阅读说明：本技术 包含官能氟化硅烷化合物的含氟聚合物组合物 (Fluoropolymer compositions comprising functional fluorinated silane compounds ) 是由 迈克尔·H·米切尔 米格尔·A·格拉 于 2018-12-20 设计创作，主要内容包括：本发明提供了可固化组合物,该可固化组合物包含至少一种氟化弹性体胶；和至少一种根据式I的化合物：X-(CF<Sub>2</Sub>)<Sub>n</Sub>-(O)<Sub>p</Sub>-(CH<Sub>2</Sub>)<Sub>m</Sub>-Si-Y<Sub>3</Sub> (I)其中X为Br、I、CF<Sub>2</Sub>＝CF-O-、CH<Sub>2</Sub>＝CHCH<Sub>2</Sub>-O-、CH<Sub>2</Sub>＝CH-或CH<Sub>2</Sub>＝CHCH<Sub>2</Sub>-,n为2至8的整数,m为2至5的整数,p为0或1,并且Y为Cl-或-OR,其中R为具有1至4个碳原子的直链或支链烷基。在一些实施方案中,Y为-O(CH<Sub>2</Sub>)<Sub>x</Sub>CH<Sub>3</Sub>,其中x为0至3的整数。(The present invention provides a curable composition comprising at least one fluorinated elastomeric gum; and at least one compound according to formula I: x- (CF) 2 ) n ‑(O) p ‑(CH 2 ) m ‑Si‑Y 3 (I) Wherein X is Br, I, CF 2 ＝CF‑O‑、CH 2 ＝CHCH 2 ‑O‑、CH 2 CH-or CH 2 ＝CHCH 2 -n is an integer from 2 to 8, m is an integer from 2 to 5, p is 0 OR 1, and Y is Cl-OR, wherein R is a linear OR branched alkyl group having from 1 to 4 carbon atoms. In some embodiments, Y is-O (CH) 2 ) x CH 3 Which isWherein x is an integer of 0 to 3.)

1. A curable composition comprising:

at least one fluorinated elastomer gum; and

at least one functional fluorinated silane compound according to formula I:

X-(CF₂)_n-(O)_p-(CH₂)_m-Si-Y₃(I)

wherein X is Br, I, CF₂＝CF-O-、CH₂＝CHCH₂-O-、CH₂CH-or CH₂＝CHCH₂-，

n is an integer of 2 to 8,

m is an integer of 2 to 5,

p is 0 or 1, and

y is Cl-OR-OR, wherein R is a linear OR branched alkyl group having 1 to 4 carbon atoms.

2. The curable composition of claim 1, wherein Y is-O (CH)₂)_xCH₃Wherein x is 0 to 3.

3. The curable composition of claim 1 or 2, wherein the fluorinated elastomer gum comprises at least 0.05 weight percent cure sites and at most 5 weight percent of the cure sites.

4. The curable composition of claim 2, wherein the cure site comprises at least one of bromine, iodine, nitrile, or a combination thereof.

5. The curable composition of any one of the preceding claims, wherein the fluorinated elastomer gum is partially fluorinated.

6. The curable composition of any one of the previous claims, wherein the fluorinated elastomer gum is derived from at least one of TFE, HFP, VDF, fluorinated vinyl ether monomers, fluorinated allyl ether monomers, or combinations thereof.

7. The curable composition of any one of the preceding claims, wherein the fluorinated elastomeric gum comprises at least one of the following copolymers: (i) copolymers comprising TFE and perfluoroalkyl vinyl ether monomer units; (ii) a copolymer comprising TFE and perfluoroalkoxy vinyl ether monomer units; (iii) copolymers comprising TFE and propylene monomer units; (iv) copolymers comprising TFE, propylene, and VDF monomer units; (v) a copolymer comprising VDF and HFP monomer units; (vi) copolymers comprising TFE, VDF, and HFP monomer units; (vii) a copolymer comprising VDF and perfluoroalkyl vinyl ether monomer units; (viii) a copolymer comprising CTFE and VDF monomer units; (ix) copolymers comprising TFE and VDF monomer units; (x) Copolymers comprising TFE, VDF and perfluoroalkyl vinyl ether monomer units; and (xi) combinations thereof.

8. The curable composition of any one of the preceding claims, wherein the fluorinated elastomeric gum is a block copolymer comprising at least one A block and at least one B block.

9. The curable composition of claim 8 wherein the a block comprises 30-85 wt% TFE; 5-40 wt% HFP; and 5-55 wt% VDF; and the B block comprises from 25 to 65 weight percent VDF and from 15 to 60 weight percent HFP; or even 35-60 wt% VDF and 25-50 wt% HFP.

10. The curable composition of any one of the preceding claims comprising at least 0.1 part by weight up to 30 parts by weight of the functional fluorinated silane compound of formula I per 100 parts by weight of the fluorinated elastomer gum.

