Vinylidenefluoride and geksaftorpropilenom cured copolymers

 

(57) Abstract:

The invention relates to utverzhdennym forecaster - copolymers vinylidenefluoride and hexaferrite, which are used for production of industrial products such as gaskets, seals for shafts, sleeves and seals with metal inserts. The copolymers have the composition: 60-85 mol. % vinylidenefluoride and 15-40 mol.% hexaferrite. They otverzhdajutsja using 0.5 to 15 hours at 100 hours copolymer and 0.05 to 5.0 hours 100 hours copolymer curing and accelerating agents. Caulk copolymers are highly stable spatial structure, having a residual deformation when compressed below 20%. Products derived from the copolymers according to the invention have excellent sealing properties, measured at high temperature. 3 C. and 16 h.p. f-crystals, 5 PL.

The invention relates to utverzhdennym forecasters with great sealing properties, measured at a high temperature, such as residual deformation of the compression ring on the gasket, which is lower than 20%, as defined hereafter.

It is particularly important that caulk forecaster of the present invention, which are settled without the required long days of curing, commonly used in industrial practice. The results are even more surprising when you consider that the time required for the above values of residual deformation under compression, is 30' or less in comparison with the commonly used 24 hours.

In addition, it should be noted that, after pressing, as described here below, the values of residual strain during compression are already quite low for many applications.

It is well known that one of the most important applications of forecasters associated with the manufacture of ring seals. Get them from forecasting copolymers containing Monomeric units derived from vinylidenefluoride (WDF), hexaferrite (HFP) and optionally tetrafluoroethylene (TPV).

Commercial products used for this purpose have a high elastomeric characteristics at low and at high temperatures and show good machinability, thus they can be easily molded by pressing with the automatic cycles.

WDF-containing forecaster show low values of residual deformation under compression, even lower than 20%. However, they require long tip current WDF-containing forecaster is that is impossible automation of production cycles casting pressing and curing due to the fact that excessively long time stay in a continuous furnace devices.

Felt the need to have available WDF-containing forecaster for the manufacture of o-rings that require very short curing times at least less than or equal to 30', in order to make possible the automatic production cycles, as mentioned above.

Forecaster having the time of curing for 1 hour, received peroxide curing is known from the prior knowledge. In particular, see the application for the European patent EP 661304, which describes terpolymer based on WDF, HFP and/or performancelimiting and TPV showing low permanent deformation under compression, but not below 20. These lower values of residual deformation in compression only get when terpolymer has a high fluorine content (higher than 68% by weight). The residual deformation under compression, resulting from the use of WDF/HFP copolymer and/or performancelimiting in the absence of TPV termokamera shows more wlno discover cured by ionic mechanism WDF-containing copolymer with good low temperature properties, which can be handled by less expensive technology without the use of peroxide curing, which, as is well known, represents a significant challenge for the transformational cycle. In particular, peroxide curing is more difficult and requires a combination of techniques due to the instability of the peroxide in addition to problems with harmful toxic emissions during curing.

Taking into account prior knowledge on curing ion mechanism, there is no guidance as to reduce the time of curing to a value lower than 30' in order to use the above automatic, continuous production cycles for molded industrial products.

For example, in US patent 4123603 and EP 445839 in the name of the applicant describes terpolymer formed from WDF, HFP and TPV links in a very narrow concentration range. They otverzhdajutsja ion mechanism, showing a satisfactory combination of properties at high and at low temperatures, and at the same time have good machinability, especially with regard to release from the mold after curing. For this reason they are particularly suitable for the production of ring subsequent curing to obtain the production of products with a good final properties and, in particular, residual deformation under compression.

From the prior knowledge of the above, you may receive significantly lower values of residual deformation in compression at high temperatures lower than 20%. In particular, these copolymers are able to meet commercial specifications, such as "Military Specification (MIL-R-83248B)", according to which the maximum value required for permanent deformation under compression at 200oWith over 70 hours, equal to 20%. It should be noted that the above-mentioned good residual values of deformation in compression only get after a long curing times: 250oWith in 24 hours.

