JPS62500784A - Method for producing chloroformate composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Chloroformate compositions and methods of making the same This application is filed under pending U.S. Patent Application No. 6 This is a partial continuation of No. 76.353 (filed on November 29, 1984).

The present invention is useful in the production of various polycarbonates and other materials. The present invention relates to a composition. More specifically, the present invention provides novel bischloroformate compositions. Concerning things and their manufacturing methods.

Chloroformates are a group of known useful organic intermediates. In particular, dihydroxy The compound bischloroformate and its oligomers are used in the manufacture of polycarbonate. It is known to be useful for construction. These are the pending U.S. Disclosed in National Patent No. 704,122 (issued February 22, 1985 ll1) As such, it can also be used as an intermediate in the production of cyclic polycarbonate oligomers. The resulting cyclic polycarbonate oligomer is converted into a polycarbonate with a very large molecular weight. Can be converted to Bonate. The disclosure content of the above patent application is hereby referred to as prior art. I'll list it here.

Many methods of making chloroformates are known in the art.

For example, in U.S. Pat. No. 3,189,640, water-soluble alkylidene diphenols are Bischloroformate composition by reacting the salt with phosgene in an aqueous buffer system. The production of the product is described. As with aqueous solvents, sometimes with organic diluents, A similar method for producing mono- and bischloroformates is described in U.S. Pat. No. 3,31 No. 2,661, No. 3.959.335, No. 3,974,126 and No. 3, No. 966.785. In all these methods, p of the reaction mixture u on the alkaline side, typically in the range 9-12, and in some cases 12 or more need to be kept. Another method described in U.S. Pat. No. 3,255,230 , dihydric phenol with phosgene and quaternary ammonium catalyst in an inert organic solvent medium. react in the presence of

The methods described in the prior art mentioned above have a number of drawbacks. First of all, Koushi The resulting bischloroformate products are mostly derived from dihydroxy compounds. oligomeric bischloroformates containing as many as 15 repeating units. Contains a considerable amount of total. Second, a significant excess of phosgene is required over the stoichiometric amount. Often the molar ratio of phosgene to dihydroxy compound is 5:1. (i.e. equivalence ratio as high as 2.5:1 as defined later). There is. Although phosgene is not a particularly expensive chemical, it is highly toxic and therefore Care must be taken to avoid leakage of sugen into the atmosphere. unreacted phos To decompose carbon, it is usually decomposed using sodium hydroxide, and the carbon produced in this way is Since the sodium acid solution is neutralized with mineral acids, a large amount of carbon dioxide is generated. This way Such protective measures are troublesome.

Therefore, the main object of the present invention is to provide novel roloformates, especially dihydroxy compounds. An object of the present invention is to provide a bischloroformate composition and a method for producing the same.

Another object of the invention is to produce chloroformates with minimal phosgene requirements. The goal is to provide a method for creating

Another object of the present invention is to provide bicarbonates useful in the production of cyclic polycarbonate oligomer mixtures. The present invention is to produce a schloroformate composition.

Yet another object of the present invention is to provide primarily monomeric, dimeric and trimeric dihydrocarbons. A composition containing the compound bischloroformate and a method for producing the same are provided. There is a particular thing.

Other objectives will be partly self-explanatory and partly apparent from the description below. .

In its first aspect, the present invention essentially comprises the following formula: (wherein R1 is a divalent aliphatic alicyclic or aromatic group, n is 1 or more) a composition in which about 45-90% by weight of the chloroformate component of the composition has n. to provide a composition in which not more than 10% are compounds where n is greater than 3. Ru.

The R1 groups that are aliphatic or cycloaliphatic in the compositions of the invention usually have up to about 8 Contains carbon atoms. Specific examples of R1 groups include ethylene, propylene, trimethylene, Tetramethylene, hexamethylene, dodecamethylene, poly-1,4-(2-butene) nylene), poly-1,1O-(2-ethyldecylene), 1,3-cyclobenzene 1,3-cyclohexylene, 1,4-cyclohexylene, m-phenylene, p-phenylene, naphthylene, 4,4'-diphenylene, 2゜2-bis(4-hylene) Droxyphenylene) propylidene, benzene-1,4-dimethylene (ethylene (with similar properties) and substituted derivatives of these . Specific substituents (one or more) include alkyl, cycloalkyl, alkenyl (e.g. crosslinkable and graftable components such as vinyl and allyl), halogens (particularly fluorine), (fluoro, chloro and/or bromo), nitro and alkoxy.

