阅读说明：本技术 包含用官能氟化硅烷化合物官能化的纳米粒子的含氟聚合物组合物 (Fluoropolymer compositions comprising nanoparticles functionalized with functional fluorinated silane compounds ) 是由 迈克尔·H·米切尔 米格尔·A·格拉 小吉米·R·巴兰 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,所述可固化组合物包含至少一种氟化弹性体胶；和用至少一种根据式I的化合物官能化的纳米粒子：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>＝CHCH<Sub>2</Sub>-或CH<Sub>2</Sub>＝CH-,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 nanoparticles functionalized with 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 ＝CHCH 2 -or CH 2 -CH-, n is an integer from 2 to 8, m is an integer from 2 to 5, p is 0 or 1, and YIs 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 ) x CH 3 Wherein x is an integer of 0 to 3.)

1. A curable composition comprising:

at least one fluorinated elastomer gum; and

nanoparticles functionalized with 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-、CH₂＝CHCH₂-or CH₂＝CH-，

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 an integer of 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 3, wherein the cure site comprises at least one of: bromine, iodine, nitrile, or combinations 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 preceding 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 elastomer gum comprises at least one of: (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% by weight of HFP; and 5-55 wt% VDF; and the B block comprises 25 wt% to 65 wt% VDF and 15 wt% to 60 wt% HFP; or even 35-60 wt% VDF and 25-50 wt% HFP.

10. A curable composition according to any one of the preceding claims comprising at least 0.1 part by weight up to 30 parts by weight of a compound of formula I per 100 parts by weight of the fluorinated elastomeric gum.

11. A curable composition according to any one of the preceding claims comprising at least 2 parts by weight up to 10 parts by weight of a compound of formula I per 100 parts by weight of the fluorinated elastomeric gum.

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

13. The curable composition of claim 13, 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.

14. 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 (meth) allyl isocyanurate, triallyl isocyanurate, tri (meth) allyl cyanurate, poly-triallyl isocyanurate; or a combination thereof.

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

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

17. The curable composition of any one of the preceding claims, wherein Y is-O (CH)₂)_xCH₃And wherein x is 0.

18. 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)。

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

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)。

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

CH₂＝CHCH₂C₄F₈CH₂CH₂CH₂SiCl₃(AC4PTCS), and

CH₂＝CHCH₂C₄F₈CH₂CH₂CH₂Si(OCH₃)₃(AC4PTMS)。

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

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

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

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

CH₂＝CHC₄F₈CH₂CH₂SiCl₃(VC4ETCS), and

CH₂＝CHC₄F₈CH₂CH₂Si(OCH₃)₃(VC4ETMS)。

23. the curable composition according to any one of the preceding claims, wherein the nanoparticles are selected from carbon, silica or a combination thereof.

24. The curable composition of any one of the preceding claims, wherein the nanoparticles have an average diameter of 5nm to 75 nm.

25. A cured composition comprising the cured curable composition of any one of the preceding claims.

26. An article comprising the cured composition of claim 25.

27. The article of claim 26, wherein the article is a packer, an o-ring, a seal, a gasket, a hose, or a sheet.

Technical Field

The present disclosure relates to compositions comprising a peroxide cured fluoropolymer and nanoparticles functionalized with a functional fluorinated silane compound.

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

The present invention provides a curable composition comprising: a fluorinated elastomeric gum and a nanoparticle functionalized with 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-、CH₂＝CHCH₂-or CH₂-CH-, 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 1 to 4 carbon atoms. In some embodiments, Y is-O(CH₂)_xCH₃Wherein x is an integer of 0 to 3.

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

Unless defined otherwise, all scientific and technical terms used herein have the same meaning as commonly understood in the art. The definitions provided herein will facilitate understanding of certain terms used frequently herein and are not meant to limit the scope of the present disclosure.

As used in this specification and the appended claims, the singular forms "a", "an", and "the" encompass embodiments having plural referents, unless the content clearly dictates otherwise.

As used in this specification and the appended claims, the term "or" is generally employed in its sense including "and/or" unless the content clearly dictates otherwise. The term "and/or" means one or all of the listed elements or a combination of any two or more of the listed elements.