The object of the present invention are vinylidenefluoride (WDF) and hexaferrite (HFP) containing caulk ion mechanism copolymers, representing highly stable mesh structure giving a cured material, but requires very little or almost zero time subsequent curing (in any ratio less than 30 minutes) to get the value of the residual strain in compression is lower than 20%; the copolymer, before curing coming from a polymerization reactor and after latex coagulation, which is heat-treated at a temperature of 250oC for 1 hour, does not show in FT-IR analysis, the presence of peaks, and/or strips and/or halogen double bond-CH=CF - frequency of 1720 cm-'; moreover copolymer, before curing subjected to gel chromatography (GPC) shows the number of less than 3% by weight, preferably lower than 2.5% by weight polymer fractions having a molecular weight lower than 10,000, when the viscosity by viscometer Mooney (ML 1+10 at 121oC) equal to 20 and less than 0.5% by weight, when the viscosity of the Mooney viscometer is equal to 50.

The viscosity Mooney viscometer, shown above, is determined in accordance with ASTM D 1646-82.

Measurement by gel chromatography (GPC) molecular weight distribution is performed according to the following:

Equipment used:

Pump: Waters-Mod.590

Detector: refractive index (HP 1047A)

Speakers: predalone plus 4106Angstrom (A), 105AND, 104, 103And, (ultrastyragel) speakers

Injection: injector (Rheodyne 7010)

Conditions:

Eluent: tetrahydrofuran (THF)

The flow rate of eluent: 1 cm3rpm

Concentration of sample: 0.5% by weight

Loop injection: 200 microlitres (l)

Temperature: 30oYu curve is obtained by fractionation of Tecnofloncopolymer WDF/HFP (80/20 by mole) in THF solution.

The processes of coagulation, washing and drying of the polymer from the polymerization latex the following:

adding electrolytic agent (aluminum sulfate) in an amount of 5 g/l latex; 6 rinses with demineralized water (each rinse hold 1 l of water per l of the original latex); drying in an oven at 80oWith in 24 hours.

In General, the viscosity Mooney viscometer copolymer before curing and without the addition of curing ingredients, as mentioned here below, which can be used in the above-mentioned injection and direct pressing, is from 15 to 150, preferably from 20 to 100.

Curing forecaster, the object of the present invention, is obtained using as a radical initiator, an organic peroxide, which may be selected in particular from:

(a) dialkylamides, where alkyl has from 1 to 12 carbon atoms, for example, durational butylperoxide (DTBP);

(b) dialkyldithiocarbamato, where alkyl has from 1 to 12 carbon atoms, for example, diisopropylperoxydicarbonate;

(c) diarilpirimido, where the acyl has from 2 to 12 carbon at tertBUTYLPEROXY.

The method of producing forecasters of the invention includes the copolymerization of the corresponding monomers in aqueous emulsion in the presence of an organic peroxide, as mentioned above. Polymerization in the emulsion can be carried out according to known methods such as, for example, described in Kirk Othmer, Encyclopaedia of Chemical Technology, vol.8, pages 500 and seq., 1979.

The temperature of the method lies between 100 and 150oWith, preferably between 105 and 130oC. It can be carried out at pressures between 10 and 100 bar, preferably between 20 and 50 bar.

As is known, the method of emulsion polymerization requires the presence of surfactants. Especially preferred are at least partially fluorinated surfactants corresponding to General formula

Rf-X-M+,

where Rfmeans (per)alkyl fluoride chain C5-C6or (per)ftorpolimernoj chain, X - means-COO - or-SO3-, M+selected from: H+, NH4+, alkali metal ion. Among typically the most used, we may mention: perforateed ammonium, (TRANS)forpolitical, terminated by one or more carboxyl groups, optionally forming Sol. See, for example, US patent 4524197.

Agents migrate chain selected from usually the most used in the synthesis of forecasters, can be added to the reaction mixture. We can mention: hydrogen, hydrocarbons having from 1 to 12 carbon atoms, such as methane, ethane, Methylcyclopentane; chlorine(fluorine)hydrocarbons having from 1 to 10 carbon atoms, optionally containing hydrogen, for example chloroform, Trichlorofluoromethane; esters, alcohols, ethers having from 1 to 12 carbon atoms, such as ethyl acetate, diethylmalonate, diethylether, isopropanol, etc.

