CN2701614Y - Device for preparing polymer composite additive - Google Patents
Device for preparing polymer composite additive Download PDFInfo
- Publication number
- CN2701614Y CN2701614Y CNU2004200408154U CN200420040815U CN2701614Y CN 2701614 Y CN2701614 Y CN 2701614Y CN U2004200408154 U CNU2004200408154 U CN U2004200408154U CN 200420040815 U CN200420040815 U CN 200420040815U CN 2701614 Y CN2701614 Y CN 2701614Y
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- additive
- composite additive
- polymkeric substance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The utility model relates to a device for preparing polymer composite additive, which orderly comprises an extrusion device, a cooling device, a grain crushing device and a size grading device. By utilizing different melting points of each component in additive mixtures and through the aid of an extrusion device which melts material with a low-melting point in the extruding process, the utility model makes the additive mixtures a substance with certain viscosity and plasticity. Then, through a mold opening of the extrusion device, the substance enters a calender to be calendered into sheets which are cooled and enter a grain crushing device so that the sheets formed from additive are crushed of grains. Unqualified grains formed in the grain-crushing process are reprocessed after collection. Irregular polyhedral granular composite-plastic additive with the diameter from 0.1 mm to 10 mm can be fabricated by the method of the utility model which has the characteristics of avoidance of the excessive heat of polymer additive, wide application ranges, high mechanical strength of the additive and capacity of regulating the granularity according to need.
Description
Technical field
The utility model relates to the particularly production unit of polyolefine composite additive of polymkeric substance.
Background technology
Polymkeric substance (as polyethylene, polypropylene, polyvinyl chloride etc.) needs to add many kinds of additives in the course of processing; so that the easier processing of polymkeric substance; or polymer properties is improved; or polymkeric substance is protected in the course of processing, avoiding degrading etc. is unfavorable for the variation of polymer performance.For example, can make polymkeric substance in the course of processing, avoid the over-drastic oxidation to make ageing of performance, also can make polymer product that arranged longer work-ing life thereby add oxidation inhibitor; In crystal polymer things such as polypropylene, add nucleator and can improve crystallinity of polymer and crystal habit, thereby improve the transparency and the shock resistance of polymkeric substance; Add lubricant such as stearic acid Tegin 55G in polymkeric substance, can reduce the viscosity of polymkeric substance work in-process, reduce the adhesion between polymer melt and the equipment, thereby make the easier processing of polymkeric substance, goods is apparent also brighter attractive in appearance simultaneously.
Involved additive is very many in the polymer processing, as oxidation inhibitor, lubricant, static inhibitor, acid absorber, nucleator, photostabilizer etc., these additives generally offer polymer production or processing enterprise by manufacturer with the powder form.Polymer production or processing enterprise are mixed powder additives and polymkeric substance again, make polymkeric substance intermediates or the finished product.
Powder additive in use tends to cause dust pollution; thereby cause additive losses; the harm operator are healthy; and the additive of powder is because mobile poor; reasons such as easily adhesion, caking; be not easy in the polymer production course of processing of some serializations, use continuous metering device to add; so in the polymer production processing industry also exploring the granulation or title " dustlessization " technology of suitable polymer blend additive the most, to improve above-mentioned polymeric additive all drawbacks in use.
Chinese patent application number 01235722.7 and application number 01114677.X disclose a kind of equipment of making polyolefine composite assistant.This technology is that the powder additive with various required granulations joins in the heatable reactor; after various additive fusings; import in the distributor of band protective guard of a heating through conduit again; rotation by distributor again; material with fusing; drop by drop be distributed on the coolable revolution steel band; the additive of fusing is cooled to solid dome-type particle; this technology can become the additive preparation of specific components form composite additive particle preferably; but its disadvantage is all binder components all must be melted; additive is stopped under comparatively high temps for a long time; can make portions additive jaundice variable color like this; even influence the performance of additives function, the performance of final impact polymer goods.And if the viscosity of melting materials capable is higher, or the fusing point of portions additive (as some nucleator) is when higher, and this equipment is such preparation of composite additives can't be become particle.