As used herein, "having," including, "" comprising, "and the like are used in their open sense and are generally meant to" include, but are not limited to. It is to be understood that "consisting essentially of … …", "consisting of … …", and the like are encompassed by "comprising" and the like. For example, a composition "comprising" silver can be a composition "consisting of" or "consisting essentially of" silver.

As used herein, when "consisting essentially of … …" refers to a composition, device, system, method, etc., it is meant that the elements of such composition, device, system, method, etc., are limited to the enumerated elements and any other elements that do not materially affect one or more of the basic and novel characteristics of such composition, device, system, method, etc.

The words "preferred" and "preferably" refer to embodiments that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the disclosure, including the claims.

Also herein, the recitation of numerical ranges by endpoints includes all numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc. or 10 or less includes 10, 9.4, 7.6, 5, 4.3, 2.9, 1.62, 0.3, etc.). In the case where a range of values is "at most" a particular value, that value is included in the range.

The use of "first," "second," etc. in the foregoing description and the following claims is not necessarily intended to indicate that an enumerated number of objects are present. For example, a "second" substrate is only intended to be distinguished from another substrate (such as a "first" substrate). The use of "first," "second," etc. in the description above and in the claims that follow is also not necessarily intended to indicate that one is earlier in time than another.

"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;

"Cross-linking" refers to the use of chemical bonds or groups to link two preformed polymer chains, 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 phases are generally associated with, for exampleBrittle, hard, rigid, or a combination thereof. In contrast, high elastic states are generally associated with materials such as flexibility and elasticity.

"interpolymerized" refers to monomers polymerized together to form a polymer backbone;

"millable" is the ability of a material to be processed on rubber mills and internal mixers; "monomer" is a molecule that can be polymerized and then form part of the basic structure of a polymer;

"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; and is

"Polymer" refers to a macrostructure comprising interpolymerized units of monomers.

The present disclosure relates to a composition comprising at least a partially fluorinated polymer and nanoparticles functionalized with a functional fluorinated silane compound. The disclosed compositions may be referred to as nanoparticle-containing compositions.

Functional fluorinated silane compounds

The disclosed functional 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 2To 4 or an integer from 2 to 3. In some embodiments, Y may be-O (CH)₂)_xCH₃Wherein x is 0, i.e. Y is-OCH₃。

Generally, X represents a functional group of the functional fluorinated silane compound. Thus, for example, when X is Br, the compound of formula I may be referred to as a bromo-functional fluorinated silane compound. Similarly, for example, when X is CH₂＝CHCH₂When the compound of formula I is an allyl functional fluorinated silane compound.

Exemplary specific functional 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-Cl₃

Scheme 1

Wherein X, n, m, p and X are as defined above for formula I. 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-Cl₃

Scheme 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)₃

Scheme 3

In scheme 3, X, n, m, p and X are as defined above for formula I. 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)₃

Scheme 4

The disclosed compositions may comprise not less than 0.5 weight percent (wt%), not less than 1 wt%, or not less than 1.5 wt% of the functional fluorinated silane compound, based on the total weight of the composition. The disclosed compositions may 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 composition. In some embodiments, the presently disclosed compositions may comprise from about 1.5 wt% to about 5 wt%, and in some embodiments, about 2 wt%, of the functional fluorinated silane compound, based on the total weight of the composition.

Nanoparticles

As used herein, the term "nanoparticle" refers to a particle having a maximum dimension of at most 180 nm. Nanoparticles suitable for use in the present invention may have an average particle size, for example, of between as small as 5nm, 8nm or 10nm and as large as 120nm, 150nm or 180nm, or may encompass particles within a size distribution range, for example, of between as small as 5nm, 8nm or 10nm and as large as 120nm, 150nm or 180 nm. In another embodiment, the nanoparticles have an average size equal to or greater than 30nm and may have an average particle size, for example, between as small as 30nm, 40nm or 60nm and as large as 70nm, 90nm or 120nm or possibly as large as 150nm, 160nm or 180nm, or may encompass particles within a size distribution range, for example, between as small as 30nm, 40nm or 60nm and as large as 70nm, 90nm or 120nm or possibly as large as 150nm, 160nm or 180 nm. In one embodiment, the average particle size of the nanoparticles may be as small as 30nm, 40nm, or 60nm, or as large as 75nm, 90nm, 100nm, 110nm, or 120nm, or within any range bounded by the foregoing values and/or by the values in the examples herein.

