BE733916A - - Google Patents

Description

  

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  Process for the production of polymers of tetrahydrofuran

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This invention relates to processes for producing polymers of tetrahydrofuran, and, more particularly, it results in an improvement of such processes. hence polymers of tetrahydrofuran are produced in appreciably improved yield.



   Pure tetrahydrofuran is polymerized in a substantially anhydrous system, in the presence of one or more catalysts well known in the art. As used * herein, the abbreviation THF refers to tetrahydrofuran.



   The present invention provides a process for polymerizing t6trahydrofuran comprising the steps of: (1) contacting t6trahydrofuran = anne and a tetrahydrofuran polymerization catalyst selected from the group consisting of: (ClSO3H); (FSO3H); $ (HClO4); (H2S2O7); (HIO3); (SbCl5); (SnCl4); (BF3); (PF5);

   (Li + PF6-); Lewis acids in the presence of a member selected from the group of epoxides, acid anhydrates, and a halogen-containing compound active strong acids in the presence of an acid anhydrous; mineral acid anhydrates in the presence of a member selected from the group consisting of mineral esters and acid halides of compounds containing carbonium ion; compounds containing the diazonium ion: and tertiary oxonium compounds; said contact being carried out at an average contact temperature of between 20 and 80 C, thereby forming a catalytically active mixture:

   (2) cooling the mixture below the cooling threshold temperature, said cooling threshold temperature being defined as being
5 C lower than the maximum contact temperature when the maximum can reach 37 C. and said threshold temperature is defined as 32 C when the maximum contact temperature is greater than
37 C.



   (3) maintaining the mixture resulting from step 2 at a temperature below the threshold temperature for a period of up to 4 hours;

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 (4) mixing the mixture resulting from step 3 'with a catalytic activity terminator, in an amount greater than the stoichiometric amount calculated with respect to its reaction with the catalyst;

   and (5) maintaining the temperature of the mixture resulting from step 4 below the threshold temperature until the catalytic activity is terminated, the time interval separating the contact from step 1 and the time at which the threshold temperature is reached in step 2, which can reach 240 minutes when the average contact temperature can reach 50 C, and for an average contact temperature between 50 C and 80 C, this interval of tempe is a time that can reach the time corresponding to the temperature on a regular part of the temperature curve as a function of the time that passes through the tips:

     
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   An object of this invention is to provide a process for the production of polymers of tetrahydrofuran, with considerably higher yields, and a considerably shorter time, than those obtained by prior art processes which are otherwise equivalent.



   Another object of this invention is to provide a process for the production of polymers of tetrahydrofuran, providing efficient use of a catalyst, as evidenced by the number of moles of polymer formed per mole of catalyst.



   Another object of this invention is to provide a process for the production of polymers of tetrahydrofuran, whereby tetrahydrofuran is polymerized with high catalyst efficiency, at temperatures below 32 ° C and even below 20 ° C.



   Another object of this invention is to provide a novel process for the production of polytetramethylene ether glycol,

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 :: CU :: ". 1.::::a."l these very high yields, in relatively short times, with high catalyst efficiency.



   Another object of this invention is to provide a process which gives improved yields of tetrahydrofuran polymers without the need to crystallize the active polymers in the reaction mixture.



   These and other objects, which appear herein, are achieved according to this invention by a process for polymerizing THF, comprising the steps: (1) contacting tetrahydrofuran and a catalyst for polymerizing tetrahydrofuran, at a temperature
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 contact temperature between 200C and 80C, thereby forming a catalytically active mixture: (2) cooling the mixture below the cooling threshold temperature, said cooling threshold temperature being defined as so many
5 C lower than the maximum contact temperature when the maximum can reach 37 C, and said tem-
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 renil temperature being defined as 32 "C, when the maximum contact temperature is greater than
37 C;

   (3) maintaining the mixture resulting from step 2 at a temperature below the threshold temperature, for a period of time up to 4 hours; (4) mixing the resulting mixture from step 3 with a terminating agent for the catalytic activity, in an amount
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 greater than the quantity 8tofcbiC86tri.que calculated with respect to its reaction to the entalyseurt and (5) maintenance of the temperature of the rebellant mixture of step 4 at <t-4m o <M of the t88p6rataEe of * mile jos¯ that ' until the catsiytiqoe mit taadnte activity, the temperature interval expires the contact of stage 1 and the moment when the threshold of stage 2 is reached, which can reach 240 minotee qa8I4 the average temperature of con - tact can extinguish 3Oc.

   and, for the same temperetour average of 0C8pri- contact between 90 * C and MC, this teeme interval is a temple capable of: attaindwa the t8IIp8 oocrapoort 18 t: Y'-aU & 9 on a degvli6n part of the temperature curve in tomctiea of tempe which passes through painted IT

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 SOOC 240 minutes ".
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<tb> 55 C <SEP> 200 <SEP> minutes
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<tb> 65 C <SEP> 90 <SEP> minutes
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<tb> 70 C <SEP> 45 <SEP> minutes
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   A more specific embodiment of this invention is the process comprising contacting THF and a polymerization catalyst at a temperature above about 20 ° C.
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 thereby a TUF-catalyst-polymer mixture, catalytically active, cooling the active mixture to a temperature.
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 temperature below about 15 ° C., and mixing the cooled active mixture with a catalytic activity terminator, at a temperature below about 15 ° C., until the catalytic activity is substantially terminated.



   A preferred embodiment of this invention is a process comprising the steps of: (1) contacting tetrahydrofuran with a catalyst of
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 polymerization of tetrahydrofuran selected from the "" group consisting of fluoeulfonic acid, perchloric acid and phosphorus pentafluoride, at a contact temperature within the range
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 from 2'.C to 50C. for a period of up to 4 hours:

   (2) xrtroidisaeweat of mixture resulting from step 1 Cta-ae880U8 of the temperature of the cooling threshold temperature, said cooling threshold temperature being defined as being SOC lower than the contact point 18 when 1 ....... à- can reach 37 C, and said threshold temperature
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 being defined awre being 32.C. when the contact temperature madmle is 8ap6ri.eare at 37 Ci (3) oemntion of the new angel met from step 2 to a tu ....- aW1: '8 b, * 4rt¯x. i la t .If lIta1: 8 of 881d.l during a tempe lape can atU1Dc1n 4 beana, fez.) mix of the d8a1t: 8Dt mixture: from step 3, with an agent of JII8I8OD of 1 '** iVi% catalytic, quantity 1-.ze to the quantity 8t '. produced by nqoed a - reaction aeae on aauJ.r81:

   

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 (5) maintaining the temperature of the mixture resulting from step 4 below the threshold temperature until the catalytic activity is terminated.



   The polymerization catalysts used in this invention are any well known catalysts for the polymerization of THF. These catalysts include all catalysts selected from the following groups: 1. Strong acids giving anions which are weak nucleophiles such as (CISOH). (FS03H), (HC10), (H2S207) '(HIO3);
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 2. Metal halides such as SbCl, t SnCl4, BP 3: 3. Non-metallic halides 1! Is that BF 3 # PF 5: 4. Non-metallic halides such as BF3 in the presence of a) H2O, b) PeC'3 ' c) diazole compounds, eg diazotized ethyl acetate, diazomethane: 5.

   Friedel-Crafts halides (Lewis acids) such as
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 Alci 3 # BP 3 'FeCl3, Sbcist Snc14' in the presence of a reactive halogen, such as: (a) Alkyl halides, for example, CH3OCH2Cl,
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 CC1 (CBz '; 20.1 C2HSF. COa (CBz'4Cl; (b) Acid halides, for example, CHCOCl, C6H5COCl,
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 poe'4, SOC12 'C6H580ZC3' (c) Halogenated acids, for example, HCl;
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 (d) Other metal halides, by ample, ABC13 'Sbci3a S'C'4, TiCl4, ZltCl2' zrc'4; (e) Non-metallic fialogens, by comple, OC1., Br3 'PC'3 1 mis 0 SC'2 - S2Cl2' (f) Aryl chloride * 1880ni \ 8, by, C611s82Cl.



