CN100363407C - Surface fluorination treatment process for off-line polymer product - Google Patents
Surface fluorination treatment process for off-line polymer product Download PDFInfo
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- CN100363407C CN100363407C CNB2005100223960A CN200510022396A CN100363407C CN 100363407 C CN100363407 C CN 100363407C CN B2005100223960 A CNB2005100223960 A CN B2005100223960A CN 200510022396 A CN200510022396 A CN 200510022396A CN 100363407 C CN100363407 C CN 100363407C
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- 238000000034 method Methods 0.000 title claims description 62
- 238000003682 fluorination reaction Methods 0.000 title claims description 46
- 229920000642 polymer Polymers 0.000 title claims description 19
- 239000007789 gas Substances 0.000 claims description 42
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 34
- 229910052731 fluorine Inorganic materials 0.000 claims description 34
- 239000011737 fluorine Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- 238000004334 fluoridation Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 14
- 230000000149 penetrating effect Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 9
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 9
- 238000013459 approach Methods 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 229920001903 high density polyethylene Polymers 0.000 description 6
- 239000004700 high-density polyethylene Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention discloses a fluorination treatment technology for the surfaces of off-line polymer products. The technology comprises the steps that first, a reactor is heated by cyclic nitrogen in order that the temperature in the reactor is controlled between 20 DEG C and 60 DEG C, the vacuum is pumped, a first portion of mixture gas of the fluorine gas and the nitrogen is filled in the reactor, the concentration of the fluorine gas in the reactor is between 0.5%(V/V) and 10.0%(V/V), and the cyclic reaction of polymer products in the reactor lasts for 0.5 to 4.0 hours; the temperature is raised to 30 DEG C to 90 DEG C, then a second portion of mixture gas of the fluorine gas and the nitrogen is filled in the reactor, the use quantity of the second portion of mixture gas is 20% to 200%(V%) of that of the first portion of mixture gas of the fluorine gas and the nitrogen, and the cyclic reaction lasts for 0.5 to 5.0 hours; the pressure of the reactor in the fluorination treatment technology process is smaller than one atmospheric pressure. When the present invention is used, the fluorination reaction on the surfaces of polymer materials is uniform and effective, the baffling property of products can be enhanced by 2 to 5 times, and simultaneously the total consumption of the mixture gas of the fluorine gas and the nitrogen can be further reduced.
Description
Technical field
The present invention relates to a kind of production technique of surfaces of polymeric articles fluoridation, specifically, relate to a kind of off-line type fluoridation surfaces of polymeric articles technology.
Background technology
Polymer product comprises the fuel tank made by polyethylene, polypropylene material, oil pipe, Plastic Bottle, polymeric film etc.After surfaces of polymeric articles carried out fluoridation, can form a large amount of carbon fluorine chemistry bond structures, and make crosslinking reaction takes place between the polymer chain on its surface.The process of this substitution reaction is irreversible, and the barrier layer of formation and whole polymeric matrix form indivisible integral body with covalent bonding.This barrier layer is similar to the tetrafluoroethylene structure, has good obstruct, chemical resistance.The anti-solvent penetrating quality of the polymer product after fluoridation can improve significantly.Because above-mentioned fluoridation occurs over just the surface as thin as a wafer of polymer product, about 50～500 dusts, thereby the mechanical property of polymer materials is unaffected.
At present, the method for fluoridation surfaces of polymeric articles mainly comprises online fluorination method and off-line fluorination method.Online fluorination method, its advantage are blow-moulding process is organically combined with fluoridation technology, thereby have improved production efficiency.But it only limits to the goods of blow molding, and complex structure, massive article are seemed powerless, so this flaorination process is mainly used in the production of fluoridizing bottle.Last century the eighties, the off-line type flaorination process is developed, back fluorination process just, the goods that are about to after the moulding carry out fluoridation again.This fluorination process to shape of products, size and forming method in advance without limits, and flaorination process is safer, operating procedure elasticity is bigger, can carry out the adjustment of technology at an easy rate according to technical requirement.
