KR20170099946A - Curable partially fluorinated polymer compositions - Google Patents

Abstract

Curable partially fluorinated polymer compositions and methods thereof are described herein. The composition comprises
(i) a partially fluorinated amorphous fluoropolymer comprising a carbon-carbon double bond or capable of forming a carbon-carbon double bond along a partially fluorinated amorphous fluoropolymer chain;
(ii) the formula _{CX 1 X 2 = CX 3 -LM} ( _wherein, X _1, X _2, and X ₃ are independently selected from H, Cl, and is selected from F; X _1, X _2, and X _3, at least one of 1 to 10 parts of a curing agent per 100 parts of the partially fluorinated amorphous fluoropolymer, wherein H is H, L is a bond or a linking group, and M is a nucleophilic group;
(iii) an acid acceptor; And
(iv) an organonium compound.

Description

[0001] CURABLE PARTIALLY FLUORINATED POLYMER COMPOSITIONS [0002]

Curing of a composition comprising a partially fluorinated amorphous fluoropolymer using a curing agent comprising a terminal olefin having at least one olefinic hydrogen and a nucleophilic group is disclosed.

There is a need to identify novel curing systems for partially fluorinated amorphous fluoropolymers.

In one aspect,

(i) partially fluorinated amorphous fluoropolymer-partially fluorinated amorphous fluoropolymer may comprise a carbon-carbon double bond or may form a carbon-carbon double bond along a partially fluorinated amorphous fluoropolymer chain;

(ii) from 1 to 10 millimoles of curing agent-curing agent per 100 parts of partially fluorinated amorphous fluoropolymer, the curing agent having the formula CX ₁ X ₂ = CX ₃ -LM wherein X ₁ , X _2, and X ₃ are independently H, Cl, And F; at least one of X ₁ , X _2, and X ₃ is H, L is a bond or a linking group, and M is a nucleophilic group;

(iii) an acid acceptor; And

(iv) an organonium compound.

In another aspect, an article comprising a cured prior art composition is disclosed.

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

The content of the invention is not intended to describe each embodiment. The details of one or more embodiments of the invention are also set forth in the detailed description that follows in order to practice the invention. Other features, objects, and advantages will be apparent from the following detailed description and from the claims.

As used herein, the term < RTI ID = 0.0 >

The indefinite articles ("a", "an", and "the") are used interchangeably and mean one or more;

"And / or" are used to indicate that one or both may occur, for example A and / or B comprises (A and B) and (A or B);

"Skeleton" refers to the main contiguous chain of the polymer;

"Crosslinking" refers to linking two pre-formed polymer chains using chemical bonds or chemical groups;

"Cure-site" refers to a functional group capable of participating in cross-linking;

"Interpolymerized " refers to monomers that are polymerized together to form the polymer backbone;

Also, in this specification, a reference to a range by an endpoint includes all numbers contained within that range (e.g., 1 to 10 include 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

Also, in this specification, reference to "at least one" includes all numbers of one or more (e.g., 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 the present invention, it has been found that partially fluorinated amorphous fluoropolymers such as those disclosed herein can be cured using a curing agent comprising a terminal olefin having at least one olefinic hydrogen, with an acid acceptor and an onium compound .

Fluoropolymer

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

The amorphous fluoropolymers of the present invention may also comprise and / or form carbon-carbon double bonds, or may form carbon-carbon double bonds along the polymer chains. In one embodiment, the partially fluorinated amorphous fluoropolymer comprises a carbon-carbon double bond along the backbone of the partially fluorinated amorphous fluoropolymer or forms a carbon-carbon double bond along the backbone of the partially fluorinated amorphous fluoropolymer can do. In another embodiment, the partially fluorinated amorphous fluoropolymer comprises a carbon-carbon double bond or may form a carbon-carbon double bond in the pendant group from the skeleton of the partially fluorinated amorphous fluoropolymer.

The ability of a fluoropolymer to form a carbon-carbon double bond means that the fluoropolymer contains units capable of forming a double bond. Such units include, for example, two adjacent carbons along the polymer backbone or pendant side chain, where hydrogen is attached to the first carbon and a leaving group is attached to the second carbon. During the elimination reaction (e. G., Thermal reaction, and / or use of an acid or base), the leaving group and hydrogen are removed to form a double bond between the two carbon atoms. Exemplary leaving groups include halides, alkoxides, hydroxides, tosylates, mesylates, amines, ammoniums, sulfides, sulfoniums, sulfoxides, sulfones, and combinations thereof. Fluoropolymers containing adjacent carbon atoms, both of which have bromine atoms attached or both attached to iodine atoms, which lead to the elimination of Br ₂ or I ₂ will also be considered.

The amorphous fluoropolymer contains a plurality of these groups (groups capable of forming a carbon-carbon double bond or a double bond), resulting in sufficient curing. Generally, this means 0.1, 0.5, 1, 2, or even 5 mol% or more, 7, 10, 15, or even 20 mol% or less (i.e., the mole of such a carbon- carbon double bond or its precursor per mol of polymer) do.