  6. Ilalog6Dan. of Prieoel-Crafte (Lewis acids) such as AlCl3, 3.parA3 # obel5l snc'4, in pr61N8D08 of epoxides such as 11 GKyd8 of ethylen *, axyd8 of pz'OpfltD8, oay4M of baqltn8, 10 1 & w oxide, lobaIo8 oxides, epidtiothydrinw, bvtaaüns bicaqrde, 1 "" ", b18cb1oftl8fthyl llG186tan8., 1,4 fl-w 7. Strong eaid88 such as BC104. Ra80., in 6MDae
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 4 'Aid²- de 8eide tltll que (#, CO) 20 # 00 %% 0

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 8. Friedel-Craftn halides (Lewis acids) such as AlCl3 'BF3' FeCl, 8 SbCl, in the presence of anhydrides
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 of acid such as (CH3C0) 20, C82CO, * Co C82CO 1 - *, 0 (i CO "CH 1 CO" "cor 9.

   Anrydrides of mineral acids such as 503, in the presence
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 of: (a) mineral esters, for example, dimethyl sulfate;
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 (b) acid halides, for example, c6H 5COC1, phos- gen 10. Compounds containing the carbonium ion such as triphenylcarbonium hexa-chloroantitaonate, hexafluor-. triphenylcar! 1ium pbosphate, tropylium hexachlorosntimonate 11. CC8p0 ". containing the diazonium ion such as para-chlorophenyldiazonium hexafluorophosphate; 12. Tertiary oxoalpha compounds such as tri61: hyloxoniua tetrafluoroborate prepared, for example, by reacting boron trifluoride thethride with γ-epichlorohydrin. Li + Pr-.



  P1U8i.ut of ci. Catalysts produce polymers of tftr "t1" "oxide having various end groups.



  A particularly important ethylene oxide polpho is polyethylene glycol: et: hylan, 4 hereinafter BOM. Preferred aatalysts for the manufacture of ipTll are fluorescent acid, perchloric acid, and phosphorus iron.



  As used herein, the contact t- / erature rqppts at the Average contact leepestuse, skipping the appropriate indication. The preferred contact tures are the t- rature in the interval of. about 25 C about 5O C. ael qat it is aUU86 here, the average tex "t8llp6rI.tw:e of 0ont4mte is defined CI 1 being Au in the eotpreaaion
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 EMI8.1
 where the sum symbol t has this usual meaning, the t represents the ok the '1' npr6MDto the teapisature in degdl centigrade. To illustrate the use of this formula to determine the contact teup6 atu 110] t81U18 for a particular production test, one can
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 1.plot the curve of t8IIp6ratun versus temple for particular operating conditions # 2.

   Split the curve in increments1..² \ ITt., By mple, a regular cut for a 4 hour contact tehtpe at elevated temperature can be crossed in increments of 10 minutes, but a curve varying in a way The greater of a half hour contact time at a higher elevated temperature can be broken down into one minute increments of the time used to calculate the average contact temperature from the addition of the catalyst and ending when
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 the cooling threshold temperature is reached in step Zt 3.

   aerate each increasing average temperature by adding the temperature at the beginning and end of each increase and dividing each sum by two;
4. Add all the mean values of the rising temperatures and divide the sum total by the time elapsed. The result is "@", given above, ie, the average contact temperature for the particular test.



   Polymerization conditions determine, to a large extent, the molecular weight of the polymer. for example, the report
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 molar catalyst - TOF helps determine the molecular weight of the polymer. If you want to have a product with a molecular weight more
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 low, it is necessary to employ larger catalyst: THF ratios for a specific set of conditions. Therefore, this invention is not limited to the use of particular catalyst ratios. The preferred ratios, however, are in the range of 0.01 to 0.25 moles of catalyst per mole of THF.



  At a given temperature, the molecular weight first increases rapidly to a maximum, and then gradually decreases to a lower, practically constant value. So,

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 shorter tempo * lead to a weight 8016cùùJ :. opl \ at - lli'av..pou .: a. t, -4ap6r & tu and a catalyuur.'1W ratio given *. 1-A "molecular po140" text as it is termed herein, restricted to aoyeooe vals. laspolyariaatior medium titsahyds values. It has been reported that the polymerization of tetrahydrofuran takes place regularly at low t88p6xatw: .. for example 0 C-5 C, and, also, that at a temperature below about 20 C, the rate of the polymerization of tetrahydrofuran is too low. to have industrial utility.
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  However, when t6trahydrofuram is polymerized according to this invention, the molecular weight, instead of continuing to decrease, suddenly increases when the active THF-catalyzed mixture.
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 ly.ur-polY1Mxe is cooled to the lower temperature.



  Longer times at a lower temperature now lead to higher molecular weights, unless a substantially constant molecular weight is obtained. This usually occurs within a one to two hour lapse of time at the lower temperature. There is also a sudden increase
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 tion of the polymer yield when the THF-ketalyst-polymer mixture is cooled to a lower temperature, according to this event, particularly when the temperature is lowered to 2 * F * C and below, for example, at below about 15 * C, and more preferably below about 10 C.

   The lower temperature is at least 5 ° C lower than the contact temperature and preferably at least 10 C lower than the contact temperature. In general, the greater the temperature drop, that is, the greater the difference between the contact temperature and the termination temperature of the catalytic activity, the more the yield increases, until l about 0 C. Although temperatures below 0 C. are useful, they generally do not provide an increase in yield over that obtained when the reaction mixture is cooled to about 0 C. In addition, the viscosity of most polymers becomes very high when cooled below 0 C.



   After having brought the THF and the catalyst into contact, at a contact temperature above 20 ° C., the mixture is preferably cooled.
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 The resulting THF-catalyst-polymer mixture is below 15 ° C, and more preferably below 10 ° C, the temperature at which the catalytic terminator is mixed therein. , and the temperature is preferably kept below

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 of about Isoce and, more preferably, - ¯1780'- d '..., izaD 10'C, until the catalytic activity appreciably twr- 1IiD6e.



  Numerous 1 (. (It .......... here illastrsraat that the eusmttnte- tion of the render this striking * and immediately when the temperature is lowered, and that the variation dG: RD-- - pEQQIIi. poew the most gr) md <part, d8D8 the pn8i.itn8 minutes waivamt the rwfroi- dissarnt. The addition of ... glac6a in 1861 ..... ioan81. that is to say, the active ailaoge 'IIII'-cat.alY88UE'-pol. Qoaad the reaction mixture is at the t -, .. 6ratu: e of contact, pEOda1 not of unexpected advantages for this invention and is not in accordance with the invention.
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  Of number.-1 .. don ... here illvastrero4t 6galt (see Ex (.1. 7) that the lowering of the t-TP8tu: e must take place at the specified lover in order to achieve 1 mw-tatioo of the yield. Therefore, if the reaction-mixture is Mintenn at high bIIIp6- erasures, that is, above 50C, for laypit of teeps greater than those specified, by eateaple, for two hours at 65 ° C or for 30 minutes at 75 ° C, the cooling step has no appreciable effect in increasing the yield over that obtained at elevated temperature.
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  In the embodiments using contact temperature below 50 ° C., it is preferred that the time during which a temperature above the threshold temperature prevails is less than or equal to 150 minutes, this being followed by a time.
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 or it is not found at a temperature below the threshold temperature less than or equal to 150 minutes before adding the agent for terminating the catalytic activity.



   Many agents are given by the prior art
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 for the termination of the catalytic activity for an active mixture 'IIIF-polymer-catalyst. The reaction by which the teaining agent deactivates the TBF-catalyst-pelymere mixture is not fully understood. However, she is extremely fast
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 and exothermic. By simply contacting the active mixture with a terminating agent, the almost instantaneous 1: 8 ... -in 80D of the catalytic activity is obtained.

   Although cm does not want to be a prisoner of any theory, the following theory, which is based on experience, may be valid for various results which can be obtained when the catalytic activity of various active agents.

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 'I8'-sol.peu.r is terminated by -long of 1 enu. This poatal theory 1'881-- of a dissociated 08DDiwa ion. we make a hypotbbae that this ion can form a bond with an anecule of UU8bydnfu811D8 which then opens a cycle, and this results in a longer eatoniom ion. this longer oxmium ion reacts with another ketrahydrofurano molecule, again the ewle opened. and a longer oxonium ion encoxes is obtained, and so at night *.