The R1 moiety is usually aromatic and preferably has the formula:

-At -Y-A2- (It) Here, AI and A2 are each a divalent monocyclic aromatic group, and Y is one or It is a linking group that separates AI and A2 by two atoms. The free valence bond in the formula ■ is It is usually in the meta or rose position of A1 and A2 with respect to Y.

In formula H, AI and A2 groups are unsubstituted phenylene or substituted derivatives thereof. and the substituents are as defined for R+. Unsubstituted phenylene group is preferred . Preferably A' and A2 are both p-phenylene, but both are 0- or or m-phenylene, one is 〇- or m-phenylene and the other is p-phenylene. Niren may also be used.

The linking group Y is one or two atoms, preferably one atom, separating A1 from A2. It is a group that separates. The linking group is most often a hydrocarbon group, especially a saturated 01-1° Aliphatic or cycloaliphatic groups, such as methylene, cyclohexylmethylene, 2-[2, 2,1] Bicyclohebutylmethylene, ethylene, ethylidene, 2,2-propylene Ridene, 1.1-(2,2-dimethylpropylidene), cyclohexylidene, cyclopentadecylidene, cyclohexylene or 2,2-adamantylidene, Especially alkylidene groups. Aryl substituted groups and unsaturated groups and carbon Also included are groups containing atoms other than hydrogen, such as oxy groups. Aliphatic, alicyclic group of Y group Substituents as described above may be present in the formula and aromatic moieties. Obtained Among the radicals of formula Derived from Nord A, where Y is 2,2-propylidene and A' and A2 are each 2,2-bis(4-)unicine)propane group, which is p-phenylene, is preferred. .

The distribution of molecular species in bischloroformate compositions was determined using reverse-phase high-pressure liquid-liquid chromatography. It was measured in fi. This composition was first mixed with equimolar amounts of phenol and triethylamine. The corresponding mixture is reacted with the mixture and is resistant to hydrolysis under the conditions of chromatographic analysis. A phenyl ester was produced. Phenyl ester in tetrahydrofuran and water Dissolved in a mixed solution and analyzed by chromatography using a relatively non-polar packing. The low molecular weight components eluted first. Two values for each molecular species, i.e. when retained. (expressed in minutes) and the area of the ultraviolet absorption peak at 254 nm was determined as 71Il+ , used for identification purposes. This value can be used for unique identification of this type of compound.

Standards used to assign retention times and 254++I11 absorptions to specific compounds. Quasi-samples include bisphenol A mono and diphenyl carbonate and bisphenol A. A separately prepared linear compound containing diphenyl carbonate of NorA dimer. Ru. Higher order oligomers were determined by similar methods.

An important feature of the bischloroformate component of the compositions of the invention is that it a low proportion of oligomers, i.e. oligomers with n greater than 3 (10 weight% or less). The presence of such higher-order oligomers results in Utility of Roforme-1 composition for the production of cyclic polycarbonate oligomers The properties, the key q requirements of the compositions of the invention, are significantly reduced. Typically, black The roformate component contains approximately 45-90% monotoxic bischloroformate, and most Even if it contains crab dimers, trimers, and in some cases monochloroformates. good.

There are no substances in the compositions of the invention that do not contribute significantly to the novel and useful properties of the compositions. may also exist. These are mostly essentially inert solvents for bischloroformates. It is a sexually active organic liquid. Examples of such liquids will be described later.

In another aspect, the present invention provides chloroformate compositions, particularly primarily monolayer, trimeric and a trimer (i.e. a compound of formula I where n is 1-3) A method of making a compound bischloroformate composition is provided. This method is Substantially inert organic liquid and the following formula: % formula % () (wherein R2 is an aliphatic, alicyclic or aromatic group, and X is 1 or more) Pass phosgene through the heterogeneous mixture with the droxy compound, bringing the solution to about 10-40 Maintain the temperature within the range of ℃, but when X is greater than 1 and the temperature is higher than 30℃ The addition rate of phosgene is high enough to combine the phosgene with the dissolved hydroxy compound. reactions of alkali metals or alkaline earth metals at the same time. A hydrogen chloride scavenger consisting of an aqueous base solution is introduced as needed, and during this time the aqueous The p)I of the phase is maintained in the range 0.5-8 and the total phosgene to hydroxy compound used is The equivalent ratio is about 1.0-1°1:1.

