Patent Application
20100317815
The present invention relates to a process for manufacturing a fluoroelastomer. More specifically, the present invention relates to a process for manufacturing a fluoroelastomer suitable for injection molding by reducing the polymer Mooney viscosity to improve the fluidity.
Various fluorine-containing compounds are known to be used as emulsifiers in the polymerization reaction of fluorinated olefins. Examples thereof are as follows:
(1) an emulsifier represented by the general formula:
Rf1O(CFXCF2O)pCFXCOOM,
Rf2CF2(CH2)nO(CFXCF2O)pCFXCOOM,
M1OCO(CF2)mCOOM2, or
Rf3(CH2)nOCOCH(SO3M)CH2COO(CH2)nRf3,
and having less impact on the environment and ecosystem;
(2) an emulsifier represented by the general formula:
F(CF2CF2)nCH2CH2SO3M;
(3) an emulsifier comprising a polyperfluoroether carboxylic acid represented by the general formula:
CnF2n+1O(CnF2nO)mCn−1F2n−2COOH
or a salt thereof;
(4) an emulsifier comprising a fluorine-containing sulfobutanedioic acid ester derivative represented by the general formula:
YRf1(CH2)mOCOCH(SO3M)CH2COO(CH2)nRf2Y; and
(5) an emulsifier comprising an aromatic fluorine-containing surfactant represented by the general formula:
C3nF6n−1OArZ.
Further, there is a proposal to conduct the polymerization reaction of fluorinated olefins using a surfactant represented by the general formula: R1R2R3CL−M+(L−:SO3−, —OSO3−, —PO3−, —OPO3−, or —COO−). When using this surfactant, the polymerization reaction can be performed in the presence of a small amount of the surfactant with high production efficiency.
Meanwhile, with regard to fluoroelastomers, materials having excellent fluidity are demand for efficient injection molding. Generally, in order to increase the fluidity, the polymer Mooney viscosity is reduced by lowering the molecular weight; however, such a lower molecular weight causes a decrease in the polymerization reaction rate, resulting in a reduction of productivity. Furthermore, since deterioration of physical properties, such as tensile strength, compression set characteristics, and hot tear resistance, is induced, it is necessary to improve these properties.
An object of the present invention is to provide a method for manufacturing a fluoroelastomer suitable for injection molding by reducing the polymer Mooney viscosity to improve the fluidity.
The object of the invention is achieved by a method for manufacturing a fluoroelastomer, which comprises subjecting to a polymerization reaction of a fluorinated olefin using a ωH perfluorocarboxylic acid represented by the general formula: H(CF2)nCOOM (wherein M is hydrogen atom, alkali metal, or ammonium group; and n is 6, 7, or 8) or a salt thereof, as an emulsifier.
The fluoroelastomer produced by the process of the present invention has a lower Mooney viscosity ML1+10(121° C.) and thereby has an improved fluidity, which is essential for injection molding materials, as a result of the polymerization reaction of a fluorinated olefin using a ωH perfluorocarboxylic acid (salt) as an emulsifier. Accordingly, the productivity in injection molding can be enhanced. Moreover, there is neither remarkable decrease in the polymerization rate of the polymerization reaction nor deterioration of the physical properties of the vulcanizate, such as tensile strength, compression set characteristics, and hot tear resistance.
Here, when the polymerization reaction of fluorinated olefins using the emulsifiers used in the present invention is compared with the polymerization reaction of fluorinated olefins using ammonium perfluorooctanoate, which is commonly used as a general-purpose emulsifier, there is almost no difference in the vulcanizate physical properties between the present fluoroelastomers and the corresponding fluoroelastomers having the same copolymerization compositions and vulcanization compositions. That is, the effect of remarkably reducing the value of Mooney viscosity ML1+10(121° C.) with little effect on the vulcanizate physical properties is demonstrated.