   In this way, one makes the assumption that the ioDe ommim are r8pi ,, - "'¯t of the chains of po3yeès loagoea, c8talyUt., Dt., Or makes 69 & lmmnt the assumption that the polymerization activity doum chatae of polymers cat: alytiq1: M! 8Dt active, z namely an oaonisw ion, which is therefore supposed to be the 'active' species of the active catalytic mixture of the IIF-c: atalpeur-polymer. is terminated when this dissociated oaiooniua ion reacts to form n any undissociated CC8pUs6 For example, water is believed to react with the active oxonium and destroy it by forming an unreliable alcohol.
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 dissociated, and atom therefore the continuation of polymerization.

   Else. bodies, for example HC1, can react with the oxonium ion, and thereby produce a stable, sound-dissociated, non-polio! -rising species, that is, a species having a chlorinated terminal group. stable, according to theory. We notice that this destruction
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 of the active polyaerizing species is identical to the termination of the 'catalytic' activity of a polymer chain and that the destruction of the catalytic activity of all the chains is identical to the termination of the catalytic activity of the mixture
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 active 2lW-catalyst-polyuea.



   So, theory suggests that termination of catalytic activity may involve different chemical reactionsa from the simple destruction of the 'catalyst', for example, acid
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 fluo8Ulònique, by its reaction with the deactivation reagent.



  But whatever the mechanism, the ease of contacting an adequate amount of an activity-terminating agent with the
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 catalytically active mixture of bW-catalyst-polymer, in general results in an almost instantaneous sound of catalytic activity. However, the catalytic activity terminator is consumed by its reaction.

   If we use a quantity
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 less than the ..C8etric amount, calculated with respect to its reaction with the catalyst, the catalytic activity of the -catalgsenr-polynere mixture may not be completely

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 finished.
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 The use of an inhibitor of insufficient activity
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 sant can lead to the formation of a polymer having
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 end mente resulting from the action of 11 e; .êc: e active and a decomposition product of the catalyst.

   By .....- 1., It was shown that the nature of the catalyst, and that the nature 0.9. produced from the catalyst, influence the nature of the undissociated compound formed when the catalytic activity of a T8F-mixture: assists this pre-watered terainie, in particular if the water is not suitable for the reaction in large quantities. It has been shown that when the catalyst reacts with water, it can form various reactive decomposition products, such as organic acids or midcial acids (for example, from the decomposition of 8DhJdrid88 or b8log6r.ô1E88 dlacyl) t such as hydrohalic acids (for e! Mmple, from 'hydn-1.Y88 of certain companies containing a halogen).

   We still make the hypothesis that this composition is made with water for the reaction to the active cteonium ion euppoeée, to form innctive and non-c11811OCi ... opu ate terminMOt. aluool, par. ¯1., -CI, -Q71. So this theory can help A 88pU.qaer the fact ... dee, J :(. 411P, ta terminals other than the hydroxyl gicoupemaMt pnisssst etze tonate when the catalytic activity of um 1161 ... active is tezainée in pc (.T cS'88U.



  U8DIJ GD wishes to have a terminal b / l moHpmaant, it is preferred that the c: at: a1 801t teoatnée activity per m6lmge of the melune @me of the .... ea qpmutft m great moult by y these cyt 4 quantity etaéchioaetztqee R1al..atn texalaer activity cat: a1] 't1c88 of 861 ....- ...... 111., d88 - preferred embodiment pmr p8siro 18 - teatime "1 tivitâ eetalytiqme du melanae ea adding 0 - from to 5GO 81 1 ...'- cold per size of C! IIt: a1p. ", Vy3 s ... 1 ..- JI. one of enauzw la, m 1 sas-1si, of "-" "" A.18 .. 18 Il '' J - - ..lua pI. He laailitd dm maints "4 18 el m e..iw .. d68id. T'oetivity 08ta1 ... daimme eett JI88 & 49almm * ets- ternie" Pm m 8I-t ... have mute drom. Pm 1 J18. l'.uftd and "'' '' '1 ..if .. Ut8l..8t- ..1. 1 .... an tsaastaie Pm da 9.s 1¯¯ .. - mà ,, - - - .11 - for an -. 1--11 J t fi ........ I. "" "7i, .14

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 hydroxyl.

   Alcohols selected from the group of primary and secondary monohydro-xyl alcohols having 1 to 5 carbon atoms, or
 EMI13.1
 although from the group of primary dihydric alcohols having 2 to 6 carbon atoms, can also be used to terminate the catalytic activity. In this case, ether bonds are formed. The use of glycols as agents for terminating the catalytic activity results in association and terminal hydroxyl groups. For example, when using water or 1,4-butanediol to terminate the catalytic activity
 EMI13.2
 of a THF-catalyst-polymer mixture such as a THF-fluoeulfonic acid-polymer mixture, it closes from EGP'1'M.

   Therefore, the catalytic activity terminators used to terminate the catalytic activity of the active HF-: analyzer-polyi8h'e mixtures of this invention are any well-known agents in this regard, for example. example, water, ammonia, amines, alcohols, glycols, and mixtures thereof, among many others.



   In addition to reactions with activity terminators and with decomposition products, the active THF-catalyst-polymer mixture can react with certain catalysts to form
 EMI13.3
 stable structures which do not polymerize, for example esters. Therefore, these end groups (thus fumet) must be hydrolyzed whenever the maximum HGPTM randamments are desired. It will be noted that the termination of the catalytic activity by addition of water is not identical to the hydrolysis of these more or less stable end groups.



   A preferred embodiment of this invention comprises mixing a suitable catalyst and THF, at a temperature.
 EMI13.4
 compriee between about 230C and soec, preferably about 35 ° C, and hang a buffer lap of less than 4 hours, and maintaining the stelenge sati! r68u1.t: aDt: 'IRF-polJllk8-eat: alpear to a t:

   (4- ratu lower than SoeC # of pz iferam at around 33-C, followed by refm14i.s.lnt of 1I6l .... = Ut '1W-polMU' at ass temp Mother inferior to about 20'C, 48 way pl- prefer- ate to test stMt'e idl1..n at around 15 * C, and the 88iDt.i- da ..1-- .... tmoperetare inferior to around 208C, so more prematurely at full inferior to otviron beak, âs pdHnaa8, t - lape of totpe inferior to about 4,118 ... oek the terminitan of D8ClUriW aalslyliqoe, and ....- te, the 1111II1II8 of native metenoe cooled with agart in 8th temsineieon ua the 8Iftid '"aaAl, and the mainum dia 811 ... siraltaot

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 EMI14.1
 at sight temperature below about 2O.C. it, -de -faiJo pi ... preferable, above about 15 ° C, jll8lJ1l8 - that the # DIÏDai- mon of Catalytic Inactivity is admirably COIIIplêt: e- A aui;

  re 80de de rEa1isatioa pre ± 6rE of c: ett: e: i.awe! 1t: ion is; 1st p for the pzoëiact: iOD of BtiHIt --.- eoaDt: 188 following steps: a (1) caatact of and a c: abI1ysear of po1} '116ri- satioa i! me to be contacted at e: ariran 2o C, (2) cooling of .nauge 1t + t of 18ftap6 1 to nme tus- p6ratare plus balee which is inferior to! avirnn 2S.C. and iDf6- rfeurc d. an 8OÍ! I8 SOC at 1aaU: and: "± contact c., and (3) nélaage of the cooled mixture and a catalytic inactivity termimdmm agent at 1 eairoa 'C and i ... a8 .. 8DÍD8 sec to l.8U.t: and - .8 from. JU8q1l8 until 18 aet: i. ,, t: .6 catalytic or 88D'rib1 tormi - ..tue6M for a4oa-d.re.

   Ad W ¯IGD c: ett: e 1DwDt: ioD e.oc1 1ea ft ... ed ..... s (1) CIDDt: 8eI: cJa 'IIIP and :. of a -: at: a1 of by C '.. ,, - 1. l 'c1d8 i'1aoeô1l.- 6JD1qa8, a ... t ¯' ± "'. 1 ... 48 a etlri.aID zoec. forming an ailaoge cet- 9 aet: 1 ± 211F-cau1-po1r - 1Ik8. (Z) = rfàiss.n.nt aa aElange sialtaat àe 1 stage 1 to .... t --ab1Z8 qui. 88t: i.DHd ... a eari.Dz.oIIa 15ec :. and (3 ) "" 81119- da 1111 ...... 01- lIW'8e de 1'-. On bim - 1 - le with 1, -botanodioi oa xn ilamge aa ls- ac a.en, a-- t / nddd8 qai 8ft 1D & ri.ue a 8IIdza8 15- ':, j1l8lJ83 a ce CJ88 1 ** iOité eaba1.7t mit -----' h. ni qrra this iDlIIMUOIII paI¯ .. 'a d88 -..., ., .. pogr la u UoD .. poJJI! 't. - c1e ... - pd .. 8Dlf - I E8 aa.11 & - "" "",' aU 2GO 81: 1O.oao. it is - âar lns peoi la po8ac, .i, we lot. rls aant 8s lialalrs nor ierita a iras 5.000.