11. The curable composition of any one of the preceding claims, further comprising a peroxide.

12. The curable composition of claim 12, wherein the peroxide comprises at least one of: benzoyl peroxide, benzoyl peroxide dichloride, dicumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, di-t-butyl peroxide, t-butyl peroxybenzoate, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane-3, lauryl peroxide, or combinations thereof.

13. The curable composition of claim 12 or 13 further comprising a non-fluorinated polyunsaturated compound, wherein the non-fluorinated polyunsaturated compound comprises at least one of: tri (methyl) allyl isocyanurate, triallyl isocyanurate, tri (methyl) allyl cyanurate, poly-triallyl isocyanurate; or a combination thereof.

14. The curable composition of any one of the preceding claims, wherein n is an integer from 2 to 4.

15. The curable composition of any one of the preceding claims, wherein m is an integer from 2 to 3.

16. The curable composition of any one of the preceding claims, wherein Y is-OCH₃。

17. The curable composition of claim 1 wherein the functional fluorinated silane compound is selected from the group consisting of:

Br-C₂F₄-CH₂CH₂-SiCl₃(BTFETCS) and

Br-C₂F₄-CH₂CH₂-Si(OCH₃)₃(BTFETMS)。

18. the curable composition of claim 1 wherein the functional fluorinated silane compound is selected from

CF₂＝CF-O-C₄F₈-CH₂CH₂-SiCl₃(MV4ETCS)、

CF₂＝CF-O-C₄F₈-CH₂CH₂-Si(OCH₃)₃(MV4ETMS)、

CF₂＝CF-O-C₄F₈-CH₂CH₂CH₂-SiCl₃(MV4PTCS) and

CF₂＝CF-O-C₄F₈-CH₂CH₂CH₂-Si(OCH₃)₃(MV4PTMS)。

19. the curable composition of claim 1 wherein the functional fluorinated silane compound is selected from

CH₂＝CHCH₂C₄F₈CH₂CH₂CH₂SiCl₃(AC4PTCS) and CH₂＝CHCH₂C₄F₈CH₂CH₂CH₂Si(OCH₃)₃(AC4PTMS)。

20. The curable composition of claim 1 wherein the functional fluorinated silane compound is selected from

CH₂＝CHCH₂-O-C₄F₈-O-CH₂CH₂CH₂SiCl₃(AEC4EPTCS) and

CH₂＝CHCH₂-O-C₄F₈-O-CH₂CH₂CH₂Si(OCH₃)₃(AEC4EPTMS)。

21. the curable composition of claim 1 wherein the functional fluorinated silane compound is selected from

CH₂＝CHC₄F₈CH₂CH₂SiCl₃(VC4ETCS) and

CH₂＝CHC₄F₈CH₂CH₂Si(OCH₃)₃(VC4ETMS)。

22. a cured article comprising the cured curable composition of any one of claims 1-22.

23. The article of claim 23, wherein the cured article is a molded part, a hose, a gasket, or a seal.

Technical Field

The present disclosure relates to compositions comprising a functional fluorinated silane compound and a fluorinated elastomeric gum (e.g., a peroxide cured fluoropolymer).

Background

Elastomers that perform well at higher temperatures (e.g., temperatures of 200 ℃ to 330 ℃) are of interest. Perfluoroelastomers (fully fluorinated molecules) have traditionally been used under these extreme temperature conditions due to the higher bond energy of the C-F bond. However, for certain applications and markets, the cost of perfluoroelastomers may make them undesirable or prohibitive. Partially fluorinated elastomers are generally less costly than perfluorinated elastomers, and because they contain some fluorine, they can perform well (e.g., chemical resistance, etc.) under some of the same extreme conditions as perfluorinated elastomers. However, they still do not always have acceptable physical properties for all applications.

Disclosure of Invention

A curable composition comprising: a fluorinated elastomer gum; and at least one compound according to formula I:

X-(CF₂)_n-(O)_p-(CH₂)_m-Si-Y₃(I)

wherein X is Br, I, CF₂＝CF-O-、CH₂＝CHCH₂-O-、CH₂CH-or CH₂＝CHCH₂-n is an integer from 2 to 8, m is an integer from 2 to 5, p is 0 OR 1, and Y is Cl-OR, wherein R is a linear OR branched alkyl group having from 1 to 4 carbon atoms. In some embodiments, Y is-O (CH)₂)_xCH₃Wherein x is an integer of 0 to 3.

Also disclosed herein are cured compositions and articles comprising the cured compositions.

The above summary is not intended to describe each embodiment of the present disclosure. The details of one or more embodiments of the disclosure are also set forth in the description below. Other features, objects, and advantages of the disclosure will be apparent from the description and from the claims.

Detailed Description

"backbone" refers to the predominantly continuous chain of the polymer;

a "block copolymer" is a polymer in which chemically distinct blocks or sequences are covalently bonded to each other.