In the method of the present invention, compounds represented by the formula:
H(CF2)6COOM,
H(CF2)7COOM, or
H(CF2)8COOM
are used as emulsifiers in the polymerization reaction of fluorinated olefins. Here, when compounds wherein n is outside the range of 6 to 8 are used, those wherein n is less than 6 result in inferior emulsifying properties, and the polymer precipitates in the course of the polymerization; whereas those wherein n is more than 8 cause inferior detergency with water, and the residual emulsifier remains in the polymer. Such ωH perfluorocarboxylic acids (salts) are known; for example, Patent Document 6, as described above, exemplifies a ωH perfluorocarboxylic acid as a surfactant usable in combination with a surfactant represented by the general formula: R1R2R3CL−M+; however, there is no example using a ωH perfluorocarboxylic acid alone in the polymerization reaction of fluorinated olefins. These compounds are produced in accordance with the process disclosed in Patent Document 7, described below. As alkali metal salts, sodium salt, potassium salt, etc., are generally used.
A fluorinated olefin to be subjected to polymerization reaction in the presence of such a ωH perfluorocarboxylic acid (salt) emulsifier is at least one of vinylidene fluoride, hexafluoropropene, tetrafluoroethylene, perfluoro(lower alkyl vinyl ether) having a lower alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably 1 carbon atom, and the like; other than these, for example, chlorotrifluoroethylene may also be used.
These fluorinated olefins are preferably used in combination to form copolymers. As such copolymers, for example, vinylidene fluoride-hexafluoropropene copolymer, vinylidene fluoride-hexafluoropropene-tetrafluoroethylene terpolymer, perfluoro(lower alkyl vinyl ether)-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoro(lower alkyl vinyl ether)-tetrafluoroethylene terpolymer, etc., are exemplified as preferable fluoroelastomers. Additionally, copolymers such as tetrafluoroethylene-ethylene copolymer are also exemplified. These copolymers are copolymerized in a known copolymerization ratio so as to have elastomeric properties.
It is also preferable to perform the polymerization reaction of fluorinated olefins in the presence of a cured site-forming monomer. Such a cured site-forming monomer is at least one of a bromine group- or iodine group-containing olefin and a bromine group-, iodine group- or nitrile group-containing vinyl ether.
Examples of bromine-containing monomer compounds to be used to form a cross-linked site include monobromoethylene, 1-bromo-2,2-difluoroethylene, bromotrifluoroethylene, perfluoroallyl bromide, 4-bromo-1,1,2-trifluorobutene-1, 4-bromo-3,3,4,4-tetrafluorobutene-1, 4-bromo-1,1,3,3,4,4-hexafluorobutene-1, bromotrifluoroethylene, 4-bromo-3-chloro-1,1,3,4,4-pentafluorobutene-1, 6-bromo-5,5,6,6-tetrafluorohexene-1, 4-bromoperfluorobutene-1,3,3-difluoroallyl bromide, and other brominated olefins; a bromine group-containing vinyl ether represented by the following general formula is preferably used:
BrRf—O—CF═CF2
Examples of such bromine group-containing vinyl ethers include those represented by CF2BrCF2OCF═CF2, CF2Br(CF2)2OCF═CF2, CF2Br(CF2)3OCF═CF2, CF3CFBr(CF2)2OCF═CF2, CF2Br(CF2)4OCF═CF2, and the like. These compounds are described in detail in U.S. Pat. No. 4,745,165.
In addition to these compounds, for example, a bromine group-containing vinyl ether represented by the general formula: ROCF═CFBr or ROCBr═CF2 (R: lower alkyl group or fluoroalkyl group), which is described in U.S. Pat. No. 4,564,662, can also be used.
Further, examples of iodine-containing monomer compounds include monoiodoethylene, iodotrifluoroethylene, 1,1-difluoro-2-iodoethylene, 4-iodo-3,3,4,4-tetrafluorobutene-1, perfluoro(2-iodoethyl vinyl ether), and the like.
Moreover, examples of cyano group-containing perfluorovinyl ethers include compounds represented by the following formulae:
CF2═CFO(CF2)nOCF(CF3)CN (n: 2-5)
CF2═CFO(CF2)nCN (n: 2-12)
CF2═CFO[CF2CF(CF3)O]m(CF2)nCN (n: 1-4; m: 1-2)
These cured site-forming monomers are used at a ratio of about 2 mol %, and preferably about 0.03 to 1 mol %, based on the total amount of comonomers used in the copolymerization reaction. Although the copolymerization of cured site-forming monomers results in desirable improvement of compression set, the use of the cured site-forming monomers at a ratio more than this range causes a decrease in elongation of the vulcanizates.
