JP2017538025A - Curable partially fluorinated polymer composition - Google Patents

Abstract

Described herein are curable partially fluorinated polymer compositions and methods. Such a composition is:
(I) A partially fluorinated amorphous fluoropolymer, wherein the partially fluorinated amorphous fluoropolymer chain comprises a carbon-carbon double bond or is partially fluorinated amorphous fluoropolymer A partially fluorinated amorphous fluoropolymer capable of forming carbon-carbon double bonds along the main chain of
(Ii) 1 to 10 parts of a curing agent per 100 parts of partially fluorinated amorphous fluoropolymer of formula CX ₁ X ₂ = CX ₃ -LM, wherein X ₁ , X ₂ , and X ₃ is independently selected from H, Cl, and F, at least one of X ₁ , X ₂ , and X ₃ is H; L is a bond or linking group, and M is , Which is a nucleophilic group]
(Iii) an acid acceptor; and (iv) an organic onium compound.

Description

  Disclosed is a curing of the composition comprising a partially fluorinated amorphous fluoropolymer with a curing agent comprising a terminal olefin having at least one olefinic hydrogen and a nucleophilic group.

  It would be desirable to identify new curing systems for partially fluorinated amorphous fluoropolymers.

In one aspect, curable partially fluorinated polymers are disclosed and such polymers are
(I) A partially fluorinated amorphous fluoropolymer, wherein the partially fluorinated amorphous fluoropolymer contains a carbon-carbon double bond or is partially fluorinated amorphous fluoropolymer chain A partially fluorinated amorphous fluoropolymer capable of forming a carbon-carbon double bond along
(Ii) 1 to 10 millimoles of curing agent per 100 parts of partially fluorinated amorphous fluoropolymer of formula CX ₁ X ₂ = CX ₃ -LM, wherein X ₁ , X ₂ , and X ₃ is independently selected from H, Cl, and F, at least one of X ₁ , X ₂ , and X ₃ is H; L is a bond or linking group; and M Is a nucleophilic group]
(Iii) an acid acceptor; and (iv) an organic onium compound.

  In another aspect, an article comprising a cured product of the above composition is disclosed.

  In yet another aspect, a method of making a partially fluorinated elastomer is disclosed that includes curing the curable partially fluorinated polymer composition disclosed above.

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

As used herein, the terms “a”, “an”, and “the” are used interchangeably and mean one or more.
“And / or” is used to indicate that either or both of the notations can occur, eg, A and / or B includes (A and B) and (A or B) Is done.
“Main chain” refers to a continuous chain that is the main part of the polymer.
“Crosslinking” refers to linking two preformed polymer chains using chemical bonds or chemical groups.
“Curing site” refers to a functional group that can participate in crosslinking.
“Copolymerization” refers to the polymerization of monomers together to form a polymer backbone.
Similarly, in this specification, reference to a range by endpoints includes all numbers subsumed within the range (eg 1 to 10 is 1.4, 1.9, 2.33, 5.75). , 9.98, etc.).

  Also, in this specification, the description of “at least one” means any number greater than or equal to 1 (eg, at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).

  In this disclosure, a partially fluorinated amorphous fluoropolymer, such as those disclosed herein, with a curing agent comprising a terminal olefin comprising an acid acceptor with at least one olefinic hydrogen and an onium compound. It has been found that it can be cured.

  Fluoropolymer

  The amorphous fluoropolymer of the present disclosure is a partially fluorinated polymer. As disclosed herein, an amorphous partially fluorinated polymer is a polymer comprising at least one carbon-hydrogen bond and at least one carbon-fluorine bond on the polymer backbone. In one embodiment, the amorphous partially fluorinated polymer is highly fluorinated and at least 60, 70, 80, or even 90% of the polymer backbone contains C—F bonds.

  Amorphous fluoropolymers of the present disclosure may also include carbon-carbon double bonds and / or form carbon-carbon double bonds along the polymer chain. In one embodiment, the partially fluorinated amorphous fluoropolymer comprises carbon-carbon double bonds along the backbone of the partially fluorinated amorphous fluoropolymer or is partially fluorinated amorphous. A carbon-carbon double bond can be formed along the main chain of the functional fluoropolymer. In another embodiment, the partially fluorinated amorphous fluoropolymer contains carbon-carbon double bonds, or the carbon-carbon double in the pendant group rather than the partially fluorinated amorphous fluoropolymer backbone. Bonds can be formed.

A fluoropolymer capable of forming a carbon-carbon double bond means a fluoropolymer containing units capable of forming a double bond. Such units include, for example, two adjacent carbons along the polymer backbone or pendant side chain in which hydrogen is bonded to the first carbon and the leaving group is bonded to the second carbon. Is mentioned. During the removal reaction (eg, thermal reaction and / or using acid or base), the leaving group and the elimination of hydrogen form a double bond between two carbon atoms. Representative leaving groups include halides, alkoxides, hydroxides, tosylate, mesylate, amines, ammonium, sulfide, sulfonium, sulfoxide, sulfone, and combinations thereof. Similarly, fluoropolymers containing adjacent carbon atoms are conceivable in which both bromine atoms or both iodine atoms are bonded, resulting in the elimination of Br ₂ or I ₂ .

  The amorphous fluoropolymer contains a plurality of these groups (groups capable of forming carbon-carbon double bonds or double bonds) so that sufficient curing occurs. Generally, a plurality is at least 0.1, 0.5, 1, 2, or even 5 mol%, up to 7, 10, 15, or even 20 mol% (ie, these carbon-carbons per mol of polymer). The number of moles of double bonds or the number of moles of these precursors).

  In one embodiment, the amorphous partially fluorinated polymer is derived from at least one hydrogen-containing monomer such as vinylidene fluoride.

  In one embodiment, the amorphous fluoropolymer is an adjacent copolymer unit of vinylidene fluoride (VDF) and hexafluoropropylene (HFP); a VDF that can deliver acidic hydrogen atoms to a polymer backbone such as trifluoroethylene. (Or tetrafluoroethylene) and a fluorinated comonomer copolymer unit; vinyl fluoride; 3,3,3-trifluoropropene-1; pentafluoropropene (eg, 2-hydropentafluoropropylene and 1-hydropentafluoropropylene) ); 2,3,3,3-tetrafluoropropene; and combinations thereof.