Off-line type flaorination process inventor is the union carbide corporation (Union Carbide Corporation) of the U.S., its relevant patent US4484954, US4142032 has related generally to some basic concrete fluorination treatment process parameters of off-line type fluoridation, has established the fundamental technology method of off-line type fluoridation.In U.S. Pat 3998180, what relate generally among the US4081574 is the equipment and the corresponding flaorination process technology of off-line type flaorination process, and its Technology mainly is to shift hydrofluoric process unit of by product and using method thereof about increased absorption in fluorination reaction process.U.S. Pat 457687 adopts in fluorination process, by pressurization, the operation of circulation technologies such as decompression, thereby the by product hydrogen fluoride that helps the fluoridation generation takes off suction from product surface as far as possible, and help deeply carrying out of fluoridation, with the fluorination effect of raising goods, but the operating procedure complexity is had relatively high expectations to device systems.In addition, there is report to adopt carbon dioxide to replace nitrogen to mix, utilizes the bigger heat enthalpy value of carbon dioxide, reach the purpose that improves fluorination effect with fluorine gas; Also have to adopt fluorine gas to be cooled to-160～0 ℃ earlier, carry out the method for fluoridation again, reach the purpose that improves the goods barrier property.Above fluoridation all is to adopt the disposable method that charges into fluorine gas.Because the high chemically reactive of fluorine gas, control fluoridation speed just becomes the key of technology.In the method that once charges into fluorine gas; the concentration of initial fluorine gas is higher relatively; regular meeting is owing to the violent heat effect of initial reaction causes fluoridizing the product surface local damage, thereby makes the fluorinated layer of product surface inhomogeneous, not fine and close, causes the barrier property of goods to descend.
Summary of the invention
The technical problem to be solved in the present invention is based on the basis of traditional off-line type single stage method flaorination process, provide a kind of fluoridation more even, more effective two-step approach flaorination process, this technology can improve the barrier property of fluoridizing goods, can reduce the total flow of delivery of fluorine/nitrogen gas mixture simultaneously.
For solving the problems of the technologies described above, the fluorination treatment process on off-line polymer product of the present invention surface comprises the following steps:
(1) goods that will treat fluoridation are put into reactor, and behind air in the nitrogen replacement fluorination reactor, by the heat exchanger heating that circulates, reactor temperature is controlled at 20～60 ℃ to the ON cycle pump under normal pressure;
(2) vacuumize;
(3) charge into first part of delivery of fluorine/nitrogen gas mixture, make that the fluorine gas concentration of volume percent is 0.5～10.0% in the reactor, reactor interpolymer goods circulating reaction 0.5～4.0 hour;
(4) elevated temperature to 30～90 ℃, charge into second part of delivery of fluorine/nitrogen gas mixture again, its consumption is 20%～200% of first part of delivery of fluorine/nitrogen gas mixture consumption volume, circulating reaction 0.5～5.0 hour, and the pressure of described fluorination treatment process process reactor is less than a normal atmosphere.
Step (2), (3) described first part of delivery of fluorine/nitrogen gas mixture and second part of delivery of fluorine/nitrogen gas mixture are with a kind of delivery of fluorine/nitrogen gas mixture.
The optimization of reaction conditions is as follows in the described processing step:
Reactor temperature is controlled at 30～50 ℃ in the step (1).Vacuumize make reactor pressure reduce to-0.06～-0.04MPa, further be optimized for-0.05MPa.The concentration of volume percent of the interior fluorine gas of reactor is 2～5% in the step (3), and the amount of the delivery of fluorine/nitrogen gas mixture that charges among the present invention is calculated with the concentration of fluorine gas in the reactor; Reaction times is 1 hour.Reactor temperature is controlled at 40～80 ℃ in the step (4); The consumption of the second part of delivery of fluorine/nitrogen gas mixture that charges into is 50%～150% of first part of delivery of fluorine/nitrogen gas mixture consumption volume; Reaction times is 0.5 hour.
The invention has the advantages that, with the disposable delivery of fluorine/nitrogen (F that charges into
2/ N
2) gas mixture technology changes the mode that controlled two-step approach charges into into, i.e. fluoridation initial stage low temperature, low concentration of fluorine; Later stage charges into F once more by the rising reactor temperature
2/ N
2Gas mixture makes the surface of polymer material fluoridation be in gentleness all the time, stablizes, continues the state that carries out, thereby makes fluorinated layer compact structure, evenly, and the barrier property of resulting product can improve 2～5 times.This technology has overcome in the disposable flaorination process that charges into fluorine gas, and it is excessive to fluoridize the initial stage fluorination rates, and later stage speed is too low shortcoming obviously.Simultaneously, adopt the two-step approach flaorination process, also can further reduce the total consumption of delivery of fluorine/nitrogen gas mixture.
Embodiment below in conjunction with the drawings and specific embodiments further specifies technical process of the present invention and beneficial effect.
