst of claim 1.
4, according to the light-sensitive catalyst of claim 1, it is characterized in that γ-ferrocene acid.
5,, it is characterized in that positive capryloyl ferrocene according to the light-sensitive catalyst of claim 1.
6,, it is characterized in that the hendecene acyl Ferrocene according to the light-sensitive catalyst of claim 1.
7, the molecular formula according to claim 1 is
The preparation method of light-sensitive catalyst, wherein R and R ' is characterized in that passing through paying-the Ke acylations of ferrocene with aforementioned, and step of one in the gloomy reduction of Ke Caimen or other reduction and the catalytic esterification or the reaction of a few step make.
8, the controlled photodegradable polyethylene film that contains claim 1 described ferrocene deriv light-sensitive catalyst is characterized in that containing one or two or more kinds molecular formula and is
The light-sensitive catalyst of long-chain substituting group ferrocene deriv, R ' in the formula=H or R, R=C
7-C
11Alkyl, thiazolinyl, carboxylic acid group, carboxylic acid ester groups or COR ", and R " is C
6-C
10Alkyl, thiazolinyl, carboxylic acid group or carboxylic acid ester groups.
9, according to the controlled photodegradable polyethylene film of claim 8, it is characterized in that containing the octyl ferrocene light-sensitive catalyst.
10,, it is characterized in that containing γ-ferrocene acid butyl ester light-sensitive catalyst according to the controlled photodegradable polyethylene film of claim 8.
11,, it is characterized in that containing γ-ferrocene acid light-sensitive catalyst according to the controlled photodegradable polyethylene film of claim 8.
12,, it is characterized in that containing positive capryloyl ferrocene light-sensitive catalyst according to the controlled photodegradable polyethylene film of claim 8.
13,, it is characterized in that containing hendecene acyl Ferrocene light-sensitive catalyst according to the controlled photodegradable polyethylene film of claim 8.
14, claim 8,9,10,11,12 or 13 described controlled photodegradable polyethylene films is characterized in that containing the above-mentioned long-chain substituting group ferrocene light-sensitive catalyst that weight percentage is 0.01-0.50%.
15, claim 8,9,10,11,12 or 13 described controlled photodegradable polyethylene films is characterized in that containing the above-mentioned long-chain substituting group ferrocene light-sensitive catalyst that weight percentage is 0.05-0.30%.
16, claim 8,9,10,11,12 or 13 described controlled photodegradable polyethylene films is characterized in that film thickness is the 3-15 micron, and optimum thickness is the 5-10 micron.
17, the poly-second film of claim 8,9,10,11,12 or 13 described controlled photodegradables is characterized in that can be used as the topped mulch film of farm crop.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85100494 CN1015465B (en) | 1985-04-01 | 1985-04-01 | Photo-degradated polyethylene film and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85100494 CN1015465B (en) | 1985-04-01 | 1985-04-01 | Photo-degradated polyethylene film and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85100494A true CN85100494A (en) | 1986-08-13 |
| CN1015465B CN1015465B (en) | 1992-02-12 |
Family
ID=4791205
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85100494 Expired CN1015465B (en) | 1985-04-01 | 1985-04-01 | Photo-degradated polyethylene film and its use |
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| Country | Link |
|---|---|
| CN (1) | CN1015465B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049228C (en) * | 1993-12-27 | 2000-02-09 | 中国科学院上海有机化学研究所 | Aminoalkyl ferrocene derivative photosensitizer and its prepn. and application |
| CN1049227C (en) * | 1993-12-27 | 2000-02-09 | 中国科学院上海有机化学研究所 | Controllably graded polyolefine plastics containing amidoalkyl ferrocene, derivative production and application |
| CN103743839A (en) * | 2013-12-30 | 2014-04-23 | 西北工业大学 | HPLC (High Performance Liquid Chromatography) method for measuring n-octyl ferrocene and impurity content |
| CN103772442A (en) * | 2013-12-30 | 2014-05-07 | 西北工业大学 | Method for separating and purifying n-octylferrocene through reduced pressure distillation process in combination with chromatography |
| CN112795072A (en) * | 2021-01-19 | 2021-05-14 | 洛阳绿之汇塑料降解科技有限公司 | Natural light-microorganism dual-degradation master batch and preparation method thereof |
-
1985
- 1985-04-01 CN CN 85100494 patent/CN1015465B/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049228C (en) * | 1993-12-27 | 2000-02-09 | 中国科学院上海有机化学研究所 | Aminoalkyl ferrocene derivative photosensitizer and its prepn. and application |
| CN1049227C (en) * | 1993-12-27 | 2000-02-09 | 中国科学院上海有机化学研究所 | Controllably graded polyolefine plastics containing amidoalkyl ferrocene, derivative production and application |
| CN103743839A (en) * | 2013-12-30 | 2014-04-23 | 西北工业大学 | HPLC (High Performance Liquid Chromatography) method for measuring n-octyl ferrocene and impurity content |
| CN103772442A (en) * | 2013-12-30 | 2014-05-07 | 西北工业大学 | Method for separating and purifying n-octylferrocene through reduced pressure distillation process in combination with chromatography |
| CN112795072A (en) * | 2021-01-19 | 2021-05-14 | 洛阳绿之汇塑料降解科技有限公司 | Natural light-microorganism dual-degradation master batch and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1015465B (en) | 1992-02-12 |
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