CN102153689A

CN102153689A - Ethylene-tetrafluoroethylene copolymer

Info

Publication number: CN102153689A
Application number: CN2008102380758A
Authority: CN
Inventors: 于淑芳
Original assignee: Individual
Current assignee: Individual
Priority date: 2008-12-08
Filing date: 2008-12-08
Publication date: 2011-08-17

Abstract

The invention discloses an ethylene-tetrafluoroethylene copolymer which is copolymerized from four monomers, including ethylene, tetrafluoroethylene, hexafluoropropylene and 1,2,2-trifluorostyrene, wherein the ethylene and tetrafluoroethylene account for 90-99.9 mol% in the copolymer, and the rest of monomers account for 0.1-10 mol% in the copolymer. The ethylene-tetrafluoroethylene copolymer disclosed by the invention has the advantages of high-heat cracking resistance at high temperature, and excellent mechanical properties.

Description

Ethylene-tetrafluoroethylene copolymer

Technical field

The invention belongs to the fluoro-containing macromolecule material field, relate to the preparation of ethylene-tetrafluoroethylene copolymer.

Background technology

Ethylene-tetrafluoroethylene copolymer (ETFE or F40) was found the forties in 20th century, and successively go into operation in the U.S. and Japan the seventies in 20th century.The multipolymer that simple ethylene/tetrafluoroethylene mol ratio is 1:1 has very high fusing point, and fusing point approaches heat decomposition temperature, long slightly just easy oxygenolysis of time in the course of processing, cause polymkeric substance variable color, foaming and be full of cracks, at high temperature the mechanical property of multipolymer is degenerated, even under far below the high temperature of its fusing point, can not use, very little stress will make polymeric film ftracture, therefore, usually contain the 3rd monomer in the ETFE resin as commodity, be the ethylene-tetrafluoroethylene copolymer of modification, therefore in fact it is a terpolymer.The ETFE of modification has good electrical property, chemical resistant properties and ageing resistance, because the introducing of ethene has improved radioresistance greatly, the improvement of its mechanical property is more outstanding, main is that its processing characteristics is improved greatly, particularly it improves greatly to the sticking power of metallic surface, and the tight lining technology of fluoroplastics and steel really is achieved.These premium propertiess make this multipolymer a member as high performance engineering plastics, develop very rapidly, are widely used in the wire cable insulating material of automobile, aviation and robot and the lining of pipe line coating of transmission special liquid medium.

As the 3rd monomer of modification, enumerated 18 class modifications the 3rd monomer in the United States Patent (USP) 4338237, almost contained whole operable modified monomer kind; United States Patent (USP) 3308107 has provided the hydrogeneous long-chain alkene of other ether monomer; United States Patent (USP) 6602167 and 3444148 has provided the part Fluorine containing olefine monomer of a class hydroxyl; In patent EP0123306, provide some again and can be used as the alkene of modified monomer, mention simultaneously the perfluoro alkane of long-chain or the perfluoro alkoxy alkene ether of long-chain again and must use big excessive participation reaction because polymerization activity is too low, just can synthesize and calculate designed molecule, react wayward; In United States Patent (USP) 3847881, provided (CF ₃) ₂C=CH ₂(CF ₃) (CH ₃) C=CF ₂Two kinds of modified monomers are added bright picture iso-butylene ((CH simultaneously ₃) ₂C=CH ₂) and R 1216 (CF ₃CF=CF ₂) this class side group chain length has only the modified monomer of a carbon atom, because the side chain volume is too little, is not enough to the intramolecularly volume that provides big, can't provide big improvement to material at high temperature tensile property aspect, also just can not solve material at high temperature rimose phenomenon fully.Japan AGC Co., Ltd. has prepared a kind of composition in order to improve melting behavior and mechanical property in the patent application CN1497013 (03127237.1) of China tetrafluoroethylene-ethylene copolymer composition.

Summary of the invention

At the deficiencies in the prior art, the invention provides a kind of ethylene-tetrafluoroethylene copolymer that at high temperature has heat-resisting cracking ability.

Technical scheme of the present invention is as follows:

Ethylene-tetrafluoroethylene copolymer, by ethene, tetrafluoroethylene, R 1216 and 1,2, four kinds of monomer copolymerizables of 2-trifluorostyrene make, wherein, ethene and tetrafluoroethylene shared mol ratio sum in multipolymer is 90～99.9%, and the mol ratio of ethene and tetrafluoroethylene is (30～70): (70～30); R 1216 and 1,2,2-trifluorostyrene shared mol ratio sum in multipolymer is 0.1～10%, R 1216 and 1,2, and the mol ratio of 2-trifluorostyrene is (10～90): (90～10).