"copolymer" refers to a polymeric material comprising at least two different interpolymerized monomers (i.e., monomers that do not have the same chemical structure) and includes terpolymers (three different monomers), tetrapolymers (four different monomers), and the like;

"crosslinking" refers to linking two preformed polymer chains with chemical bonds or chemical groups, and may be used interchangeably with "curing";

"cure site" refers to a functional group that can participate in crosslinking;

"glass transition temperature" or "T_g"refers to the temperature at which a polymeric material transitions from a glassy state to a highly elastic state. Glassy states are typically associated with materials such as brittle, hard, rigid, or combinations thereof. In contrast, high elastic states are generally associated with materials such as flexibility and elasticity.

"perfluorinated" means a group or compound derived from a hydrocarbon in which all hydrogen atoms have been replaced by fluorine atoms. However, the perfluorinated compounds may also contain other atoms than fluorine atoms and carbon atoms, such as chlorine atoms, bromine atoms, and iodine atoms.

The present disclosure relates to a composition comprising at least a functional fluorinated silane compound and a fluorinated elastomer gum. The compositions disclosed herein may be referred to as curable compositions.

Functional fluorinated silane compounds

Disclosed fluorinated silane compounds include those having the following formula I.

X-(CF₂)_n-(O)_p-(CH₂)_m-Si-Y₃(I)

Wherein X can be selected from Br, I, CF₂＝CF-O-、CH₂＝CHCH₂-O-、CH₂CH-or CH₂＝CHCH₂-; n may be an integer from 2 to 8; m may be an integer of 2 to 5; p is 0 or 1; and Y is Cl-OR-OR, wherein R is a linear OR branched alkyl group having 1 to 4 carbon atoms. In some embodiments, Y is-O (CH)₂)_xCH₃Wherein x is an integer of 0 to 3. In some embodiments, X may be CH₂＝CHCH₂-or CH₂CH-. In some embodiments, n may be an integer from 2 to 7, 2 to 6, or even 2 to 4. In some embodiments, m may be an integer from 2 to 4 or from 2 to 3. In some embodiments, Y may be-O (CH)₂)_xCH₃Wherein x is 0, i.e. Y is-OCH₃。

Exemplary specific fluorinated silane compounds disclosed and/or useful herein can include:

Br-C₂F₄-CH₂CH₂-SiCl₃(BTFETCS)、

Br-C₂F₄-CH₂CH₂-Si(OCH₃)₃(BTFETMS)、

CF₂＝CF-O-C₄F₈-CH₂CH₂-SiCl₃(MV4ETCS)、

CF₂＝CF-O-C₄F₈-CH₂CH₂-Si(OCH₃)₃(MV4ETMS)、

CF₂＝CF-O-C₄F₈-CH₂CH₂CH₂-SiCl₃(MV4PTCS)、

CF₂＝CF-O-C₄F₈-CH₂CH₂CH₂-Si(OCH₃)₃(MV4PTMS)、CH₂＝CHCH₂C₄F₈CH₂CH₂CH₂SiCl₃(AC4PTCS)、CH₂＝CHCH₂C₄F₈CH₂CH₂CH₂Si(OCH₃)₃(AC4PTMS)、

CH₂＝CHCH₂-O-C₄F₈-O-CH₂CH₂CH₂SiCl₃(AEC4EPTCS)、

CH₂＝CHCH₂-O-C₄F₈-O-CH₂CH₂CH₂Si(OCH₃)₃(AEC4EPTMS)、CH₂＝CHC₄F₈CH₂CH₂SiCl₃(VC4ETCS) and

CH₂＝CHC₄F₈CH₂CH₂Si(OCH₃)₃(VC4ETMS)。

other exemplary compounds include trialkoxysilane analogs of such trimethoxysilane, such as triethoxysilane.

In some embodiments, a method of making useful functional fluorinated silane compounds includes bonding a compound having a functional terminus to a fluorinated carbon, then to an olefin on the opposite terminus, and hydrosilylation with a trichlorosilane using a platinum catalyst. This synthetic method is illustrated by general scheme 1 below.

X-(CF₂)_n-(O)_p-(CH₂)_m-CH＝CH₂+HSiCl₃(Pt)→X-(CF₂)_n-(O)_p-(CH₂)_m-Si-Cl₃Scheme 1

In scheme 1, X may be selected from Br, I, CF₂＝CF-O-、CH₂＝CHCH₂-O-、CH₂CH-or CH₂＝CHCH₂-; n may be an integer from 2 to 8; m may be an integer of 2 to 5; p is 0 or 1; and Y may be Cl-OR-OR, wherein R is a linear OR branched alkyl group having 1 to 4 carbon atoms. In some embodiments, Y may be-O (CH)₂)_xCH₃Wherein x is an integer of 0 to 3. Scheme 2 represents a more specific example of this particular synthetic method, where p ═ 0.

X-(CF₂)_n-(CH₂)_m-CH＝CH₂+HSiCl₃(Pt)→X-(CF₂)_n-(CH₂)_m-Si-Cl₃Scheme 2

In some methods, the trichlorosilane compound may be reacted with an alcohol to produce a trialkoxysilane that is easier to handle. This synthetic method is illustrated by general scheme 3 below, which uses a linear alcohol as an exemplary alcohol.