The size distribution and the average size of the particles are determined by a laser diffraction/scattering method using an optical analyzer such as, for example, a laser diffraction/scattering particle size distribution analyzer model LA-950 available from Horiba, ltd., Japan. This method is widely used and is also known in the art as low angle laser light scattering ("LALLS"). Laser diffraction/scattering particle size analysis is based on the observation that: particles passing through the laser beam scatter light at an angle inversely proportional to their size. As the particle size decreases, the observed scattering angle increases logarithmically. The scattering intensity also depends on particle size, decreasing with particle volume. Thus, large particles scatter light at a narrow angle and high intensity, while small particles scatter light at a wider angle but low intensity.

Suitable nanoparticles include: inorganic oxides, carbides, nitrides and borides of aluminum, silicon, titanium, zirconium, cerium, zinc, tungsten, tantalum, boron, antimony, nickel and iron; metal oxides including indium tin oxide, barium titanate, and yttria-stabilized zirconia; core-shell particles comprising titanium dioxide on silica, aluminum oxide on silica, and silver on silica; and metals, including silver and nickel. Particularly suitable nanoparticles include, for example, Silica (SiO)₂) Titanium dioxide (TiO), titanium dioxide (titanium/titanium dioxide)₂) And aluminum oxide (Al/aluminum oxide, Al)₂O₃)。

Silica nanoparticles, for example in the form of colloidal silica, can be added in amounts, for example, as low as 0.5 wt.%, 1.0 wt.%, or 1.5 wt.% and as high as 3.0 wt.%, 5.0 wt.%, 7.5 wt.%, or 10 wt.% of the solids content of the fluorinated silane composition, based on the "wet" weight of the coating in the form of a liquid dispersion. In a more specific embodiment, the nanoparticles may be added in an amount ranging from as low as 1.0 wt.%, 1.25 wt.%, or 1.5 wt.% to as high as 2.5 wt.%, 2.75 wt.%, or 3 wt.% of the solids content of the fluoropolymer coating composition, based on the "wet" weight of the coating in liquid dispersion form.

Nanoparticles are available in the form of colloidal silica, which is typically in the form of a suspension of fine amorphous, non-porous, spherical silica particles in a liquid phase. The colloidal silica may include silica particles having the average particle size described above, and the colloidal silica may have a solids content of, for example, as low as 10, 15, or 20 weight percent, or as high as 35, 40, or 45 weight percent. The colloidal silica may also contain a stabilizer, such as sodium or ammonia ions, to keep the particles in their colloidal state and prevent precipitation.

The nanoparticles are functionalized with a functional fluorinated silane compound. Methods of functionalizing nanoparticles with silanes are known. Any suitable method may be used, including those described in the examples herein.

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 via 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 cannot be so soft that it sticks to the grinder, and also not so hard that it cannot be pressed onto the grinder. In some embodiments, useful fluorinated elastomer gums may have a molecular weight of at least 0.1MPa (megapascals), at least 0.3MPa, or even at least 0.5MPa at 100 ℃; and a modulus of no greater than 2.5MPa, no greater than 2.2MPa, or no greater than 2.0MPa, as measured at, for example, 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 does not include initiation and termination sites for 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 up to 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, 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-methoxy-ethyl vinyl ether, perfluoro-methoxy-methyl vinyl ether (CF)₃-O-CF₂-O-CF＝CF₂) And CF₃-(CF₂)₂-O-CF(CF₃)-CF₂-O-CF(CF₃)-CF₂-O-CF＝CF₂And itThe composition of the above-mentioned materials.

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

CF₂＝CFCF₂O(R_f1O)_n(R_f2O)_mR_f3(III)

Wherein R is_f1And R_f2Independently 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_f3Is 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-methoxy-ethyl allyl ether, perfluoro-methoxy-methyl allyl ether, and CF₃-(CF₂)₂-O-CF(CF₃)-CF₂-O-CF(CF₃)-CF₂-O-CF₂CF＝CF₂And combinations thereof.