Moreover, an iodine- and bromine-containing compound represented by the general formula: RBrnIm (wherein R is fluorohydrocarbon group, chlorofluorohydrocarbon group, chlorohydrocarbon group, or hydrocarbon group; and n and in are independently 1 or 2) can also be used. This compound acts as a chain transfer agent, which adjusts the molecular weight to improve the processability.
The iodine- and bromine-containing compound represented by the above formula is selected from those that do not undergo side reactions under polymerization conditions to lose effectiveness. The R group is generally selected from C1-C10 fluorohydrocarbon group, chlorofluorohydrocarbon group, chlorohydrocarbon group, or hydrocarbon group, any of which may be linked to functional groups, such as —O—, —S—, ═NR, —COOH, —SO2, —SO3H, and —PO3H.
Examples of such iodine- and bromine-containing compounds include saturated or unsaturated, aliphatic or aromatic compounds; those wherein n and m are independently 1 are preferably used. Compounds wherein n and/or m are 2 are desirably used in the range where the processability is not impaired, because fluoroelastomers produced therefrom have a three-dimensional structure.
Although the polymerization reaction using a ωH perfluorocarboxylic acid (salt) as an emulsifier can be carried out by an emulsion polymerization method, a suspension polymerization method, or a seed polymerization method; an emulsion polymerization method is preferably used in terms of a higher degree of polymerization and economic efficiency.
The emulsion polymerization reaction is carried out using as a catalyst a water-soluble inorganic peroxide, such as ammonium persulfate, or a redox system thereof with a reducing agent in the presence of a ωH perfluorocarboxylic acid (salt) emulsifier, which is generally used at a ratio of about 0.01 to 20 wt. %, preferably about 0.1 to 10 wt. %, based on the total amount of feed water, generally under conditions where the pressure is about 0 to 10 MPa, preferably about 0.5 to 4 MPa, and where the temperature is about 0 to 100° C., preferably about 20 to 80° C. At this time, it is preferable to supply fluorinated olefins by a divided addition method so that the reaction pressure is maintained at a constant range. In order to adjust the pH in the polymerization system, Na2HPO4, NaH2PO4, KH2PO4, and other electrolyte materials that have buffer capacity, or sodium hydroxide may be added and used. Additionally, chain transfer agents, such as ethyl malonate, acetone, and isopropanol, are suitably used, if necessary.
The polymerization reaction is generally completed for about 180 to 600 minutes, although depending on various polymerization conditions. This does not much differ from when an ammonium perfluorooctanoate emulsifier is used. After the completion of the reaction, a potassium alum aqueous solution, sodium chloride aqueous solution, calcium chloride aqueous solution, or the like is added to the obtained aqueous emulsion to coagulate the resulting polymer, followed by washing with water and drying, thereby obtaining a rubbery polymer.
The vulcanization of the obtained fluoroelastomer is generally carried out using an organic peroxide. Examples of organic peroxides include 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexine-3, benzoyl peroxide, bis(2,4-dichlorobenzoyl)peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, tert-butylperoxybenzene, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, α,α′-bis(tert-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylperoxy isopropyl carbonate, and the like.
Together with these organic peroxides, a polyfunctional unsaturated compound is generally used as a co-crosslinking agent. Examples thereof include tri(meth)allyl isocyanurate, tri(meth)allyl cyanurate, triallyl trimellitate, N,N′-m-phenylene bismaleimide, diallyl phthalate, tris(diallylamine)-s-triazine, triallyl phosphite, 1,2-polybutadiene, ethyleneglycol diacrylate, diethylene glycol di(meth)acrylate, trimethylolpropane trimethacrylate, and the like.
The amount of each crosslink-based component is generally as follows: with respect to 100 parts by weight of fluoroelastomer, the organic peroxide content is used about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight; and the co-crosslinking agent is used about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight.
