Process for manufacturing a dispersion of a vinylidene fluoride polymer

Patent metadata

Field	Value
Publication number	US-9920141-B2
Application number	US-201013516017-A
Country	US
Kind code	B2
Filing date	Dec 15, 2010
Priority date	Dec 18, 2009
Publication date	Mar 20, 2018
Grant date	Mar 20, 2018

Abstract

A process for manufacturing a dispersions of a vinylidene fluoride (VDF) thermoplastic polymer [polymer (F)], said process comprising polymerizing VDF in an aqueous phase comprising:
at least one surfactant selected from the group consisting of non-fluorinated surfactants [surfactant (HS)] and fluorinated surfactants having a molecular weight of less than 400 [surfactant (FS)]; and at least one functional (per)fluoropolyether (functional PFPE) comprising at least one (per)fluoropolyoxyalkylene chain [chain (R′ F )] and at least one functional group, said functional PFPE having a number average molecular weight of at least 1000 and a solubility in water of less than 1% by weight at 25° C.,

wherein said functional PFPE is present in the aqueous phase in an amount of 0.001 to 0.3 g/l.

First claim

The invention claimed is:

1. A process for manufacturing a dispersion of a vinylidene fluoride (VDF) thermoplastic polymer [polymer (F)], said process comprising polymerizing VDF in an aqueous phase comprising:
at least one fluorinated surfactant (FS) complying with formula (IB) here below:

wherein:
X 1 , X 2 and X 3 , equal to or different from each other, are independently selected from the group consisting of H, F and C 1 -C 6 (per)fluoroalkyl groups, optionally comprising one or more catenary or non-catenary oxygen atoms,
R F represents a divalent perfluorinated C 1 -C 3 bridging group,
L represents a bond or a divalent group and
Y represents an anionic functionality, selected from the group consisting of:

wherein X a is a hydrogen atom, a monovalent metal, or an ammonium group of formula —N(R′ n ) 4 , wherein R′ n , equal or different at each occurrence, is a hydrogen atom or a C 1 -C 6 hydrocarbon group;
wherein the at least one fluorinated surfactant has a molecular weight of less than 400; and
at least one functional (per)fluoropolyether (functional PFPE) comprising at least one (per)fluoropolyoxyalkylene chain [chain (R′ F )] and at least one functional group, said functional PFPE having a number average molecular weight of at least 1000 and a solubility in water of less than 1% by weight at 25° C.,
wherein said functional PFPE is present in the aqueous phase in an amount of 0.001 to 0.3 g/L.

2. The process of claim 1 , wherein the fluorinated surfactant (FS) complies with formula (IIIB) here below:

wherein:
X 1 , X 2 and X 3 , equal to or different from each other, are independently selected from the group consisting of H, F and C 1 -C 6 (per)fluoroalkyl groups, optionally comprising one or more catenary or non-catenary oxygen atoms,
R F represents a divalent perfluorinated C 1 -C 3 bridging group, and
X a is a hydrogen atom, a monovalent metal, or an ammonium group of formula —N(R′ n ) 4 , wherein R′ n , equal or different at each occurrence, is a hydrogen atom or a C 1 -C 6 hydrocarbon group.

3. The process of claim 1 , wherein the fluorinated surfactant (FS) complies with formula (VIIIB) here below:

wherein:
R F represents a divalent perfluorinated C 1 -C 3 bridging group;
X a is a hydrogen atom, a monovalent metal, or an ammonium group of formula —N(R′ n ) 4 , wherein R′ n , equal or different at each occurrence, is a hydrogen atom or a C 1 -C 6 hydrocarbon group;
X* 1 and X* 2 , equal to or different from each other, are independently a fluorine atom, a —R′ f group or a —OR′ f group, wherein R′ f is a C 1 -C 3 perfluoroalkyl group;
R* f is a divalent fluorinated group; and
k is an integer from 1 to 3.

4. The process of claim 3 , wherein the fluorinated surfactant (FS) complies with formula (IXB) here below:

wherein
R F represents a divalent perfluorinated C 1 -C 3 bridging group; and
X a is a hydrogen atom, a monovalent metal, or an ammonium group of formula —N(R′ n ) 4 , wherein R′ n , equal or different at each occurrence, is a hydrogen atom or a C 1 -C 6 hydrocarbon group;
X* 1 and X* 2 , equal to or different from each other, are independently a fluorine atom, a —R′ f group or a —OR′ f group, wherein R′ f is a C 1 -C 3 perfluoroalkyl group, R F 1 is a fluorine atom or a —CF 3 group and k is an integer from 1 to 3.