X-(CF₂)_n-(O)_p-(CH₂)_m-Si-Cl₃+HO(CH₂)_xCH₃→

X-(CF₂)_n-(O)_p-(CH₂)_m-Si-(O(CH₂)_xCH₃)₃Scheme 3

In scheme 3, X, m, n and p are as defined above. Scheme 4 represents a more specific example of this particular synthetic method, where p ═ 0.

X-(CF₂)_n-(CH₂)_m-Si-Cl₃+HO(CH₂)_xCH₃→X-(CF₂)_n-(CH₂)_m-Si-(O(CH₂)_xCH₃)₃Scheme 4

In some embodiments, the disclosed compositions comprise no less than 0.5 weight percent (wt%), no less than 1 wt%, or no less than 1.5 wt% of the functional fluorinated silane compound, based on the total weight of the fluorinated elastomeric gum and the functional fluorinated silane compound. In some embodiments, the disclosed compositions comprise no greater than 20 wt.%, no greater than 15 wt.%, no greater than 10 wt.%, or no greater than 5 wt.% of the functional fluorinated silane compound, based on the total weight of the fluorinated elastomeric gum and the functional fluorinated silane compound. In some embodiments, the disclosed compositions comprise from about 1.5 to about 5 weight percent of the functional fluorinated silane compound, and in some embodiments about 2 weight percent of the functional fluorinated silane compound, based on the total weight of the fluorinated elastomeric gum and the functional fluorinated silane compound.

Fluorinated elastomer adhesive

The disclosed compositions also comprise at least one fluorinated elastomer gum. As used herein, the phrase "fluorinated elastomer gum" refers to a fluoropolymer that can be processed as a conventional elastomer. By conventional elastomer processing is meant fluoropolymers that can be processed using a two-roll mill, an internal mixer, or a combination thereof. For example, mill blending by a two-roll mill is a method used by rubber manufacturers to combine polymer gums with curatives and/or additives. For abrasive blending, the fluorinated elastomer gum must have sufficient modulus. In other words, the glue must not be so soft that it sticks to the grinder, and also not so hard that it cannot be pressed against the grinder. In some embodiments, useful fluorinated elastomer gums may have a modulus of at least 0.1MPa (megapascals), at least 0.3MPa, or even at least 0.5MPa at 100 ℃; and no greater than 2.5MPa, no greater than 2.2MPa, or no greater than 2.0MPa, as measured, for example, at a strain of 1% and a frequency of 1Hz (hertz).

Useful fluorinated elastomer gums may be perfluorinated or partially fluorinated. As disclosed herein, in perfluorinated polymers, the carbon-hydrogen bonds along the polymer backbone are all replaced by carbon-fluorine bonds and optionally some carbon-chlorine bonds. Note that the backbone of the polymer does not include initiation and termination sites for the polymer. As disclosed herein, in a partially fluorinated polymer, the polymer comprises at least one carbon-hydrogen bond and at least one carbon-fluorine bond in the polymer backbone that excludes the initiation and termination sites of the polymer. In some embodiments, useful fluorinated elastomeric gums may be highly fluorinated, wherein at least 50%, 60%, 70%, 80%, or even 85% of the polymer backbone comprises C-F bonds, and at most 90%, 95%, or even 99% of the polymer backbone comprises C-F bonds.

In some embodiments, useful fluorinated elastomer gums may be derived from one or more fluorinated monomers such as Tetrafluoroethylene (TFE), Vinyl Fluoride (VF), vinylidene fluoride (VDF), Hexafluoropropylene (HFP), pentafluoropropene, trifluoroethylene, Chlorotrifluoroethylene (CTFE), perfluorovinyl ether (PMVE), perfluoroallyl ether, or combinations thereof.

In some embodiments, perfluorovinyl ethers that may be used as fluorinated elastomer gums may have the formula II:

CF₂＝CFO(R_f1O)_mR_f2(II)

wherein R is_f1Is a linear or branched perfluoroalkylene group containing 2,3, 4, 5 or 6 carbon atoms, m is an integer selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9 and 10, and R is_f2Is a perfluoroalkyl group containing 1,2, 3, 4, 5, or 6 carbon atoms. Exemplary specific perfluorovinyl ether monomers include: perfluoro (methyl vinyl) ether (PMVE), perfluoro (ethyl vinyl) ether (PEVE), perfluoro (n-propyl vinyl) ether (PPVE-1), perfluoro-2-propoxypropyl vinyl ether (PPVE-2), perfluoro-3-methoxy-n-propyl vinyl ether, perfluoro-2-methoxyethyl vinyl ether, perfluoromethoxymethyl vinyl ether, perfluoromethoxy methyl vinyl ether, perfluoro (methyl vinyl) ether, perfluoro (ethyl vinyl) ether, perfluoro (n-propyl vinyl) ether, perfluoro (n-,

(CF₃-O-CF₂-O-CF＝CF₂) And CF₃-(CF₂)₂-O-CF(CF₃)-CF₂-O-CF(CF₃)-CF₂-O-CF＝CF₂And combinations thereof.