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 comprises adjacent copolymerization units of vinylidene fluoride (VDF) and hexafluoropropylene (HFP); VDF (or tetrafluoroethylene) and fluorinated comonomers capable of transferring an acidic hydrogen atom to the polymer backbone, such as, for example, trifluoroethylene; Vinyl fluoride; 3,3,3-trifluoropropene-1; Pentafluoropropene (e.g., 2-hydro- pentafluoropropylene and 1-hydro- pentafluoropropylene); Copolymer units of 2,3,3,3-tetrafluoropropene; And combinations thereof.

In some embodiments, a small amount (e.g., less than 10, 5, 2, or even less than 1 wt%) of additional monomer may be added, as long as the amorphous fluoropolymer can be cured using the curing agents disclosed herein have.

In one embodiment, the amorphous fluoropolymer is further derived from a hydrogen containing monomer that additionally comprises pentafluoropropylene (e.g., 2-hydro- pentafluoropropylene), propylene, ethylene, isobutylene, and combinations thereof .

In one embodiment, the amorphous fluoropolymer is additionally derived from perfluorinated monomers. Exemplary perfluorinated monomers include hexafluoropropene; Tetrafluoroethylene; Chlorotrifluoroethylene; Perfluoro (alkyl vinyl ethers) 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 ethers) such as allyl methyl perfluorobutyl ether, perfluoro (alkyloxyalkyl allyl ether), for example, example perfluoro 4,8-dimethyl-oxazol-1-nonene _{(i.e., CF 2 = CFCF 2 O (} CF 2) 3 OCF 3), and include a combination of the two.

Exemplary 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 and hexafluoropropylene; (iv) hexafluoropropylene, tetrafluoroethylene, and vinylidene fluoride; (v) hexafluoropropylene and vinylidene fluoride, (vi) vinylidene fluoride and perfluoroalkyl vinyl ether; (vii) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyl vinyl ethers, (viii) vinylidene fluoride, perfluoroalkyl vinyl ether, hydro- pentafluoroethylene, 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 perfluoroalkylallyl ethers, (xiii) vinylidene fluoride and perfluoroalkylallyl ethers; (xiv) ethylene, tetrafluoroethylene, and perfluoroalkyl vinyl ether, and optionally 3,3,3-trifluoropropylene; (xv) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkylallyl ethers, (xvi) vinylidene fluoride and perfluoroalkylallyl ethers; (xvii) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl ether, (xviii) vinylidene fluoride and perfluoroalkyloxyallyl ether; (xiv) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl ether, (xv) vinylidene fluoride and perfluoroalkyloxyallyl ether; And (xvi) combinations thereof.

Advantageously, by using the curing agents disclosed herein, the amorphous fluoropolymers of the present invention can be cured without the need for pendant bromine or iodine cure sites. Often, iodine and bromine-containing cure site monomers polymerized with fluoropolymers and / or chain termini can be particularly expensive. However, in one embodiment, the partially fluorinated amorphous polymer comprises iodine and / or bromine cure sites, which may 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 capable of participating in a peroxide curing reaction.

Such bromine and / or iodine-containing cure site monomers include

(a) bromo or iodo- (per) fluoroalkyl- (per) fluorovinyl ethers having the formula:

ZR _f -O-CX = CX ₂

(Wherein each X may be the same or different and represents H or F, Z is Br or I, and R _f is C ₁ -C ₁₂ (optionally substituted with a halogen atom and / or an ether oxygen atom) per) alkylene) fluoroalkyl, for _{example, 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 perfluoro olefins 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, R' _f is a C ₁ -C ₁₂ perfluoroalkylene optionally containing a chlorine atom, and r is 0 or 1), for example, bromotrifluoroethylene, 4-bromo-perfluorobutene-1 or the like; Or bromofluoroolefins such as 1-bromo-2,2-difluoroethylene and 4-bromo-3,3,4,4-tetrafluorobutene-1;

(c) non-fluorinated bromo-olefins such as vinyl bromide and 4-bromo-1-butene.

In one embodiment, the amorphous fluoropolymer comprises a bromine and / or iodine-containing chain transfer agent, such as, for example, a compound of the formula R _f P _x where P is Br or I, Is I and _Rf is an x-alkyl radical having from 1 to 12 carbon atoms, which may optionally also contain a chlorine atom. Typically, x is 1 or 2. Useful chain transfer agents include perfluorinated alkyl monoiodide, perfluorinated alkyl diiodide, perfluorinated alkyl monobromide, perfluorinated alkyl dibromide, 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 and I (CF ₂ ) _n I wherein n is 3 to 10 (E.g., I (CF ₂ ) ₄ I), and combinations thereof.

In one embodiment, the amorphous fluoropolymer is substantially free of I, or Br, and the amorphous fluoropolymer comprises less than 0.1, 0.05, 0.01, or even 0.005 mole percent, based on the total polymer.