  ? at qa 'il ar! re-used i, d. the tome -tza o -etione 00 ....- ne - 10-: t J & .. 8 / I'A rh ..,. - .. e ... - fIIII.



  .'88 & ... U 1 1 a (IIIIftIr da "'4 ta1 ....., and they have -..-",' 1 ..: 1 .. "& .. -4.1:" 18 ea --- 4. 88iJa ... it & la-t.1c8 - ùùl.À à * la -1 µ - p "PMM alimm" il qnsl .c tüi id. 1 r. Sapoee. Aa ", -l r11- VI - ......... 18 - .... ....... & J ..t ll P. 8 & il ... 1 ..- .., -.... 18 -lin ....... Mr.

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 EMI15.1
 Weight of RRIIMÈM recovered at 100 regulclestent Weight of royalty bzz ¯ Weight of "IBF 'X 100-yield
 EMI15.2
 The term “loss” represents the percentage by weight of the feed which is not re-operated as monomer or polymer. In the
 EMI15.3
 The following ej (¯, 1ee, took great care to avoid aecanitlue losses, and the subsequent ether stripping of the aqueous washes indicated that most of the -loss- results from the extraction of the low molecular weight polymer. in the ravage water.



  Therefore, whenever the 1 = wage L 1 water procedures used in a number of THF polymerization trials are identical, the relative amount of 'loss' gives a good indication of the
 EMI15.4
 relative amount of soluble molecular weight fault polymer
 EMI15.5
 in Igem produced by the different polymerization processes.
 EMI15.6
 Note that if an appreciable amount of polymer is formed
 EMI15.7
 soloble c18IIII 1 .'..., WI8 appreciable amount of the tramfoil body is lost during the washing of the raw product, therefore, the transformation is 0oW high, and the efficiency may be low. Therefore, the problem of obtaining normal transformation accompanied by a low roadmunt is a particularly acute problem in the dentodaetion processes of low weight glycol polymers 16e81a1.z8.
 EMI15.8
 



  This Invention is illustrated in more detail, but is not
 EMI15.9
 limited pMr 1ms sMmpiss following, in which, unless indicated t & .. I.z8, the amounts given are in parts by weight, and the pdc18 mut the mean values calculated from - indic 4'.i18 of the polymer, on the basis of two = pe- sots haosle pdar polymer molecule.



  I have 481 tmia pdsert of polymerization sâseCi4ns were carried out using 4 rappokta Cllt: a1.pl.L1.12IIP which were supposed "'.4z' ... weight this po1 81IX at aiswnmimatjl- wrot 500. 100p and 350. EI8-.r4k! T: .iy r -. In each of these i JD111 "" 1: 11.81: 108, we used SOS parts of anhydrous top. 1 "" '11 .. Quality naNalfoniA \ w fluid trsehni.- 4tr (tilsat! "1, $ tit 11 Glue J071} was used in quantity he- to 18 ± .7. M, 4 and 38.0 parts for each of the tests con- e1: s111 A11 poias 11l, - ..- cUYS8M &, 500. 1COO and MOO. Se JI1.J .. ai - IJIII '- a lapse of time from a to 10 lablr, aaers doe CM. and, from chmm des en *, ca aLaeL! 18' - IL "'...-. Radale has earrfser 3Sec.

   In tones

 <Desc / Clms Page number 16>

 
 EMI16.1
 leu tent, 4.0 heun8 ce. '* = oul818Dt: since 1.' "tbt eo -in adjeute the eatalyeenr UNTIL C catalytic activity is KMcmiaée by addition of water, One of the additional tests 8s the concomitant pair each of the molecular weights was a "control" method reprHewtaat an 8Dt method; ûi. :: - .. The other saaai for each
 EMI16.2
 pair concerning the same molecular weight was carried out Ion
 EMI16.3
 this invention and one 1 '..- milk -retEoid1¯¯t and 8i88. IIOn8. In the case of the .d8DiD8 test, the ¯1aDy8 UuabckcIur8DD ... mother-catalyst pol was mninKMMt at ¯Y1E \ 8 3S.C for the entire 4 hours and, 8D8Ui.t8, 15m pextias of water were introduced with asbiant mole-rature Élan the 8I18D8 siactiomel, while shaking rigoreu8w-nt.

   In the case of OMai 8nfEOidi8 ..- nt and put 8Ort8, the m61anga ûtrabydrofuraGDe-polJMre-cat1yaeur was. kept at about 35 ° C for 3 bour ,, and then the mixture was cooled to about 70C and 0L1 kept it there until
 EMI16.4
 the catalytic activity ended with an identical addition
 EMI16.5
 of 1MO part * of water, 4 hours 8PE '.. the start of the reaction -
 EMI16.6
 tion of polymerization. All the tents were made with a
 EMI16.7
 proceeded identically, in the following manner at the sasss r64f..i?: melle deactivated - including the added water was heated for -: I, a ... r tetrahydrofuran and it was subsequently treated with steam
 EMI16.8
 during one hour. The aqueous layer is then removed, and another 1500 parts of water are added and the treatment is repeated.
 EMI16.9
 steam while stirring.

   The series of steps consisting of adding water, steaming during a batch, and separating the phosas is called CCIn8 a wash. A total of three of these scientific washes were used. After the final phase separation, the trimmed polymer phase was finally released by heating at 100 ° C for one hour at 0.2 µsi Hg pressure.



  We recovered e. in each of the tests, the BGPTM was weighed.
 EMI16.10
 



  The result of these polymerization tests is summarized in
 EMI16.11
 the able3u 3, in which the closed "yield", "loss", and "molecular weight" are defined above, the term reacted muon means the percentage by weight of the TW feed which is recovered as monomer after the retention of catalytic activity, and the term -differ, - e 71 'is the difference between the values for the cooled test .. s8'tCftt and ratt mine and 14 control test, experiment as a percentage by weight of the control test.

 <Desc / Clms Page number 17>

 



  TABLE I
 EMI17.1
 Weight 80160u- -¯ ¯ Rewind process (wire) Troidissemmt process Expected difference t6lo1D and 111 .. a
 EMI17.2
 
<tb> dead
<tb>
 
 EMI17.3
 (500) Mt m 48Q 581 aend888nt m 25.3 39t4 + 52% No r4agi m 37.2 29.1 --22% loss m 37.5 32, S -13%
 EMI17.4
 
<tb> @
<tb>
 
 EMI17.5
 (1000) PM 920 1080 itendarent 44.8 61.7 + 38%
 EMI17.6
 
<tb> No <SEP> reacted <SEP> - <SEP> 34.6 <SEP> 2S.5 <SEP> -26%
<tb>
<tb> Gate <SEP> = <SEP> 20.6 <SEP> 12.8 <SEP> -38%
<tb>
 
 EMI17.7
 (2500) PlI m 2220 2i66S Efficiency m 66.0 7588 + 15%
 EMI17.8
 
<tb> No <SEP> reacted <SEP> = <SEP> 29.0 <SEP> 19.4 <SEP> -35%
<tb>
<tb> Loss <SEP> = <SEP> 5.0 <SEP> 4.8 <SEP> + 4%
<tb>
 
Example 2
Three polymerization runs were carried out over a period of 4 hours.

   In each of these tests, 89.4 parts of fluosulfonic acid was added to 505 parts of anhydrous, freshly distilled THF, at room temperature, over a period of about 10 minutes. The reaction mixture from Test X was allowed to reach 35 ° C. and kept at that temperature for 4 hours. Four hours after the addition of the catalyst, 1500 parts of water at room temperature was poured into this reaction mixture to terminate the catalytic activity. Four hours after the addition of the catalyst in Run Y was completed, dry ice, i.e. solid carbon dioxide, was added to the reaction mixture to quickly lower the temperature.