As is clear from the comparison of Formula 1 and ■, the hydroxy compounds useful in the method of the present invention include are monohydroxy, dihydroxy, trihydroxy and other polyhydroxylated There is a compound.

The value of X is usually 1 or 2, especially 2. Although the R2 group is usually an aromatic group, , aliphatic or cycloaliphatic. When aliphatic or cycloaliphatic, the group is usually Hydrocarbons containing no acetylenic unsaturation and usually no olefinic unsaturation It is an elementary group. Examples of R2 groups when X is 1 include 1-butyl, 2-butyl, 1- Hexyl, cyclohexyl and phenyl. When X is 2, R2 is R It can be a group of the type described above for 1. Therefore, dihydroxy compounds Then, ethylene glycol, propylene glycol,! -Rimethylene glycol tetramethylene glycol, hexamethylene glycol, dodecamethylene glycol Recol, poly-1,,4-(2-butenylene) glycol, poly-1,1,0 -(2-ethyldecylene)glycol, 1.3-cyclobentanediol, 1. 3-cyclohexanediol, 1,4-cyclohexanediol, resorcinol hydroquinone, 4,4'-diphenol, bisphenol A and 1,4- Bis(hydroxymethyl)benzene is useful.

Suitable diols are those in which R2 is aromatic, and especially those of the formula; %formula% (In the formula, AI, A2 and Y are as defined above). child Bisphenols such as I will mention them. However, instead of these bisphenols, other It should be understood that polyhydroxy and polyhydroxy compounds can be used. B Sphenol A is optimal.

According to the method of the invention, bisphenols are combined with a substantially inert organic liquid. Forms a heterogeneous mixture. This means that the liquid dissolves a substantial amount of bisphenols. There is no need to

The liquid must be a chloroformate product free solvent and is usually substantially free from water. Must be insoluble. Specific liquids include aliphatic hydrocarbons, such as hexa and n-heptane; chlorinated aliphatic hydrocarbons, such as methylene chloride, chlorophon lum, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane and 1°2-dichloroethylene; aromatic hydrocarbons, e.g. toluene and xylene; substituted aromatic hydrocarbons such as chlorobenzene , 0-dichlorobenzene, chlorotoluenes, nitrobenzene and acetophene and carbon disulfide. Chlorinated aliphatic hydrocarbons, especially methylene chloride, are preferred. Delicious.

Phosgene is passed through the heterogeneous bisphenol-liquid mixture while the mixture is ．． Maintain the temperature within the range of O-40℃.

Phosgene is usually introduced in the base state, but it can also be introduced as a liquid or as a solution in a suitable solvent. It is also within the scope of the present invention to introduce it as

When using temperatures higher than 30°C and when X is greater than 1, the phosgene flow rate should be The dissolved portion of the hydroxy compound and phosgene in the organic liquid are kept at high levels. react quickly and completely. This is necessary because it does not react with phosgene. If there is a strong hydroxy compound, this will react with the bischloroformate to form a higher order bischloroformate oligomers, but the bischloroformate oligomers of higher order This is because it is necessary to minimize the proportion in the schloroformate composition. general Under these conditions, the time to complete the reaction of the hydroxy compound must be within 30 minutes. Must be.

At lower temperatures, phosgene forms with bischloroformate, regardless of its addition rate. To the extent that there is sufficient competition, the solubility of phosgene increases and the solubility of the hydroxy compound increases. decrease.

” The two consecutive conditions are that when X is greater than 1 and the temperature is greater than 30°C, the phosgene flow rate is 0.15 or more equivalents per equivalent of hydroxy compound per minute, preferably about 0.2-0 ．． Keeping it at 4 equivalents is easiest to maintain. (For the purpose of this invention, The equivalent weight of a Roxy compound is the quotient of its molecular weight divided by the number of hydroxy groups; The equivalent weight of a compound is equal to its molecular weight. ) At lower temperatures or when X is 1, the phosphor Although the gene flow rate is not critical, at temperatures up to about 25°C A value within the range of about 0.05-0.2 hits per hit base is preferred, at 25-30°C. is preferably about 0.05-0.25 equivalents per equivalent of hydroxy compound per minute. .