5. The process of claim 4 , wherein the fluorinated surfactant (FS) is selected from the group consisting of surfactants (FS) having formulae (X) and (XI) here below:

wherein X a is a hydrogen atom, a monovalent metal, or an ammonium group of formula —N(R′ n ) 4 , wherein R′ n , equal or different at each occurrence, is a hydrogen atom or a C 1 -C 6 hydrocarbon group.

6. The process of claim 1 , wherein the functional PFPE complies with formula (XII) here below:
T 1 -(CFW 1 ) p1 O—R F —(CFW 2 ) p2 -T 2   (XII)

wherein:
R F is a (per)fluoropolyoxyalkylene chain [chain (R′ F )] such that the number average molecular weight of the functional PFPE is at least 1000;
T 1 and T 2 , equal to or different from each other, are selected from:
i) functional end-groups selected from the group consisting of carboxylic acid, phosphonic acid and sulphonic acid groups, in their acid or salt form, and
ii) non-functional end-groups selected from a group consisting of a fluorine atom, a chlorine atom and a C 1 -C 3 (per)fluoroalkyl group comprising, optionally, one or more chlorine atoms, with the proviso that at least one of T 1 and T 2 is a functional end-group as defined above;

W 1 and W 2 , equal to or different from each other, independently represent a fluorine atom or a —CF 3 group;
p 1 and p 2 , equal to or different from each other, are independently integers comprised between 1 and 3.

7. The process of claim 6 , wherein the functional PFPE complies with formula (XIV) here below:
X p OOC—CF 2 —O—(CF 2 ) n′ (CF 2 CF 2 O) m′ —CF 2 —COOX p   (XIV)

wherein n′ and m′ are independently integers >0 such that the number average molecular weight of the functional PFPE is at least 1000, wherein the recurring units of (CF 2 ) and (CF 2 CF 2 O) are generally statistically distributed along the perfluoropolyoxyalkylene chain, and wherein X p , equal to or different from each other, is a hydrogen atom, a monovalent metal, or an ammonium group of formula —N(R′ n ) 4 , wherein R′ n , equal or different at each occurrence, is a hydrogen atom or a C 1 -C 6 hydrocarbon group.

8. A process for manufacturing a dispersion of a vinylidene fluoride (VDF) thermoplastic polymer [polymer (F)], said process comprising polymerizing VDF in an aqueous phase comprising:
at least one surfactant selected from the group consisting of non-fluorinated surfactants [surfactant (HS)] and fluorinated surfactants having a molecular weight of less than 400 [surfactant (FS)]; and
at least one functional (per)fluoropolyether (functional PFPE) that complies with formula (XIV) here below:
X p OOC—CF 2 —O—(CF 2 ) n′ (CF 2 CF 2 O) m′ —CF 2 —COOX p   (XIV)

wherein n′ and m′ are independently integers >0 such that the number average molecular weight of the functional PFPE is at least 1000, wherein the recurring units of (CF 2 ) and (CF 2 CF 2 O) are generally statistically distributed along the perfluoropolyoxyalkylene chain, and wherein X p , equal to or different from each other, is a hydrogen atom, a monovalent metal, or an ammonium group of formula —N(R′ n ) 4 , wherein R′ n , equal or different at each occurrence, is a hydrogen atom or a C 1 -C 6 hydrocarbon group, said functional PFPE having a solubility in water of less than 1% by weight at 25° C.,
wherein said functional PFPE is present in the aqueous phase in an amount of 0.001 to 0.3 g/L.

9. The process of claim 8 , wherein the surfactant is a surfactant (FS) complying with formula (IA) here below:
R f —(OCF 2 CF 2 ) k-1 —O—CF 2 —COOX a   (IA)

wherein R f is a C 1 -C 3 perfluoroalkyl group comprising, optionally, one or more ether oxygen atoms, k is 2 or 3 and X a is selected from the group consisting of a m

Assignees

• Spada Fabrizio
• Kent Bradley Lane
• Solvay Specialty Polymers It

Inventors

• Spada Fabrizio
• Kent Bradley Lane

Classifications

• C08F14/22 Primary

  Vinylidene fluoride · CPC title

• C08F2/16

  Aqueous medium · CPC title