CN1091119C - Controllable optic biological degradation polyolefine type nacrous resin and preparation method thereof - Google Patents
Controllable optic biological degradation polyolefine type nacrous resin and preparation method thereof Download PDFInfo
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- CN1091119C CN1091119C CN96109078A CN96109078A CN1091119C CN 1091119 C CN1091119 C CN 1091119C CN 96109078 A CN96109078 A CN 96109078A CN 96109078 A CN96109078 A CN 96109078A CN 1091119 C CN1091119 C CN 1091119C
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Abstract
The present invention relates to polyolefin pearlite resin with the function of controllable light biodegradation, which comprises polyolefin resin, pearlite master batches and polyolefin resin master batches with the function of controllable light biodegradation. The polyolefin pearlite resin can also comprise polyolefin resin, pearlite master batches and starch-based degradable master batches. The polyolefin pearlite resin can also comprise polyolefin resin, pearlite master batches, polyolefin resin master batches with the function of controllable light biodegradation and starch-based degradable master batches. The components are processed by an ordinary film blowing device, and then various degradable pearlite resin films with pearlite colors can be produced.
Description
The present invention relates to controllable optic biological degradation polyolefine type nacrous resin and preparation method thereof.
In recent years, along with pearly-lustre plastics the widening day by day of use range in daily life and industrial and agricultural production, the pollution problem increasingly significant that the pearly-lustre plastics bring for city and rural area, the history of pearlescence manufacturing process originates from the seventies, mainly adopted two kinds of raw materials at that time, one is a raw material with natural hairtail squama, and its two chlorination mercury, lead carbonate and bismuthyl chloride with synthetic are raw material, also use the chloride bismuth in addition.But the pearlescence that natural hairtail squama is made is the Guanin crystal that extracts from fish scale, and this natural guanin is of great rarity, and produced in small quantities only is used in makeup at present.Because the source is rare, price is extremely expensive.And the synthetic pearlescent pigment, containing of having is toxic, the photostabilization that has, heat-resisting, chemical proofing is not good.
The object of the present invention is to provide a kind of controllable optic biological degradation polyolefine type nacrous resin and preparation method thereof.The present invention utilizes the mica Mineral resources of China's abundant, the technology of bond oxide compound inclusion sheet mica, realize the quantum jump of pearly-lustre series, prepare various sudden strain of a muscle look glossy degradation polyolefin type nacrous resins, be widely used in each big field such as luxurious packing, daily chemical product, printing-ink, automobile, burning lacquer, coating, pearling agent, building decoration, sports equipment, map, thoroughly change and use PbCO
3Make the pearly-lustre film with chloride bismuth etc. and poison, harmful auxiliary agent, especially be, with the situation of children's health foods such as this packing of product ice lolly, ice cream, cake with what it came wrap food, toiletry, especially severe.This is one of the object of the invention.
In addition, non-degradative plastics works the mischief to environment, and burning can bring obnoxious flavour, enters the ocean and can be eaten by mistake by biology again, influences the eubiosis.Thereby some countries of Northern Europe, passed through relevant restriction or banned use of the rules of non-degradative plastics goods as far back as nineteen ninety.At present, this way is accepted by most countries, has formulated similar regulation or policy in succession.In order to respond the requirement of international environmental protection organization to Nonpoisonous, non-environmental-pollution degradative plastics product, the present invention manufactures experimently out controllable optic biological degradation polyolefine type nacrous resin finally through research improvement again and again.This nacrous resin film has solved that domestic and international luxurious pearly-lustre packing plastics and pearly-lustre mulch film can not be degraded and the problem brought.After this pearly-lustre film used up, kiss the earth was accepted ultraviolet irradiation, can be controlled in inductive phase 60-200 days, after inductive phase, can degrade quickly, and under field conditions (factors), resolve into small shreds, resolved into carbonic acid gas and water at last.This is two of the object of the invention.
Controllable optic biological degradation polyolefine type nacrous resin provided by the present invention can be to comprise polyolefin resin, pearly-lustre masterbatch, controllable optic biological degradation vistanex mother material.
Controllable optic biological degradation polyolefine type nacrous resin provided by the present invention also can be to comprise polyolefin resin, pearly-lustre masterbatch, starch-based degrading masterbatch.
Controllable optic biological degradation polyolefine type nacrous resin provided by the present invention can also be to comprise polyolefin resin, pearly-lustre masterbatch, controllable optic biological degradation vistanex mother material, starch-based degrading masterbatch.
The ratio of polyolefin resin, pearly-lustre masterbatch, controllable optic biological degradation vistanex mother material is 100 parts of polyolefin resines in the controllable optic biological degradation polyolefine type nacrous resin provided by the present invention: 5-15 part pearly-lustre masterbatch: 5-15 part controllable optic biological degradation vistanex mother material.