The acidity of the reaction mixture is another important point in the process of the invention. Conventional technique Contrary to most scientific recommendations, relatively low acidity values reduce the amount of monomers in the product. It was found that this method is disadvantageous because it increases the amount of bischloroformate in the body.

On the other hand, hydrogen chloride combines hydroxy compounds with phosgene and/or bischloroform. It is a strongly acidic by-product of the reaction with carbonate, and its removal accelerates the reaction. Therefore , an alkali metal or alkaline earth metal base, typically a hydroxide, e.g. Chlorinated water consisting of an aqueous solution of sodium chloride, potassium hydroxide or calcium hydroxide water in contact with the secondary heterogeneous mixture, with the addition of an optional scavenger. The pH in the sexual phase is 8 or less, usually within the range of 0.5-8, preferably within the range of 2-8. maintain. (In the absence of base, the hydrogen chloride concentration increases, so p H approaches O. ) The proportion of bases required can be easily determined by routine experiment; Usually about 1.25-1.5 equivalents per equivalent of bisphenol. base to add The concentration of the solution is not critical and can be, for example, about 1-16N.

A major advantage of the process of the invention is that the phosgene required to obtain the desired chloroformate is However, the percentage of

About 1.0-1.1 equivalents per equivalent m of bisphenol, preferably 1.05-1. It is only necessary to use one equivalent of phosgene.

After producing the chloroformate composition by the method of the present invention, the solvent is removed and the composition is The individual components of products, e.g. bisphenol bischloroformate, can be distilled, chroma- They can be separated by conventional means such as toography, fractional crystallization, etc. But this Such separation operations are often unnecessary. For many purposes, the chloroform This is because the coated composition can be used without solvent removal or purification.

The method of the present invention will be specifically explained in the following examples.

Example 1-7 While stirring a heterogeneous mixture of bisphenol A and methylene chloride at a constant temperature, At a constant flow rate of phosgene, 1.05 equivalents of phosgene per 1 melon of bisphenol A It was introduced over a period of time until it was given. At the same time as adding phosgene, add 5N sodium hydroxide. Aqueous thorium solution was added to keep the pH value within the desired range. Mix for another 15 minutes Stir briefly, remove the methylene chloride layer, and remove the methylene chloride layer. Wash once with IN hydrochloric acid and phenol and triethylamine to end-capped and chromatinized as described above. was analyzed by topography. The reaction conditions and analytical values of the products are shown in the table below. "Comparative example" does not comply with the present invention due to high temperature or low phosgene flow rate, and was not used for the purpose of comparison. It is shown by .

Example 1234567 Control example Bisphenol A CBP＾):ff1 (Hk per millimeter) 100 100 200 200 200 224 224 6 00 equivalents/chloride Methylene II O, 80, 81, B 1.6 2.0 2.0 2.0 2.0 phosgene direct rental (equivalent 1 0P^1 equivalent/min) 0.174 0.1?4 0.101 0.101 0.0 51 0.179 0!59 0.033 1u11 of aqueous phase 4-5 7-8 3-4 5-8 0.5-2 2-5 2-5 3-4 iQ degree ('C) 20 20 30 30 30 40” 40” 40”Product (wt%) l'lP^bischloro Formate 87 79 48 49 50 87 g3 17 monochloro Formate 4.5 11.2 14 +2 21 5 0 5 Dimer bisque Roloformate 8-9 21 21 19 18 11 20 Trimer bisque Loloforme) 0 4 10 9 B 5 3 1g Higher Vista Roloformate 0 0 8 8 3 2 1 241 Reflux temperature of methylene chloride Comparing Examples 6 and 7 with the control example, the lower phosgene flow rate of the control example shows that 24% Higher bischloroformates are formed whereas at high phosgene flow rates 2% The effect of phosgene flow rate on product distribution is clearly seen below.

The combined effects of pH value and flow rate are shown in Examples 3-5; carried out at 0 °C and a relatively low phosgene flow rate, and at high pH values 8% higher bis Chloroformate is formed (values at high flow rates and (relatively high number), and only 3% of the highest p112 No monochloroformate was formed (but 21% monochloroformate).