In one embodiment, the amorphous fluoropolymer of the present invention is not grafted, and it is not grafted, and it may be vinyl, allyl, acrylate, amido, sulfonate, pyridine, carboxylic acid ester, carboxylic acid salt, aliphatic or aromatic triether Or a hindered silane which is a triester. In one embodiment, the amorphous fluoropolymer does not comprise a monophenol graft.

Hardener

The curing agent of the present invention is a compound containing at least one terminal olefin having at least one olefinic hydrogen. In one embodiment, the curing agent of the present invention is represented by the formula (I)

(I)

CX ₁ X ₂ = CX ₃ -LM

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; L is a bond or a linking group; And M is a nucleophilic group.

L represents a single bond or a linking group. The linking group may be a catenated O, S, or N atom (e. G., An ether bond), or optionally a catenated heteroatom (e. G. O, S or N) , And d is an organic group. The divalent organic group may be linear, branched, or cyclic. The divalent organic groups may be aromatic or aliphatic. The divalent organic groups may be non-fluorinated or non-fluorinated (including fluorine atoms), partially fluorinated (including at least one CH bond and at least one CF bond), or perfluorinated Containing at least one CF bond).

In one embodiment, the divalent organic group is - (CH ₂ ) _n (O) _m -P- (R f) _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 wherein n is an integer from 1 to 10; Rf is (CF _{2) n} (where, n is an integer of 1 to 10), and C (CF ₃₎ is selected from at least one of _2, Rf is a cyclic or aliphatic, and / or at least one category nahyeong heteroatoms , Such as O, S, and N; p is 0 or 1; And q is 0 or 1. Exemplary 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 -OC ₆ H ₄ -C CF ₃ ) ₂ -C ₆ H ₄ -, and -CH ₂ -OC ₆ H ₄ -C (CF ₃ ) ₂ -C ₆ H ₄ -O-CH ₂ -.

M is a nucleophilic group, which means that it includes a non-covalent electron pair. Exemplary nucleophilic groups include alcohols (-OH), amines (-NH ₂ , -NHR, and -NRR ', where R and R' are organic groups), thiol (-SH), and carboxylic acid ).

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.

Exemplary curing agents include,

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

The curing agent should be used in an amount substantially sufficient to cause the amorphous fluoropolymer to cure, as evidenced by a rise in torque in a moving die rheometer. For example, at least 1, 1.5, 2, 2.5, 3, or even 4 millimoles or more per 100 parts of the amorphous fluoropolymer is used. If too little curing agent is used, the amorphous fluoropolymer will not cure. For example, 20, 15, 10, or even 8 millimoles of curing agent per 100 parts of amorphous fluoropolymer is used. If too much curing agent is used, the amorphous fluoropolymer can become brittle.

In one embodiment, the curable partially fluorinated polymer composition is substantially free of monophenol, which means that the composition comprising the amorphous fluoropolymer is less than 0.1, 0.01, or even less than 0.001% monophenol relative to the moles of the amorphous fluoropolymer Moles. ≪ / RTI >

Acid receptor

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

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

Onium compound

In one embodiment, the organonium compound is added to the composition as a phase transfer catalyst to aid in the crosslinking of the amorphous fluoropolymer, or to aid in the formation of a double bond on the fluoropolymer through dehydrofluorination . Such organonium 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 a central atom of phosphorus or nitrogen covalently bonded to four organic moieties by a carbon-phosphorus (or carbon-nitrogen) covalent bond, Lt; / RTI > The organic moieties may be the same or different.

Briefly, a sulfonium compound is a sulfur-containing organic compound in which at least one sulfur atom is covalently bonded to three organic moieties having from 1 to 20 carbon atoms by a carbon-sulfur covalent bond, and is ion-bonded to anions. The organic moieties may be the same or different. Sulfonium compounds may have more than one relatively positive sulfur atom (e.g., [(C ₆ H ₅ ) ₂ S ⁺ (CH ₂ ) ₄ S ⁺ (C ₆ H ₅ ) ₂ ] ₂ Cl ^- ), the two carbon-sulfur covalent bonds may be between the carbon atoms of the divalent organic moiety, i.e., the sulfur atom may be a heteroatom in the cyclic structure.

Organonium compounds suitable for use in the present invention are known and described in the art. See, for example, U.S. Patent 5,262,490 (Kolb et al.) And 4,912,171 (Grootaert et al.), Which are incorporated herein by reference.