As known to those skilled in the art, 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. 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 percent of the fluorinated elastomer gum, in some embodiments less than 10 mole percent of the fluorinated elastomer gum, and even less than 3 mole percent 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 character detectable by DSC (differential scanning calorimetry), which means that if studied under DSC, when a DSC thermogram is usedWhen conducting the test, wherein the first thermal cycle starts at-85 ℃ and ramps up to 350 ℃ at 10 ℃/min, cools to-85 ℃ at a rate of 10 ℃/min, and the second thermal cycle starts at-85 ℃ and ramps up to 350 ℃ at 10 ℃/min, the fluorinated elastomer gum, starting with 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; copolymers comprising VDF and perfluorinated vinyl ether monomer units (such as comprising VDF and CF)₂＝CFOC₃F₇Copolymers of monomeric units); ethylene and HFP monomeric units; a copolymer comprising CTFE and VDF monomer units; copolymers comprising TFE and VDF monomer units; copolymers 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)₃OCF₃Copolymers of monomeric units); 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 secondA 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 macromolecule beyond its nearest neighbor). 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, with an enthalpy of 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 weight (wt/weight)% -85 weight% TFE; 5-40% by weight of HFP; and 5-55 wt% VDF; 30-75% by weight of TFE; 5-35% by weight HFP; and 5-50 wt% VDF; or even 40% to 70% by weight of TFE; 10-30 wt% HFP; and 10 wt% to 45 wt% VDF. In some embodiments, 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 wt% to 65 wt% VDF and 15 wt% to 60 wt% 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 weight of the a and B blocks is independently selected from at least 1000 daltons, 5000 daltons, 10000 daltons, or even 25000 daltons; and up to 400000 daltons, 600000 daltons 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 ═ 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 brominated radicals of the formula RBr_xWherein (i) R is a perfluoroalkyl or chloroperfluoroalkyl group having 3 to 12 carbon atoms; and (ii) x ═ 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 O atoms; 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 from 2 to 12; CF (compact flash)₂＝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. ComprisesExamples of nitrile 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 during dynamic mixing temperatures, may be utilized.

In many embodiments, for example, t-butyl peroxides in which a tertiary carbon atom is 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-butylperoxyisopropyl carbonate (TBIC), 2-ethylhexyl t-butylperoxycarbonate (TBEC), 2-ethylhexyl t-amylperoxycarbonate, t-hexylperoxyisopropyl carbonate, carbon peroxy acid, O '-1, 3-propanediyl OO, OO' -bis (1, 1-dimethylethyl) ester, t-butyl peroxybenzoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, bis (4-methylbenzoyl) peroxide, lauryl peroxide, 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 during 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 block 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, CRC Press, New York, 1996, Vol.1, p.432-440 (Polymeric Materials Encyclopedia, by J.C. Salamone, ed., CRCPResses Inc., New York, (1996) Vol.1, page 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 the precursor of the polyamine compound 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 block 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 block 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 may include magnesium oxide, lead oxide, calcium hydroxide, lead dihydrogen phosphite, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, hydrotalcite, alkali stearate, 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 block copolymer.

The filler may include, for example, organic or inorganic fillers such as clay, 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 can produce a compound that is capable of maintaining a preferred elasticity and physical stretch (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 nanoparticles can be functionalized with the functional fluorinated silane compounds using known methods, including those described herein. The composition comprising nanoparticles functionalized with a functional fluorinated silane compound, a fluorinated elastomeric gum, and other components may be mixed with a curing agent and optionally conventional adjuvants. The method for mixing may include kneading using, for example, 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 can then be heated to cure the gum composition and form a cured elastomeric article.

The compounded mixture is typically pressurized (i.e., press cured) at a temperature of about 120 ℃ to 220 ℃, or even at a temperature of about 140 ℃ to 200 ℃, for a period of about 1 minute to about 15 hours, typically about 1 minute to 15 minutes. Pressures of about 700kPa (kilopascals) to 20,000kPa or even about 3400kPa to 6800kPa are typically used when molding the composition. 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 at a temperature of about 160 ℃ to 230 ℃ for a time of about 1 hour to 24 hours or more, depending on the cross-sectional thickness of the sample. 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.

Curing composition

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 material deformation). 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.