In some embodiments, perfluoroallyl ethers that may be used as fluorinated elastomer gums may have the formula III:

CF₂＝CFCF₂O(R_f1O)_n(R_f1O)_m-R_f2(III)

wherein each R_f1Independently a linear or branched perfluoroalkylene group containing 2,3, 4, 5 or 6 carbon atoms, m and n are independently integers selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9 and 10, and R is_f2Is a perfluoroalkyl group containing 1,2, 3, 4, 5, or 6 carbon atoms. Exemplary specific perfluoroallyl ether monomers include: perfluoro (ethyl allyl) ether, perfluoro (n-propyl allyl) ether, perfluoro-2-propoxypropyl allyl ether, perfluoro-3-methoxy-n-propyl allyl ether, perfluoro-2-methoxyethyl allyl ether, perfluoromethoxymethyl allyl ether, and

CF₃-(CF₂)₂-O-CF(CF₃)-CF₂-O-CF(CF₃)-CF₂-O-CF₂CF＝CF₂and combinations thereof.

The fluorinated elastomer gum may optionally be modified during its formation by the addition of small amounts of other copolymerizable monomers (which may or may not contain fluorine substitution), such as ethylene, propylene, butylene, and the like, as known to those skilled in the art. The use of these additional monomers (which may also be referred to as comonomers) is within the scope of the present disclosure. When present, these additional monomers may be used in amounts no greater than 25 mole%, in some embodiments less than 10 mole%, and even less than 3 mole% of the fluorinated elastomer gum.

In some embodiments, the fluorinated elastomeric gum may be a random copolymer, which is amorphous, meaning that there is no long range order (in which it is understood that the arrangement and orientation of the macromolecules beyond their nearest neighbors is not present). Amorphous fluoropolymers have no crystalline properties detectable by DSC (differential scanning calorimetry), which means that if studied under DSC, when tested using a DSC thermogram, with a first thermal cycle starting from-85 ℃ and ramping up to 350 ℃ at 10 ℃/min, cooling to-85 ℃ at a rate of 10 ℃/min, and a second thermal cycle starting from-85 ℃ and ramping up to 350 ℃ at 10 ℃/min, the fluorinated elastomeric gum, starting from the second heating of the heat/cold/heat cycle, will have no melting point or will have a melt transition with an enthalpy of greater than 0.002J/g, 0.01J/g, 0.1J/g or even 1J/g. Exemplary specific amorphous random copolymers may include: copolymers comprising TFE and perfluorinated vinyl ether monomer units (such as copolymers comprising TFE and PMVE, and copolymers comprising TFE and PEVE); a copolymer comprising TFE and perfluorinated allyl ether monomer units; copolymers comprising TFE and propylene monomer units; copolymers comprising TFE, propylene, and VDF monomer units; a copolymer comprising VDF and HFP monomer units; copolymers comprising TFE, VDF, and HFP monomer units; copolymers comprising TFE and Ethyl Vinyl Ether (EVE) monomer units; copolymers comprising TFE and Butyl Vinyl Ether (BVE) monomer units; a copolymer comprising TFE, EVE, and BVE monomer units; comprising VDF and perfluoroCopolymers of vinyl ether monomer units (such as containing VDF and CF)₂＝CFOC₃F₇A monomer unit; copolymers of ethylene and HFP monomer units); a copolymer comprising CTFE and VDF monomer units; copolymers comprising TFE and VDF monomer units; copolymer comprising TFE, VDF, and perfluorinated vinyl ether monomer units (such as copolymers comprising TFE, VDF, and PMVE) monomer units; copolymers comprising VDF, TFE and propylene monomer units; copolymers comprising TFE, VDF, PMVE, and ethylene monomer units; copolymers comprising TFE, VDF, and perfluorinated vinyl ether monomer units (such as copolymers comprising TFE, VDF, and CF)₂＝CFO(CF₂)₃OCF₃A monomer unit); and combinations thereof. In some embodiments, the fluorinated elastomer gum is not a copolymer comprising VDF and HFP monomer units.