  In some embodiments, if the curing agent disclosed herein can be used to cure the amorphous fluoropolymer, a small amount of additional monomer (eg, 10, 5, 2, or even more). Less than 1% by weight) may be added.

  In one embodiment, the amorphous fluoropolymer is additionally derived from hydrogen-containing monomers such as pentafluoropropylene (eg, 2-hydropentafluoropropylene), propylene, ethylene, isobutylene, and combinations thereof.

In one embodiment, the amorphous fluoropolymer is addition derived from a perfluorinated monomer. Representative perfluorinated monomers include hexafluoropropene; tetrafluoroethylene; chlorotrifluoroethylene; perfluoro (alkyl vinyl ether), such as perfluoromethyl vinyl ether, CF ₂ = CFOCFCF ₂ CF ₂ OCF ₃ , CF ₂ = CFOCF ₂ OCF ₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₂ OCF ₂ CF ₃ , CF ₂ = CFOCF ₂ OCF ₃ , and CF ₂ = CFOCF ₂ OC ₃ F ₇ , perfluoro (alkyl allyl ether), eg, per fluoromethyl allyl ether, perfluoro (alkyloxy allyl ether), for example, perfluoro-4,8-dioxa-1-nonene _{(i.e., CF 2 = CFCF 2 OCF 2} ) 3 OCF 3], and these pairs Combined, and the like.

  Representative types of polymers include (i) vinylidene fluoride, tetrafluoroethylene, and propylene; (ii) vinylidene fluoride, tetrafluoroethylene, ethylene, and perfluoroalkyl vinyl ethers such as perfluoro (methyl vinyl ether). (Iii) vinylidene fluoride with hexafluoropropylene; (iv) hexafluoropropylene, tetrafluoroethylene, and vinylidene fluoride; (v) hexafluoropropylene and vinylidene fluoride, (vi) vinylidene fluoride and par (Vii) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyl vinyl ethers, (viii) vinylidene fluoride, perfluoroalkyl vinyl ethers, hydro (Ix) tetrafluoroethylene, propylene, and 3,3,3-trifluoropropene; (x) tetrafluoroethylene, and propylene; (xi) ethylene, tetrafluoroethylene, And perfluoroalkyl vinyl ethers, and optionally 3,3,3-trifluoropropylene; (xii) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyl allyl ethers, (xiii) vinylidene fluoride and perfluoroalkyl allyl ethers; (Xiv) ethylene, tetrafluoroethylene, and perfluoroalkyl vinyl ether, and optionally 3,3,3-trifluoropropylene; (xv) vinylidene fluoride, tetrafluoroethylene, and perfluoro Roalkyl allyl ether, (xvi) vinylidene fluoride and perfluoroalkyl allyl ether; (xvii) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl ether, (xviii) vinylidene fluoride and perfluoroalkyloxyallyl ether Copolymer units derived from (xiv) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl ether, (xv) vinylidene fluoride and perfluoroalkyloxyallyl ether; and (xvi) combinations thereof; Including polymers.

  Advantageously, the amorphous fluoropolymers of the present disclosure can be cured without the need for pendant bromine or iodine cure sites by using the curing agents disclosed herein. In many cases, iodine and bromine containing cure site monomers that are polymerized to fluoropolymers and / or chain ends can be particularly expensive. However, in one embodiment, the partially fluorinated amorphous polymer includes iodine cure sites and / or bromine cure sites that can be used, for example, to enhance the cure of the fluoropolymer.

  In one embodiment, the partially fluorinated amorphous polymer is further derived from bromine and / or iodine containing cure site monomers that can participate in a peroxide cure reaction.

Such bromine and / or iodine containing cure site monomers are:
(A) Formula:
Z—R _f —O—CX═CX ₂
Wherein each X may be the same or different and represents H or F, Z is Br or I, R _f optionally contains chlorine and / or ether oxygen atoms, bromo having a C ₁ -C ₁₂ (per) fluoroalkylene] - or iodo (per) fluoroalkyl (per) fluoro vinyl ethers _{such, BrCF 2 -O-CF = CF} 2, BrCF 2 CF 2 -O- _{CF = CF 2, BrCF 2 CF} 2 CF 2 -O-CF = CF 2, CF 3 CFBrCF 2 -O-CF = CF 2, ICF 2 CF 2 CH = CH 2, ICF 2 CF 2 CF 2 -O-CF = CF ₂ and the like;
(B) Bromo- or iodo- (per) fluoroolefins such as those having the formula:
Z ′ — (R _f ′) _r —CX═CX ₂ ;
[Wherein each X independently represents H or F, Z ′ is Br or I, and R ′ _f optionally contains a chlorine atom, perfluoroalkylene C ₁ -C ₁₂ and r is 0 or 1]; for example, bromotrifluoroethylene, 4-bromo-perfluorobutene-1, or the like, or a bromofluoroolefin, such as 1-bromo-2,2-difluoroethylene And 4-bromo-3,3,4,4-tetrafluorobutene-1 and the like;
(C) includes non-fluorinated bromo-olefins such as vinyl bromide and 4-bromo-1-butene.

In one embodiment, the amorphous fluoropolymer is prepared in the presence of a bromine and / or iodine-containing chain transfer agent, as known in the art, eg, the formula R _f P _X , wherein P is Br or I , and the preferably I, R _f is a X-valent alkyl radical having 1 to 12 carbon atoms, optionally polymerized in the presence of a chain transfer agent having a chlorine atom may also contain ' Is done. Typically x is 1 or 2. Useful chain transfer agents include perfluorinated alkyl monoiodides, perfluorinated alkyl diiodides, perfluorinated alkyl monobromides, perfluorinated alkyl dibromides, and combinations thereof. Specific examples include CF ₂ Br ₂ , Br (CF ₂ ) ₂ Br, Br (CF ₂ ) ₄ Br, CF ₂ ClBr, CF ₃ CFBrCF ₂ Br, I (CF ₂ ) _n I [where n is And an integer of 3 to 10 (for example, I (CF ₂ ) ₄ I), and combinations thereof.

