Stable free radical as catalyst of polymerization of ethylene-unsaturated monomers

专利摘要:
Persistent perfluoroalkyl tertiary free radicals having at least 8 carbon atoms and at least one secondary or tertiary perfluorinated alkyl group attached directly to the central tri-valent carbon, and catalysts containng them are disclosed which upon thermal decomposition yield free radicals which can be used in processes to polymerize polymerizable monomers containing ethylenic unsaturation.
公开号:SU1530626A1
申请号:SU843805273
申请日:1984-10-23
公开日:1989-12-23
发明作者:В. Щерер Кирби (Младший)；Оно Тандзо；Яманоути Коуити
申请人:Дзе Грин Кросс Корпорейшн (Фирма)；Юниверсити Оф Саутерн Калифорния (Фирма)；
IPC主号:

专利说明:

This invention relates to a novel compound, namely a stable free radical of the formula
CFjCF-C-CFCFs (I)
CF (CF3) 2
where R and R, j are independently F or CFj,
as a catalyst for the polymerization of ethylenically unsaturated compounds.
Example 1. A mixture of 20 g of trimer A
(CFj) - CFCCFj)
and trimer B
(CFs CF-C-CF SGS SG (SGS) 2
(molar ratio, 7: 1) is placed in a 50 ml teflon chamber for carrying out the reaction, flushed with nitrogen at a feed rate of about 5 ml / min for 20 minutes, then fluorinated at 25 C by sparging with undiluted fluorine at a feed rate of 10 ml / min through the mixture by means of an inlet tube lowered to the bottom of the liquid trimer. The radical content is measured by the Evans method. Found that the maximum is consistent with the SL
00
about
Od
to
O5
about 35 wt. radical (1), reached after 6 hours
The reaction is repeated, but with. In this case, the same maximum concentration of the radical is reached after 18 hours. In each of the two cases, the concentration of the radical decreases if fluoridation continues for a longer time than the specified time.
The radical (l) is isolated in its pure form by gas chromatography using the stationary phase at 6 ° C.
Free radicals can also be isolated by distillation under reduced pressure.
Analyzes of solutions of the radical obtained by the described method by means of electron spin resonance spectroscopy show the presence of only one radical of the structure (l).
Analysis of the reaction mixture by gas chromatography shows that make-up artist 8 is completely consumed at the point where the maximum concentration of the radical is reached, so that trimer B reacts with fluorine faster than trimer A. In addition to TorOj, the radical (H) can be formed from both make-up artists, however more effectively from Trimer B, Radical (T.) has 9 carbon atoms, its structure has been proven by EPR-sp.
Example2. 8 a small tube with a diameter of 8 m from a stack / a. Pyrex, sealed from one co., Is placed approximately 1.0 g of freshly distilled styrene monomer and 10 kg of the solution of the radical (I) obtained in Example 1. Then the tube is degassed , sealed in vacuum and heated at 80 ° C for 6 hours. By the end of this period of time, the tube is filled with solid polymer. Control experiments show the absence of timification, if there is no radical (l). The same result is obtained with another experiment with an acrylo-nitrile monomer,
PRI me R 3. Obtaining radical (II).
1 μl of the solution of the radical (I) prepared, for example, combined with approximately 0, ml of the mixture of trimers Au B, as well as with 0.6 ml of fluorisohexane, the solution is degassed and sealed under vacuum in a mm quartz tube, which further heated k h at, the tube is cooled to
,
- Q
-15 2Q
25 Q
d d5