As vulcanizing agents other than organic peroxides, compounds represented by the following general formulae may also be used.
The composition comprising the above-described components suitably contains inorganic reinforcing agents or fillers such as carbon black and silica, acid receptors such as ZnO, CaO, Ca(OH)2, MgO, PbO, and synthetic hydrotalcite, various pigments, processing aids such as polyethyleneglycol monomethyl ether and Crown ether, plasticizers, stabilizers, and other necessary compounding agents. A vulcanizable composition is prepared by kneading using a roll, closed kneader, or the like, followed by vulcanization molding under general cross-linking conditions, for example, for about 1 to 10 minutes at about 160 to 220° C.
Since the fluoroelastomer obtained by the method of the present invention has a low Mooney viscosity ML1+10(121° C.), namely, excellent fluidity, the vulcanization molding is applied to injection molding, compression molding, etc., and is preferably applied to injection molding, to which excellent fluidity is particularly required, to produce sealing materials, such as gaskets, O rings, and packings.
The following describes the present invention with respect to examples.
Deionized water (4500 ml) and 23 g of ammonium 9H-hexadecafluorononanoate were charged in an autoclave having an inner capacity of 10 L. After the air in the autoclave was sufficiently replaced by nitrogen gas, a mixed gas of vinylidene fluoride [VDF]-hexafluoropropene [HFP] (molar ratio=18:82) was compressed until the internal pressure reached 1.3 MPa. Then, 3 g of isopropanol was charged, and the internal temperature was increased to 80° C.
After 10 g of ammonium persulfate dissolved in 100 ml of deionized water was charged therein, a mixed gas of VDF-HFP (molar ratio=56:44) was additionally compressed until the internal pressure reached 3.5 MPa, starting the polymerization reaction. Since the pressure dropped immediately after the reaction was started, the above additional mixed gas was recompressed at the time when the internal pressure dropped to 3.3 MPa, until the internal pressure reached 3.5 MPa. While maintaining the pressure at 3.3 to 3.5 MPa in this manner, the polymerization reaction was continued for 230 minutes.
After the reaction was completed, a 5 wt. % potassium alum aqueous solution was added to the obtained aqueous emulsion to coagulate the resulting copolymer, followed by washing with water and drying, thereby obtaining 1500 g of rubbery copolymer [Polymer A] (copolymer composition molar ratio analyzed by 19F-NMR: VDF/HFP=78/22).
Deionized water (4500 ml), 12 g of 1-bromo-2-iodoperfluoroethane, and 23 g of ammonium 9H-hexadecafluorononanoate were charged in an autoclave having an inner capacity of 10 L. After the air in the autoclave was sufficiently replaced by nitrogen gas, a mixed gas of vinylidene fluoride [VDF]-hexafluoropropene [HFP]-tetrafluoroethylene [TFE] (molar ratio=35:45:20) was compressed until the internal pressure reached 0.8 MPa. Then, 6.5 g of 1,1-difluoro-2-bromoethylene was charged, and the internal temperature was increased to 50° C.
After a mixture of 10 g of ammonium persulfate, 1 g of a ferrous sulfate.heptahydrate, and 1 g of sodium sulfite dissolved in 100 ml of deionized water was charged therein, a mixed gas of VDF-HFP-TFE (molar ratio=52:27:21) was additionally compressed until the internal pressure reached 1.8 MPa, starting the polymerization reaction. Since the pressure dropped immediately after the reaction was started, the above additional mixed gas was recompressed at the time when the internal pressure dropped to 1.7 MPa, until the internal pressure reached 1.8 MPa. While maintaining the pressure at 1.7 to 1.8 MPa in this manner, the polymerization reaction was continued for 398 minutes.
After the reaction was completed, a 5 wt. % potassium alum aqueous solution was added to the obtained aqueous emulsion to coagulate the resulting copolymer, followed by washing with water and drying, thereby obtaining 1250 g of rubbery copolymer [Polymer B] (copolymer composition molar ratio analyzed by 19F-NMR: VDF/HFP/TFE=65/17/18).