Exemplary organonium compounds include C ₃ -C ₆ symmetrical tetraalkylammonium salts, asymmetric tetraalkylammonium salts wherein the sum of the alkyl carbons is from 8 to 24, and benzyltrialkylammonium salts wherein the sum of the alkyl carbons is 7 to 19) (for example, tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltributylammonium chloride, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate and tetrabutylammonium hydroxide, phenyltrimethylammonium chloride , Tetrapentylammonium chloride, tetrapropylammonium bromide, tetrahexylammonium chloride, and tetraheptylammonium bromide, tetramethylammonium chloride); Quaternary phosphonium salts such as tetrabutylphosphonium salts, tetraphenylphosphonium chloride, benzyltriphenylphosphonium chloride, tributylallylphosphonium chloride, tributylbenzylphosphonium chloride, tributyl-2-methoxypropyl chloride (Dimethylamino) phosphonium chloride, 8-benzyl-1,8-diazobicyclo [5.4.0] 7-undecenium chloride, benzyltris (dimethylamino) phosphonium chloride, And bis (benzyldiphenylphosphine) iminium chloride. Other suitable organonium compounds include 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 organonium compound is used at 1 to 5 millimoles (mmhr) per 100 parts of amorphous fluoropolymer.

Free radical source

In one embodiment, the curable composition comprises 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 tertiary butyl peroxide attached to a peroxy oxygen tertiary carbon atom.

Exemplary peroxides include 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; Dicumyl peroxide; Di (2-t-butylperoxyisopropyl) benzene; Dialkyl peroxides; Bis (dialkyl peroxide); 2,5-dimethyl-2,5-di (tert-butylperoxy) 3-hexyne; Dibenzoyl peroxide; 2,4-dichlorobenzoyl peroxide; Tertiary butyl perbenzoate; ?,? '- bis (t-butylperoxy-diisopropylbenzene); t-butylperoxy isopropyl carbonate, t-butylperoxy 2-ethylhexylcarbonate, t-amylperoxy 2-ethylhexylcarbonate, t-hexylperoxy isopropyl carbonate, di [ 1,3-dimethyl-3- (t-butylperoxy) butyl] carbonate, carbonoperoperoxoic acid, O, O'-1,3-propanediyl OO, OO'- -Dimethylethyl) < / RTI > ester, and combinations thereof.

The amount of free radical source commonly used is 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, or even 1.5 parts by weight or more per 100 parts of amorphous fluoropolymer; 2, 2.25, 2.5, 2.75, 3, 3.5, 4, 4.5, 5, or even 5.5 parts by weight or less. In one embodiment, the curable composition is substantially free of a free radical source, i. E. 0.05 or even less than 0.01 part by weight per 100 parts of the amorphous fluoropolymer.

Typical coagents are compounds that contain terminal unsaturation sites that are incorporated into the polymer during cure to help cure, typically peroxide hardening. Exemplary adjuvants include tri (methyl) allyl isocyanurate (TMAIC), triallyl isocyanurate (TAIC), tri (methyl) allyl cyanurate, poly-triallyl isocyanurate (poly- , Triallyl cyanurate (TAC), xylylene-bis (diallyl isocyanurate) (XBD), N, N'-m-phenylene bismaleimide, diallyl phthalate, tris s-triazine, triallyl phosphite, 1,2-polybutadiene, ethylene glycol diacrylate, diethylene glycol diacrylate, and combinations thereof. Other useful adjuvants may be represented by the formula CH ₂ = CH-R _f1 -CH = CH ₂ , where R _f1 may be a perfluoroalkylene of 1 to 8 carbon atoms. By using the curing agents disclosed herein, the amorphous fluoropolymers of the present invention can be cured without the use of these adjuvants. In other words, the curable composition is substantially free of typical adjuvants (1, 0.5, or even less than 0.1 parts per 100 parts of amorphous fluoropolymer, or even below the detection limit). This may be beneficial because of the cost of the adjuvant, the incompatibility with the fluorinated polymer, and the effect on processing (e.g., bleeding out of the composition, mold fouling).

The curable composition may also contain a wide variety of additives, such as pigments, fillers (e. G., Carbon black), porogen-forming agents, and those known in the art, which are commonly used in the manufacture of elastomeric compositions .

The curable amorphous fluoropolymer composition can be prepared by mixing the amorphous fluoropolymer and curing agent in a conventional rubber processing facility with other components (e.g., acid acceptor, onium compound, free radical source and / or additional additives) Can be prepared by providing a solid mixture, i.e., a solid polymer containing additional components, also referred to in the art as "compounds ". This process of mixing the components to produce such a solid polymer composition containing the other components is typically referred to as "compounding ". Such equipment includes a rubber mill, an internal mixer such as Banbury mixer, and a mix extruder. During mixing, the temperature of the mixture will typically not rise above about 120 < 0 > C. During mixing the ingredients and additives are uniformly distributed throughout the resulting fluorinated polymer "compound" or polymer sheet. The "compound" can then be oven-cured after being pressed or extruded in a mold, for example a cavity or a transfer mold. In an alternative embodiment, the curing can be carried out in an autoclave.