  In one embodiment, the amorphous fluoropolymer is substantially free of I or Br, where I or Br included in the amorphous fluoropolymer is 0.1, 0.05, 0 relative to the total polymer. .01, or even less than 0.005 mol%.

  In one embodiment, the amorphous fluoropolymer of the present disclosure is not grafted, i.e., vinyl, allyl, acrylate, amide, sulfonate, pyridine, carboxylic ester, carboxylate, aliphatic or aromatic. Pendant groups containing hindered silanes that are triethers or triesters are not included. In one embodiment, the amorphous fluoropolymer does not include a monophenol graft.

  Hardener

The curing agent of the present disclosure is a compound comprising at least one terminal olefin having at least one olefinic hydrogen. In one embodiment, the curing agent of the present disclosure is represented by Formula I:
CX ₁ X ₂ = CX ₃ -LM (I)
Wherein X ₁ , X ₂ , and X ₃ are independently selected from H, Cl, and F, and at least one of X _1, X ₂ , and X ₃ is H; , A bond or a linking group; M is a nucleophilic group.

  L is a single bond or a linking group. The linking group may be a chained O, S, or N atom (eg, an ether bond), or an optionally chained heteroatom (eg, O, S, or N). And / or an optionally substituted divalent organic group. The divalent organic group may be linear, branched or cyclic. The divalent organic group may be aromatic or aliphatic. The divalent organic group is a non-fluorinated divalent organic group (containing no fluorine atom), a partially fluorinated divalent organic group (containing at least one C—H bond and at least one C—F bond). Or a perfluorinated (containing no C—H bond and at least one C—F bond) divalent organic group.

In one embodiment, the divalent organic group is — (CH ₂ ) _n (O) _m —P— (Rf) _p — (P) _q —, wherein n is an integer from 1 to 10. M is 0 or 1; P is selected from at least one of aromatic, substituted aromatic, and (CH ₂ ) _n , where n is an integer from 1 to 10; Rf is selected from (CF ₂ ) _{n wherein} n is an integer from 1 to 10 and C (CF ₃ ) ₂ and Rf is cyclic or aliphatic; And / or includes at least one heteroatom linked in a chain, such as, for example, O, S, and N; p is 0 or 1; q is 0 or 1. Representative divalent organic groups include —CH ₂ —C ₆ H ₄ (OCH ₃ ) —, —CH ₂ —O—CH ₂ (CF ₂ ) ₄ —CH ₂ — and —CH ₂ —O—C _6. H ₄ —C (CF ₃ ) ₂ —C ₆ H ₄ — and —CH ₂ —O—C ₆ H ₄ —C (CF ₃ ) ₂ —C ₆ H ₄ —O—CH ₂ — may be mentioned.

M is a nucleophilic group, ie contains an unoccupied pair of electrons. Exemplary nucleophilic groups include alcohol (—OH), amine (—NH ₂ , —NHR, and —NRR ′, where R and R ′ are organic groups), thiol (—SH), and Carboxylic acid (-COOH) is mentioned.

  In one embodiment, the curing agent comprises at least one non-fluorinated terminal olefin group, i.e. the olefin does not contain any fluorine atoms. In one embodiment, the curing agent comprises a non-aromatic terminal olefin and / or a non-aromatic alcohol.

及びこれらの組み合わせが挙げられ、式中、ｎは、独立して、整数１〜５０、１〜２０、１〜１０、又は更には２〜１０から選択され、Ｒｆはフッ素化アルキル基である。Ｒｆは、部分フッ素化又は全フッ素化され得る。一実施形態では、Ｒｆは、Ｏ、Ｓ、又はＮなどの連結されたヘテロ原子を含み得る。Ｒｆは、直鎖又は分岐鎖、飽和又は不飽和であってよい。一実施形態では、Ｒｆは、Ｃ１〜Ｃ１２フッ素化アルキル基である（任意に、パーフルオロ化されている）。 As a typical curing agent,

And combinations thereof, wherein n is independently selected from the integers 1-50, 1-20, 1-10, or even 2-10, and Rf is a fluorinated alkyl group. Rf can be partially or fully fluorinated. In one embodiment, Rf can include linked heteroatoms such as O, S, or N. Rf may be linear or branched, saturated or unsaturated. In one embodiment, Rf is a C1-C12 fluorinated alkyl group (optionally perfluorinated).

  The curing agent should be used in an amount substantially sufficient to cure the amorphous fluoropolymer, as indicated by an increase in torque during operation of the direometer. For example, at least 1, 1.5, 2, 2.5, 3, or even 4 millimoles or more are used per 100 parts of amorphous fluoropolymer. If too little curing agent is used, the amorphous fluoropolymer will not cure. For example, no more than 20, 15, 10, or even 8 millimoles of hardener per 100 parts of amorphous fluoropolymer. If too much curing agent is used, the amorphous fluoropolymer may become brittle.

  In one embodiment, the curable partially fluorinated polymer composition is substantially free of monophenol, i.e., the monophenol that the composition comprising the amorphous fluoropolymer comprises relative to the number of moles of amorphous fluoropolymer. It is less than 0.1, 0.01, or even 0.001 mol%.

  Acid acceptor

  In one embodiment, acid acceptors are used in the present disclosure, such acid acceptors include organic, inorganic, or blends thereof. Examples of inorganic receptors include magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic lead phosphate, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, hydrotalcite and the like. Organic receptors include amines, epoxies, sodium stearate, and magnesium oxalate. Particularly suitable acid acceptors include calcium hydroxide, magnesium oxide, and zinc oxide. Mixtures of acid acceptors can be used as well. The amount of acid acceptor will generally depend on the properties of the acid acceptor used.

  In one embodiment, at least 0.5 parts, 1 part, 2 parts, 3 parts, or even 4 parts acid acceptors are used per 100 parts of amorphous fluoropolymer. In one embodiment, 10 parts or less, 7 parts or less, or even 5 parts or less of acid acceptor per 100 parts of amorphous fluoropolymer is used.