Chinese patent application number 018903407.1 discloses a kind of " polyolefine particulate state composite additive; its manufacture method and the polyolefin compositions that contains this additive ", and this invention is the nucleator of certain species and oxidation inhibitor and other auxiliary agents and polypropylene to be mixed be squeezed into particle in extrusion machine.The shortcoming of this method is in fact just at the granulation of polypropylene nucleater, because it has introduced polypropylene in composite additive, is not pure additive mixture.When composite additive was used for polyethylene or other polymkeric substance, polypropylene wherein can become a kind of unwanted impurity combination, and the composite additive suitable application area that can prepare is narrower.
Chinese patent application 03148512.X discloses " granular particle of plastics composite additive, production technique and application "; dry method granulation processes is used in this invention, various powder additives is mixed the back rely on powerful pressure that additive agent mixture is squeezed into cylindrical particle with Squeezinggranulator.The shortcoming of this method be since the viscosity that only relies on pressure and low melting point with the powder additive extrusion molding, this method is higher to some fusing point, the material of autohension difference such as the ratio of briquetting of materials such as antioxidant 1010, calcium stearate are low, granule strength is poor; If no low melting point or low melting point content are seldom the time in the binder component, can't granulation; And when containing nucleator in the composite additive component, can cause the firm reunion of nucleator powder, influence the dispersion of nucleator in polymkeric substance, thereby influence the performance of nucleator performance.In addition, the production efficiency of this method is lower, and production energy consumption is big.
Summary of the invention
The purpose of this utility model is to provide a kind of polymeric additive of avoiding excessively to be heated, and is applied widely, the production unit of the polymkeric substance composite additive that the additive physical strength is high.
The equipment of manufacturing polymkeric substance composite additive of the present utility model, it is characterized in that comprising successively extrusion device, calender device, refrigerating unit, broken whole grain device and gradation device, the discharge port of extrusion device and the opening for feed of calender device are pressed close to install up and down.
The conveying of the material between extrusion device and the calender device (twin-roll rolling unit) should be a successive, automatic, and the discharge port of preferred extrusion device and the opening for feed of calender device are pressed close to install up and down, utilize the continuous automatic transport of difference of altitude.Mass transport between calender device and refrigerating unit, refrigerating unit and broken whole grain device, broken whole grain device and the gradation device can select difference of altitude to carry, also can adopt the mode that connects e Foerderanlage to carry, as lift conveying, belt conveying, roller-way conveying, wind-force conveying etc.Cooperation between each device has realized a whole set of composite additive particulate producing apparatus.
The principle of work of the utility model equipment is: the difference of utilizing each component fusing point in the additive agent mixture, utilize forcing machine in extrusion with the low melting point fusion, additive agent mixture is become have certain viscosity and plastic material, again by the forcing machine die orifice, enter the rolling press calendering in flakes, by cooling, enter broken whole grain equipment, with the broken whole grain of the thin slice of additive formation.The undesirable particle that forms in the whole grain of fragmentation process is reprocessed after collecting.
The utility model forms mixture by the additive mixing of different melting points, and wherein low-melting component accounts for the 10-90% of composite additive gross weight, and high melting point component accounts for the 10-90% of composite additive gross weight; The control of the temperature of extrusion equipment guarantees the low-melting component fusing and high melting point component does not melt.
Above-described low-melting component is meant needs the component that melts in extrusion, its amount accounts for the 10-90% of composite additive gross weight, preferred 20-80%, and more preferably 20-60% can be a kind of component, also can be that more than one components are formed.When forming by various ingredients, the temperature of forcing machine is controlled in the low-melting component the wherein melting temperature of peak melting point component, guaranteeing all low-melting components fusings, but their is decomposed, single with regard to this technology, those skilled in the art all can understand its implication and can implement.
High melting point component described in the utility model is meant does not need the component that melts in extrusion, because its fusing point height in order to guarantee its use properties, is not suitable for being heated for a long time, it is that the low-melting component that is melted mixes.The amount of high melting point component accounts in the scope of 10-90% of composite additive gross weight, can be a kind of component, also can be that more than one components are formed.