   When the temperature reached 5.5 ° C, the catalytic activity was terminated by 1500 parts of water-ice mixture which was added to the reactor. Three hours after the addition of the catalyst in test Z, the reaction mixture was cooled by external cooling, to a temperature of 5 ° C., over a period of about 10 minutes, and kept at this temperature for 4 hours after addition of the catalyst. A water-ice mixture (1500 parts) was then added to the reactor to terminate the catalytic activity. The raw product mixtures from these trials were then

 <Desc / Clms Page number 18>

 
 EMI18.1
 treated ¯10- 1. p & "GcM8 U'a1tTÍ- Used dàé 11 Jil. 1.



  LrtttwttQrétMttéwdNMtlw b & e-1 xz, du.8 1. ". 1 1- @ m + -weight 8Dlflculain- and '* t <nd! MMnt * 80Dt defines CL-40 Us. And te = * 8d1ffÛ811C8%" Mptént la différa = * between the MMadMttat obtMMt da 11 ¯aa1 and the rea ----- t abteDa of 11..aU X, expressed <a pcM \ RI8DtllP - poiao cbrendumat obt <nu 4on 1 a a & * "X.



  TABLE II
 EMI18.2
 35 'Se P1I NMttMMnt Dlft6reace Ir.



  B888J. X 4 bour 0 920 14, 8 Test Y 4 hour. aoisats 934 49.4 + 10% Test Z 3 hour. 11 hours 1000 61.7; 379G
Example 3
Five rounds of THF polymerizations consisting of 22 individual runs were performed in substantially identical fashion except that the times and temperatures differed. In each one
 EMI18.3
 In the tests of this example, 505 parts of anhydrous THF ckstill6 was polymerized by the addition of 89.4 parts of fluorescent acid catalyst.

   In each case, the catalyst was added to the stirred THF over a time lapse equal to about 4 minutes.
 EMI18.4
 For comparison, we carried out a series of tests at 3 + c 2., and we carried out a second series at 6 C + 3 ', and it is clear
 EMI18.5
 that neither of these two series of tests was performed according to this invention. In a third series of tents the polymerization temperature was maintained at 35 ° C. + 2 'for one hour and the temperature was then lowered by external cooling.



  In this series of tests, the lower temperature, i.e.
 EMI18.6
 6'C + ¯ 3 * <was held for one hour, two hours,., And three hours. respectively, after the polymerization for one hour at 35 ° C. and before the termination of the catalytic activity. In the fourth series of tests, the polymerization step at 35 ° C. was maintained for two hours, the reaction was lowered. then the temperature and a second polymerization temperature was maintained at 6 C for, respectively, a quarter of an hour, a half hour, two and three hours, before
 EMI18.7
 that the catalytic activity is terminated.

   The series ciDquilrne was a single test in which the temperature was maintained

 <Desc / Clms Page number 19>

 
 EMI19.1
 of 3sec psodwt three Man..t dam which one .bà1..ai ;; 1. T rature at 6, OC, 18 Pt u hour before isacuvit6 ca.alyt: i.cue is finished.



     The catalytic activity was terminated in each of the runs of this example by adding 750 parts of water-ice mixture.
 EMI19.2
 pounded. The first series of tests was also cooled in an estesw fashion during the addition of the water-ice mixture, for aaiatetus i * tMO ['trtui: gold & * soue of 50 ° C during the addition. water-glms m6lane. The aerial n.ta. "1te. Were kept at an intd¯ilt1 t3 * C tavib6r & ture during the addition of the ice-water melena *.



  All the cases in this example were then treated identically, using a solvent recovery process which allows rapid purification and recovery of the polymer. The treatment process was as follows: all of the water added was heated to remove unreacted DIr which was recovered and d :: - .. 6. Steam was then introduced into the mixture. After one hour of steaming, the entire contents were cooled to above 84 ° C., and 866 parts of toluene were added, and stirred.
 EMI19.3
 igoureuaasat for about 5 minutes. after stirring has ended, it breaks down into two phases, and the top layer of toluene is removed.

   The acidity of the toluene layer was determined, and calcium hydroxide was added to the toluene layer to neutralize the acidity and provide a 10% excess of calcium hydroxide. The toluene phase was then subjected to azeotropic distillation to remove water. The substantially dry toluene polymer solution was then filtered to remove suspended solids. Volatiles were removed from the filtrate under reduced pressure, and the weight of the EGPTM residue, dry, and free of volatiles, was determined. The average molecular weight of each of the polymers was then de-
 EMI19.4
 terminated with lg index dlhydcoxyl.

   The yield of BGP'1'II, as defined above, obtained in these tests is plotted against the polymerization time in the graph.



  Curve A represents the results obtained for the series of tests at 35 C + 2 *. These tests are identified by the numbers 1 to 8 in Table III.L @ curve B represents the results obtained in the series of polymerizations carried out at 6 C + 3. These tests are identified by the numbers 9 to 14 in Table III. Curve C

 <Desc / Clms Page number 20>

 
 EMI20.1
 represents four of the ese "n which were carried out according to this
 EMI20.2
 invention. These polymerizations were carried out for two
 EMI20.3
 hours at 35 ° C + 2 * and ze% zoidi88ai.1t and then maintained at fi'C t 3 'for, WI.8D. 1ID quarter hour, half hour, 0. hour and two beaz88. before texminaiaon of catalytic activity. Tests on l-.qtl81. curve C is based on tests 18 to 21 in the -r8b1.81111 III.

   The time shown on the graph represents the time (hour) elapsed since the. end of 11 addition of the catalyst j1l8qQI to 1. -c: - - the dissivation of the catalytic activity. D8D8 Oeusa-4 e.ploy6ea conditions about 10 minutes were needed to lower the temperature of the DIP-c Mixture: ata1po1J i Ci of avirom 350C to about 6 "C, and this lapa of tt18F8 is 4-'1. ... the given duration dealbb
 EMI20.4
 here. So the first assay used to prepare curve C,
 EMI20.5
 who used two hours at eaviMM 35ex then a quarter of an hour at the lower teepératuze, actually repturing a 5 minute monk at about 6'C. The r68u1.bb are z66 "'.'" Table IIi, in which the tera are defined herein.

 <Desc / Clms Page number 21>

 



  TABLE III
 EMI21.1
 
<tb> Test <SEP> Time <SEP> (hours) <SEP> Efficiency <SEP> My <SEP> reaction <SEP> Loss <SEP> Weight
<tb>
<tb> to <SEP> 35 <SEP> (hours) <SEP>% <SEP> My <SEP> Molecular <SEP> loss
<tb>
<tb> ¯¯¯¯ <SEP> to <SEP> 35 <SEP> to <SEP> 6 <SEP> Molecular <SEP> loss
<tb> 1 <SEP> 1/4 <SEP> 0 <SEP> 54.6 <SEP> 44.0 <SEP> 1.4 <SEP> 1868
<tb> 2 <SEP> 1/2 <SEP> 0 <SEP> 57.2 <SEP> 42.2 <SEP> 0.6 <SEP> 1463
<tb> 3 <SEP> 1 <SEP> 0 <SEP> 59.9 <SEP> 38.3 <SEP> 1.2 <SEP> 1067
<tb> 4 <SEP> 2 <SEP> 0 <SEP> 58.6 <SEP> 37.6 <SEP> 3.8 <SEP> 735
<tb>
<tb> 5 <SEP> 3 <SEP> 0 <SEP> 60.2 <SEP> 34.8 <SEP> 5.0 <SEP> 707
<tb>
<tb> 6 <SEP> 4 <SEP> 0 <SEP> 59.5 <SEP> 34.0 <SEP> 6.5 <SEP> 644
<tb>
<tb> 7 <SEP> 8 <SEP> 0 <SEP> 54.8 <SEP> 37.4 <SEP> 7.8 <SEP> 602
<tb>
<tb> 8 <SEP> 20 <SEP> 0 <SEP> 53.9 <SEP> 37.1 <SEP> 9.0 <SEP> 602
<tb>
<tb> 9 <SEP> 0 <SEP> 1 <SEP> 59,