The ratio of polyolefin resin, pearly-lustre masterbatch, starch-based degrading masterbatch is 100 parts of polyolefin resines, 5-15 part pearly-lustre masterbatch, 5-15 part starch-based degrading masterbatch in the controllable optic biological degradation polyolefine type nacrous resin provided by the present invention.
The ratio of polyolefin resin, pearly-lustre masterbatch, controllable optic biological degradation vistanex mother material, starch-based degrading masterbatch is 100 parts of polyolefin resines, 5-15 part pearly-lustre masterbatch, 5-15 part controllable optic biological degradation vistanex mother material, 5-15 part starch-based degrading masterbatch in the controllable optic biological degradation polyolefine type nacrous resin provided by the present invention.
Include pearlescence and polyolefin resin in the wherein related pearly-lustre masterbatch; The ratio of wherein said pearlescence and polyolefin resin is 10-50 part pearlescence and 100 parts of polyolefin resines;
Also including paucidisperse agent and fluorescent bleaches in the wherein related pearly-lustre masterbatch mixes; Described dispersion agent is a low molecular weight polyethylene.
Include polyolefin resin and starch among the wherein related starch-based degrading mother; The ratio of the two is the starch that adds the 5-40 weight part in the polyolefin resin of 100 weight parts.
Wherein related controllable optic biological degradation vistanex mother material comprises polyolefin resin, photosensitizers, photostabilizer.
Wherein related controllable optic biological degradation vistanex mother material also comprises other Synergist S-421 95; Described Synergist S-421 95 comprises oxidation inhibitor and UV light absorber.
Wherein related controllable optic biological degradation vistanex mother material also comprises the starch-based degrading masterbatch.
Wherein related controllable optic biological degradation vistanex mother material, wherein said photosensitizers comprises the compound of metallic iron, nickel, cobalt, manganese, zirconium, cerium or osmium: described metallic compound is metal oxide or salt.
Wherein related controllable optic biological degradation vistanex mother material, wherein said photostabilizer are the organic nickel compounds.
Wherein related controllable optic biological degradation vistanex mother material, wherein said 0.36-0.52 weight part photosensitizers, the photostabilizer of the ratio of each component is: 100 weight part polyolefin resines.
Wherein related controllable optic biological degradation vistanex mother material, the weight ratio of wherein said photosensitizers, photostabilizer are 1-1.4: 1.
Wherein related controllable optic biological degradation vistanex mother material, described starch-based degrading masterbatch accounts for 2/3rds of total weight parts, in the described starch-based degrading mother liquor, adds the starch of 5-40 weight part in the polyolefin resin of 100 weight parts.
Wherein related controllable optic biological degradation vistanex mother material, the consumption of wherein said oxidation inhibitor are 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 wherein related controllable optic biological degradation vistanex mother material can be base-materials such as polyethylene, polypropylene.
Wherein related photosensitizers is the compound of some metal, and these metals are iron (Fe), manganese (Mn), cobalt (Co), copper (Cu), zirconium (Zr), cerium (Ce), osmium (Os), and 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.
Wherein related photostabilizer 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.
Wherein related oxidation inhibitor component 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 wherein related preferred salicylate of UV light absorber component, benzophenone, benzotriazole compound.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 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.
Olefin resin, photosensitizers, photostabilizer, oxidation inhibitor, UV light absorber are mixed with mixture in proportion, and processing to become controllable optic biological degradation vistanex mother material again.Wherein said polyolefin resin masterbatch mixture opens 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 ℃, plays 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, air-cooled pelletizing in the tablets press; it is good to make inner quality at last, and outward appearance is good; the controllable optic biological degradation vistanex mother material of color and luster.
In the preparation processing of controllable optic biological degradation vistanex mother material, 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 the grain-making machine running, the rotating speed of screw rod is slow as best one can, to avoid destroying granulation because of shearing knife up.
The preparation method of controllable optic biological degradation polyolefine type nacrous resin provided by the present invention comprises: 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.Promptly at first prepare the pearly-lustre masterbatch, comprising 10-50 part pearlescence is mixed with 100 parts of polyolefine, 3-15 part dispersion agent, 0.001-0.01% part fluorescent bleaches, add mixing plasticizing in the Banbury mixer, temperature is controlled at 140-160 ℃, enter the mill compressing tablet then, play the triangle bag repeatedly, be rolled into the 9-11cm sheet, be cooled to the pelletizing of 20-30 ℃ of input tablets press screw rod head wire drawing water-cooled, granularity is at the 30-40 order; Prepare controllable optic biological degradation vistanex mother material then, comprise and to 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 ℃, plays 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; Prepare controlled starch-based degrading masterbatch by existing method again; Said components is mixed by proportioning and polyolefin base material, adopt conventional film blowing method can prepare controllable biologically degraded nacrous resin.