In some embodiments, the fluorinated elastomeric gum may be a block copolymer in which chemically distinct blocks or sequences are covalently bonded to each other, wherein the blocks have different chemical compositions and/or different glass transition temperatures. In some embodiments, the block copolymer comprises a first block a block, which is a semi-crystalline segment. If studied under Differential Scanning Calorimetry (DSC), the block will have at least one melting point temperature (T) greater than 70 ℃_m) And a measurable enthalpy, for example, greater than 0J/g (joules/gram). The second block or B block is an amorphous segment, meaning that there is no long range order (i.e., in long range order, it is understood that the arrangement and orientation of the macromolecules except their nearest neighbors). The amorphous segment has no crystalline character detectable by DSC. If studied under DSC, the B block will have no melting point or melt transition, enthalpy greater than 2 mJ/g according to DSC. In some embodiments, the a block is a copolymer derived from at least the following monomers: tetrafluoroethylene (TFE), Hexafluoropropylene (HFP), and vinylidene fluoride (VDF). In one embodiment, the a block comprises 30 to 85 weight percent TFE; 5-40 wt% HFP; and 5-55 wt% VDF; 30-75 wt% TFE; 5-35 wt% HFP; and 5-50 wt% VDF; or even 40-70 wt% TFE; 10-30 wt% HFP; and 10-45 wt% VDF. In some embodiments of the present invention, the substrate is,the B block is a copolymer derived from at least the following monomers: hexafluoropropylene (HFP) and vinylidene fluoride (VDF). In some embodiments, the B block comprises 25 to 65 weight percent VDF and 15 to 60 weight percent HFP; or even 35-60 wt% VDF and 25-50 wt% HFP. Monomers other than those described above may also be included in the a block and/or the B block. Generally, the weight average molecular weights of the a and B blocks are independently selected from at least 1000, 5000, 10000, or even 25000 daltons; and at most 400000, 600000 or even 800000 daltons. Such block copolymers are disclosed in WO 2017/013379(Mitchell et al); and U.S. provisional applications 62/447675, 62/447636, and 62/447664, each filed on 2017, month 1, day 18; these documents are incorporated herein by reference.

The fluorinated elastomer gums useful herein comprise a cure site that serves as a reaction site for crosslinking the fluoropolymer to form a fluoroelastomer. Typically, the fluorinated elastomer gum comprises at least 0.05 mole%, 0.1 mole%, 0.5 mole%, 1 mole%, or even 2 mole% of cure sites and at most 5 mole%, or even 10 mole% of cure sites relative to moles of fluorinated elastomer gum.

In some embodiments, the fluorinated elastomer gum may be polymerized in the presence of a chain transfer agent and/or a cure site monomer to introduce a cure site into the fluorinated elastomer gum.

Exemplary specific chain transfer agents may include, for example: iodine-containing chain transfer agents and bromine-containing chain transfer agents. For example, suitable iodine-containing chain transfer agents in the polymerization include those of formula RI_xWherein (i) R is a perfluoroalkyl or chloroperfluoroalkyl group having 3 to 12 carbon atoms; and (ii) x is 1 or 2. The iodine-containing chain transfer agent may be a perfluorinated iodo-compound. Exemplary perfluorinated iodocompounds include 1, 3-diiodoperfluoropropane, 1, 4-diiodoperfluorobutane, 1, 6-diiodoperfluorohexane, 1, 8-diiodoperfluorooctane, 1, 10-diiodoperfluorodecane, 1, 12-diiodoperfluorododecane, 2-iodo-1, 2-dichloro-1, 1, 2-trifluoroethane, 4-iodo-1, 2, 4-trichloroperfluorobutane, and mixtures thereof. In some embodiments, bromine may be derived from a brominated formula: RBr_xWherein (i) R isPerfluoroalkyl or chloroperfluoroalkyl groups having 3 to 12 carbon atoms; and (ii) x is 1 or 2. The chain transfer agent may be a perfluorinated bromo compound.

The cure site monomer (if used) may comprise at least one of bromine, iodine, and/or nitrile cure moieties.

In some embodiments, the cure site monomer may be derived from one or more compounds of the formula: (a) CX₂Cx (z), wherein: (i) each X is independently H or F; and (ii) Z is I, Br, R_f-U, wherein U ═ I or Br, and R_fIs a perfluorinated or partially perfluorinated alkylene group optionally containing an O atom. Or (b) Y (CF)₂)_qY, wherein: (i) y is Br or I or Cl, and (ii) q ═ 1 to 6. In addition, non-fluorinated bromoolefins or iodoolefins, such as ethylene iodide and allyl iodide, may be used. In some embodiments, the cure site monomer is derived from a compound such as: CH (CH)₂＝CHI、CF₂＝CHI、CF₂＝CFI、CH₂＝CHCH₂I、CF₂＝CFCF₂I、ICF₂CF₂CF₂CF₂I、CH₂＝CHCF₂CF₂I、CF₂＝CFCH₂CH₂I、CF₂＝CFCF₂CF₂I、CH₂＝CH(CF₂)₆CH₂CH₂I、CF₂＝CFOCF₂CF₂I、CF₂＝CFOCF₂CF₂CF₂I、CF₂＝CFOCF₂CF₂CH₂I、CF₂＝CFCF₂OCH₂CH₂I、CF₂＝CFO(CF₂)₃–OCF₂CF₂I、CH₂＝CHBr、CF₂＝CHBr、CF₂＝CFBr、CH₂＝CHCH₂Br、CF₂＝CFCF₂Br、CH₂＝CHCF₂CF₂Br、CF₂＝CFOCF₂CF₂Br、CF₂＝CFCl、CF₂＝CFCF₂Cl or a combination thereof.