The ethylene-tetrafluoroethylene copolymer molecular weight is between 250000-1200000.

In the above-mentioned ethylene-tetrafluoroethylene copolymer, further preferred ethene and the mol ratio (40～60) of tetrafluoroethylene in multipolymer: (60～40).Preferred ethene and the tetrafluoroethylene mol ratio (45～55) in multipolymer: (55～45).

In the above-mentioned ethylene-tetrafluoroethylene copolymer, further preferred R 1216 and 1,2, the mol ratio of 2-trifluorostyrene is (40～90): (60～10).

Multipolymer of the present invention is by increasing R 1216 and 1,2, and 2-trifluorostyrene compound monomer is formed modification to ethylene-tetrafluoroethylene copolymer, further improves the heat-resisting cracking grade of multipolymer and the mechanical property of raising multipolymer.This ethylene-tetrafluoroethylene copolymer is at 297 ℃, melt flow index under the load of 5Kg power is at 1～100g/10min, melt flow index is measuring of molecular weight, the big expression molecular weight of melt flow index is little, the melt fluidity height, otherwise, the little expression molecular weight of melt flow index is big, melt fluidity is poor, if melt flow index is less than 1g/10min, and melt molding performance deficiency, if and melt flow index is greater than 100g/10min, then dimensional stability is poor after physical strength and the moulding, and therefore in preferred range of the present invention, the melt molding performance is good, physical strength is good, and the dimensional stability during moulding is also excellent.Ethylene-tetrafluoroethylene copolymer of the present invention, its topmost characteristics are that this multipolymer at high temperature has heat-resisting cracking ability, and long-term maximum operation (service) temperature can be up to 200 ℃.

The present inventor is unexpected to be found, by R 1216 and 1,2, compound monomer after the 2-trifluorostyrene is composite and ethene, tetrafluoroethylene copolymerization, not only can provide a kind of resin of high fusion index of high temperature resistant cracking performance, and this resin have the temperature resistant grade and the excellent mechanical property of superelevation.

Ethene-TFE copolymer of the present invention can prepare by the polymerization process of routine, and as (1) solution polymerization process: the copolyreaction of carrying out in organic solvent, solvent are selected from the suitable organic reaction solvent of fluorocarbon solvent or fluorochloroparaffins and other; (2) suspension polymerization: carry out the reaction of dispersion polymerization or suspension copolymerization at aqueous phase, in the presence of dispersion agent, described dispersion agent is selected from perfluoroalkyl carboxylate, perfluoro alkoxy carboxylate salt, fluorinated alkyl sulfonate, perfluoro alkoxy sulfonate, triazines dispersion agent, perfluorocarboxylic acid ammonia salt; (3) emulsion polymerization: at the emulsion polymerization that aqueous phase carries out, the concentration of emulsifying agent is 0.2～3%, and described emulsifying agent comprises anionic emulsifier and nonionic emulsifier; (4) mixed solvent polymerization method: the polyreaction of carrying out in the mixed system of organic solvent and water, appropriate organic solvent is selected from fluorochloroparaffins, can be the fluorochloroparaffins that contains a hydrogen atom on the end group.

The comonomer tetrafluoroethylene that ethene-TFE copolymer of the present invention is adopted in building-up process, ethene and R 1216 (CF ₂=CFCF ₃) can buy and obtain, also can prepare by approach well known.

Ethene-TFE copolymer of the present invention in building-up process, adopted 1,2, the 2-trifluorostyrene can prepare according to techniques well known, the preparation method that the present invention recommends is referring to " organic chemistry magazine " 1988,53:2714-2720 (JournalOrganic Chemistry, 1988,53:2714-2720).1,2,2-trifluorostyrene structural formula is as follows:

(1,2, the 2-trifluorostyrene) (I)

Embodiment

Advance-go on foot explanation the present invention by the following examples, but do not limit the present invention.The perfluoroalkyl initiator that is adopted in building-up process among the embodiment can prepare according to techniques well known, the preparation method that the present invention recommends is referring to " organic chemistry magazine " 1982,47 (11): 2009-2013 (Journal Organic Chemistry, 1982,47 (11): 2009-2013).