  Onium compounds

  In one embodiment, an organic onium compound is added to the composition as a phase transfer catalyst to assist in the crosslinking of the amorphous fluoropolymer, and / or the organic onium compound is double bonded to the fluoropolymer by a dehydrofluorination reaction. Can be used to generate Such organic onium compounds include quaternary ammonium hydroxides or salts, quaternary phosphonium hydroxides or salts, and tertiary sulfonium hydroxides or salts.

  Briefly, phosphonium and ammonium salts or compounds each contain, as a central atom, phosphorus or nitrogen covalently bonded to four organic moieties by carbon-phosphorus (or carbon-nitrogen) covalent bonds and ionically associated with anions. . The organic portions can be the same or different.

Briefly, a sulfonium compound is a sulfur in which three organic moieties having 1 to 20 carbon atoms are covalently bonded by a carbon-sulfur covalent bond to at least one sulfur atom, and is ionically associated with an anion. Contains organic compounds. The organic moieties can be the same or different. The sulfonium compound can have a relatively positive sulfur atom, for example, [(C ₆ H ₅ ) ₂ S ⁺ (CH ₂ ) ₄ S ⁺ (C ₆ H ₅ ) ₂ ] ₂ Cl ⁻ and is divalent. Two carbon-sulfur covalent bonds may be included between carbon atoms of the organic moiety, that is, the sulfur atom may be a heteroatom of a cyclic structure.

  Suitable organic onium compounds for use in the present disclosure are known and reported in the art. See, for example, US Pat. Nos. 5,262,490 (Kolb et al.) And 4,912,171 (Grootaert et al.), Incorporated herein by reference.

Representative organic onium compounds include C ₃ -C ₆ symmetric tetraalkylammonium salts, asymmetric tetraalkylammonium salts having a total of 8 to 24 alkyl carbons, and benzyl trialkyls having a total of 7 to 19 alkyl carbons. Alkylammonium salts (eg tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltributylammonium chloride, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate and tetrabutylammonium hydroxide, phenyltrimethylammonium chloride, tetrapentylammonium chloride, tetra Propyl ammonium bromide, tetrahexyl ammonium chloride, and tetraheptyl ammonium bromide tetramethyl ammonium Quaternary phosphonium salts such as tetrabutylphosphonium chloride, tetraphenylphosphonium chloride, benzyltriphenylphosphonium chloride, tributylallylphosphonium chloride, tributylbenzylphosphonium chloride, tributyl-2-methoxypropylphosphonium chloride, benzyldiphenyl (dimethylamino) ) Phosphonium chloride, 8-benzyl-1,8-diazobicyclo [5.4.0] 7-undecenium chloride, benzyltri (dimethylamino) phosphonium chloride, and bis (benzyldiphenylphosphine) iminium chloride Is mentioned. Any suitable organic onium compound includes 1,8-diazabicyclo [5.4.0] undec-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene. Phenolate is the preferred anion for quaternary ammonium and phosphonium salts.

  In one embodiment, the organoonium compound is used at 1 to 5 millimoles (mmhr) per 100 parts of amorphous fluoropolymer.

  Free radical source

  In one embodiment, the curable composition includes a free radical source that is used to initiate curing. Such free radical sources include peroxides such as organic peroxides. In many cases, it is preferred to use a tertiary butyl peroxide having a tertiary carbon atom bonded to peroxy oxygen.

  Representative peroxides include 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; dicumyl peroxide; di (2-t-butylperoxyisopropyl) benzene; dialkyl peroxide; bis (dialkyl peroxide) 2,5-dimethyl-2,5-di (tertiary butyl peroxy) 3-hexyne; dibenzoyl peroxide; 2,4-dichlorobenzoyl peroxide; tertiary butyl perbenzoate; α, α′-bis (t -Butyl peroxy-diisopropylbenzene); t-butyl peroxyisopropyl carbonate, t-butyl peroxy 2-ethylhexyl carbonate, t-amyl peroxy 2-ethylhexyl carbonate, t-hexyl peroxyisopropyl carbonate, di [1,3-dimethyl -3- (t-butylperoxy) butyl] carbonate, carbonoperoxoacid, O, O'-1,3-propanediylOO, OO'-bis (1,1-dimethylethyl) ester, and combinations thereof Can be mentioned.

  The amount of free radical source used is generally at least 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, or even 1 per 100 parts of amorphous fluoropolymer. .5 parts by weight; up to 2, 2.25, 2.5, 2.75, 3, 3.5, 4, 4.5, 5, or even 5.5 parts by weight. In one embodiment, the curable composition is substantially free of free radical sources, i.e., less than 0.05 parts by weight of free radical sources included per 100 parts of amorphous fluoropolymer, or even 0.01 parts by weight.

Typical cross-linking aids are compounds that contain terminal unsaturation sites that are incorporated into the polymer during cure to aid cure and typically assist in peroxide cure. Typical crosslinking aids include tri (methyl) allyl isocyanurate (TMAIC), triallyl isocyanurate (TAIC), tri (methyl) allyl cyanurate, poly-triallyl isocyanurate (poly-TAIC), triary. Rucyanurate (TAC), xylylene-bis (diallyl isocyanurate) (XBD), N, N′-m-phenylenebismaleimide, diallyl phthalate, tris (diallylamine) -s-triazine, triallyl phosphite, 1,2- Polybutadiene, ethylene glycol diacrylate, diethylene glycol diacrylate, and combinations thereof. Another useful coagents can be represented by the formula _{CH 2 = CH-R f1 -CH} = CH 2 [ _{wherein, R f1} is a carbon atom can be a 1-8 perfluoroalkylene] . By using the curing agent disclosed herein, the amorphous fluoropolymer of the present disclosure can be cured without the use of these crosslinking aids. That is, the curable composition is substantially free of typical crosslinking aids (less than 1 part, less than 0.5 part, or even less than 0.1 per 100 parts of amorphous fluoropolymer%, or Below detection limit). Since crosslinking aids are expensive, insoluble in fluorinated polymers and affect processing (eg, composition bleed out, mold fouling), it is beneficial to be substantially free of crosslinking aids. obtain.