In some embodiments, the cure site monomer comprises a nitrile-containing cure moiety. Useful nitrile-containing cure site monomers include nitrile-containing fluorinated olefins and nitrile-containing fluorinated vinyl ethers such as:

perfluoro (8-cyano-5-methyl-3, 6-dioxa-1-octene); CF (compact flash)₂＝CFO(CF₂)_LCN, wherein L is an integer of 2 to 12, CF₂＝CFO(CF₂)_uOCF(CF₃) CN, wherein u is an integer from 2 to 6; CF (compact flash)₂＝CFO[CF₂CF(CF₃)O]_q(CF₂O)_yCF(CF₃)CN；CF₂＝CFO[CF₂CF(CF₃)O]_q(CF₂)_yOCF(CF₃) CN, wherein q is an integer from 0 to 4, and y is an integer from 0 to 6; CF (compact flash)₂＝CF[OCF₂CF(CF₃)]_rO(CF₂)_tCN, wherein r is 1 or 2, and t is an integer from 1 to 4; and derivatives and combinations of the foregoing. Examples of nitrile containing cure site monomers include CF₂＝CFO(CF₂)₅CN、CF₂＝CFOCF₂CF(CF₃)OCF₂CF₂CN、CF₂＝CFOCF₂CF(CF₃)OCF₂CF(CF₃)CN、CF₂＝CFOCF₂CF₂CF₂OCF(CF₃)CN、CF₂＝CFOCF₂CF(CF₃)OCF₂CF₂CN; and combinations thereof.

Peroxides and their use in the preparation of pharmaceutical preparations

The compositions disclosed herein may also contain a peroxide-containing compound or peroxide. The peroxide forms a covalent bond between the fluorinated elastomer gum and the compound of formula I. Peroxide curatives include organic or inorganic peroxides. In some embodiments, organic peroxides, especially those that do not decompose at dynamic mixing temperatures, may be utilized.

In some embodiments, for example, t-butyl peroxides that utilize a tertiary carbon atom attached to a peroxy oxygen can be utilized.

Illustrative specific examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane, 2, 4-dichlorobenzoyl peroxide, 1-bis (t-butylperoxy) -3,3, 5-trimethylchlorohexane, t-butyl peroxyisopropylcarbonate (TBIC), t-butyl peroxy2-ethylhexyl carbonate (TBEC), t-amyl peroxy2-ethylhexyl carbonate, t-hexyl peroxyisopropylcarbonate, carbon peroxy acid, O '-1, 3-propanediyl OO, OO' -bis (1, 1-dimethylethyl) ester, t-butyl peroxybenzoate, t-hexyl peroxy2-ethylhexanoate, t-butyl peroxy2-ethylhexanoate, Bis (4-methylbenzoyl) peroxide, lauryl peroxide, and cyclohexanone peroxide, and combinations thereof. Other suitable peroxide curatives are listed in U.S. Pat. No. 5,225,504(Tatsu et al), the disclosure of which is incorporated herein by reference.

The amount of peroxide used will generally be at least 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, or even 1.5 parts by weight per 100 parts of fluorinated elastomer gum; and up to 2 parts by weight, 2.25 parts by weight, 2.5 parts by weight, 2.75 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, or even 5.5 parts by weight.

Additional components in the composition

The composition comprising the fluorinated elastomer gum may or may not be crosslinked. Crosslinking of the resulting composition can be carried out using curing systems known in the art such as peroxide curing agents, 2, 3-dimethyl-2, 3-diphenylbutane and other free radical initiators such as azo compounds, as well as other curing systems such as polyols, and polyamine curing systems.

Peroxide curatives include organic or inorganic peroxides. In some embodiments, organic peroxides, especially those that do not decompose at dynamic mixing temperatures, may be utilized.

Usually by using organic peroxides as crosslinking agents and, if desired, crosslinking assistants, including, for example, diolefins (such as CH)₂＝CH(CF₂)₆CH＝CH₂And CH₂＝CH(CF₂)₈CH＝CH₂) Diallyl ethers of glycerol, triallyl phosphate, diallyl adipate, diallyl melamine and triallyl isocyanurate (TAIC), fluorinated TAIC comprising fluorinated olefin bonds, tri (methyl) allyl isocyanurate (TMAIC), tri (methyl) allyl cyanurate, poly-triallyl isocyanurate (poly-TAIC), xylylene-bis (diallyl isocyanurate) (XBD) and N, N' -m-phenylene bismaleimide, crosslinking using peroxides can be performed.

Examples of azo compounds that can be used to cure compositions comprising the fluorinated copolymers of the present disclosure are those having high decomposition temperatures. In other words, they decompose above the upper use temperature of the resulting product. Such azo compounds can be found, for example, in Encyclopedia of Polymer Materials, New York, CRC Press, 1996, Vol.1, p.432-440, written by J.C.Salamone ("Polymeric Materials Encyclopedia, J.C.Salamone, ed., CRC Press Inc., New York, (1996) Vol.1, p.432-440).

Crosslinking using polyamines is generally performed by using polyamine compounds as crosslinking agents, and oxides of divalent metals such as magnesium, calcium, or zinc. Examples of the polyamine compound or polyamine compound precursor include hexamethylenediamine and its carbamate, 4 '-bis (aminocyclohexyl) methane and its carbamate, and N, N' -bis-cinnamaldehyde-1, 6-hexamethylenediamine.