Therefore low-melting component of the present utility model is relative with high melting point component, as long as reach above purpose, can determine according to the situation of additive.As when composite additive is made up of 4 kinds of components, proportioning between them will be determined according to the function to polymkeric substance, the low-melting component that might determine is a kind of (its amount is enough), also might be two or three component (total amount is fit to), but also will guarantee the amount of high melting point component simultaneously.If a kind of quantity not sufficient of low-melting component need be two or three component, equally also to guarantee the amount of high melting point component.
The additive types that polymkeric substance composite additive of the present utility model can comprise without limits, its proportioning can be selected according to the different situations of polymkeric substance.Limited by the extrusion equipment temperature-controlled precision, the fusing point difference of peak melting point component and minimum fusing point component should be more than the forcing machine temperature-controlled precision in the binder component, and is preferred more than 5 ℃.Composite additive also can comprise a certain amount of polymer powders identical with the composite additive suitable polymers, requiring polymkeric substance can not be minimum fusing point component, and each binder component weight sum that fusing point is lower than melting point polymer is in the scope of 10-90% of gross weight.
Be not particularly limited for the type of polymer of adding composite additive of the present utility model, comprise new LDPE (film grade), linear low density polyethylene, high density polyethylene(HDPE), polypropylene, poly-1-butylene, polystyrene, polyvinyl chloride, polymeric amide, polycarbonate, poly-to two phthalic acid esters etc.
Below than describing the technical solution of the utility model in greater detail:
1, extrusion equipment.It can be single screw extrusion machine, it also can be twin screw extruder, it also can be planetary screw extrusion press, or other general extrusion equipments that can be used for plastic working, or other have the similar screw extruder that structure in the same way can be used for mass transport that has, and preferred parallel twin screw extruder, screw slenderness ratio can be 12～56 even wideer scope, preferred 16～36, more preferably 24～28.Forcing machine must be equipped with heating and temperature regulating device, and its temperature control scope can be at 30～250 ℃, and control accuracy is ± 5 ℃, and is preferred ± 1 ℃.The outlet position of this forcing machine can be direct barrel outlet form, also can install the mould of flat slit additional.
2, calender device preferably adopts twin-roll rolling unit.It can be fixed that thickness is also promptly rolled in slit between the two rollers of this twin-roll rolling unit, and such as any width between 0.5～20mm, preferably its slit is adjustable.3, refrigerating unit.Can be air-cooled, rotary drum cooling, belt cooling or steel band cooling.Preferred revolution steel band cooler, this equipment is driven by two rotating shaft tensionings that have tightening device, and pair steel band refrigerative device of spraying water is arranged below the revolution steel band.
4, broken whole grain device.The material of cooling curing by mechanical impact or material self collision under mechanical effect, is broken into short grained composite assistant with the composite additive of large volume.Can select jaw examination crusher, hammer mill, ring hammer crusher etc. for use.Preferred ring hammer crusher.
5, gradation device.Can be linear vibrating screen, disc type vibratory screening apparatus, cyclonic separator etc.Preferred linear vibrating screen.
The utility model has the advantages that additive agent mixture residence time in forcing machine is very short, generally only need 0.5～5 minute; Secondly can not cause decomposition in the extrusion to material; The 3rd, because the outlet of extruder relative aperture is big and material is in plastic state, the pressure that whole binder component bears is little, can not cause the pressurized of high-melting-point material in the binder component such as components such as nucleator, antiblocking agent to reunite, and influences its dispersion in polymkeric substance; The 4th, direct granulating but the broken whole grain in calendering cooling back has effectively improved particle intensity after extruding has prevented adhesion between the particle, has enlarged the scope of application of this equipment; The 5th, because the calendering thickness of rolling press is adjustable, the screen cloth of sieve apparatus is replaceable, so can produce the composite additive particle of variable grain granularity very easily, help composite additive, make it more even with mixed with polymers at the polymer production different-grain diameter of different-grain diameter; The 6th, can reduce the additive level in the composite additive by adding the method for resin carrier, help the accuracy of additive when metering is added, can also improve the composite additive dispersiveness in polymkeric substance in use.Utilize equipment of the present utility model can produce the particulate state composite plastic additive that is irregular polyhedrons shape of diameter 0.1～10mm.Outstanding feature is to avoid polymeric additive excessively to be heated, and is applied widely, additive physical strength height, and granularity can be adjusted as required.