Embodiment 1: solution polymerization process, fluorocarbon solvent, perfluoroalkyl acyl superoxide initiator

Being equipped with stirring; temperature regulating device; the circulation heating; the 10L stainless steel autoclave of recirculated cooling water is cleaned also and is vacuumized after the thorough drying; inflated with nitrogen displacement three times; until oxygen level below 10ppm; be evacuated to 0.0001MPa; with 5.8L perfluorocarbon solvent; 150g (1mol) R 1216 monomer; 158g (1mol) trifluorostyrene adds in the reactor; stirring also is warming up to 40 ℃; after treating that system temperature is constant; the ethene that in system, adds mol ratio 1:1 with compressor; tetrafluoroethylene mixes gas; until pressure is 2MPa, adds 70ml with volume pump and contains 0.5g peroxidation perfluor butyryl radicals compound (CF ₃CF ₂CF ₂CO-OO-OCCF ₂CF ₂CF ₃) initiated polymerization, the mixed gas that lasting feeding ethene-tetrafluoroethylene mol ratio is 1:1 is kept pressure constantly carries out reaction at 2MPa, calculate when mixed gas add-on reaches 1100g by pressure change, stop to add mixed gas, allow reaction proceed stopped reaction behind the 10min, with unreacted ethene, tetrafluoroethylene, the R 1216 MONOMER RECOVERY is gone in the accumulator tank, reclaim the trifluorostyrene monomer, put into rake type dryer by discharging valve of reaction kettle goalkeeper material, reclaim reaction solvent and, obtain the white powder multipolymer with deionized water washing material under heating state repeatedly.Further with product in 100 ℃ of vacuum-dryings 8 hours, obtain the 806g resin.Through F ¹⁹NMR, IR analyze to confirm in the multipolymer that it is 49.3% that the tetrafluoroethylene composition accounts for molar content; It is 41.5% that the ethene composition accounts for molar content; It is 5.5% that the R 1216 composition accounts for molar content; It is 3.7% that the trifluorostyrene composition accounts for molar content.

Polymer data: the melting index of measuring resin by fusion index instrument be 10.5g/10mim (297 ℃, 5kg); 1% weight decomposition temperature (Td) of TGA test resin is 432 ℃; DSC data presentation multipolymer fusing point is at 284 ℃.

Embodiment 2: mixed solvent polymerization method, and at the organic and mixed solvent system polymerization of water, perfluoroalkyl acyl superoxide initiator

Being equipped with stirring; temperature regulating device; the circulation heating; the 10L stainless steel autoclave of recirculated cooling water vacuumizes after cleaning; inflated with nitrogen displacement three times; until oxygen level below 10ppm; be evacuated to 0.0001MPa; with 3.8L perfluorocarbon solvent; the 2L deionized water; 150g (1mol) R 1216 monomer; 79g (0.5mol) trifluorostyrene adds in the reactor; stirring also is warming up to 22 ℃; after treating that system temperature is constant; the ethene that in system, adds mol ratio 2:3 with compressor; tetrafluoroethylene mixes gas; until pressure is 1MPa, adds 50ml with volume pump and contains 0.45g peroxidation perfluoro propionyl compound (CF ₃CF ₂CO-OO-OCCF ₂CF ₃) initiated polymerization, the mixed gas that lasting feeding ethene-tetrafluoroethylene mol ratio is 1:1 is kept pressure constantly carries out reaction at 1MPa, calculate when mixed gas add-on reaches 850g by pressure change, stop to add mixed gas, allow reaction proceed stopped reaction behind the 10min, with unreacted ethene, tetrafluoroethylene, the R 1216 MONOMER RECOVERY is gone in the accumulator tank, reclaim the trifluorostyrene monomer, put into rake type dryer by discharging valve of reaction kettle goalkeeper material, reclaim reaction solvent and, obtain the white powder multipolymer with deionized water washing material under heating state repeatedly.Further with product in 100 ℃ of vacuum-dryings 8 hours, obtain the 726g resin.Through F ¹⁹NMR, IR analyze to confirm in the multipolymer that it is 50.3% that the tetrafluoroethylene composition accounts for molar content; It is 38.5% that the ethene composition accounts for molar content; It is 7.5% that the R 1216 composition accounts for molar content; It is 3.7% that the trifluorostyrene composition accounts for molar content.

Polymer data: the melting index of measuring resin by fusion index instrument be 21.3g/10mim (297 ℃, 5kg); 1% weight decomposition temperature (T of TGA test resin _d) be 422 ℃; DSC data presentation multipolymer fusing point is at 273 ℃.