  3 <SEP> 34.8 <SEP> 5.9 <SEP> 4954
<tb>
<tb> 10 <SEP> 0 <SEP> 2 <SEP> 60.6 <SEP> 33.3 <SEP> 6.1 <SEP> 4342
<tb>
<tb> 11 <SEP> 0 <SEP> 3 <SEP> 64.2 <SEP> 32.2 <SEP> 3.6 <SEP> 3320
<tb>
<tb> 12 <SEP> 0 <SEP> 4 <SEP> 67.2 <SEP> 30.1 <SEP> 2.7 <SEP> 2635
<tb>
<tb> 13 <SEP> 0 <SEP> 8 <SEP> 67.6 <SEP> 29.0 <SEP> 3.4 <SEP> 1974
<tb>
<tb> 14 <SEP> 0 <SEP> 20 <SEP> 70.2 <SEP> 27.3 <SEP> 2.5 <SEP> 1078
<tb>
<tb> 15 <SEP> 1 <SEP> 1 <SEP> 66.4 <SEP> 26.6 <SEP> 7.0 <SEP> 1131
<tb>
<tb> 16 <SEP> 1 <SEP> 2 <SEP> 71.0 <SEP> 25.4 <SEP> 3.6 <SEP> 1215
<tb>
<tb> 17 <SEP> 1 <SEP> 3 <SEP> 74.1 <SEP> 23.0 <SEP> 2.9 <SEP> 1179
<tb>
<tb> 18 <SEP> 2 <SEP> 1/4 <SEP> 67.6 <SEP> 28.2 <SEP> 4.2 <SEP> 854
<tb>
<tb>
<tb> 19 <SEP> 2 <SEP> 1/2 <SEP> 69.9 <SEP> 26.2 <SEP> 3.9 <SEP> 923
<tb> 20 <SEP> 2 <SEP> 1 <SEP> 72.6 <SEP> 23.9 <SEP> 3.5 <SEP> 869
<tb>
<tb> 21 <SEP> 2 <SEP> 2 <SEP> 73.6 <SEP> 23,

  8 <SEP> 2.6 <SEP> 923
<tb>
<tb> 22 <SEP> 3 <SEP> 1 <SEP> 71.0 <SEP> 24.6 <SEP> 4.4 <SEP> 821
<tb>
 

 <Desc / Clms Page number 22>

 
 EMI22.1
 µ2g the f1U08Ul.foDiqae acid (29.2 parts) was a:; out.6 ftIF (SOS parts) in a ten minute period. The reaction mixture was heated by heating the airtight for 1% of the catalyst used, and was not allowed to leave an amount equal to ap (Kox.1aaUv lat 35-C. Four hours * after the addition of the catalyst. , we re ± king4iasa1t the 186lanqe reaction 1 until eaviroa 7 "c and this teaperratare was maintained by a hmwe, 1000 parts of water were then added. In the course of 1 * Mitioo of water, an external cooling was applied. to maintain tab1r8 of the M61ange reactiommi au-deu80W1 of 15c.

   The product was treated ¯1 la proc: 6M of treating agent used In * lltt- 5''118 1, and GD recovered aD BOPM having aD poi48 8Dl6ca1aire equal to 8IIriron 3000, with aD ren4..Tnt c1e 799L Ihr 185 On d & ct: 1milk: six tests of po17116risatiGD 8D 1lisaDt: the Ir "l 'qaaat: 1t68 de and this catalyssva qne cml1.ea ntiliaies On * 1 m-> 3. D8b8 chmm das testrs, the tone" 68 polym6ri- 8ati.ca total was 91. qaaae 1- mm Polishing the first or everything. q.ai is 18 binoin. cm mi 1 bperatace at 3'C 20 pig la totalibi 6 488 ".....- and CID tmmimit llec: t: irit6 eat: a1yd.q88 eo., .. 1 ...- la t / I" at: 88. Dboe. this: test b8tiA ..6t: ai.t: paa d 8et: al ..1Iaa this iawatioa. oar les aatres qaatJL ..... 1 .. year - 1 - 1 piratew law at 3S Z '01 1 three rare, and CID housed eosoite r8pil, t la jdqe '8IWizGD. EIJt.1..1 ..

   He. 20-c :. dry isoeu # -15-C. -33 "C, and at 1 '¯1'" It: p + & - qre 1'ft.til cat: a1 aata- 11 .. mat tda. 0a it, pom 1 - ......- Ie. l'IIIIU9I.t6 aaQ1 .. 08t: .. --le .. 81t11.t: i8a z .. 'de 750 partim ear 1161 Ja 18111 91aD8 pilie. lloe. 188 -... 1 ... aft. 18 "1 Uaie68 pmw 16- v 1e sodat m pom art 1e! Polll" u ... 18 .... .., ... - pu8 'a88t. la y m t m IIW m pmw CIIIIâ. and 1e 04b 1..4 .. "P04ufte 6ait 6 par 18 d 1- --lit 3. CII8 z8.N1't8h - il .......



  18 --Il T1.

 <Desc / Clms Page number 23>

 
 EMI23.1
 TABLE IV
 EMI23.2
 3 beur .... 35 "C and 1 hour. 2 '
 EMI23.3
 
<tb> witness
<tb>
 
 EMI23.4
 T - 35 "c 20.c 15.c SOC -1Soc -35 C pl 644 729 762 821 779 7ï3 riAD!" 8IfDt 2HP% - 59.5 64.6 66.5 71.0 72.6 71.5 THF recovered- 34.0 29.9 24.1 24.6 22.4 24.4 THFpw (rda% - 6.5 5.5 9.4 4.4 5.0 4.1
 EMI23.5
 Bivemple Fluosulfonic acid (82.2 parts by weight) was added to the THF (1010 parts by weight), maintaining the temperature ¯w4¯1e, 3sC 1, and the resulting mixture was maintained at 1ID8 r.tur8 of 35 * C 1. for a period equal to three hours. We then quickly lowered the tezq> drature of the 861aDge - IL to 6C 3. and we kept it at this time to think four hours. from the moment we performed the 8d & Ut: 1oa to the cmtalyamw.

   Four hundred parts by weight to ufthawl, which has been cooled to about SIC, 6q1- * then .joat6e8.t: oat: stirring, in the cooled active medium 'II8 "-oat: a1.J'8 & ¯-polYllke. The temperature was r "'J ,. Dt jU8q9 '. eaviran 14 * C. Stirring was continued during emwirea <nmim <t <Mt. the fairytonal mixture was then steamed and this recovered 807.4 parts by weight of polyafte, in the solvent recovery process daMdMMtl'tmma3ii.] powoDhMdiret Polymère, .t.6. by mmMarww to Otaanatr was 1704. Based on the analysis daw 9roatpawtb 18, ost est3aai.t that the product 0b !! 11t carina 8J poar 6'l'Q in moles of thy1 and1I8Ir ft ,, 1yool. . po1t'rlhe ftber and about 17 per cmt an 801 -.... 1 L brpla 1 if the te 99tation de rende- a) M d8dt8at ar prooiai of this inventive.

   Or should note that 1 '' '' u.at.ioa s..t, iw àa w, - 0 la - - 1 1, wet np6rieare in tawtw pe) ar taaqaala ce 4 "fte Obtain d mol weight products - e << iaizw pI8s tasau. zIL ---- ¯ - "" makes: 4 'l'sacotple 2, that leang- - - -tatim ea & ..' c1R r8fro14ia. 1118Ilt .. "" W1J8 .l " f..1 118ft -4. '"v," rapiüs and: that the great ace, 1.1 1- dm 1 1 a - 1 if produced in coma 4 Instant * oa la ..1' 1 -ce 8ft .. .ec # .u. goum this iIn8IdaD. This

 <Desc / Clms Page number 24>

 also appears from the run c in the graph. Figures 15-22 of Example 3 represent embodiments of this invention.

   It appears from these results that an unexpected increase in performance resulting from this invention is striking in both speed and magnitude. A comparison of runs 4 and 18, for example, shows the sharp increase in the polymer date. This sharp increase is totally unexpected when referring to the change in the amount of polymer during the 6 test or the 35 test, as shown in the graph. It should be noted that, within the limits of experimental error, all of the runs of Example 3 have, identically, the same catalyst quart and they have identical recovery treatment.

   A comparison of tests 18 and 13 shows an operation of two hours at 35 ° C., followed by half an hour during which the temperature is lowered to about 6, gives an efficiency as high as that which was achieved in eight. hours in the 6 ° C test, and additionally provided the lower molecular weight of 854, indicating greater catalyst usage. a comparison of runs 12 and 21 of Example 3 shows a Molecular weight of 2635 vs. 923, respectively, for a four hour run at 6 C vs. two hour run at 35 C, followed by two hours at 6 C. The lower molecular weight indicates much greater catalyst usage.