50
55
natal temperature and analyzed by the method of EPR spectroscopy. The radical (I) containing 10 carbon atoms is detected at a concentration approximately equal to the initial concentration of the radical (l). The structure of the radical is proved by the EPR spectrum.
PRI me R 4. Preparation of the diethyl x-propyl methyl radical (radical III) (has 8 carbon atoms).
The solution of the radical (l) obtained by the method described above is decomposed by heating at 100 ° C to obtain a reaction mixture containing the E- and Z-isomers of G-3 isopropyl-2-pentene. The isomers of 3-isopropyl-2-pentene are isolated by distillation using a column like spiral ribbon. The resulting mixture is fluorinated at room temperature by bubbling pure fluorine or fluorine diluted with nitrogen for several hours.
According to the EPR spectroscopy, the mixture contains a diethyl isopropylmethyl radical, which is resistant to air oxidation. The proposed free radical has the following characteristics: a half-life of days at 20 ° C, 19.8 years at 0 ° C. The structure is proved by EPR-spectrum data.
PRI me R 5. A mixture of 20 g of trimer L. and trimer B (molar ratio A to B 1.751) was placed in a 50 ml Teflon reaction chamber, purged with nitrogen at a flow rate of 5 ml / min for 20 minutes, then, at 25 ° C, it is fluorinated by bubbling through a mixture of undiluted fluorine at a rate of 10 ml / min through a tube reaching the bottom of the reactor with liquid trimers. After 6 h, the reaction is stopped. The resulting radical (1) is isolated in its pure form by gas chromatography using as a stationary phase a perfluorinated polyether with the company name Fomlin at 60 ° C. The resulting radical (l) at and 1 atm is v liquid, the yield of the radical Zb%. The radical (l) and its thermal decomposition products are analyzed by EPR and NMR spectroscopy to determine the structure.
The radical (l) has a branched structure, contains 9 carbon atoms and corresponds to the following formula: (CFj) 2CF-C-CF2CF3
The radical (ll) has a branched structure, contains 10 carbon atoms and corresponds to the following formula:
(Cf5) 2CF-C-CF (CFj) 2 CE (SGS) 2:
The radical (III) has a branched structure, contains 8 carbon atoms and corresponds to the following formula:
 -CPCFj
SG (CPP) 2
Compared radical 1 has a branched structure (the degree of branching is low), contains 7 carbon atoms 4 × DA and corresponds to the following formula:
CFsCF-CF-CFCF- 1 I L
CF3
U
Compared radical 2 has a normal structure, contains 8 carbon atoms and corresponds to the following formula;
CE, (CP2) BSK
Each radical is stored for a month at 2S ° C under the influence of recolymerization can be carried out using conventional techniques, for example, periodically, continuously, in multistage. For example, operations on a periodic basis require the use of systems of closed capacitive polymerization. In continuous operations, heated tubes are used, through which the gas radical is passed through the reaction with oxygen or not.
The results are shown in tableJ
Radical
spirit, after which the determined-30 different reagents are determined. Polymerization is needed to complete the two-step and conventional batch polymerization, which is carried out continuously. The duration of polymerization can be varied in
J, wide limits, however, it should be in the range from 10 minutes to 8 hours. Conventional measuring techniques, such as visco, can be used to monitor the progress of the polymerization.
40 gauge for measuring intrinsic viscosity. To stop the polymerization, shut off the flow of monomers or cool the reaction mixture to about.
I
Interaction with oxygen
I
II
III
Compare 1 Compare 2
excellent stability in comparison with the known.
The proposed radicals can be used to polymerize one or more ethylenically unsaturated monomers in an aqueous or non-aqueous reaction medium. Tetrafluoroethylene, trifluoroethylene, vinilidene fluoride, vinyl fluoride, hexafluoropropane, chlorotrifluoroethylene, 3,3,3-trifluoropropane and fully fluorinated alkoxytrifluoroethylene can be used as monomers.
Ethylene, propylene, butene, acrylic acid, methacrylic acid can also be used as monomers.
The proposed catalysts are used in an amount of 0.01 - 2.0 May ..
Polymerization can be carried out using conventional techniques, for example, periodically, continuously, in multistage steps. For example, intermittent operation requires the use of closed-capacitance polymerization systems. In continuous operations, heated tubes are used through which gas is passed
EXAMPLE 4 and n. E. The - - radical does not react with oxygen and remains unchanged; + - radical
interacts with the plant
oxygen and the loss from the results shown in the table shows that the compared radicals, having a normal structure (or a low degree of branching), are highly reactive with respect to oxygen and completely disappear when stored for 1 month in air at. Thus, the proposed branched radicals possess
45
Formula
acquisitions
The stable free radical of the general formula
RI I .1
CFjCF -C -CFCFj
CF (CF3) 2
where R and Ka independently denote or CPZ,
as a catalyst for the polymerization of ethylenically unsaturated monomers.