Embodiment 3: suspension polymerization, and fluorine-containing organo-peroxide is made initiator, and water is as dispersion medium

Vacuumize after the 10L stainless steel autoclave that is equipped with stirring, temperature regulating device, circulation heating, recirculated cooling water cleaned, in reactor, add and contain 13g perfluor propoxy-carboxylic acid ammonium (CF ₃CF ₃CF ₂OCFCF ₃CF ₂-OCFCF ₃COONH ₄), the 3300g pure water, vacuum nitrogen filling gas displacement three times below 10ppm, is evacuated to 0.0001MPa until oxygen level,

150g (1mol) R 1216 monomer, 49.5g (0.25mol) trifluorostyrene are added in the reactor; stirring also is warming up to 45 ℃; after treating that system temperature is constant; the mixed gas of ethene, tetrafluoroethylene that in system, adds mol ratio 1:1 with compressor; until pressure is 3.5MPa, adds 100ml with volume pump and contains 0.9g peroxidation perfluor butyryl radicals compound (CF ₃CF ₂CF ₂CO-OO-OCCF ₂CF ₂CF ₃) initiated polymerization, the mixed gas that lasting feeding ethene-tetrafluoroethylene mol ratio is 1:1 is kept pressure constantly carries out reaction at 3.5MPa, calculate when mixed gas add-on reaches 1300g by pressure change, stop to add mixed gas, allow reaction proceed stopped reaction behind the 10min, reclaim unreacted ethene, tetrafluoroethylene, R 1216 list, trifluorostyrene monomer, put into rake type dryer by discharging valve of reaction kettle goalkeeper material, with deionized water washing material under heating state repeatedly, obtain the white powder multipolymer.Further with product in 100 ℃ of vacuum-dryings 8 hours, obtain the 1220g resin.Through F ¹⁹NMR, IR analyze to confirm in the multipolymer that it is 54.3% that the tetrafluoroethylene composition accounts for molar content; It is 41.5% that the ethene composition accounts for molar content; It is 3.2% that the R 1216 composition accounts for molar content; It is 1.0% that the trifluorostyrene composition accounts for molar content.

Polymer data: the melting index of measuring resin by fusion index instrument be 16.5g/10mim (297 ℃, 5kg); 1% weight decomposition temperature (T of TGA test resin _d) be 421 ℃; DSC data presentation multipolymer fusing point is at 270 ℃.

Embodiment 4: emulsion polymerization, the preparation method of described ethene-TFE copolymer is the emulsion polymerization that carries out at aqueous phase, the steps include:

1) reactor is cleaned after, add tensio-active agent and pure water; The concentration of emulsifying agent is 0.2～3%; The ratio of water and total monomer weight is 60:40;

2) reactor vacuumizes and directly takes out 0.0001MPa, adds R 1216 and trifluorostyrene monomer, and two kinds of monomeric mol ratios are 50:50;

3) in system, add the mixed gas to 0.45 of ethene, tetrafluoroethylene～3MPa of mol ratio 50:50 with compressor;

4) be warming up to 20～100 ℃, add initiator with volume pump, the mixed gas that feeds ethene-tetrafluoroethylene mol ratio and be 1:1 is kept pressure and is reacted;

5) by pressure change, control enters the gas volume of reactor, after finishing to react, reclaims unreacted monomer; The washing of the material breakdown of emulsion that obtains, in 120 ℃ of oven dry, obtain ethene-TFE copolymer.

Described emulsifying agent comprises anionic emulsifier and nonionic emulsifier.Anionic emulsifier comprises sodium soap, sodium lauryl sulphate, alkyl sodium sulfonate, sodium alkylarysulfonate etc.; Nonionic emulsifier comprises the alkyl phenol polyether alcohols, as polyoxyethylene nonylphenol ether, polyoxyethylene fatty acid, polyoxyethylene fatty acid ether.Mentioned emulsifier can use separately also can mix use.

Claims

1. ethylene-tetrafluoroethylene copolymer is characterized in that by ethene, tetrafluoroethylene, R 1216 and 1,2, and four kinds of monomer copolymerizables of 2-trifluorostyrene make, wherein,

Ethene and tetrafluoroethylene shared mol ratio sum in multipolymer is 90～99.9%, and the mol ratio of ethene and tetrafluoroethylene is (30～70): (70～30);

R 1216 and 1,2,2-trifluorostyrene shared mol ratio sum in multipolymer is 0.1～10%, R 1216 and 1,2, and the mol ratio of 2-trifluorostyrene is (10～90): (90～10);

The melt flow index of this multipolymer under 297 ℃, 5Kg load is 1～100g/10min.

2. ethylene-tetrafluoroethylene copolymer as claimed in claim 1 is characterized in that ethene and the tetrafluoroethylene mol ratio (40～60) in multipolymer: (60～40).

3. ethylene-tetrafluoroethylene copolymer as claimed in claim 1 is characterized in that ethene and the tetrafluoroethylene mol ratio (45～55) in multipolymer: (55～45).

4. ethylene-tetrafluoroethylene copolymer as claimed in claim 1 is characterized in that R 1216 and 1,2, and the mol ratio of 2-trifluorostyrene is (40～90): (60～10).