Example 8-13 The procedure of Example 7 was repeated, but bisphenol A was added on an equimolar basis to the following dihydro It was replaced with an xyl compound.

Example 8 Hydroquinone Example 9 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propyl hmm Example 102.2-bis(4-hydroxy-3,5-dibromophenyl)propyl hmm Example 111.1-bis(4-hydroxyphenyl)cyclohexane Example 121.1-bis(4-hydroxyphenyl)cyclododecane Example 13 1-bis(4-hydroxyphenyl)-2,2-dichloroethyle hmm In each example, similar bischloroformates containing a significant proportion of monomeric bischloroformate A formate composition was obtained.

Examples 14-17 The procedure of Example 7 was repeated, but bisphenol A was added on an equimolar basis to the following dihydro It was replaced with an xyl compound.

Example 14 Resorcinol Example 15 Bis(4-hydroxyphenyl)methane Example 162.2-bis( 4-hydroxyphenyl)butane Example 17 Bis(4-hydroxyphenyl)ether In each example, a considerable proportion A similar bischloroformate composition containing monomeric bischloroformate of It was.

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Claims (17)

[Claims] 1. Essentially the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (R1 in the formula is a divalent aliphatic, alicyclic or an aromatic group, and n is 1 or more), About 45-90% by weight of the chloroformate component of the composition is a compound in which n is 1; Bischloroformate compositions in which 0% or less are compounds in which n is greater than 3. 2. The composition according to claim 1, wherein R1 is an aromatic group. 3. R1 is the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (A1 and A2 in the formula are respectively A divalent monocyclic aromatic group, where Y is 1 or 2 atoms and A1 and A2 . to isolate The composition according to claim 2, which has a linking group). 4. Furthermore, the amount of the essentially inert organic liquid that is the solvent for bischloroformate is reduced. The composition according to claim 3, containing at least one species. 5. Claim 4, wherein A1 and A2 are each p-phenylene Composition. 6. 6. The composition according to claim 5, wherein Y is 2,2-propylidene. 7. 7. A composition according to claim 6, wherein the solvent is methylene chloride. 8. A substantially inert organic liquid and the following formula: R2(OH)x(III) (R2 in the formula is an aliphatic or cyclic group containing no acetylenic unsaturation, or an aromatic aromatic group, x is 1 or more) with a hydroxy compound. of x, maintaining the mixture at a temperature within the range of about 10-40°C, with the proviso that x 1 and the temperature is higher than 30°C, the phosgene addition rate should be sufficiently high. The reaction of phosgene with dissolved hydroxy compounds is rapid and complete, and At the same time, a hydrogen chloride solution consisting of an aqueous alkali metal or alkaline earth metal hydroxide solution A scavenger is introduced as needed, during which time the pH of the aqueous phase is maintained in the range 0.5-8. and the equivalent ratio of total phosgene to hydroxy compound used is about 1.0-1.1:1. A method for producing a chloroformate composition comprising: 9. 9. A method according to claim 8, wherein the pH is maintained in the range 2-8. 10. Claim 9, wherein the hydrogen chloride scavenger is a sodium hydroxide solvent. Method described. 11. 11. The method according to claim 10, wherein x is 2 and R2 is an aromatic group. 12. R2 is the following formula: -A1-Y-A2-(II) (A1 and A2 in the formula are each a divalent monocyclic aromatic group, and Y is 1 or 2 in claim 11, which is a connecting group separating A1 and A2 with the atom of Method described. 13. Claim 12, wherein A1 and A2 are each p-phenylene. How to put it on. 14. 14. The method of claim 13, wherein Y is 2,2-propylidene. 15. The temperature was kept below about 25°C, and the phosgene flow rate was 1 equivalent of hydroxy compound per minute. 15. The method of claim 14, wherein about 0.05-0.2 equivalents per portion. 16. The temperature was 25-30°C, and the phosgene flow rate was 1 equivalent of hydroxy compound per minute. 15. The method of claim 14, wherein about 0.05-0.25 equivalents per portion. 17. The temperature was increased above 30°C and the phosgene flow rate was increased to 1 equivalent of hydroxy compound per minute. 15. The method of claim 14, wherein the amount is about 0.2-0.4 equivalents.