  The curable composition may also contain various types of additives commonly used in the preparation of elastomeric compositions, such as pigments, fillers (such as carbon black), pore formers, and those known in the art. .

  The curable amorphous fluoropolymer composition may be used in conventional rubber processing equipment to replace the amorphous fluoropolymer and the curing agent with other components (eg, acid acceptors, onium compounds, free radical sources, and / or further components). In the art), to provide a solid mixture, also referred to in the art as a “compound”, ie, a solid polymer containing additional raw materials. The process of mixing such components to produce a solid polymer composition containing other components is typically referred to as “compounding”. Examples of such apparatuses include rubber roll machines, closed mixers such as Banbury mixers, and mixed extrusion molding machines. The temperature of the mixture during mixing typically does not rise above about 120 ° C. During mixing, the components and additives are uniformly dispersed throughout the resulting fluorinated polymer “compound” or polymer sheet. This “compound” can then be extruded or pressed in a mold such as, for example, a cavity or transfer mold, followed by oven curing. In an alternative embodiment, curing can be done in an autoclave.

  Curing is typically accomplished by heat treating the curable amorphous fluoropolymer composition. The heat treatment is conducted at a temperature and for an effective time to produce a cured fluoroelastomer. Optimal conditions can be tested by evaluating the cured fluoroelastomer for its mechanical and physical properties. Typically, curing is performed at a temperature above 120 ° C or above 150 ° C. Typical curing conditions include curing at a temperature of 160 ° C to 210 ° C or 160 ° C to 190 ° C. Typical cure periods include 3 to 90 minutes. Curing is preferably performed under pressure. For example, a pressure of 10-100 bar can be applied. A secondary vulcanization cycle may be applied to ensure complete cure process. The secondary vulcanization may be performed at a temperature of 170 ° C. to 250 ° C. for a period of 1 to 24 hours.

  In the curable composition, the partially fluorinated amorphous fluoropolymer is ASTM D1646, a MV 2000 instrument (available from Alpha Technologies (Ohio, USA)) using a large rotor (ML 1 + 10) at 121 ° C. It has a Mooney viscosity according to -06 TYPE A. Curing using the curing agents described herein turns the amorphous fluoropolymer into an elastomer and becomes a non-flowable fluoropolymer with an infinite viscosity (and thus an unmeasurable Mooney viscosity). It becomes like this.

  In one embodiment of the present disclosure, a curing system comprising a curing agent and an amorphous fluoropolymer disclosed herein relates to chemical resistance with respect to typical iodine / bromine and auxiliaries including a peroxide curing system. It exhibits both chemical resistance, but does not contain bromine or iodine, so it has improved thermal resistance over conventional iodine or bromine-containing fluoroelastomers with poor thermal resistance, and as a result The cured fluoropolymer can have sufficient thermal and chemical resistance at the same time.

  Cured fluoroelastomers are particularly useful as seals, gaskets, and molded parts, especially in automotive, chemical processing, semiconductor, aerospace, and petroleum industry applications.

  Exemplary embodiments of the present disclosure include:

Embodiment 1. FIG.
(I) A partially fluorinated amorphous fluoropolymer, wherein the partially fluorinated amorphous fluoropolymer contains a carbon-carbon double bond or is partially fluorinated amorphous fluoropolymer chain A partially fluorinated amorphous fluoropolymer capable of forming a carbon-carbon double bond along
(Ii) 1 to 10 millimoles of curing agent per 100 parts of partially fluorinated amorphous fluoropolymer of formula CX ₁ X ₂ = CX ₃ -LM [wherein X _1, X ₂ and X ₃ are independently selected from H, Cl and F, at least one of X _1, X ₂ and X ₃ is H; L is a bond or linking group , M is a nucleophilic group];
A curable partially fluorinated polymer composition comprising: (iii) an acid acceptor; and (iv) an organic onium compound.

  Embodiment 2. FIG. A partially fluorinated curable amorphous fluoropolymer (i) adjacently copolymerized VDF units and HFP units; (ii) fluorinated comonomer units having copolymerized VDF units and acidic hydrogen atoms; The curable partially fluorinated polymer composition of embodiment 1, comprising iii) a copolymerized TFE unit and a fluorinated comonomer unit having an acidic hydrogen atom; and (iv) a combination thereof.

  Embodiment 3. FIG. The fluorinated comonomer having an acidic hydrogen atom is selected from trifluoroethylene; vinyl fluoride; 3,3,3-trifluoropropene-1; pentafluoropropene; and 2,3,3,3-tetrafluoropropene The curable partially fluorinated polymer composition of embodiment 2.

  Embodiment 4. FIG. Partially fluorinated amorphous fluoropolymers are (i) vinylidene fluoride, tetrafluoroethylene, and propylene; (ii) vinylidene fluoride, tetrafluoroethylene, ethylene, and perfluoroalkyl vinyl ethers such as perfluoro ( (Iii) vinylidene fluoride with hexafluoropropylene; (iv) hexafluoropropylene, tetrafluoroethylene, and vinylidene fluoride; (v) hexafluoropropylene and vinylidene fluoride, (vi) fluoride Vinylidene and perfluoroalkyl vinyl ethers; (vii) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyl vinyl ethers, (viii) vinylidene fluoride, perfluoroalkyl vinyl ethers (Ix) tetrafluoroethylene, propylene, and 3,3,3-trifluoropropene; (x) tetrafluoroethylene, and propylene; (xi) ethylene, Tetrafluoroethylene, and perfluoroalkyl vinyl ether, and optionally 3,3,3-trifluoropropylene; (xii) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyl allyl ether, (xiii) vinylidene fluoride, and per (Xiv) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl ether, (xv) vinylidene fluoride and perfluoroalkyloxyallyl ether; (xvi) Any of Embodiments 1-3, derived from vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl ether, (xv) vinylidene fluoride and perfluoroalkyloxyallyl ether; and (xvi) combinations thereof A curable partially fluorinated polymer composition according to any one of the preceding embodiments.