Description of drawings
Fig. 1 is one of structural representation of the present utility model;
Fig. 2 is two of a structural representation of the present utility model;
Among the figure: 1 screw extrusion press, 2 two roll calenders, 3 refrigerating units, 4 broken pelletizing machine 5 gradation devices 6 coarse breaking rollers 7 high angle belt conveyer transfer rollers
Embodiment
The utility model is described in detail by embodiment, comparative example, assessment example below in conjunction with accompanying drawing.But the utility model is not limited in following embodiment, comparative example, assessment example.
Fig. 1 or whole plant shown in Figure 2 are used in the preparation of test sample.As Fig. 1, equipment comprises screw extrusion press 1, two roll calender 2, revolution steel band cooler (refrigerating unit 3), broken pelletizing machine 4, sieve apparatus (gradation device 5).Have difference of altitude to install up and down between each device, the opening for feed of a device wherein turns round the discharge port position of steel band cooler and can set up a baffle plate after the discharge port correspondence of last device, is convenient to material and enters into broken pelletizing machine.Cooperation between each device has realized a whole set of composite additive particulate producing apparatus, and the dotted line among the figure between the device is represented the working line of material.
As Fig. 2, be parallel conveying between different with Fig. 1 is revolution steel band cooler (refrigerating unit 3) and the broken pelletizing machine 4, be added with the e Foerderanlage conveying.End at revolution steel band cooler is fixed with the coarse breaking roller, and the sheet material that two roll calender 2 is rolled carries out coarse breaking, is convenient to flow to broken pelletizing machine 4 by high angle belt conveyer transfer roller 7.
Various additives are mixed in high-speed mixer; in screw extrusion press 1 with the low melting point fusion; additive agent mixture is become have certain viscosity and plastic material; again by the forcing machine die orifice; enter two roll calender 2 calenderings in flakes,, enter broken pelletizing machine 4 by 3 coolings of revolution steel band cooler; the broken whole grain of thin slice with additive forms sieves out the product of release mesh by sieve apparatus (gradation device 5) at last.
High-speed mixer is used in the preparation of comparative sample, and pair roller is suppressed tablets press.
Embodiment 1: the manufacturing of test sample A
Four [β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) propionic acid] pentaerythritol ester that mixes 40 mass parts, the tricresyl phosphite of 40 mass parts (2, the 4-di-tert-butyl-phenyl) ester, the calcium stearate of 20 mass parts.Extruder temperature is set from the feeding part to the head section 110 ℃, 110 ℃, 115 ℃, 120 ℃.Screw speed 70rpm, 1.5mm, screen cloth 14 orders are set in the rolling press slit.Make the particle of size about 1.5mm.
Embodiment 2: the manufacturing of test sample B
Four [β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) propionic acid] pentaerythritol ester that mixes 20 mass parts, the tricresyl phosphite of 20 mass parts (2, the 4-di-tert-butyl-phenyl) ester, the calcium stearate of 10 mass parts, the polypropylene powder of 50 mass parts.Extruder temperature is set from the feeding part to the head section 120 ℃, 120 ℃, 120 ℃, 120 ℃.Screw speed 60rpm, 1.5mm, screen cloth 14 orders are set in the rolling press slit.Make the particle of size about 1.5mm.
Embodiment 3: the manufacturing of test sample C
Four [the β-(4-hydroxyl-3 that mix 12.5 mass parts, the 5-di-tert-butyl-phenyl) propionic acid] pentaerythritol ester, the tricresyl phosphite of 25 mass parts (2, the 4-di-tert-butyl-phenyl) ester, 12.5 the calcium stearate of mass parts, the diethyl benzal sorbyl alcohol as nucleator of 50 mass parts.Extruder temperature is set from the feeding part to the head section 120 ℃, 120 ℃, 120 ℃, 120 ℃.Screw speed 50rpm, 1.5mm, screen cloth 14 orders are set in the rolling press slit.Make the particle of size about 1.5mm.