The present invention is added to 300-800 order mica sheet and metal oxide and calcines in the muffle furnace in 500-1100 ℃ the time, and mica sheet is outer to produce nacreous pigment coated with metal oxygen fat thing.Outward appearance is a powder transparent, flats, has bigger diameter and characteristics such as smooth flat and high index of refraction than general pigment.The preferred metal oxide of the present invention is a titanium dioxide, is called for short the mica titanium perlatolic powder by the mica sheet of titanium dioxide inclusion, and this pearlescence is water insoluble, and is harmless, can be used for packaging material for food (according to various countries' rules and regulations).The size of particles of this pearlescence can influence pearliness: particle is bigger, and pearliness is stronger, cover power a little less than; Particle is littler, demonstrates soft gloss as the line satin, and the preferable power of covering. and pearliness is that the multipath reflection of light produces.Therefore the mica titanium perlatolic powder mixes with the material transparent that heals, and more can produce graceful pearliness.The mica titanium perlatolic powder also can mix with transparent pigment or dyestuff, with the coloured light that obtains being fit to.Should avoid pigment and usefulness with opaque composition or strong covering power, as TiO
2, pigment such as PbO, in order to avoid influence the pearliness effect.
Among the present invention; mica titanium perlatolic powder and polyolefine are mixed and made into the mica titanium perlatolic masterbatch; with 10-50 part mica titanium perlatolic powder and 100 parts of polyolefine (PE or PP); 3-15 part dispersion agent (low molecular weight polyethylene); 0.001-0.01% part fluorescent bleaches mixes; add mixing plasticizing in the Banbury mixer; temperature is controlled at 140-160 ℃; enter the mill compressing tablet then; play the triangle bag repeatedly; be rolled into the 9-11cm sheet, be cooled to 20-30 ℃ of input tablets press screw rod, rotating speed is good more more slowly; (avoid high shear force to destroy its particle; influence the pearliness effect), the pelletizing of head wire drawing water-cooled, the order number all can at the 30-40 order.
Embodiment 1
In the polyvinyl resin base-material of 100 weight parts, the 7# photosensitizers of 1# photosensitizers, 3.5 weight parts that adds 0.4 weight part is (respectively by 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)
2Form), 3.5 the N of weight part, 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, to add in this mixture in the Banbury mixer, the banburying temperature is 160 ℃, and pressure is 8Pa, discharging after 15 minutes, send into mill through conveying belt, the preceding roll temperature of mill is 110 ℃, and back roll temperature is 125 ℃, following sheet after 20 minutes, be cooled to 20-30 ℃, send into tablets press, the tablets press temperature is respectively 140 ℃ from hopper sentence heading, 170 ℃, 170 ℃, 150 ℃, 150 ℃, screw speed is 40 rev/mins, through air-cooled pelletizing, controllable optic biological degradation vistanex mother material: 300-800 order sheet mica and titanium dioxide are added in the muffle furnace, calcine in the time of 500-1100 ℃, obtain having glossy pigment mica titanium perlatolic powder; Adopt banburying then, open refining and extruding and pelletizing process and prepare the nacreous mica masterbatch, wherein prescription is:
100 parts of LDPE
30 parts in mica titanium perlatolic powder
7 parts of low molecular weight polyethylenes
0.005 part of white dyes
Processing condition are:
Banburying: 150 ℃ of temperature
10 minutes time
Open refining: I10 ℃ of temperature preliminary roller
110 ℃ on back roller
15 minutes time
Forcing machine body temperature: be from charging opening-head:
80℃、110℃、130℃、14℃、145℃
The masterbatch of pressing different ingredients is with after polyolefin base material mixes, again through extruding, blown film, batching and make the controllable optic biological degradation vistanex film.
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 banburying, open refining, granulation process is identical with embodiment 1, makes controllable optic biological degradation vistanex mother material; 300-800 order sheet mica and titanium dioxide are added in the muffle furnace, calcine in the time of 500-1100 ℃, obtain having glossy pigment mica titanium perlatolic powder; Adopt banburying then, open refining and extruding and pelletizing process and prepare the nacreous mica masterbatch, wherein prescription is:
100 parts of LDPE
50 parts in mica titanium perlatolic powder
10 parts of low molecular weight polyethylenes
0.005 part of white dyes
Processing condition are:
Banburying: 160 ℃ of temperature
15 minutes time
Open refining: 130 ℃ of temperature preliminary rollers
140 ℃ on back roller
20 minutes time
Forcing machine body temperature: be from charging opening-head
80℃、110℃、130℃、140℃、145℃
The masterbatch of pressing different ingredients is with after polyolefin base material mixes, again through extruding, blown film, batching and make the controllable optic biological degradation vistanex film.