Other agents transfer circuit can be mainly used as molecular weight regulators. Among them included iodirovannoye and/or brominated agents transfer circuit, such as, for example, compounds of General formula Rfb(I)x(Br)y(Rfb= perfluorinated hydrocarbon radical containing from 1 to 8 carbon atoms, x, y = integers concluded between 0 and 2, with at least x or y = 1 and x+y 2).

If desirable, can be used iodides and/or bromides of alkaline or alkaline-earth metals according to the application for the European patent 407937 who are not agents of the transfer chain.

the diversified methods such as coagulation by addition of electrolytes or cooling. The detailed method was described above.

Getting forecasters, the object of the present invention can be favorably carried out in the presence of microemulsions of performanceoriented according to US patent 4864006 or microemulsions of forpolitical with hydrogenomonas the ends and/or hydrogenomonas the repeating unit according to European patent 625526.

The polymerization can be favorably carried out using emulsion or dispersion of performanceoriented and water according to the method described in US patent 4789717.

Emulsion and dispersion performancelevel and water, as described, for example, in applications to the European patent 196904, 280312 and 360292, can be used.

Forecaster, the object of the present invention include WDF-HFP copolymers. Typical coralstone copolymer compositions of the following:

WDF 60-85% by moles, HFP 15-40% by moles, preferably WDF 75-80% by moles, HFP 20-25% in moles.

In addition to the copolymers can also be obtained terpolymer or terpolymer having the required characteristics listed above for WDF/HFP copolymers. Thecraft-C6for example performativity, can be used as terminally.

Suitable compounds are the following:

WDF 60-75% by moles

HFP 12-22

PAVE 0-5

TPV 3-20

When present HAVE, basically it is partially substituted GRF.

A small amount of units derived from the fluorinated bis-olefin may be present in the polymer, as described in the application for the European patent EP 661304 on behalf of the applicant, given here as a reference; the amount of bis-olefin mainly concluded between 0.01-1% by moles.

Forecaster, the object of the present invention may also contain units derived from non-fluorinated Ethylenediamine monomers, in particular non-fluorinated olefins (Ol) C2-C8in quantity, mainly concluded between 0-10% by moles, such as, for example, ethylene and propylene, preferably ethylene.

Forecaster, an object of the present invention, solidified ion mechanism known from the prior knowledge.

In the process of cross-linkage using curing and accelerating agents, well known from the prior knowledge. The amount of the accelerating agent signed majeskie or aliphatic polyhydroxylated compounds or their derivatives can be used, as described for example in EP 335705 and US 4233427. Among them, in particular, can be mentioned: Yes-, three - and tetrahydrocarbazole, naphthalenes or anthracene; bisphenol, in which two aromatic rings are linked together via a bivalent aliphatic, cycloaliphatic or aromatic radical, or via an oxygen atom or sulfur, or carbonyl group. The aromatic ring can be substituted by one or more atoms of chlorine, fluorine, bromine or CARBONYLS, alkilani, atilov. In particular, bisphenol AF preferred. As accelerating agents, we may mention, for example: Quaternary ammonium or postname salt (see, for example, EP 335705 and US 3876654); aminophosphonate salt (see, for example, US 4259463); phosphorane (see, for example, US 3752787); aminosidine described in EP 182299 and EP 120462 etc., Quaternary ammonium or postname salt and aminophosphonate salts are preferred.

Instead of using the accelerator and curing agent separately adduct of two compounds in a molar ratio of from 1:2 to 1:5, preferably from 1:3 to 1:5, can be used in an amount of from 1 to 5 phr (from 2 to 4.5, preferably). The accelerating agent is one of onieva-organic compounds having protesti di - or polyhydroxylated, or di - or politially. The adduct obtained by melting of the reaction product between the accelerator and curing agent in the indicated molar ratios, or by melting 1:1 mixture of the adduct with the curing agent in the indicated amounts. Optionally there may also be present an excess of precipitating agent in relation to its content in the adduct, mainly in the amount of from 0.05 to 0.5 phr.

To obtain the adduct of the following cations are particularly preferred: 1,1-diphenyl-1-benzyl-N-diethyl-phosphoranes and tetrabutyl phosphonium or ammonium; among the particularly preferred anions are bisphenol compounds in which two aromatic rings sewn bivalent radical selected among performanceline groups of 3 to 7 carbon atoms, and IT is in the para-position.