Embodiment 4: the manufacturing of test sample D
β-positive octadecanol the ester of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid that mixes 10 mass parts, the erucicamide of 40 mass parts, the Zinic stearas of 20 mass parts, the dihydroxy ethyl octadecylamine of 20 mass parts, the polyethylene powders of 10 mass parts.Extruder temperature is set from the feeding part to the head section 50 ℃, 55 ℃, 60 ℃, 60 ℃.Screw speed 50rpm, 1.5mm, screen cloth 14 orders are set in the rolling press slit.Make the particle of 1.5mm size.
Embodiment 5: the manufacturing of test sample E
β-(the 4-hydroxyl-3 that mixes 5 mass parts, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, the tricresyl phosphite (2 of 5 mass parts, the 4-di-tert-butyl-phenyl) ester, the erucicamide of 30 mass parts, the Zinic stearas of 15 mass parts, the dihydroxy ethyl octadecylamine of 15 mass parts, the silicon-dioxide as antiblocking agent of 30 mass parts.Extruder temperature is set from the feeding part to the head section 55 ℃, 60 ℃, 65 ℃, 70 ℃.Screw speed 50rpm, 1.5mm, screen cloth 14 orders are set in the rolling press slit.Make the particle of 1.5mm size.
Embodiment 6: the manufacturing of test sample F
Four [β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) propionic acid] pentaerythritol ester that mixes 11.1 mass parts, the tricresyl phosphite of 11.1 mass parts (2, the 4-di-tert-butyl-phenyl) ester, the Zinic stearas of 11.1 mass parts, the polyethylene powders of 66.7 mass parts.Extruder temperature is set from the feeding part to the head section 120 ℃, 120 ℃, 120 ℃, 120 ℃.Screw speed 60rpm, 2.0mm, screen cloth 10 orders are set in the rolling press slit.Make the particle of 2.0mm size.
Comparative example 1: the manufacturing of comparative sample a
Four [the β-(4-hydroxyl-3 that mix 12.5 mass parts, the 5-di-tert-butyl-phenyl) propionic acid] pentaerythritol ester, the tricresyl phosphite of 25 mass parts (2, the 4-di-tert-butyl-phenyl) ester, 12.5 the calcium stearate of mass parts, the diethyl benzal sorbyl alcohol as nucleator of 50 mass parts.Use pair roller to suppress the tablets press granulation.Make the particle of size about 1.5mm.
Assessment example 1:
Will be according to the banburying 5 minutes in Banbury mixer of the composition of the proportioning (actual prescription is identical) of table two record, the melt blending temperature is at 195 ℃, and blend sample temperature with 230 ℃ on the compression molding instrument is molded into film, and slowly reduces to room temperature.Estimate its transparent rate and haze value, the result as shown in Table 1:
Table one:
| Sequence number | Proportioning | Transparent rate | Haze value |
| Comparative Examples | 100 parts of polypropylene, 0.4 part of comparative sample a, | 86.2 | 31.9 |
| Embodiment | 100 parts of polypropylene, 0.4 part of test sample C | 86.8 | 30.6 |
There is table one to confirm, uses the composite additive of the band nucleator of the utility model manufacturing, result of use is preferably arranged.
Claims (5)
1, a kind of equipment of making the polymkeric substance composite additive is characterized in that comprising successively extrusion device, calender device, refrigerating unit, broken whole grain device and gradation device, and the discharge port of extrusion device and the opening for feed of calender device are pressed close to install up and down.
2, the equipment of manufacturing polymkeric substance composite additive according to claim 1 is characterized in that described extrusion device is the screw rod extrusion device.
3, the equipment of manufacturing polymkeric substance composite additive according to claim 1 is characterized in that described extrusion device is a parallel double-screw extruder.
4, the equipment of manufacturing polymkeric substance composite additive according to claim 1 is characterized in that described calender device is a twin-roll rolling unit.