   Test at 6 (Test 12) gave a yield of 67.2%, compared to the yield of 74.1% (Test 17), that of 73.6% (Test in 21), and at that of 71% (Test 22), obtained / the same time period according to this invention. A comparison of tests 17, 14 and 8 shows that in four hours a better yield is obtained according to this invention than that obtained in the test at 6 (test 14) in twenty hours, or else in the test at 35 (Test 8) in twenty hours.



   Example 5 shows that a great advantage is obtained according to this invention by cooling the active THF-catalyst-polymer mixture to lower temperatures before the termination of the catalytic activity to a temperature of up to. about 0 C. Although a temperature below 0 C gives improved yields of this invention, there is no additional yield gain resulting from the use of a temperature below about zero.

 <Desc / Clms Page number 25>

 



   Example 7 -..- -..- ..- ... ..



   Nineteen individual cases were done, in much the same way, except that time and temperatures were varied. In each of the runs of this example, 505 parts of anhydrous distilled THF was polymerized by the addition of 17.3 parts of technical grade fluoeulfonic acid catalyst.



  In each case, the catalyst was added to the stirred THF over a lapse of about 15 seconds.



   In the Individual tests of this example, the temperature was kept at 65 ¯ 2 C for a period of time shown in Table v, and then cooled and maintained for a period of time shown in Table V , the temperature to 25 ¯ 2 C. The catalytic activity was terminated by this time.



   Note that in some tests the temperature of 65 C ¯ 2 C was not used and that in others the temperature of 25 C ¯ 2 C. In these tests, the catalytic activity was terminated at the temperature used. Of course, these tests were not according to this invention. In each of the tests, the catalytic activity was terminated by adding 750 parts of water-crushed ice mixture. In all of the runs of this example, treatment was carried out identically (using the solvent recovery method and the treatment methods given in Example 3, here), to determine the molecular weight and EGPTM yield. The interesting results of this example are given in Table V.

 <Desc / Clms Page number 26>

 



  TABLE V.
 EMI26.1
 
<tb>



  Time <SEP> in <SEP> hours
<tb>
<tb>
<tb>
<tb>
<tb> to <SEP> 65 C <SEP> to <SEP> 25 C
<tb>
<tb>
<tb>
<tb> ¯ <SEP> 2 <SEP> ¯ <SEP> 2 <SEP> PM <SEP>% <SEP> randement
<tb>
<tb>
<tb>
<tb> 7-1 <SEP> 0 <SEP> 1 <SEP> 3994 <SEP> 24.1
<tb>
<tb>
<tb> 7-2 <SEP> 0 <SEP> 2 <SEP> 6172 <SEP> 54.7
<tb>
<tb>
<tb>
<tb> 7 = 3 <SEP> 0 <SEP> 3 <SEP> 6010 <SEP> 67.3
<tb>
<tb>
<tb>
<tb> 7-4 <SEP> 0 <SEP> 4 <SEP> 4661 <SEP> 70.6
<tb>
<tb>
<tb>
<tb> 7-5 <SEP> 1/4 <SEP> 0 <SEP> 2382 <SEP> 26.0
<tb>
<tb>
<tb>
<tb>
<tb> 7-6 <SEP> + <SEP> 1/4 <SEP> 1 <SEP> 4467 <SEP> 60.0
<tb>
<tb>
<tb>
<tb> 7-7 <SEP> 1/4 <SEP> 2 <SEP> 3820 <SEP> 70.2
<tb>
<tb>
<tb>
<tb> 7-8 <SEP> 1/2 <SEP> 0 <SEP> 2394 <SEP> 33.4
<tb>
<tb>
<tb>
<tb> 7-9 <SEP> @ <SEP> 1/2 <SEP> 1 <SEP> 2987 <SEP> 59.1
<tb>
<tb>
<tb>
<tb>
<tb> 7-10 <SEP> @ <SEP> 1/2 <SEP> 2 <SEP> 2970 <SEP> 67,

  5
<tb>
<tb>
<tb>
<tb> 7-11 <SEP> 1 <SEP> 0 <SEP> 2065 <SEP> 39.5
<tb>
<tb>
<tb>
<tb> 7-12 <SEP> @ <SEP> 1 <SEP> 1 <SEP> 1973 <SEP> 43.2
<tb>
<tb>
<tb>
<tb>
<tb> 7-13 <SEP> @ <SEP> 1 <SEP> 2 <SEP> 2212 <SEP> 54.1
<tb>
<tb>
<tb>
<tb> 7-14 <SEP> @ <SEP> 1 <SEP> 3 <SEP> 2762 <SEP> 60.8
<tb>
<tb>
<tb>
<tb> 7-15 <SEP> 2 <SEP> 0 <SEP> 1860 <SEP> 38.5
<tb>
<tb>
<tb>
<tb> 7-16 <SEP> 2 <SEP> 1 <SEP> 1713 <SEP> 3 (, 5
<tb>
<tb>
<tb>
<tb>
<tb> 7-17 <SEP> 2 <SEP> 2 <SEP> 1794 <SEP> 40.5
<tb>
<tb>
<tb>
<tb> 7-18 <SEP> 3 <SEP> 0 <SEP> 1707 <SEP> 39.7
<tb>
<tb>
<tb>
<tb> 7-19 <SEP> 3 <SEP> 1 <SEP> 1740 <SEP> 38.0
<tb>
   @ According to this invention.



   The results of Example 7 further illustrate this invention. The comparison of tests 7-1 and 7-6 shows that by preceding a contact of one hour at 25 by a lapa of time at 65 ° C., the yield is improved from 24.1% to 60.0%.



  It should be noted, however, that this is accompanied by a slight increase in molecular weight which can be attributed to the slightly longer overall reaction time. The two hour runs at 25 C ¯ 2 C gave only a yield of 54.7% and an EGPTM molecular weight of 6172 (see Test 7-2).



   When contacting at temperatures above 50 ° C, the maximum advantage of this invention is achieved by using only a fraction (i.e. up to one-third) of the contact time which may be allowed. contact temperature, and using a time of up to two hours at a temperature below the threshold temperature. So to compare tests in which a test of one hour at 25 is preceded

 <Desc / Clms Page number 27>

 
 EMI27.1
 by a quarter of an hour, a half hour, and an e-65C hour. we caapare your 888ai. 7-6, 7-9, and 7-12. The readeatanta sasrt 60%.



  59.1% and 43.2%, r..pect1v III ', indicating that the useful catalytic activity of alane rapidly decreases at some point after exposure to 65 ° C.



  "QI8P has been defined here, the refro1diss88eDt to-dea60U8 of the threshold t.8IIp6rat #. Must be drawn in .or .. of 9G oinntes for an average contact teepereture of 65" C, in order to be in accoxd with the invention. Thus, in Test 7-16, in which a one hour contact at 25 "C is preceded by two hours at 65" C, the yield is only z. There is no diau6licwatixm compared to the yield obtained pou = two hours .. at 650C (see Test 7-15) or three hours at 25 C (see Test 7-3). Therefore, Test 7-16 does not agree with this invention, since the contact step extends beyond the time limit for 65 C.
 EMI27.2
 



  A match of the Bssai 7-12 with 7-2; 7-13 with 7-3; 1-1 with 7-4, illustrates that for the same total time, the yield is lower in the tests carried out by Belon this invention under these specified conditions. However, the increased efficiency with regard to the best use of the catalyst is however well achieved in these tests according to this
 EMI27.3
 invention, that is to say, we have a molecular weight of 1973 against 6172 for a two hour test of 2212 against 6010 for a three hour test, and 2762 against 4661 for a one hour test.



   Therefore, as indicated above, when contact temperatures above 50 ° C are used, the practice of this invention results in both an increase in catalyst efficiency and an increase in efficiency. - ment (in comparison with the efficiency for the same period of time at the lower temperature), only if the contact time above the threshold temperature can reach one third of the defined maximum contact time that can be allowed, and the time below the threshold temperature can reach two hours.

   Embodiments of this invention using times longer than these generally show a lower efficiency than that normally obtained at the lower temperature, but a much greater efficiency than that obtained normally at the higher contact temperature, and they

 <Desc / Clms Page number 28>

 show in addition a greater efficiency of the catalyst than that obtained at lower temperatures.