The adduct can be obtained as follows.

The cross-linking agent, such as polyhydroxylated or policealne connection, reacts in aqueous solution or in a suitable solvent, for example methanol, in which the accelerating agent is soluble in the first stage with a basic compound (for example, NaOH, KOH, CA(Oh)2and tBuO-TO+when using mainly gram-equivalent primary jamesii salt precipitating agent (e.g., chloride). The desired salt precipitates. After filtering and drying the product melts and upon cooling solidifies in the form of flakes or balls, giving the adduct used in the present invention. Thus, the prepared adduct is particularly suitable for its treatment and for their inclusion in the cross-stitched joint.

Getting adduct described in the application for the European patent EP 684277 on behalf of the applicant, given here as a reference.

Curing the mixture contains, in addition:

i) one or more inorganic acid acceptors selected from those known in the curing ion mechanism vinylidenechloride copolymers, in amounts of 1-40 parts per 100 parts forecasting copolymer;

ii) one or more basic compounds selected from those known in the curing ion mechanism vinylidenechloride copolymers, in amounts of from 0.5 to 10 parts per 100 parts forecasting copolymer.

The basic compounds mentioned in paragraph (ii), usually selected from the group of CA(Oh)2, Sr(OH)2BA(OH)2, metal salts of weak acids, such as, for example, carbonates, benzoate, oxalates and phosphites of CA, Sr, Ba, Na and what it should be mentioned MgO.

The specified number of connection components correspond to 100 phr of a copolymer or terpolymer invention. Other standard additives, such as thickeners, pigments, antioxidants, stabilizers, etc. can be added in curing compound.

In addition, it was found that the caulk forecaster of the present invention can find use as gaskets, seals for shafts, sleeves.

They are also suitable for gaskets with metal inserts used for parts of large dimensions for the automotive and chemical industries. It is well known that for items of considerable size, the curing process is extremely difficult.

For these applications forecaster of the present invention after curing under pressure at high temperature, mainly between 170 and 230oTo show the values of the target properties, such as mechanical properties and residual strain in compression, already matching their final stable values. This means that at high temperature operating conditions, mainly between 100 and 200oWith the values of the final properties remain almost unchanged Uchenie few minutes, mostly within 10 minutes, reaches values lower than 30%. This is a low value, which is required for these types of industrial products. This result is obtained without the need for a long time and high temperature subsequent curing process.

When you need a higher chemical resistance, such as higher resistance to polar solvents, can be used in formulations based on WDF and other above-mentioned comonomers, in mixtures having a content of fluorine is higher than 68% by weight.

The present invention will be better now illustrated by the following examples which are only illustrative purpose, but do not limit the scope of the present invention.

EXAMPLES

Obtaining a microemulsion.

In a glass reactor equipped with a stirrer, under mild stirring, the following components to produce 1 kg of microemulsion served as follows. Corresponds to the volume is equal to 782 ml

1)170 ml of acid introduced into the reactor, which has an average molecular weight of 600 and has the formula:

< / BR>
where n/m=10,

2) added 170 ml of 30% aqueous emulsion of ammonium hydroxide;

3) added 340 is UB>2-CF(CF3)O)n(CF2O)mCF2COOH,

where n/m=20, and having an average molecular weight of 450.

EXAMPLE 1

21 l horizontal reactor, equipped with stirrer working at 50 rpm, put 15 litres of water and 150 g of the microemulsion obtained according to the described procedure.

The reactor is heated to 122oC and then brought to a pressure of 35 bar relative supply of monomers up until you receive the following composition of the gas phase at the reactor bottom:

WDF=53% moles of HFP=47% of moles.

After the introduction of 12 g durational of butylperoxide (DTBP), the reaction begins, and the pressure is kept constant throughout the polymerization by feeding a mixture consisting of:

WDF=78.5% of moles

HFP=21.5% moles

After a predetermined amount of unreacted Monomeric mixture corresponding to 4500 g, the reaction is stopped. The total time of polymerization is equal to 265 minutes.

Latex having a concentration of 271 g/l latex is then coagulated using an electrolytic agent (aluminum sulfate), washed, and dried at 80oWith in 24 hours.