Curing is typically accomplished by heat-treating the curable amorphous fluoropolymer composition. Heat treatment is performed at an effective temperature and an effective time to produce a cured fluoroelastomer. Optimum conditions can be tested by examining the cured fluoroelastomer for mechanical and physical properties. Typically, the curing is carried out at temperatures above 120 ° C or above 150 ° C. Typical curing conditions include curing at a temperature of from 160 캜 to 210 캜 or from 160 캜 to 190 캜. A typical curing period includes 3 to 90 minutes. The curing is preferably carried out under pressure. For example, a pressure of 10 to 100 bar can be applied. A post curing cycle may be applied to ensure that the curing process is completely completed. Post cure may be performed at a temperature of 170 ° C to 250 ° C for a period of 1 to 24 hours.

The partially fluorinated amorphous fluoropolymer in the curable composition was analyzed by ASTM D1646-06 by using MV 2000 instrument (available from Alpha Technologies, Ohio, USA) using a large rotor (ML 1 + 10) at 121 ° C. It has Mooney viscosity according to type A. At the time of curing, the amorphous fluoropolymer is made of an elastomer, made of a non-flowing fluoropolymer, and has an infinite viscosity (thus having no measurable Mooney viscosity) using the curing agent disclosed herein.

In one embodiment of the present invention, the curing system comprising the curing agent and the amorphous fluoropolymer disclosed herein can exhibit the chemical resistance of typical iodine / bromine and curing system containing peroxide, while at the same time, Thereby improving the poor heat resistance of these conventional iodine or bromine containing fluoroelastomers and thus producing a cured fluoropolymer having sufficient heat resistance 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 invention include:

Embodiment 1

(i) partially fluorinated amorphous fluoropolymer-partially fluorinated amorphous fluoropolymer may comprise a carbon-carbon double bond or may form a carbon-carbon double bond along a partially fluorinated amorphous fluoropolymer chain;

(ii) from 1 to 10 millimoles of curing agent-curing agent per 100 parts of partially fluorinated amorphous fluoropolymer, the curing agent having the formula CX ₁ X ₂ = CX ₃ -LM wherein X _1, X _2, and X ₃ are independently H, Cl, And F; at least one of X _1, X _2, and X ₃ is H, L is a bond or a linking group, and M is a nucleophilic group;

(iii) an acid acceptor; And

(iv) Organonium compounds

≪ / RTI >

Embodiment 2 A partially fluorinated amorphous fluoropolymer comprises (i) adjacent copolymerization units of VDF and HFP; (ii) copolymerization units of VDF and fluorinated comonomers having acidic hydrogen atoms; (iii) a fluorinated comonomer having an acidic hydrogen atom and a copolymerization unit of TFE; And (iv) combinations thereof. ≪ Desc / Clms Page number 13 >

Embodiment 3. A fluorinated comonomer having an acidic hydrogen atom is selected from the group consisting of trifluoroethylene; Vinyl fluoride; 3,3,3-trifluoropropene-1; Pentafluoropropene; And 2,3,3,3-tetrafluoropropene. ≪ RTI ID = 0.0 > 21. < / RTI >

Embodiment 4. A partially fluorinated amorphous fluoropolymer comprising: (i) vinylidene fluoride, tetrafluoroethylene, and propylene; (ii) vinylidene fluoride, tetrafluoroethylene, ethylene, and perfluoroalkyl vinyl ethers such as perfluoro (methyl vinyl ether); (iii) vinylidene fluoride and hexafluoropropylene; (iv) hexafluoropropylene, tetrafluoroethylene, and vinylidene fluoride; (v) hexafluoropropylene and vinylidene fluoride, (vi) vinylidene fluoride and perfluoroalkyl vinyl ether; (vii) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyl vinyl ethers, (viii) vinylidene fluoride, perfluoroalkyl vinyl ether, hydro- pentafluoroethylene, 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 perfluoroalkylallyl ethers, (xiii) vinylidene fluoride, and perfluoroalkylallyl ethers; (xiv) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl ether, (xv) vinylidene fluoride and perfluoroalkyloxyallyl ether; (xvi) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl ether, (xv) vinylidene fluoride and perfluoroalkyloxyallyl ether; And (xvi) a combination of these. ≪ Desc / Clms Page number 19 >

Embodiment 5. A partially fluorinated amorphous fluoropolymer comprising a carbon-carbon double bond along the backbone of the partially fluorinated amorphous fluoropolymer or forming a carbon-carbon double bond along the backbone of the partially fluorinated amorphous fluoropolymer Lt; RTI ID = 0.0 > fluorinated < / RTI > polymer composition according to any one of the preceding embodiments.

Embodiment 6. The curable partially fluorinated polymer composition of any of the preceding embodiments, wherein the nucleophilic group is selected from alcohols, amines, and thiols.

Embodiment 7. The curable partially fluorinated polymer composition of any of the preceding embodiments, wherein the curative agent comprises a non-fluorinated terminal olefin group.

Embodiment 8. The curable partially fluorinated polymer composition of any of the preceding embodiments, wherein the curing agent comprises a non-aromatic alcohol.