Deionized water (4500 ml) and 23 g of ammonium 9H-hexadecafluorononanoate were charged in an autoclave having an inner capacity of 10 L. After the air in the autoclave was sufficiently replaced by nitrogen gas, a mixed gas of vinylidene fluoride [VDF]-hexafluoropropene [HFP]-tetrafluoroethylene [TFE] (molar ratio=35:45:20) was compressed until the internal pressure reached 0.8 MPa. Then, 3 g of isopropanol was charged, and the internal temperature was increased to 50° C.
After a mixture of 10 g of ammonium persulfate, 1 g of a ferrous sulfate.heptahydrate, and 1 g of sodium sulfite dissolved in 100 ml of deionized water was charged therein, a mixed gas of VDF-HFP-TFE (molar ratio=52:27:21) was additionally compressed until the internal pressure reached 1.8 MPa, starting the polymerization reaction. Since the pressure dropped immediately after the reaction was started, the above additional mixed gas was recompressed at the time when the internal pressure dropped to 1.7 MPa, until the internal pressure reached 1.8 MPa. While maintaining the pressure at 1.7 to 1.8 MPa in this manner, the polymerization reaction was continued for 273 minutes.
After the reaction was completed, a 5 wt. % potassium alum aqueous solution was added to the obtained aqueous emulsion to coagulate the resulting copolymer, followed by washing with water and drying, thereby obtaining 1250 g of rubbery copolymer [Polymer C] (copolymer composition molar ratio analyzed by 19F-NMR: VDF/HFP/TFE=65/17/18).
A mixed gas of TFE-FMVE (molar ratio=65:35) was added for 7 hours so that the pressure in the reactor was maintained in the range of 0.9 to 1.0 MPa (total polymerization time: 478 minutes).
After the reaction was completed, a 5 wt. % potassium alum aqueous solution was added to the obtained aqueous emulsion to coagulate the resulting copolymer, followed by washing with water and drying, thereby obtaining 1480 g of rubbery copolymer [Polymer D] (copolymer composition molar ratio analyzed by 19F-NMR: TFE/FMVE=65/35).
A mixed gas of TFE-FMVE (molar ratio 65:35) was added for 7 hours so that the pressure in the reactor was maintained in the range of 0.9 to 1.0 MPa (total polymerization time: 536 minutes).
After the reaction was completed, a 5 wt. % potassium alum aqueous solution was added to the obtained aqueous emulsion to coagulate the resulting copolymer, followed by washing with water and drying, thereby obtaining 1700 g of rubbery copolymer [Polymer E] (copolymer composition molar ratio analyzed by 19F-NMR: TFE/FMVE=65/35).
Deionized water (4500 ml), 6 g of 1-bromo-2-iodoperfluoroethane, and 40 g of ammonium 9H-hexadecafluorononanoate were charged in an autoclave having an inner capacity of 10 L. After the air in the autoclave was sufficiently replaced by nitrogen gas, a mixed gas of vinylidene fluoride [VDF]-perfluoro(methyl vinyl ether) [FMVE]-tetrafluoroethylene [TFE] (molar ratio=70:20:10) was compressed until the internal pressure reached 2.0 MPa. Then, 12 g of 1,1-difluoro-2-bromoethylene was charged, and the internal temperature was increased to 50° C.
After a mixture of 10 g of ammonium persulfate, 1 g of a ferrous sulfate.heptahydrate, and 1 g of sodium sulfite dissolved in 100 ml of deionized water was charged therein, a mixed gas of VDF-FMVE-TFE (molar ratio=70:20:10) was additionally compressed until the internal pressure reached 3.1 MPa, starting the polymerization reaction. Since the pressure dropped immediately after the reaction was started, the above additional mixed gas was recompressed at the time when the internal pressure dropped to 3.0 MPa, until the internal pressure reached 3.1 MPa. While maintaining the pressure at 3.0 to 3.1 MPa in this manner, the polymerization reaction was continued for 476 minutes.