Description of drawings
Accompanying drawing is a process flow diagram of the present invention.
Embodiment
High density polyethylene(HDPE) (HDPE) bottle of 120ml and 500ml is put into fluorination reactor 1 shown in the drawings, with nitrogen (N
2) in the displacement fluorination reactor 1 behind the air, ON cycle pump 4 under normal pressure by heat exchanger 2 heating that circulates.After treating that temperature reaches 40 ℃ of set(ting)values, be evacuated to pressure in the fluorination reactor 1, charge into the F of first part for behind-the 0.05MPa
2/ N
2Gas mixture, at this moment, F in the fluorination reactor
2The concentration of volume percent of gas is 2.0%, and the control of its concentration adopts gas meter 7 to finish.Behind the circulating reaction 1.0 hours, elevated temperature to 75 ℃ charges into second section F again
2/ N
2Gas mixture, its amount of charging into volume be for the first time the amount of charging into volume 150%, and continue 75 ℃ of reactions after 1.5 hours down, open vacuum system 6 again and carry out reaction end gas through exhaust gas treating device 5 and handle.Open fluorination reactor 1, taking-up is fluoridized bottle and is got final product.In the whole fluorination reaction process, the by product hydrogen fluoride that fluoridation produces is removed immediately by hydrogen fluoride resorber 3.This fluoridize the bottle penetrating quality and with do not fluoridize the bottle, single stage method fluoridize the bottle penetrating quality more as shown in table 1.In the table single stage method fluoridize the bottle preparation technology carry out according to patent US4484954 and US4142032, following examples are identical.
Table 1 the present invention fluoridizes the penetrating quality and the contrast experiment thereof of bottle
| The test result of 50 ℃ of following ten days dimethylbenzene | ||||
| The sample title | The fluoridation condition | The loss amount of dimethylbenzene | ||
| F 2Gas concentration, % | Reaction times, h | Temperature of reaction, ℃ | ||
| Do not fluoridize bottle | - | - | - | -50％ |
| Single stage method is fluoridized bottle | 5.0 | 2.5 | 60 | -0.5％ |
| Two-step approach is fluoridized bottle | 2.0，3.0 | 2.5 | 40，75 | -0.15％ |
The HDPE bottle of 120ml and 500ml is put into fluorination reactor 1, use N
2In the displacement fluorination reactor 1 behind the air, ON cycle pump 4 under normal pressure by heat exchanger 2 heating that circulates.After treating that temperature reaches 30 ℃ of set(ting)values, be evacuated to pressure in the reactor, charge into the F of first part for behind-the 0.06MPa
2/ N
2Gas mixture, at this moment, F in the reactor
2The concentration of volume percent of gas is 0.5%, and the control of its concentration adopts gas meter 7 to finish.Behind the circulating reaction 0.5 hour, elevated temperature to 60 ℃ charges into second section F again
2/ N
2Gas mixture, its amount of charging into volume be for the first time the amount of charging into volume 200%, and continue 60 ℃ of reactions after 1 hour down, open vacuum system 6 again and carry out reaction end gas through exhaust gas treating device 5 and handle.Open fluorination reactor 1, taking-up is fluoridized bottle and is got final product.In whole fluorination reaction process, the by product hydrogen fluoride that fluoridation produces is removed immediately by hydrogen fluoride resorber 3.This fluoridize the bottle penetrating quality and with do not fluoridize the bottle, single stage method fluoridize the bottle penetrating quality more as shown in table 2.
Table 2 the present invention fluoridizes the penetrating quality and the contrast experiment thereof of bottle
| The test result of 50 ℃ of following ten days dimethylbenzene | ||||
| The sample title | The fluoridation condition | The loss amount of dimethylbenzene | ||
| F 2Gas concentration, % | Reaction times, h | Temperature of reaction, ℃ | ||
| Do not fluoridize bottle | - | - | - | -50％ |
| Single stage method is fluoridized a bottle two-step approach and is fluoridized bottle | 5.0 0.5，1.0 | 2.5 1.5 | 60 30，60 | -0.5％ -0.25％ |
The HDPE bottle of 120ml and 500ml is put into fluorination reactor 1, use N
2In the displacement fluorination reactor 1 behind the air, ON cycle pump 4 under normal pressure by heat exchanger 2 heating that circulates.After treating that temperature reaches 20 ℃ of set(ting)values, be evacuated to pressure in the reactor, charge into the F of first part for behind-the 0.04MPa
2/ N
2Gas mixture, at this moment, F in the reactor
2The concentration of volume percent of gas is 2.0%, and the control of its concentration adopts gas meter 7 to finish.Behind the circulating reaction 2.0 hours, elevated temperature to 80 ℃ charges into second section F again
2/ N
2Gas mixture, its amount of charging into volume are with for the first time identical, and continuation, is opened vacuum system 6 again and carried out the reaction end gas processing through exhaust gas treating device 5 after 0.5 hour in reaction under 80 ℃.Open fluorination reactor 1, taking-up is fluoridized bottle and is got final product.In whole fluorination reaction process, the by product hydrogen fluoride that fluoridation produces is removed immediately by hydrogen fluoride resorber 3.This fluoridize the bottle penetrating quality and with do not fluoridize the bottle, single stage method fluoridize the bottle penetrating quality more as shown in table 3.