   Example 8
Three tests were carried out which were identical to the tests of Example 7 except for temperatures and contact times.



  The first test used a contact time of three hours at 50 C ¯ 2 C, the temperature at which the catalytic activity was terminated. The second test used one hour at 50 C ¯ 2 C, followed by two hours at 30 C ¯ 2 C, the temperature at which catalytic activity was terminated. So the first and second trials each took about three hours to complete. In the first test a yield of 52.1% was obtained, while a yield of 66.7% was obtained in the second test. This second run, which is according to this invention, provided a product having a molecular weight of 4799. In the third run, using four hours at 30 ° C, the product produced had a molecular weight of 6371.



  This indicates that a much better use was made of the catalyst from a second run according to this invention than from the third run which was not according to this invention. In this test, a yield approximately identical to that obtained in the third test was obtained, and much greater in the second test than in the first test.



   Placing the catalytically active mixture, at a temperature above the threshold temperature, in an ice-water mixture to terminate the catalytic activity does not produce any unexpected advantages of this invention and is not according to the invention. invention.

 

Claims (1)

CLAIMS 1. A process for the polymerization of tetrahydrofuran, comprising the steps: (1) contacting the tetrahydrofuran and a catalyst for the polymerization of tetrahydrofuran selected from the group consisting of: EMI29.1 (C1SOH): (FS03H): (HC10): IH2S20): (HI03): 5 '(SnCl4): (BF3); (PFS): (Li): Lewis acids in the presence of an element selected from the group consisting of epoxides, acid anhydrides and compounds containing an active halogen; strong acids in the presence of acid anhydride; mineral acid anhydrides in the presence of a member selected from the group consisting of mineral esters and halides. acid: compounds containing the ion EMI29.2 carbonium; compounds containing the aliazonium ion; and tertiary oxonium compounds; said contact being effected at an average contact temperature of between 20 and 80 ° C., thereby forming a catalytically active mixture; EMI29.3 (2) cooling the + angel below the threshold temperature of refs.QidiaMl88Dt, said cooling threshold temperature being defined as being 5 C lower than the maximum contact temperature when the maximum can reach 37 C, and said threshold temperature is set EMI29.4 Lomme are 32 C when the temperature of ccntact -r4-.18 is above 37 "C; (3) maintaining the mixture resulting from step 2 to tumble ass below the threshold temperature for up to 4 hours., (4) lI6laag8 the actual mixture from step 3 with an agent of WW'84. ".. t8OD of the catelytic activity, em a q \ l8Dt..i ere the qq8DUU etoechiometriqtte calaa1M compared to its r6acuicm with the entalyomm and (5) maintain the temperature of the zeemiting mixture of the step EMI29.5 4 ...-....... of the t Mp <Mt <urw of threshold jtilll1ll. - Illm- tivitf entalytiq is tnxinéw, 11 iDt: 8 & 'Ya11e de tps since the aontaot of step 1 jtMqpt 1 / fJ ï *. mL oe 1108 la t / '-aun c18 ¯11 d8UI l'ft8pI 2. pcI4W <Desc / Clms Page number 30> reach 240 minutes when the average contact temperature can reach 50 C, and for an average contact temperature com- EMI30.1 taken between SOOC and BOOC, the time interval is a time that can reach the time corresponding to the temperature on the part, regularly: of the temperature curve as a function of the time that passes through the points: EMI30.2 <tb> 50 C <SEP> 240 <SEP> timed <tb> <tb> 55 C <SEP> 200 <SEP> minutes <tb> <tb> 60 C <SEP> 150 <SEP> minutes <tb> <tb> 65 C <SEP> 90 <SEP> timed <tb> <tb> 70 C <SEP> 45 <SEP> timed <tb> <tb> 75 C <SEP> 10 <SEP> minutes <tb> <tb> 80 C <SEP> 1 <SEP> minute. <tb> 2. A method according to claim 1, wherein said EMI30.3 Contact temperature is campriae between 25'C and SO-C, and the contact temperature can reach 4 hours. 3. A process according to claim 2, comprising cooling the catalytically active mixture resulting from EMI30.4 step 1, jU8CJU 'has a temperature lower than 25 "C, and at least 5 ° C above said contact temperature, maintaining the refrolcJ1e maoae. CIIiC: t8 lower temperature for a tempe lower than 4 bour, and contacting a cooled mixture with a catalytic terminator at a temperature below 25 "Co and below SOC aa-c1e880D8 of said contact temperature, until the contact temperature is reached. catalytic activity was terminated. EMI30.5 4. We proceed for poIJ8Ir1..r from tftnhJdm ..., eD8Dt 1- ft8pe8 8a1Y8b8. (1) contact of metrahydrofurman and a selected catalymvar d8I8 group 0 (-, D86 oa aeidm O, aoaal6JlWpe. Of 19 perchloric acid, alaloE'08al6JlWpe acid and pouta Daonn of phoephorus, at the time <mmMFiaeentre2S * Ce 50 * C during a tempe lap that can atWiDC1r8 4 J81n8. (2) the cooliaeemmttt dn 811898 active of 1II) aII aat: 81. ND8DL '' '' 1. j88rj (8 '. Um attémme lafftiomm a arc, et la atiea t ilo9e srts, di a mm baapSaCos iorfre a' C peodaot oa lapa de t8III'8 la rimw homrm, and (3 ) 18 81181 '. Dm melanmm metif nfnidi 8Na - nmettt of t8z8i --- 1IOIt of activity aâal7tf488 and 18 amaum ..1If1- .. d881t8 *. Brperatm. Infériemtw .208C. Jufflla ce q la tMmhMdoeit c1 ad8I. mit Maputo, 188 & amott says ----...- says l'8Dl: idd <Desc / Clms Page number 31> EMI31.1 catalytic being used at least in a stoedaometric quantity, EMI31.2 calculated with respect to its reaction with the catalyst. EMI31.3 5.! X: proceeds according to claim 1, 2, 3 or 4, wherein the catalytic activity terminator selected from the group consisting of water, primary and secondary alcohols having 1 to 5 atoms. carbon, and primary dihydro-oeyated alcohols having 2 to 6 carbon atoms. EMI31.4 6. The process according to any one of the preceding claims, wherein the catalytic activity terminator is 1,4-butanediol. EMI31.5 7. A process for polymerizing tetrabydrofuran, COI8 taking EMI31.6 Steps : EMI31.7 (1) contact of Utrahydrofuran with a catalyst of EMI31.8 polymerization of tetrahydrofuran chosen from EMI31.9 groupa composed of the acid f! uoselque, perch1.oric acid. chloroisulfoniqm acid, and phosphorus pentatluorum, at a contact temperature in the range of 250C to SOIIC, peiulant a laps EMI31.10 of time of up to 4 hours, the aforesaid EMI31.11 lyser and tftr8hydEofur: - being used in amounts providing a molar ratio of catalyst to tetrahydrofuran in the range of 0.01 to 0.259 (2) ze to oi.dI-. Dt of the r.6aul.talP.c mixture of step 1 aa-cJe880- of the cooling temperature as only, said threshold temperature of Y-cooled 1 itant defined as oasie being 5 ° C lower than the ./l'..4- .. maximum contact when the mtnfimm can 37 "c, and said threshold temperature being defined as 32" c when the maximum contact temperature is greater than 37 * Cy (3) maintenance of the M'1 W'r resulting from 11 2 to mm t infézimura at the a.p6rabu.-a threshold paadmttt my lapse of time being able to -1 hours t (4) 1161-- of the malango resulting from the ebpe 3 with an amaet of taaainaison of the catalytic activity, to the qasstiti at the qMMt4- "..G8ftri.que CI81aû" by reacting 898C the Oâ81PI4, - (µ) maintian ds the tamparatura 6a l1li1 .. zaaaltant of <Desc / Clms Page number 32> step 4 at the threshold temperature 4000 until the catalytic activity is complete. 8. A process according to claim 7, wherein the catalyst is fluosulfonic acid, the catalytic activity terminator is water, the time remaining at the contact temperature can be achieved. will reach 150 minutes, and the temperature of the mixture resulting from step 2 is maintained below the threshold temperature for a mole lapse of up to 150 minutes. 9. A process for polymerizing tetrahydrofuran, substantially as described herein.