After the reaction was completed, a 5 wt. % potassium alum aqueous solution was added to the obtained aqueous emulsion to coagulate the resulting copolymer, followed by washing with water and drying, thereby obtaining 1500 g of rubbery copolymer [Polymer F] (copolymer composition molar ratio analyzed by 19F-NMR: VDF/FMVE/TFE=73/17/10).
Polymers G to L, which were rubbery elastomers, were obtained in the same manner as in Examples 1 to 6 except that a predetermined amount of ammonium perfluorooctanoate [FOAA] was used in place of ammonium 9H-hexadecafluorononanoate as an emulsifier, and each polymerization time was changed. The yields and copolymerization compositions of Polymers G to L are the same as those of Polymers A to F, respectively.
Deionized water (4500 ml) and 23 g of ammonium perfluorooctanoate were charged in an autoclave having an inner capacity of 10 L. After the air in the autoclave was sufficiently replaced by nitrogen gas, a mixed gas of vinylidene fluoride [VDF]-hexafluoropropene [HFP] (molar ratio=18:82) was compressed until the internal pressure reached 1.3 MPa. Then, 6 g of isopropanol was charged, and the internal temperature was increased to 80° C.
After 10 g of ammonium persulfate dissolved in 100 ml of deionized water was charged therein, a mixed gas of VDF-HFP (molar ratio=56:44) was additionally compressed until the internal pressure reached 3.5 MPa, starting the polymerization reaction. Since the pressure dropped immediately after the reaction was started, the above additional mixed gas was recompressed at the time when the internal pressure dropped to 3.3 MPa, until the internal pressure reached 3.5 MPa. While maintaining the pressure at 3.3 to 3.5 MPa in this manner, the polymerization reaction was continued for 313 minutes.
After the reaction was completed, a 5 wt. % potassium alum aqueous solution was added to the obtained aqueous emulsion to coagulate the resulting copolymer, followed by washing with water and drying, thereby obtaining 1400 g of rubbery copolymer [Polymer M] (copolymer composition molar ratio analyzed by 19F-NMR: VDF/HFP=78/22).
The polymer Mooney viscosities ML1+10(121° C.) of Polymers A to M obtained in the examples and comparative examples were measured according to JIS K6300 corresponding to ASTM D2084, and the results shown in Table 2 below were obtained.
The results demonstrate that in Polymers A to F and corresponding Polymers G to L having copolymerization compositions equal respectively to those of Polymers A to F, the Mooney viscosities of Polymers A to F, which were prepared by using ammonium 9H-hexadecafluorononanoate as an emulsifier, were remarkably reduced in comparison with the Mooney viscosities of Polymers G to L, which were prepared by using ammonium perfluorooctanoate as an emulsifier. As for Comparative Example 7, although the Mooney viscosity was as low as that of Example 1, the compression set was inferior.
The components other than a crosslinking agent and crosslinking aid were kneaded with each of Polymers A to M using a 1 L kneader manufactured by Moriyama, and the crosslinking agent and crosslinking aid were then added and mixed by an open roll. The compositions obtained by kneading were vulcanized under the following heating conditions:
As for the obtained vulcanizates, each of the following items was measured.
Normal State Value:
Compression Set:
Hot Tear Resistance:
The measurement results are shown in Table 3 (Reference Examples corresponding to Examples) and Table 4 (Reference Examples corresponding to Comparative Examples) below, together with the constituents of the compositions (part by weight; Polymers A to M: 100 parts by weight).
The comparison of the results between Table 3 (Reference Examples corresponding to Examples) and Table 4 (Reference Examples corresponding to Comparative Examples) shows that there is almost no difference in the vulcanizate physical properties between Polymers A to F and corresponding Polymers G to L having copolymerization constitutions and vulcanization compositions equal respectively to those of Polymers A to F; therefore, the use of ammonium 9H-hexadecafluorononanoate as an emulsifier can remarkably reduce the values of Mooney viscosity ML1+10(121° C.) with little effect on the vulcanizate physical properties, compared to the use of ammonium perfluorooctanoate as an emulsifier.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2007-306870 | Nov 2007 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2008/053776 | 3/3/2008 | WO | 00 | 5/27/2010 |