Embodiment 9. The curable partially fluorinated polymer composition of any of the preceding embodiments, substantially free of monophenols.

Embodiment 10. A curing agent

And combinations thereof, wherein n is an integer from 1 to 10. The curable partially fluorinated polymer composition of any of the preceding embodiments.

Embodiment 11. The curable partially fluorinated polymer composition of any of the preceding embodiments, wherein the organonium compound is selected from at least one of phosphonium or sulfonium.

Embodiment 12. A curable partially fluorinated polymer composition according to any 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.

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

Embodiment 14. The method of any one of the preceding embodiments, wherein the acid acceptor is selected from at least one of magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, dibasic phosphate, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, and hydrotalcite Lt; RTI ID = 0.0 > fluorinated < / RTI > polymer composition.

Embodiment 15. The curable partially fluorinated polymer composition of any of the preceding embodiments, further comprising a free radical source.

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. The curable partially fluorinated polymer composition of Embodiment 16, wherein the composition is substantially free of adjuvants.

Embodiment 18. An article comprising the cured composition of any of embodiments 1 to 17.

Embodiment 19:

Providing a curable partially fluorinated polymer composition of any one of Embodiments 1 to 17; And

Curing the curable partially fluorinated polymer composition

≪ / RTI >

Example

The advantages and embodiments of the present invention are further illustrated by the following examples, but the specific materials and amounts thereof recited in these examples and other conditions and details should not be construed as unduly limiting the present invention. In these embodiments, all percentages, ratios, and ratios are by weight unless otherwise indicated.

All materials are available from, for example, Sigma-Aldrich Chemical Company, Milwaukee, Wisconsin, USA, or otherwise known to those skilled in the art, unless otherwise stated or apparent.

These abbreviations are used in the following examples: phr = part per hundred rubber; g = gram, kg = kilogram; min = min; mol = mol; hr = hour, C = degrees Celsius; mL = milliliters; L = liters; mm = millimeter; kN = kilo-newton; ㎪ = kilo pascal; GC / MS = gas chromatography mass spectrometry; Pa = Pascal; psig = pounds per square inch; LC / UV = liquid chromatography ultraviolet detection; And phr = 100 parts of rubber (or amorphous polymer).

material

Manufacture of VDF / BTFE / MA31

A 4 liter kettle was charged with 3400 mL of deionized water under anaerobic conditions. To 12 g of _{CF 3 -O- (CF 2) 3} -O-CFH-CF 2 -COONH 4 was added as an emulsifier. After heating to 90 占 폚, 40 g of tetrafluoroethene (TFE), 77 g of VDF and 3 g of 1-bromotrifluoroethene (BTFE) were added and 140 g of perfluoro-4, (Prepared similarly to "PMEAE" in MA 31, U. S. Patent No. 5,891, 965 (Worm et al.)) Was added as a pre-emulsion (described in International Patent Publication No. WO200149752) . 1.4 g of ammonium peroxodisulphate (APS) dissolved in 280 mL of deionized water was added by continuous introduction to initiate the reaction. At a pressure of 10 bar and at 90 占 폚, 200 g of TFE, 380 g of VDF, 6.2 g of BTFE, 560 g of MA31 (as a pre-emulsion) were fed over a period of 190 min. The resulting latex had a solids content of 27%, which was coagulated with 12 g of MgCl ₂ . The resulting 1.1 kg of polymer was dried at 130 占 폚.

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

Curable monoallyl ether of bisphenol AF (BF6MAE)

To a 3-liter 2 liter round bottom flask equipped with a mechanical stirrer, condenser and thermocouple was added 250 g, 0.7 mol HO-C ₆ H ₄ C dissolved in 4 g of deionized water (DI water) and 500 g of glime (CF ₃ ) ₂ C ₆ H ₄ -OH, 30 g, 0.3 mol of allyl bromide, 5 g, 0.02 mol of tetrabutylammonium bromide. The solution was stirred and heated to 50 < 0 > C. A solution of 16 g of 0.3 mol of KOH dissolved in 18 g of deionized water was added dropwise over 15 min to obtain a precipitate and the temperature was increased to 62 ° C. The reaction was heated to 65 ° C for 1 hr and then cooled to 25 ° C. The upper glaze solution phase was removed and placed in a round bottom flask and rotary evaporated at 50 ° C / 2 torr. Thereafter, it was heated to 50 DEG C at 0.13 K (1 Torr) using a vacuum pump for 1 hour, then 400 g of chloroform was added and the slurry was stirred for 20 hours. The slurry was filtered and the solution was rotary evaporated at 50 [deg.] C / 20 torr to isolate 50 g of viscous oily product. A second chloroform extraction performed on the solid yielded 21 g of additional oily product in 76% yield. LC / UV analysis provided the following mol%: 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% HO-C ₆ H ₄ C (CF ₃ ) ₂ C ₆ H ₄ -OH. Isolation of allyletherphenylhexafluoroisopropylidene phenol was first eluted with heptane as the nonpolar solvent and terminated with ethyl acetate as the polar solvent and purified by flash chromatography with a silica gel column &Quot; INTELLIFLASH 280 ", trade name of Analogix Co.). LC / UV analysis provided 99.23 mol% CH ₂ = CHCH ₂ -OC ₆ H ₄ C (CF ₃ ) ₂ C ₆ H ₄ -OH. To better promote incorporation into the polymer, the as-synthesized material was diluted in methanol at 50% solids concentration.