  Embodiment 5. FIG. The partially fluorinated amorphous fluoropolymer contains a carbon-carbon double bond along the main chain of the partially fluorinated amorphous fluoropolymer, or the main structure of the partially fluorinated amorphous fluoropolymer The curable partially fluorinated polymer composition of any one of embodiments 1-4, which can form carbon-carbon double bonds along the chain.

  Embodiment 6. FIG. The curable partially fluorinated polymer composition according to any one of embodiments 1 to 5, wherein the nucleophilic group is selected from alcohols, amines, and thiols.

  Embodiment 7. FIG. The curable partially fluorinated polymer composition according to any one of embodiments 1-6, wherein the curing agent comprises a non-fluorinated terminal olefin group.

  Embodiment 8. FIG. The curable partially fluorinated polymer composition according to any one of embodiments 1 to 7, wherein the curing agent comprises a non-aromatic alcohol.

  Embodiment 9. FIG. The curable partially fluorinated polymer composition according to any one of Embodiments 1 to 8, wherein the curable partially fluorinated polymer composition is substantially free of monophenol.

及びこれらの混合物のうちの少なくとも１つから選択され、式中、ｎは、１〜１０の整数である、実施形態１〜９のいずれか一態様に記載の硬化性部分フッ素化ポリマー組成物。 Embodiment 10. FIG. Hardener is

And a curable partially fluorinated polymer composition according to any one of the embodiments 1-9, wherein n is an integer from 1 to 10, selected from at least one of these and mixtures thereof.

  Embodiment 11. FIG. The curable partially fluorinated polymer composition according to any one of Embodiments 1-10, wherein the organic onium compound is selected from at least one of phosphonium or sulfonium.

  Embodiment 12. FIG. The curable partial fluorination according to any one of the preceding embodiments, wherein the partially fluorinated amorphous fluoropolymer is further derived from a cure site monomer comprising at least one of I and Br. Polymer composition.

  Embodiment 13. FIG. The curable partially fluorinated polymer composition of any one of embodiments 1-11, wherein the fluoropolymer is substantially free of I, Br, and Cl.

  Embodiment 14. FIG. The acid acceptor is selected from at least one of magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic lead phosphate, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, and hydrotalcite The curable partially fluorinated polymer composition according to any one of Embodiments 1 to 13.

  Embodiment 15. FIG. The curable partially fluorinated polymer composition of any one of embodiments 1-14, further comprising a free radical source.

  Embodiment 16. FIG. Embodiment 16. The curable partially fluorinated polymer composition of embodiment 15, wherein the free radical source is selected from at least one of peroxides.

  Embodiment 17. FIG. The curable partially fluorinated polymer composition of embodiment 16, wherein the composition is substantially free of auxiliaries.

  Embodiment 18. FIG. An article comprising a cured product of the composition according to any one of Embodiments 1 to 17.

Embodiment 19. FIG.
Providing a curable partially fluorinated polymer composition according to any one of embodiments 1-17,
Curing the curable partially fluorinated polymer composition. A method for producing a partially fluorinated elastomer.

  The advantages and embodiments of the present disclosure are further illustrated by the following examples, but the specific materials and amounts listed in these examples, as well as other conditions and details, should be construed to unduly limit the present invention. Should not be done. In these examples, all percentages, percentages, and ratios are by weight unless otherwise indicated.

  Unless otherwise stated or apparent, all materials are commercially available (eg, from Sigma-Aldrich Chemical Company Milwaukee, Wis.) Or known to those skilled in the art.

The following abbreviations are used in the following examples: phr = ratio of compounding agent to rubber 100. g = gram, kg = kilogram; min = minute, mol = mol; hr = hour, C = degree of Celsius; mL = milliliter; L = liter; mm = millimeter; kN = kilonewton; kPa = kilopascal; = Gas chromatography mass spectrometry; Pa = Pascal; psig = pounds per square inch; LC / UV = liquid chromatography-ultraviolet detection; and phr = per 100 parts of rubber (or amorphous polymer).

  Manufacture of VDF / BTFE / MA31

In the absence of oxygen, a 4 liter kettle was charged with 3400 mL of deionized water. The _{CF 3 -O- (CF 2) 3} -O-CFH-CF 2 -COONH 4 of 12g was added as an emulsifier. After heating to 90 ° C., 40 g of tetrafluoroethene (TFE), 77 g of VDF, 3 g of 1-bromotrifluoroethene (BTFE) are added, and 140 g of perfluoro as a pre-emulsion (described in WO200149752). -4,8-dioxa-1-nonene (prepared as "PMEAE" as described in MA31, Worm et al., US Pat. No. 5,891,965) was added. The reaction was initiated by continuously feeding 1,4 g ammonium peroxodisulfate (APS) dissolved in 280 mL deionized water. 200 g TFE, 380 g VDF, 6.2 g BTFE, 560 g MA31 (as a pre-emulsion) were fed over 190 minutes at a pressure of 10 bar and 90 ° C. The resulting latex had a solid content of 27% and was coagulated with 12 g MgCl ₂ . The resulting 1.1 kg of polymer was dried at 130 ° C.

  The composition of the obtained polymer was 13.5 mol% MV31, 69.7 mol% VDF, 16.1 mol% TFE, and 0.7 mol% BTFE. The glass transition temperature (DSC) was Tg = −42 ° C. and the Mooney viscosity (1 + 10 ′, 121 ° C.) was 51.