The obtained polymer shows viscosity by viscometer Mooney ML (1+10 at 121

Other chemical, physical properties, characteristic viscosity and performance polydispersity, obtained by GPC, are presented in table. 1.

The material was characterized as in table.2A. Ml means Royal 50/50 blend by weight of bisphenol AF with Tecnoflonthe copolymer 80/20 by mole WDF/HFP; M2 mean uterine mixture of 30/70 by weight of 1,1-diphenyl-1-benzyl-M-diethylethanamine. Viscometric, ODR, mechanical and residual strain during compression of data with different times subsequent curing are presented in Tables 2A, 3A, 2b and 3b.

EXAMPLE 2

Using the same reactor as in example 1. Material loading, mixing, temperature, pressure, initial load and conditions for the continuous feed of monomers correspond to example 1. Also in this case, 12 g DTBP serves to start the reaction.

In addition, 30 g of 1,6-diiodopentane (C6F12I2as agent transfer circuit in the form of a solution obtained by dissolving it in 18 ml of GaldenD02, served before the beginning of the reaction.

Add the following bis-olefin:

CH2=SN(CF2)6CH=CH2.

Initially added amount equal to 0.23 g, dissolved Each add-in is initially added to the number.

During the reaction, in addition, 6 g DTBP add after 300 minutes and 2600 g of unreacted monomer.

The reaction is stopped after a predetermined amount of unreacted monomer equal to 4200 g, which corresponds to the total time of polymerization of about 430 minutes.

The resulting latex having a concentration of 250 g/l, coagulated with aluminum sulfate, washed and dried at 80oWith in 24 hours (see the procedure in the description).

The resulting polymer has a viscosity by viscometer Mooney ML (1+10 at 121oC) equal to 39.

Analysis19F NMR shows the following composition:

79.2% by moles of HFP, 20.8% by moles of the WDF.

Other chemical, physical properties, characteristic viscosity and performance polydispersity, obtained by GPC, are presented in Table. 1.

The material was characterized as in table.3A, and viscometric, ODR, mechanical and residual strain during compression of data with different times subsequent curing are presented in Tables 3A and 3b.

EXAMPLE 3 COMPARATIVE

In 10 l of a vertical reactor, equipped with stirrer working at 545 rpm, enter 6.5 l of water. The reactor is then heated to start the second. HFP=47% of moles.

Then start reaction by addition of 9.8 g of ammonium persulfate in 150 g/l aqueous solution.

During the polymerization reaction pressure remain constant addition of monomers in the following molar ratios:

WDF=78.5% of moles

HFP=21.5% moles

After 120 minutes and the flow rate of the Monomeric mixture 2800 g, the reaction is stopped.

The resulting latex having a concentration of 350 g/l, coagulated ammonium sulfate, washed and dried at 80oWith in 24 hours, as in example 2.

The obtained polymer shows viscosity by viscometer Mooney ML (1+10 at 121oC) equal to 32.

Analysis19F NMR shows the following composition:

79.0% by moles of HFP, 21.0% by moles of the WDF.

Other chemical, physical properties, characteristic viscosity and performance polydispersity, obtained by GPC, are presented in Table.1.

The material was characterized as in table.2A, and viscometric, ODR, mechanical and residual strain during compression of data with different times subsequent curing are presented in tables 2A and 2b.

1. Caulk copolymers vinylidenefluoride and hexaferrite comprising 60-85 mol. % vinilnih monomers, representing highly stable spatial structure and having a residual deformation under compression below 20%, without curing or subsequent curing time less than 30 min, obtained by curing ion mechanism corresponding uncured copolymer with 0.5 to 15 hours at 100 hours of curing copolymer and from 0.05 to 5.0 hours 100 hours copolymer accelerating agents, and the uncured copolymers obtained from the polymerization of the latex, after coagulation, washing and drying have a Mooney viscosity (ML 1+10 at 121oC ) from 15 to 150, after the heat treatment at 250oC for 1 h did not show in the analysis of infrared spectroscopy by Fourier transform (FT-IR) the presence of peaks, and/or strips and/or halos double bond - CH= CF - frequency of 1720 cm-1and show before curing kDa in size-exclusion chromatography polymer fraction having a molecular weight lower than 10,000, the amount less than 3 weight. % when the Mooney viscosity (ML 1+10 at 121oC) equal to 20 and less than 0.5 weight. % when the Mooney viscosity of 50.