Table 3 the present invention fluoridizes the penetrating quality and the contrast experiment thereof of bottle
| The test result of 50 ℃ of following ten days dimethylbenzene | ||||
| The sample title | The fluoridation condition | The loss amount of dimethylbenzene | ||
| F 2Gas concentration, % | Reaction times, h | Temperature of reaction, ℃ | ||
| Do not fluoridize bottle | - | - | - | -50％ |
| Single stage method is fluoridized a bottle two-step approach and is fluoridized bottle | 5.0 2.0，2.0 | 2.5 2.5 | 80 20，80 | -1.0％ -0.2％ |
The HDPE bottle of 120ml and 500ml is put into fluorination reactor 1, use N
2In the displacement fluorination reactor 1 behind the air, ON cycle pump 4 under normal pressure by heat exchanger 2 heating that circulates.After treating that temperature reaches 50 ℃ of set(ting)values, be evacuated to pressure in the reactor, charge into the F of first part for behind-the 0.05MPa
2/ N
2Gas mixture, at this moment, F in the reactor
2The concentration of volume percent of gas is 1.0%, and the control of its concentration adopts gas meter 7 to finish.Behind the circulating reaction 0.5 hour, elevated temperature to 90 ℃ charges into second section F again
2/ N
2Gas mixture, its amount of charging into volume be for the first time the amount of charging into volume 200%, and continue 90 ℃ of reactions after 0.5 hour down, open vacuum system 6 again and carry out reaction end gas through exhaust gas treating device 5 and handle.Open fluorination reactor 1, taking-up is fluoridized bottle and is got final product.In whole fluorination reaction process, the by product hydrogen fluoride that fluoridation produces is removed immediately by hydrogen fluoride resorber 3.This fluoridize the bottle penetrating quality and with do not fluoridize the bottle, single stage method fluoridize the bottle penetrating quality more as shown in table 4.
Table 4 the present invention fluoridizes the penetrating quality and the contrast experiment thereof of bottle
| The test result of 50 ℃ of following ten days dimethylbenzene | ||||
| The sample title | The fluoridation condition | The loss amount of dimethylbenzene | ||
| F 2Gas concentration, % | Reaction times, h | Temperature of reaction, ℃ | ||
| Do not fluoridize bottle | - | - | - | -50％ |
| Single stage method is fluoridized a bottle two-step approach and is fluoridized bottle | 5.0 1.0，2.0 | 1.5 1 | 80 50，90 | -1.5％ -0.25％ |
From the foregoing description, fluoridize the bottle penetrating quality more as can be seen, two-step approach flaorination process of the present invention not only can improve the polymer product barrier property, also can further reduce the total flow of the delivery of fluorine/nitrogen gas mixture that charges into simultaneously.
Claims (10)
1. the fluorination treatment process on an off-line polymer product surface comprises the following steps:
(1) goods that will treat fluoridation are put into reactor, behind air in the nitrogen replacement fluorination reactor, the ON cycle pump under normal pressure by heat exchanger to the reactor heating that circulates, reactor temperature is controlled at 20～60 ℃;
(2) vacuumize;
(3) charge into first part of delivery of fluorine/nitrogen gas mixture, make that the fluorine gas concentration of volume percent is 0.5～10.0% in the reactor, reactor interpolymer goods circulating reaction 0.5～4.0 hour;
(4) elevated temperature to 30～90 ℃, charge into second part of delivery of fluorine/nitrogen gas mixture again, its consumption is 20%～200% of first part of delivery of fluorine/nitrogen gas mixture consumption volume, circulating reaction 0.5～5.0 hour, the pressure of described fluorination treatment process process reactor is less than a normal atmosphere
Step (2), (3) described first part of delivery of fluorine/nitrogen gas mixture and second part of delivery of fluorine/nitrogen gas mixture are with a kind of delivery of fluorine/nitrogen gas mixture.