5, the equipment of manufacturing polymkeric substance composite additive according to claim 1 is characterized in that described refrigerating unit adopts revolution steel band cooler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNU2004200408154U CN2701614Y (en) | 2004-05-24 | 2004-05-24 | Device for preparing polymer composite additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNU2004200408154U CN2701614Y (en) | 2004-05-24 | 2004-05-24 | Device for preparing polymer composite additive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN2701614Y true CN2701614Y (en) | 2005-05-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNU2004200408154U Expired - Lifetime CN2701614Y (en) | 2004-05-24 | 2004-05-24 | Device for preparing polymer composite additive |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966731A (en) * | 2010-07-06 | 2011-02-09 | 苏州市科创聚合物有限公司 | Device for automatically alarming breaking of water-cooling bracing wire size dicing production line of double-screw extruder |
| CN104549695A (en) * | 2014-12-19 | 2015-04-29 | 成都迅德科技有限公司 | Tablet crusher |
| CN106232221A (en) * | 2014-02-21 | 2016-12-14 | 艾得文瑞士有限公司 | Process for forming dust-free additive granules |
| CN107498740A (en) * | 2017-09-26 | 2017-12-22 | 杭州新恒诺机械有限公司 | Low temperature granulating machine and plastic film recovery system |
| CN109593269A (en) * | 2018-11-22 | 2019-04-09 | 江苏金发科技新材料有限公司 | Low melting point powder auxiliary agent master batch of high concentration and preparation method thereof |
| CN112157849A (en) * | 2020-08-28 | 2021-01-01 | 王园红 | Cooling plastic wrap device capable of controlling air cooling and water cooling combination according to moving speed |
-
2004
- 2004-05-24 CN CNU2004200408154U patent/CN2701614Y/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966731A (en) * | 2010-07-06 | 2011-02-09 | 苏州市科创聚合物有限公司 | Device for automatically alarming breaking of water-cooling bracing wire size dicing production line of double-screw extruder |
| CN106232221A (en) * | 2014-02-21 | 2016-12-14 | 艾得文瑞士有限公司 | Process for forming dust-free additive granules |
| CN104549695A (en) * | 2014-12-19 | 2015-04-29 | 成都迅德科技有限公司 | Tablet crusher |
| CN107498740A (en) * | 2017-09-26 | 2017-12-22 | 杭州新恒诺机械有限公司 | Low temperature granulating machine and plastic film recovery system |
| CN109593269A (en) * | 2018-11-22 | 2019-04-09 | 江苏金发科技新材料有限公司 | Low melting point powder auxiliary agent master batch of high concentration and preparation method thereof |
| CN112157849A (en) * | 2020-08-28 | 2021-01-01 | 王园红 | Cooling plastic wrap device capable of controlling air cooling and water cooling combination according to moving speed |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CU01 | Correction of utility model |
Correction item: Patentee Correct: Yang Baozhu|Guo Sheng|Diao Chunsen|Liu Jizhao|Shi Zhijian|Peng Guolin|Zhao Yanbin|Lian Yebo|Wang Shuhong|Zhao Yingkui|Jiang Shanjun|Qi Siqing|Li Donghua|Zhang Zhichuan|Li Dehong|Chang Xusheng|Li Yong|Ma Lijun False: Yang Baozhu|Guo Sheng|Diao Chunsen Number: 21 Volume: 21 |
|
| CU03 | Publication of corrected utility model |
Correction item: Patentee Correct: Yang Baozhu|Guo Sheng|Diao Chunsen|Liu Jizhao|Shi Zhijian|Peng Guolin|Zhao Yanbin|Lian Yebo|Wang Shuhong|Zhao Yingkui|Jiang Shanjun|Qi Siqing|Li Donghua|Zhang Zhichuan|Li Dehong|Chang Xusheng|Li Yong|Ma Lijun False: Yang Baozhu|Guo Sheng|Diao Chunsen Number: 21 Volume: 21 |
|
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |
Expiration termination date: 20140524 Granted publication date: 20050525 |