Claims (7)
1, a kind of controllable optic biological degradation polyolefine type nacrous resin is characterized in that comprising polyolefin resin, pearly-lustre masterbatch, controllable optic biological degradation vistanex mother material; The ratio of the parts by weight of described each composition is: 100 parts of polyolefin resines: 5-15 part pearly-lustre masterbatch: 5-15 part controllable optic biological degradation vistanex mother material;
Wherein, described polyolefin resin is polyethylene, polypropylene;
Comprise 10-50 part pearlescence and 100 parts of polyolefin resines in the described pearly-lustre masterbatch;
Described controllable optic biological degradation vistanex mother material comprises the photosensitizers and the photostabilizer of 0.36-0.52 weight part: 100 weight part polyolefin resines, and the weight ratio of photosensitizers and photostabilizer is 1-1.4: 1; Described photosensitizers comprises the metal oxide or the salt of metallic iron, nickel, cobalt, manganese, zirconium, cerium or osmium; Wherein said photostabilizer is the organic nickel compound.
2, the described controllable optic biological degradation polyolefine type nacrous resin of claim 1, it is characterized in that also comprising the starch-based degrading masterbatch, the parts by weight ratio of described each composition is: polyolefin resin: pearly-lustre masterbatch: controllable optic biological degradation vistanex mother material: starch-based degrading masterbatch=100: 5-15: 5-15: 5-15.
3, the described controllable optic biological degradation polyolefine type nacrous resin of claim 1 is characterized in that described photosensitizers is 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
4, controllable optic biological degradation polyolefine type nacrous resin as claimed in claim 3 is characterized in that described photosensitizers is water-fast metallic compound.
5, the described controllable optic biological degradation polyolefine type nacrous resin of claim 1 is characterized in that described photostabilizer is: 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 oxygen, sulphur, nitrogen, phospha atom.
6, the described controllable optic biological degradation polyolefine type nacrous resin of claim 1, it is characterized in that described photostabilizer 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, resinous acid nickel and nickel naphthenate; C wherein
1-80Alkyl does not contain or contains one or more oxygen, sulphur, nitrogen, phospha atom.
7, the preparation method of the controllable optic biological degradation polyolefine type nacrous resin described in a kind of as claim 1-6 each, it is characterized in that comprising 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; Promptly at first prepare the pearly-lustre masterbatch, comprising 10-50 part pearlescence is mixed with 100 parts of polyolefine, 3-15 part dispersion agent, 0.001-0.01% part fluorescent bleaches, add mixing plasticizing in people's Banbury mixer, temperature is controlled at 140-160 ℃, enter the mill compressing tablet then, play the triangle bag repeatedly, be rolled into the 9-11cm sheet, be cooled to the pelletizing of 20-30 ℃ of input tablets press screw rod head wire drawing water-cooled, granularity is at the 30-40 order; Prepare controllable optic biological degradation vistanex mother material then, comprise and to 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 ℃, plays 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; Prepare controlled starch-based degrading masterbatch by existing method again; Said components is mixed by proportioning and polyolefin base material, adopt conventional film blowing method can prepare controllable biologically degraded nacrous resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109078A CN1091119C (en) | 1996-08-22 | 1996-08-22 | Controllable optic biological degradation polyolefine type nacrous resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109078A CN1091119C (en) | 1996-08-22 | 1996-08-22 | Controllable optic biological degradation polyolefine type nacrous resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1174855A CN1174855A (en) | 1998-03-04 |
| CN1091119C true CN1091119C (en) | 2002-09-18 |
Family
ID=5120203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109078A Expired - Fee Related CN1091119C (en) | 1996-08-22 | 1996-08-22 | Controllable optic biological degradation polyolefine type nacrous resin and preparation method thereof |
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| CN103804794A (en) * | 2014-03-06 | 2014-05-21 | 常熟市江顺塑料制品有限公司 | Colored film plastic |
| CN106966913B (en) * | 2017-04-06 | 2020-07-10 | 青岛科技大学 | Preparation method of dialkylaminoethyl methacrylate |
| CN110527186A (en) * | 2019-08-14 | 2019-12-03 | 湖南登科材料科技有限公司 | A kind of preparation method of pearly-lustre plastic matrix |
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 CN96109078A patent/CN1091119C/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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|---|---|
| CN1174855A (en) | 1998-03-04 |
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