The crosslinking agent (and the crosslinking assistant, if used) may each be used in an amount conventionally known, and the amount to be used may be appropriately determined by one skilled in the art. Each of these components participating in crosslinking may be used, for example, in an amount of about 1 part by mass or more, about 5 parts by mass or more, about 10 parts by mass or more, or about 15 parts by mass or more, and about 60 parts by mass or less, about 40 parts by mass or less, about 30 parts by mass or less, or about 20 parts by mass or less per 100 parts by mass of the fluorinated copolymer. The total amount of the components participating in crosslinking may be, for example, about 1 part by mass or more, about 5 parts by mass or more, or about 10 parts by mass or more, and about 60 parts by mass or less, about 40 parts by mass or less, or about 30 parts by mass or less per 100 parts by mass of the fluorinated copolymer.

For example, conventional adjuvants such as, for example, acid acceptors, fillers, processing aids, or colorants may be added to the composition for the purpose of enhancing strength or imparting functionality.

For example, an acid acceptor may be used to promote cure stability and thermal stability of the composition. Suitable acid acceptors can include magnesium oxide, lead oxide, calcium hydroxide, lead hydrogen phosphite, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, hydrotalcite, alkali stearates, magnesium oxalate, or combinations thereof. The acid acceptor may be used in an amount ranging from about 1 part to about 20 parts per 100 parts by weight of the fluorinated copolymer.

Fillers may include (for example): organic or inorganic fillers, e.g. clays, Silica (SiO)₂) Alumina, iron oxide red, talc, diatomaceous earth, barium sulfate, wollastonite (CaSiO)₃) Calcium carbonate (CaCO)₃) Calcium fluoride, titanium oxide, iron oxide and carbon black fillers, polytetrafluoroethylene powder, PFA (TFE/perfluorovinyl ether copolymer) powder, conductive fillers, heat-dissipating fillers, and the like, may be added to the composition as optional components. Those skilled in the art will be able to select the particular filler in the required amount to achieve the desired physical characteristics of the cured compound. The filler component may produce a compound capable of maintaining a preferred elasticity and physical tension (as indicated by elongation and tensile strength values) while maintaining desired properties such as recoil at lower temperatures (TR-10). In some embodiments, the composition comprises less than 40, 30, 20, 15, or even 10 weight percent filler.

Processing of the composition

The composition comprising the functional fluorinated silane compound, the fluorinated elastomeric gum, and the other components may be mixed with a curing agent and optionally conventional adjuvants. The method for mixing may include, for example, kneading using a rubber twin roll, a pressure kneader or a banbury mixer.

The mixture can then be processed and shaped, such as by extrusion or molding, to form articles of various shapes, such as sheets, hoses, hose liners, O-rings, gaskets, packings, or seals comprised of the compositions of the present disclosure. The shaped article may then be heated to cure the gum composition and form a cured elastomeric article.

The compounded mixture is typically pressurized (i.e., pressure cured) at a temperature of about 120-220 deg.C, or even at a temperature of about 140-200 deg.C for a period of about 1 minute to about 15 hours, typically about 1 minute to 15 minutes. Pressures of about 700-. The mold may first be coated with a release agent and pre-baked.

The molded vulcanizate may be post-cured in an oven at a temperature of about 140 ℃ to 240 ℃, or even about 160 ℃ to 230 ℃ for a period of about 1 to 24 hours or more, depending on the cross-sectional thickness of the specimen. For thick sections, the temperature during post-cure is typically raised gradually from the lower end of the range to the desired maximum temperature. The maximum temperature used is preferably about 260 c and is maintained at this value for a period of about 1 hour or more.

Cured compositions

The disclosed compositions may be cured using any curing method, including radiation-induced curing, thermal curing, and the like.

It has been found that the disclosed compositions have good tensile strength and 100% modulus. Surprisingly, it has also been found that the fluorinated block copolymers of the present disclosure have good compression set. Compression set is the deformation of a polymer that remains after a force is removed. Generally, lower compression set values are better (i.e., less deformation of the material). Generally, plastics (including semi-crystalline morphologies) do not have good compression set. Thus, it is surprising that fluorinated block copolymers comprising semi-crystalline segments have good compression set. It is also surprising that the fluorinated block copolymers of the present disclosure retain their properties at high temperatures.

Article of manufacture

The disclosed compositions may be used in articles such as hoses, seals (e.g., gaskets, o-rings, packer elements, blow out preventers, valves, etc.), stators, or sheets. These compositions may or may not be post-cured.

While specific implementations of compositions comprising functional fluorinated silane compounds are described herein, other configurations and embodiments consistent with and within the scope of the present disclosure will be apparent to those of skill in the art upon reading the present disclosure. Various modifications and alterations of this disclosure will become apparent to those skilled in the art without departing from the scope and spirit of this invention.