2. the fluorination treatment process on a kind of off-line polymer product according to claim 1 surface is characterized in that, reactor temperature is 30～50 ℃ in the described step (1).
3. the fluorination treatment process on a kind of off-line polymer product according to claim 1 surface is characterized in that, in the described step (2) reactor pressure reduce to-0.06～-0.04MPa.
4. the fluorination treatment process on a kind of off-line polymer product according to claim 3 surface is characterized in that, reactor pressure is reduced to-0.05MPa in the described step (2).
5. the fluorination treatment process on a kind of off-line polymer product according to claim 1 surface is characterized in that, the interior fluorine gas concentration of volume percent of reactor is 2～5% in the described step (3).
6. the fluorination treatment process on a kind of off-line polymer product according to claim 1 surface is characterized in that, the reaction times is 1 hour in the described step (3).
7. the fluorination treatment process on a kind of off-line polymer product according to claim 1 surface is characterized in that, reactor temperature is 40～80 ℃ in the described step (4).
8. the fluorination treatment process on a kind of off-line polymer product according to claim 1 surface is characterized in that, the consumption of second part of delivery of fluorine/nitrogen gas mixture is 50%～150% of first part of delivery of fluorine/nitrogen gas mixture consumption volume in the described step (4).
9. the fluorination treatment process on a kind of off-line polymer product according to claim 1 surface is characterized in that, the reaction times is 0.5 hour in the described step (4).
10. the fluorination treatment process on a kind of off-line polymer product according to claim 1 surface is characterized in that described polymer product material comprises polyethylene and polypropylene.
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| CN101811367B (en) * | 2009-11-25 | 2012-06-27 | 瓮福（集团）有限责任公司 | Preparation method of ink permeation prevention pen sleeve |
| CN101787142B (en) * | 2009-12-31 | 2012-04-25 | 东莞广泽汽车饰件有限公司 | Surface treatment method of inert material auto parts |
| CN101880401B (en) * | 2010-06-24 | 2012-04-18 | 洛阳森蓝化工材料科技有限公司 | Polymer surface fluorination process |
| CN109486482B (en) * | 2017-09-11 | 2021-11-23 | 天津大学 | Carbon fluoride quantum dot, luminescent super-hydrophobic film, and preparation method and application thereof |
| KR102487702B1 (en) * | 2018-01-19 | 2023-01-12 | 쇼와 덴코 가부시키가이샤 | Method for producing tetrafluoromethane |
| CN111363121A (en) * | 2020-03-26 | 2020-07-03 | 上海稳优实业有限公司 | Method for improving tracking resistance of epoxy resin material |
| CN115487774A (en) * | 2022-09-20 | 2022-12-20 | 洛阳森蓝化工材料科技有限公司 | Device and method for preparing fluorinated asphalt |
| CN116535721B (en) * | 2023-06-20 | 2024-08-23 | 湖北卓熙氟化股份有限公司 | High-barrier fluorinated plastic ice box and preparation method thereof |
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| EP0816418B1 (en) * | 1996-07-01 | 2001-10-04 | Air Products And Chemicals, Inc. | An improved process for producing permeation resistant containers |
| DE10159885A1 (en) * | 2001-12-06 | 2003-06-26 | Messer Griesheim Gmbh | Fluorinating agent containing fluorine and helium, used for the treatment of plastics, especially plastic powder and plastics with a large surface area |
-
2005
- 2005-12-26 CN CNB2005100223960A patent/CN100363407C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6466246A (en) * | 1987-09-07 | 1989-03-13 | Mitsubishi Metal Corp | Method for treating surface of organic high polymer material |
| EP0816418B1 (en) * | 1996-07-01 | 2001-10-04 | Air Products And Chemicals, Inc. | An improved process for producing permeation resistant containers |
| DE10159885A1 (en) * | 2001-12-06 | 2003-06-26 | Messer Griesheim Gmbh | Fluorinating agent containing fluorine and helium, used for the treatment of plastics, especially plastic powder and plastics with a large surface area |
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| Title |
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| 聚烯烃塑料容器表面氟化改性. 陶圣如.化工进展，第3期. 1989 * |
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