  Curing monoallyl ether of bisphenol AF (BF6MAE)

In a 2 liter three-necked round bottom flask equipped with a mechanical stirrer, condenser, and thermocouple, 250 g 0.7 mol HO—C ₆ H ₄ C (CF ₃ ) ₂ C ₆ H ₄ —OH, 30 g 0.3 mol. Allyl bromide, 5 g 0.02 mol tetrabutylammonium bromide was charged and dissolved in 4 g deionized (DI) water and 500 g glyme. The solution was stirred and heated to 50 ° C. When 16 g of 0.3 mol KOH was dissolved in 18 g of deionized water and added dropwise over 15 minutes, precipitation occurred and the temperature rose to 62 ° C. The reaction was heated to 65 ° C. over 1 hour and then cooled to 25 ° C. The upper glyme solution phase was removed and placed in a round bottom flask and processed on a rotary evaporator at 50 ° C./2 torr. Subsequently, this was heated to 50 ° C. for 1 hour at 0.13 kPa (1 torr) using a vacuum pump, 400 g of chloroform was added, and the slurry was stirred for 20 hours. The slurry was filtered and the solution was processed on a rotary evaporator at 50 ° C./20 torr to isolate 50 g of a viscous oily product. When the solid was subjected to a second chloroform extraction, an additional 21 g of oily product was obtained with a yield of 76%. According to LC / UV analysis, mol% was as _{follows: 66.8% CH 2 = CHCH 2} -OC 6 H 4 C (CF 3) 2 C 6 H 4 -OH, 6.6% CH 2 _{= CHCH 2 OC 6 H 4 C} (CF 3) 2 C 6 H 4 O-CH 2 CH = CH 2, and 23.7% of _{HO-C 6 H 4 C (} CF 3) 2 C 6 H 4 -OH . Using a silica gel column, elution was performed first using heptane as a non-polar solvent, and finally using ethyl acetate as a polar solvent, and flash chromatography (trade name “INTELLIFLASH 280” (Analogix Co., Santa Clara, Calif.)). Allyl ether phenyl hexafluorofluoroisopropylidene phenol was isolated by According to LC / UV _{analysis, CH 2 = CHCH 2 -OC 6} H 4 C (CF 3) of 99.23mol% 2 _{C 6} H 4 -OH was obtained. In order to facilitate the incorporation into the polymer, the as-synthesized material was diluted with methanol to a solids concentration of 50%.

Octafluoro-hexanediol _{(OFHDAE / CH 2 = CHCH 2} -OCH 2 C 4 F 8 CH 2 -OH) curable allyl ether

50 g of 0.19 mol HO—CH ₂ C ₄ F ₈ CH ₂ —OH (commercially available from EXfluor Research Corporation (Round Rock, TX)) in a 500 mL 3-neck round bottom flask equipped with a mechanical stirrer, condenser, and thermocouple And 150 g of methyl-t-butyl ether. The solution was stirred and 12 g of 0.18 mol KOH solution dissolved in 26 g of deionized water followed by 2 g of 0.01 mol tetrabutylammonium bromide dissolved in 3 g of deionized water. The solution was stirred and heated to 50 ° C., 22 g of 0.18 mol allyl bromide was added dropwise over 20 minutes, held at 50 ° C. for 2 hours, and then cooled to 25 ° C.

The upper methyl-t-butyl ether solution phase was removed, placed in a round bottom flask and evaporated at 50 ° C./1.33 kPa (10 torr) using a rotary evaporator. The product mixture was charged with 55 g of hexane and stirred to obtain two phases. The lower phase was further extracted with 50 g of hexane. The lower phase was washed twice with chloroform to extract the desired product and filtered to remove insoluble starting diol. The chloroform solution was removed, placed in a round bottom flask and evaporated using a rotary evaporator at 55 ° C./10 torr to isolate 19 g of product mixture. According GC / MS analysis, mol% were as _{follows: 84% CH 2 = CHCH 2} -OCH 2 C 4 F 8 CH 2 -OH, 12.5% CH 2 = CHCH 2 -OCH 2 C 4 _{F 8 CH 2 O-CH 2} CH = CH 2, and _{3.9% HO-CH 2 C 4} F 8 CH 2 -OH. In order to facilitate the incorporation into the polymer, the as-synthesized material was diluted with methanol to a solids concentration of 50%.

  Preparation of VDF / TFE / HFP

  In a 2000 gallon (7570 L) kettle, put 13,180 pounds (5978 kg) deionized water, 50 pounds (22.6 kg) 50% aqueous dipotassium phosphate solution, 2 pounds (0.9 kg) hexamethyldisilane. The solution was then heated to 160 ° F. Agitation was set at 100 rpm. The kettle is pressurized to 130 psig (896 kPa) with 155 lb (70 kg) HFP, 38 lb (17 kg) VDF and 53 lb (24 kg) TFE. Polymerization was initiated using 12 pounds (5 kg) of ammonium persulfate. From the start of the reaction, VDF / TFE / HFP was added at a ratio of 1 / 0.739 / 1.330 to maintain the pressure at 130 psig (896 kPA). A reaction temperature of 160 ° F. (71 ° C.) was maintained. When 1726 pounds (783 kg) of VDF was added, the HFP valve was closed. Additional VDF and TFE were added at a ratio of VDF / TFE = 1.4 / 1 until 70 pounds (32 kg) of VDF was added. The latex was free of agglomerates and the solids content was about 28%. The polymer was coagulated with magnesium chloride, washed with deionized water and isolated by drying in an oven at 266 ° F. (130 ° C.) until the moisture content was less than 0.5% by weight.

  Preparation of VDF / TFE / P # 1

  After filling a 2000 gallon (7570 L) kettle with 12,940 pounds (5869 kg) deionized water and 50 pounds (23 kg) 50% dipotassium phosphate aqueous solution, the solution is brought to 160 ° F. (71 ° C.). Heated. Agitation was set at 100 rpm. The kettle is pressurized to a pressure of 220 psig (1516 kPa) with 189 pounds (86 kg) of VDF and 111 pounds (50 kg) of TFE. The polymerization was then initiated with 60 pounds (27 kg) of ammonium persulfate. From the start of the reaction, VDF / TFE / propylene was added at a ratio of 1 / 1.85 / 0.394 to maintain the pressure at 220 psig. A reaction temperature of 160 ° F. (71 ° C.) was maintained. When 1487 pounds (674 kg) of VDF was added, the VDF valve was closed. Additional TFE and propylene were added at a ratio of TFE / P = 4: 1 until 40 pounds (18 kg) of TFE was added. The latex was free of agglomerates and had a solids content of about 27%. The polymer was coagulated with magnesium chloride, washed with deionized water and isolated by drying at 280 ° F. (138 ° C.) until the water content was less than 0.5% by weight.