权利要求:
Claims (1)
[1]
^ Claims
Stable free radical of general formula m, in ₂ ι · ι CFj CF ~ C —CFCFj
CF (CF ₃ ) 2 where R (and Kg are independently ^F or CF ₃ , as a polymerisation catalyst for ethylenically unsaturated monomers.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3594358A|1967-09-28|1971-07-20|Phillips Petroleum Co|Catalyst composition,process of preparation,and polymerization process and product|

---

NL7408139A|1973-06-23|1974-12-30|US4698177A|1985-04-16|1987-10-06|Dainippon Ink And Chemicals, Inc.|Cyclohexylcyclohexene derivatives|

---

DE3765351D1|1986-07-31|1990-11-08|Montedison Spa|METHOD FOR THE POLYMERIZATION OF ALPHA OLEFINS OR THEIR MIXTURES WITH AETHYLENE USING A MICROSPHAEROIDAL, PARTICLE-SHAPED, SOLID CATALYST COMPONENT OR A PRE-PREPARATORY CATALYST.|

---

IT1215418B|1987-04-10|1990-02-08|Ausimont Spa|PERFLUOROALKANS OBTAINED BY PHOTOCHEMICAL FLUORURATION AND THEIR USE AS POLYMERIZATION INITIATORS.|

---

IT1228944B|1987-08-27|1991-07-10|Ausimont Spa|PERFLUORALCHENI AND THEIR FLUORURATION PRODUCTS|

---

IT1217182B|1988-04-22|1990-03-14|Ausimont Spa|POLIPERFLUORAMMINOETERI|

---

US5196595A|1988-04-22|1993-03-23|Ausimont S.R.L.|Polyperfluoroaminoethers|

---

IT1227128B|1988-09-20|1991-03-19|Ausimont Spa|PERFLUOROALKYLALOGENIDE BRANCHED AND THEIR PREPARATION|

---

US5059728A|1990-06-29|1991-10-22|Allied-Signal Inc.|Partially fluorinated alkanes having a tertiary structure|

---

US5087777A|1990-12-04|1992-02-11|Allied-Signal Inc.|Partially fluorinated alkenes having a tertiary structure|

---

CZ288922B6|1992-01-29|2001-09-12|Basf Aktiengesellschaft|Carbamates and preparations for plant protection in which the carbamates are comprised|

---

JP4227742B2|2001-11-16|2009-02-18|独立行政法人産業技術総合研究所|Highly branched perfluoroolefins, extremely stable perfluoroalkyl radicals and methods for their production|

---

JP3954363B2|2001-11-16|2007-08-08|独立行政法人産業技術総合研究所|Low molecular radical supply method, radical carrying molecule, polymer production method and polymer|

---

US7723447B2|2002-12-20|2010-05-25|Exxonmobil Chemical Patents Inc.|Polymerization processes|

---

JP4441487B2|2002-12-20|2010-03-31|エクソンモービル・ケミカル・パテンツ・インク|Polymerization process|

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CA2510860C|2002-12-20|2012-10-09|Exxonmobil Chemical Patents Inc.|Polymerization process utilizing hydrofluorocarbons as diluents|

---

US7425601B2|2002-12-20|2008-09-16|Exxonmobil Chemical Patents Inc.|Polymers with new sequence distributions|

---

WO2006009942A1|2004-06-21|2006-01-26|Exxonmobil Chemical Patents Inc.|Polymerization process|

---

US7858736B2|2004-06-21|2010-12-28|Exxonmobil Chemical Patents Inc.|Polymer recovery method|

---

WO2006009945A1|2004-06-21|2006-01-26|Exxonmobil Chemical Patents Inc.|Impact copolymers|

---

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---

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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US06/482,359|US4626608A|1983-04-05|1983-04-05|Persistent perfluoroalkyl free radicals useful as polymerization catalyst|

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