2. Caulk copolymers under item 1, characterized in that the copolymer comprises 75-80 mol. % vinylidenefluoride and 20-25 mol. % hexaferrite.

3. Response the data from tetrafluoroethylene, (lane)peralkaline, CF2= CFORfameans (lane)foralkyl1-C6.

4. Cured copolymers according to PP. 1-3, characterized in that the copolymer comprises from 0.01 to 1 mol. % fluorinated bis-olefin.

5. Cured copolymers according to PP. 1-4, characterized in that the copolymers include 0%-10 mol. % of units derived from non-fluorinated C2-C8olefins.

6. Caulk copolymers under item 5, characterized in that the olefin is ethylene.

7. A method of obtaining a solidified copolymers on PP. 1-6, including the production of relevant uncured copolymers on PP. 1-6 by copolymerization of the monomers in aqueous emulsion in the presence of an organic peroxide at 100-150oWith subsequent curing ion mechanism from 0.5 to 15 hours at 100 hours of curing copolymer and from 0.05 to 5 hours to 100 hours copolymer accelerating agents.

8. The method according to p. 7, characterized in that the organic peroxide is selected from: (a) dialkylamides, where alkyl has from 1 to 12 carbon atoms, for example, durational butylperoxide; (b) dialkyldithiocarbamato, where alkyl has from 1 to 12 carbon atoms, for example, diisopropylperoxydicarbonate; (C) diarilpirimido, where the acyl innych atoms, for example, tertBUTYLPEROXY.

9. The method according to PP. 7-8, characterized in that it also contains a surfactant.

10. The method according to p. 9, wherein the surfactant has the General formula

Rf-X-M+,

where Rfmeans (per)alkyl fluoride chain WITH5-C16, (per)ftorpolimernoj chain;

X is-COO - or-SO3-;

M+selected from H+, NH4+, alkali metal ion.

11. The method according to PP. 7-10, characterized in that the present agent transfer chain.

12. The method according to p. 11, characterized in that the agent transfer circuit selected from a number of: hydrogen, hydrocarbons having from 1 to 12 carbon atoms, Methylcyclopentane, chlorine(fluorine)hydrocarbons having from 1 to 10 carbon atoms, optionally containing hydrogen, esters, alcohols, ethers having from 1 to 12 carbon atoms, iodirovannoye and/or brominated agents transfer chain, with compounds of General formula Rfb(I)x(Br)ywhere Rfbmeans perfluorinated hydrocarbon radical containing from 1 to 8 carbon atoms, x, y are integers, concluded between 0 and 2, with at least x or y = 1 and x+U2.

14. The method according to p. 7, characterized in that the curing agents are selected from polyhydroxylated, aromatic or aliphatic compounds or derivatives of them, preferred bisphenol AF.

15. The method according to p. 7, wherein the accelerating agent is selected from Quaternary ammonium or fofanah salts, aminophosphonic salts.

16. The method according to p. 15, wherein the accelerating agent is 1,1-diphenyl-1-benzyl-N-diethylethanamine and/or tetrabutyl phosphonium.

17. The method according to PP. 14-16, characterized in that the accelerating and curing agents are combined in the form of the adduct in a molar ratio of from 1: 2 to 1: 5, preferably from 1: 3 to 1: 5, in quantities from 1 to 5 hours to 100 hours copolymer, and optional excess presence of an accelerating agent in relation to its content in the adduct, preferably in quantities from 0.05 to 0.5 hours at 100 hours copolymer.

18. The method according to PP. 14-17, characterized in that the curing compound contains: (i) one or more inorganic acid acceptors selected from those known in the curing ion mechanism vinylidenefluoride FOSS known cure ion mechanism vinylidenechloride copolymers, in the amount of from 0.5 to 10 hours 100 hours copolymer.

19. Industrial product derived from hardened copolymers vinylidenefluoride and hexaferrite on PP. 1-6, made in the form of gaskets, seals for shafts, sleeves and seals with metal inserts.

 

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