  Method

  hardness:

  The Shore A hardness (2 ″) of the secondary vulcanized sample was measured according to ASTM D-2240-05 (2010). Table 2 and Table 3 show the measured hardness.

  Tensile strength and elongation

  Using a mechanical tensile tester (Instron, Norwood, MA) with a 1 kN load cell, as shown in Tables 2 and 3, DIN 53504 (2009) (S2) at a constant crosshead displacement speed of 200 mm / min. The tensile strength and elongation of the secondary vulcanized sample were measured by DIE).

  Curing rheology

ASTM D 5289-93a using uncured, compounded samples and using a rheometer marketed by Monsanto Company (Saint Louis, Missouri) under the trade name Monsanto Moving Die Rheometer (MDR) Model 2000. The cure rheology test was performed at 177 ° C., no preheating, 30 minutes elapsed time, and 0.5 arc degree. Both the minimum torque (M _L ) and the maximum torque reached during a specific period when the plateau or maximum torque (M _H ) could not be obtained were measured. Torque _M L _(t s 2) 2 units increased time than the time the torque reaches the _{M L +0.5 (M H -M L} ), (t'50), and the torque _M L +0.9 The time to reach (M _H −M _l ), (t′90), and tan (δ) at _ML and _MH were also measured. tan (δ) is equal to the ratio between the tensile loss modulus and the tensile storage modulus (meaning that tan (δ) is more elastic).

  O-ring molding and compression set

  An O-ring having a cross-sectional thickness of 0.139 inch (3.5 mm) was formed (cured at 177 ° C. for 15 minutes), and then secondary vulcanized in air at 232 ° C. for 16 hours. The initial deflection was 25% and this O-ring was prepared in the same manner as described in ASTM 395-89 method B (analyzed in triplicate) at various times and temperatures as described in Tables 2 and 3. A compression set test was performed.

For each of Example (E) and Comparative Example (CE), the components are used in the amounts shown in Table 1 (amount per 100 parts of rubber described in parentheses) and compounded with a two-roll mill. did. Using the test methods as described above, the curing rheology was evaluated for each of the examples and comparative examples. The results are shown in Tables 2 and 3. An O-ring was molded and cured (pressure curing at 177 ° C. for 15 minutes and secondary vulcanization at 232 ° C. for 16 hours), and evaluation was performed using the method described in “O-ring molding and compression set” as described above. The results are shown in Table 4.

  Foreseeable modifications and changes to the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. The present invention is not limited to the embodiments described for purposes of illustration in this application.

Claims (10)

(I) a partially fluorinated amorphous fluoropolymer, the partially fluorinated amorphous fluoropolymer comprising a carbon-carbon double bond, or the partially fluorinated amorphous fluoropolymer; A partially fluorinated amorphous fluoropolymer capable of forming carbon-carbon double bonds along the polymer chain;
(Ii) 1 to 10 millimoles of curing agent per 100 parts of the partially fluorinated amorphous fluoropolymer, wherein CX ₁ X ₂ = CX ₃ -LM [wherein X ₁ , X ₂ , And X ₃ are independently selected from H, Cl, and F, at least one of X ¹ , X ₂ , and X ₃ is H; L is a bond or linking group; Is a nucleophilic group]
A curable partially fluorinated polymer composition comprising: (iii) an acid acceptor; and (iv) an organic onium compound.   The partially fluorinated amorphous fluoropolymer comprises: (i) adjacently copolymerized VDF units and HFP units; (ii) fluorinated comonomer units having copolymerized VDF units and acidic hydrogen atoms; (iii) The curable partially fluorinated polymer composition of claim 1 comprising copolymerized TFE units and fluorinated comonomer units having acidic hydrogen atoms; and (iv) combinations thereof.   The partially fluorinated amorphous fluoropolymer comprises (i) vinylidene fluoride, tetrafluoroethylene, and propylene; (ii) vinylidene fluoride, tetrafluoroethylene, ethylene, and perfluoroalkyl vinyl ethers such as perfluoro (Iii) vinylidene fluoride with hexafluoropropylene; (iv) hexafluoropropylene, tetrafluoroethylene, and vinylidene fluoride; (v) hexafluoropropylene and vinylidene fluoride, (vi) fluoro Vinylidene fluoride and perfluoroalkyl vinyl ethers; (vii) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyl vinyl ethers, (viii) vinylidene fluoride, perfluoroalkyl vinyls Ether, hydropentafluoroethylene, and optionally tetrafluoroethylene; (ix) tetrafluoroethylene, propylene, and 3,3,3-trifluoropropene; (x) tetrafluoroethylene and propylene; (xi) ethylene, Tetrafluoroethylene, and perfluoroalkyl vinyl ether, and optionally 3,3,3-trifluoropropylene; (xii) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyl allyl ether, (xiii) vinylidene fluoride, and per (Xiv) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl ether, (xv) vinylidene fluoride and perfluoroalkyloxyallyl ether; (x 2. The derivative of claim 1, derived from i) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl ether, (xv) vinylidene fluoride and perfluoroalkyloxyallyl ether; and (xvi) combinations thereof. A curable partially fluorinated polymer composition.   The partially fluorinated amorphous fluoropolymer comprises a carbon-carbon double bond along the main chain of the partially fluorinated amorphous fluoropolymer, or the partially fluorinated amorphous fluoropolymer The curable partially fluorinated polymer composition of claim 1 capable of forming carbon-carbon double bonds along the polymer backbone.   The curable partially fluorinated polymer composition of claim 1, wherein the nucleophilic group is selected from alcohols, amines, and thiols.   The curable partially fluorinated polymer composition of claim 1, wherein the curing agent comprises a non-aromatic alcohol.   The curable partially fluorinated polymer composition of claim 1, wherein the curable partially fluorinated polymer composition is substantially free of monophenol.   The curable partially fluorinated polymer composition of claim 1, wherein the fluoropolymer is substantially free of I, Br, and Cl.   An article comprising a cured product of the composition according to any one of claims 1 to 8. Providing a curable partially fluorinated polymer composition according to any one of claims 1-8;
Curing the curable partially fluorinated polymer composition. A method for producing a partially fluorinated elastomer.