Process for preparing long-chain polymethylene halide telomers

• US 7,893,186 B2
• Filed: 12/27/2007
• Issued: 02/22/2011
• Est. Priority Date: 12/29/2006
• Status: Expired due to Fees

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Yang, Yu, Moore, George G. I.
• Primary Examiner(s): Boykin; Terressa M
• Application Number:
  US12/519,649
• Publication Number:
  US 20090312517A1
• Time in Patent Office: 1,153 Days
• Field of Search: 528/70, 528/271, 528/272, 528/373, 528/392, 528/397
• US Class Current: 528/271
• CPC Class Codes: C07C 17/275 of hydrocarbons and halogenated hydrocarbons
• CPC Class Codes: C07C 19/14 and bromine
• CPC Class Codes: C07C 19/16 and iodine
• CPC Class Codes: C07C 309/82 of a carbon skeleton substituted by singly-bound oxygen atoms
• CPC Class Codes: C07C 311/09 the carbon skeleton being further substituted by at least two halogen atoms
• CPC Class Codes: C07C 43/126 having more than one ether bond
• CPC Class Codes: C07C 69/63 of saturated acids
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 120/24 containing perhaloalkyl radicals
• CPC Class Codes: C08F 120/36 containing oxygen in addition to the carboxy oxygen , e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
• CPC Class Codes: C08F 2/38 Polymerisation using regulators, e.g. chain terminating agents , e.g. telomerisation
• CPC Class Codes: C08F 220/24 containing perhaloalkyl radicals
• CPC Class Codes: C08F 8/10 Acylation
• CPC Class Codes: C08F 8/12 Hydrolysis
• CPC Class Codes: C08F 8/14 Esterification
• CPC Class Codes: C08G 18/2885 containing halogen atoms
• CPC Class Codes: C09D 175/04 Polyurethanes
• CPC Class Codes: D06M 15/256 containing fluorine
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers

Abstract

A process comprises combining in a batchwise, semi-continuous, or continuous manner, or a combination thereof, in the presence of at least one free radical initiator, and at a temperature sufficient to cause the initiator to fragment to form free radicals, (a) at least one telogen selected from (1) fluoroalkyl halides that comprise at least one halomethylene moiety (—CHX—) and, optionally, at least one non-fluorine heteroatom, and (2) perfluoroalkyl halides that comprise at least one halofluoromethylene moiety (—CFX—) and at least one non-halogen heteroatom, the halides being selected from iodides and bromides; and (b) ethylene; the telogen and the ethylene being combined in total amounts such that the number of moles of ethylene per mole of telogen is at least about 4.

Claims

1. A process comprising combining in a batchwise, semi-continuous, or continuous manner, or a combination thereof, in the presence of at least one free radical initiator, and at a temperature sufficient to cause said initiator to fragment to form free radicals, (a) at least one telogen selected from (1) fluoroalkyl halides that comprise at least one halomethylene moiety (—

CHX—

) and, optionally, at least one non-fluorine heteroatom, and (2) perfluoroalkyl halides that comprise at least one halofluoromethylene moiety (—

CFX—

) and at least one non-halogen heteroatom, said halides being selected from iodides and bromides; and

(b) ethylene;

said telogen and said ethylene being combined in total amounts such that the number of moles of ethylene per mole of telogen is at least 4.

2. The process of claim 1, wherein said telogen is selected from said fluoroalkyl halides and mixtures thereof.

3. The process of claim 1, wherein said halide is iodide.

4. The process of claim 1, wherein said halide is bromide.

5. The process of claim 1, wherein said telogen is saturated.

6. The process of claim 1, wherein said heteroatoms are selected from iodine, bromine, nitrogen, oxygen, sulfur, and mixtures thereof.

7. The process of claim 1, wherein said number of moles of ethylene per mole of telogen is at least 8.

8. The process of claim 1, wherein said number of moles of ethylene per mole of telogen is at least 10.

9. The process of claim 1, wherein said number of moles of ethylene per mole of telogen is at least 2 times the average number of moles of ethylene taxomons incorporated in the resulting telomer product, as calculated from the number average molecular weight of the product.

10. The process of claim 1, wherein said telogen is selected from the class of fluoroalkyl halides that is represented by the following general formula:

R′

CH(R)X 

 

(I)

wherein R′

is fluorine or a fluoroalkyl or perfluoroalkyl group of 1 to 25 carbon atoms that optionally comprises at least one non-fluorine heteroatom and/or at least one alicyclic moiety;

R is hydrogen, fluorine, or a fluoroalkyl or perfluoroalkyl group of 1 to 25 carbon atoms that optionally comprises at least one non-fluorine heteroatom and/or at least one alicyclic moiety; and

X is iodine or bromine;

with the proviso that optionally R′ and

R are bonded together to form an alicyclic ring having from 5 to 7 ring carbon atoms.