Curable Allyl Ether of Octafluorohexanediol (OFHDAE / CH ₂ = CHCH ₂ -OCH ₂ C ₄ F ₈ CH ₂ -OH)

A three-necked 500 ml round-bottomed flask equipped with a mechanical stirrer, condenser and thermocouple was charged with 50 g, 0.19 mol HO-CH ₂ C ₄ F ₈ CH ₂ -OH (Exfluor Research, Round Rock, Tex. Corporation) and 150 g of methyl-t-butyl ether. The solution was stirred and a solution of 12 g, 0.18 mol of KOH dissolved in 26 g of deionized water was added followed by the addition of 2 g, 0.01 mol of tetrabutylammonium bromide dissolved in 3 g of deionized water. The solution was stirred and heated to 50 < 0 > C and 22 g, 0.18 mol allyl bromide was added dropwise over 20 min and maintained at 50 < 0 > C for 2 hours and then cooled to 25 < 0 > C.

The upper methyl-t-butyl ether solution phase was removed and placed in a round bottom flask and evaporated at 50 ° C / 1.33 ° (10 Torr) using a rotary evaporator. 55 g of hexane was charged to the product mixture 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 the insoluble starting diol. The chloroform solution was removed and placed in a round bottom flask and evaporated at 55 ° C / 10 Torr using a rotary evaporator to isolate 19 g of the product mixture. GC / MS analysis provided the following mol%: 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. To better promote incorporation into the polymer, the as-synthesized material was diluted in methanol at 50% solids concentration.

Manufacture of VDF / TFE / HFP

A 2,000 gallon (7,570 L) kettle was charged with 13,180 pounds (5,978 kg) of deionized water, 50 pounds (22.6 kg) of a 50% aqueous solution of potassium hydrogen phosphate and 2 pounds (0.9 kg) of hexamethyldisilane, The solution was heated to 160 < 0 > F. Agitation was set at 100 rpm. The kettle was pressurized to a pressure of 130 psig (896 psi) with 155 pounds (70 kg) of HFP, 38 pounds (17 kg) of VDF and 53 pounds (24 kg) of TFE. Polymerization was initiated with 12 pounds (5 kg) of ammonium persulfate. When the reaction started, the pressure was maintained at 130 psig (896 ㎪) by adding VDF / TFE / HFP at a ratio of 1 / 0.739 / 1.330. A reaction temperature of 160 ° F (71 ° C) was maintained. The HFP valve was closed when 1,726 pounds (VDF) of VDF was added and additional amounts of 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 had no coagulated material and had a solids content of approximately 28%. The polymer was solidified by coagulation with magnesium chloride, washing with deionized water and oven drying at 266 ° F (130 ° C) until a moisture content of less than 0.5% by weight was reached.

Manufacture of VDF / TFE / P # 1

A 2,000 gallon (7,570 L) kettle was charged with 12,940 pounds (5,869 kg) of deionized water and 50 pounds (23 kg) of a 50% aqueous solution of potassium hydrogen phosphate, followed by heating the solution to 160 ℉ (71 캜). Agitation was set at 100 rpm. The kettle was pressurized to a pressure of 220 psig (1,516 psi) 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. When the reaction started, VDF / TFE / propylene was added at a ratio of 1 / 1.885 / 0.394 to maintain the pressure at 220 psig. A reaction temperature of 160 ° F (71 ° C) was maintained. When VDF was added at 1,487 pounds (VDF), the VDF valve was closed and additional amounts of TFE and propylene were added at a ratio of TFE / P = 4: 1 until 40 pounds (18 kg) of TFE were added. The latex had no coagulated material and had a solids content of approximately 27%. The polymer was solidified by coagulation with magnesium chloride, washing with deionized water, and drying at 280 ° F (138 ° C) until a moisture content of less than 0.5% by weight was reached.

Way

Hardness:

Hardness Shore A (2 ") was measured according to ASTM D-2240-05 (2010) and for post-cured samples as shown in Tables 2 and 3.

Tensile strength and elongation:

A mechanical tensile tester with a 1 kN load cell according to DIN 53504 (2009) (S2 DIE) at a constant crosshead displacement rate of 200 mm / min, as shown in Tables 2 and 3 (Instron, (Instron) was used to determine tensile strength and elongation for the postcured sample.