11. The process of claim 10, wherein said telogen is selected from CF₃CH₂I, CF₃OCH(CF₃)I, CF₃CH(CF₃)Br, H(CF₂)₆CH₂I, CF₃C₃H₆I, C₂F₅C₂H₄I, CF₃CH₂Br, C₂F₅C₂H₄Br, (CF₃)₂CFCH₂I, C₄F₉C₂H₄I, C₄F₉C₃H₆I, C₄F₉C₄H₈Br, C₆F₁₃CH₂Br, CF₃OC₂H₄I, C₄F₉OCH₂Br, C₃F₇CH₂OC₂H₄I, C₄F₉SO₂N(CH₃)C₂H₄I, C₂F₅OC₂F₄C₂H₄I, CF₃OC₂F₄CH₂Br, (CF₃)₂CHOC₂H₄I, C₂F₅SO₂N(CH₃)CH₂C(O)CH₂I, (CF₃)₂NC₂F₄CH₂I, C₃F₇N(CF₃)CF₂C₂H₄Br, FSO₂C₃F₆C₂H₄I, (CF₃)₂NCH₂I, (CF₃)₂NCF₂CH₂I, CH₃OC(O)C₄F₈CH₂I, (CF₃)₂CHI, and mixtures thereof.

12. The process of claim 1, wherein said telogen is a telogen mixture that is prepared by the process of claim 1 and recycled for further telomerization.

13. The process of claim 1, wherein said telogen is selected from the class of perfluoroalkyl halides that is represented by the following general formula:

R′

″

CF(R″

)X 

 

(II)

wherein R′

″

is a perfluoroalkyl group of 1 to 25 carbon atoms that optionally comprises at least one alicyclic moiety and/or at least one non-fluorine halogen atom;

R″

is fluorine or a perfluoroalkyl group of 1 to 25 carbon atoms; and

X is iodine or bromine;

with the proviso that at least one of R′

″ and

R″

comprises at least one non-halogen heteroatom, and with the further proviso that R′

″ and

R″

optionally are bonded together to form an alicyclic ring having from 5 to 7 ring carbon atoms.

14. The process of claim 13, wherein said telogen is selected from FSO₂C₂F₄OC₂F₄I, FSO₂C₃F₆Br, CF₃OC₂F₄I, CF₃OCF(CF₃)I, (CF₃)₂CFOC₂F₄I, C₃F₇O(i-C₃F₆O)_pCF(CF₃)I (where p is an integer of 0 to 7), C₃F₇O(n-C₃F₆O)_pCF(CF₃)I (where p is an integer of 0 to 7), C₃F₇O(i-C₃F₆O)_pCF(CF₃)Br (where p is an integer of 0 to 7), FOC(O)C₅F₁₀I, and mixtures thereof.

15. The process of claim 1, wherein said telogen comprises a sulfonamido moiety, a perfluoropolyether moiety, or a perfluoroalkyl moiety having fewer than 6 carbon atoms.

16. The process of claim 1, wherein said temperature is from 0°

C. to 250°

C.

17. The process of claim 1, wherein said process is carried out in an inert reaction environment.

18. The process of claim 1, wherein said free radical initiator is selected from azo compounds, peroxides, hydroperoxides, peracids, peresters, thermal redox initiators, and mixtures thereof.

19. The process of claim 1, wherein said process further comprises (a) combining at least one resulting polymethylene halide telomer with at least one metal carboxylate;

and (b) subjecting the resulting polymethylene carboxylate to alkanolysis;

wherein said combining and said subjecting are carried out under substantially anhydrous conditions.

20. A process comprising combining in a batchwise, semi-continuous, or continuous manner, or a combination thereof, in the presence of at least one free radical initiator selected from azo compounds, peroxides, peresters, and mixtures thereof, under substantially oxygen-free conditions, and at a temperature from 75°

C. to 125°

C., (a) at least one telogen selected from (1) the class of fluoroalkyl halides that is represented by the following general formula;

R′

CH(R)X 

 

(1)

wherein R′

is a fluoroalkyl or perfluoroalkyl group of 1 to 25 carbon atoms that optionally comprises at least one non-fluorine heteroatom;

R is hydrogen or a perfluoroalkyl group of 1 to 6 carbon atoms; and

X is iodine or bromine; and

(2) the class of perfluoroalkyl halides that is represented by the following general formula;

R′

″

CF(R″

)X 

 

(II)

wherein R′

″

is a perfluoroalkyl group of 1 to 25 carbon atoms that comprises at least one non-halogen heteroatom;

R″

is fluorine or a perfluoroalkyl group of 1 to 6 carbon atoms; and

X is iodine or bromine; and

(b) ethylene;

said telogen and said ethylene being combined in total amounts such that the number of moles of ethylene per mole of telogen is at least 8.