Hardening rheology

Using a rheometer sold under the brand name Monsanto Moving Dia Rheometer (MDR) Model 2000 by the Monsanto Company of St. Louis, Missouri, the elapsed time of 30 minutes without preheating at 177 ° C and 0.5 The hardened rheology test was carried out using an uncured, blended sample according to ASTM D 5289-93a in the arc of the figure. Both the maximum torque (M _H ) and the minimum torque (M _L ) obtained during the specified period were measured when the flatness or the maximum torque was not obtained. The torque M _L is greater than the time to increase 2 units (t _s 2), the torque _{M L + 0.5 (M H -} M L) and time (t'50), and the torque M _L + to reach the same value, The tan (delta) at M _L and M _H was measured as well as the time to reach 0.9 (M _H - M _L ) (t'90). Tan (delta) is equal to the ratio of tensile loss modulus to tensile storage modulus (lower tan (delta) means more elastic).

O-ring forming and compression deformation

An O-ring with a cross-sectional thickness of 0.139 inches (3.5 mm) was molded (15 min cure at 177 ° C) and then post cured at 232 ° C in air for 16 hr. A compression deformation test was performed on the O-rings with an initial deflection of 25% at various times and temperatures according to Tables 2 and 3 according to a method similar to that described in ASTM 395-89 Method B box).

For each Example (E) and Comparative Example (CE), the amount of ingredients used (listed in parentheses per 100 parts of rubber) as listed in Table 1 was compounded in a two-roll mill. Curing rheology evaluation was carried out for each of the Examples and Comparative Examples using the test methods described above. The results are shown in Tables 2 and 3. The O-rings were molded, cured (press cured at 177 ° C for 15 min and post cured at 232 ° C for 16 hr) and evaluated using the "O-ring forming and compressive strain" method as described above . The results are shown in Table 4.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

Without departing from the scope and spirit of the present invention, predictable variations and modifications of the present invention will be apparent to those skilled in the art. The present invention should not be limited to the embodiments described in this application for the purpose of illustration.

Claims (10)

(i) partially fluorinated amorphous fluoropolymer - partially fluorinated amorphous fluoropolymer may comprise a carbon-carbon double bond or may form a carbon-carbon double bond along a partially fluorinated amorphous fluoropolymer chain;
(ii) from 1 to 10 millimoles of curing agent-curing agent per 100 parts of partially fluorinated amorphous fluoropolymer, the curing agent having the formula CX ₁ X ₂ = CX ₃ -LM wherein X _1, X _2, and X ₃ are independently H, Cl, And F; at least one of X _1, X _2, and X ₃ is H, L is a bond or a linking group, and M is a nucleophilic group;
(iii) an acid acceptor; And
(iv) Organonium compounds
≪ / RTI > The process of claim 1, wherein the partially fluorinated amorphous fluoropolymer comprises (i) adjacent copolymerization units of VDF and HFP; (ii) copolymerization units of VDF and fluorinated comonomers having acidic hydrogen atoms; (iii) a fluorinated comonomer having an acidic hydrogen atom and a copolymerization unit of TFE; And (iv) combinations thereof. The process of claim 1, wherein the partially fluorinated amorphous fluoropolymer comprises (i) vinylidene fluoride, tetrafluoroethylene, and propylene; (ii) vinylidene fluoride, tetrafluoroethylene, ethylene, and perfluoroalkyl vinyl ethers such as perfluoro (methyl vinyl ether); (iii) vinylidene fluoride and hexafluoropropylene; (iv) hexafluoropropylene, tetrafluoroethylene, and vinylidene fluoride; (v) hexafluoropropylene and vinylidene fluoride, (vi) vinylidene fluoride and perfluoroalkyl vinyl ether; (vii) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyl vinyl ethers, (viii) vinylidene fluoride, perfluoroalkyl vinyl ether, hydro- pentafluoroethylene, 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 perfluoroalkylallyl ethers, (xiii) vinylidene fluoride, and perfluoroalkylallyl ethers; (xiv) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl ether, (xv) vinylidene fluoride and perfluoroalkyloxyallyl ether; (xvi) vinylidene fluoride, tetrafluoroethylene, and perfluoroalkyloxyallyl ether, (xv) vinylidene fluoride and perfluoroalkyloxyallyl ether; And (xvi) a combination thereof. The process of claim 1, wherein the partially fluorinated amorphous fluoropolymer comprises a carbon-carbon double bond along the skeleton of the partially fluorinated amorphous fluoropolymer or a carbon-carbon double bond along the skeleton of the partially fluorinated amorphous fluoropolymer ≪ RTI ID = 0.0 > curable < / RTI > partially fluorinated polymer composition. 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 composition is substantially free of monophenols. The curable partially fluorinated polymer composition of claim 1, wherein the fluoropolymer is substantially free of I, Br, and Cl. An article comprising the cured composition of any one of claims 1 to 8. Providing a curable partially fluorinated polymer composition of any one of claims 1 to 8; And
Curing the curable partially fluorinated polymer composition
≪ / RTI >