CN100549062C - Inhibiting catalytically active impurities in polycarbonate prepared by melt transesterification process - Google Patents

Abstract

Improvements in melt transesterification processes for the preparation of polycarbonates are disclosed. The improvement resides in the addition of at least one bridged ester of an organic sulfur-containing acid in the process between a moderate viscosity reactor and a high viscosity reactor.

Description

Catalytically active impurities in the polycarbonate of inhibition melt transesterification method preparation

Technical field

The present invention relates to a kind of method for preparing polycarbonate, especially the melt transesterification method.

Technical background

The known in the literature method for preparing polycarbonate, and in many Application Areass, state.

For the method for preparing polycarbonate by interface or melt transesterification method, can reference example as the Chemistry and Physics of Polycarbonates of " Schnell ", Polymer Review, the 9th volume, Interscience Publishers, New York, London, Sydney 1964, the 33rd page and Polymer Review, the 10th volume, " Condensation Polymers by Interfacial andSolution Methods ", Paul W.Morgan, Interscience Publishers, New York 1965, Chap.VIII, the 325th page and EP-A-971790.

After preparation, melt polycarbonate comprises the alkaline impurities of catalytic activity.On the one hand, but these impurity cause by unsegregated trace impurity, unsegregated pyrolytic basic catalyst residue or unsegregated stable basic catalyst salt in the raw material.But the pyrolytic catalyzer is interpreted as for example so-called salt.Heat-staple catalyzer can be regarded as for example basic metal or alkaline earth salt.Since their loads the material of catalytic activity, therefore, the alkaline matter in the polycarbonate is very unfavorable.

Therefore, when additive was sneaked into described polycarbonate melt, alkaline matter can be supported the chemical reaction of additive, as was attached in the polymer chain, the described additive of perhaps degrading, and this validity to additive is unfavorable.In the presence of the catalytic activity alkaline impurities, the thermal reduction reaction of the residual monomer of constant molecular weight (optics melt polycarbonate class is conventional) is (bibliographic reference LeA36697) successfully.The catalytic activity compound also can cause polycarbonate DeR to occur in conventional steps of further processing such as injection molding in the polycarbonate.

, usually inhibitor is added in the polycarbonate, inhibitor is interpreted as all compounds that suppress chemical kinetics, avoids occurring reducing in polymkeric substance the variation of quality for this reason.

The known in the literature inactivation that makes catalytic activity alkaline impurities in the melt polycarbonate by acidic cpd and ester thereof.In this case, extremely important is that used inhibitor can not form excessive free acid, and this is because free acid has also been supported the chemical reaction of described polymkeric substance and for example described additive similarly.

In DE-A 1031512, Schnell etc. have illustrated by adding in the acidic components and basic catalyst.This paper also mentions after neutralization, can remove used excess acid by vacuumizing.

EP-A 435 124 has illustrated that acid or its simple acid esters of comprising sulphur atom by adding make basic catalyst inactivation in the melt polycarbonate.In this case, reduce in a vacuum before the residual monomer, excessive acid neutralizes once more by adding epoxide.The example of described acidic components comprises phosphoric acid, Phenylsulfonic acid, toluenesulphonic acids methyl esters and toluenesulphonic acids ethyl ester.

DE-A 4438545 has illustrated and has reduced in a vacuum before the residual monomer, with the acidic components or the mixing of its ester of melt polycarbonate and pKa value＜5, with the alkaline transesterification catalyst that neutralizes.The example of acidic components has been mentioned phosphoric acid, Phenylsulfonic acid and corresponding ester.

In WO 00 07799, reduce in a vacuum before the melt polycarbonate residual monomer, by adding the salt of Witco 1298 Soft Acid, suppress basic catalyst as Si Wan Ji Phosphonium and tetraalkylammonium salt.

The sulfur-bearing quencher and the glyceryl monostearate (GMS) that will have phosphoric acid and water from WO 02 46272 as can be known are used for melt polycarbonate.Like this, by accurately adding described material, can remove described residual monomer, GMS can be used as releasing agent and adds, and takes place without any disadvantageous secondary reaction.Described effective quencher comprises simple alkyl-benzene sulfonate and tosylate, and the Phenylsulfonic acid De Phosphonium and the ammonium salt of p-replacement.Better use the toluenesulphonic acids butyl ester.

The ester of many described deactivator, especially free acids and fracture easily has corrosive shortcoming under high temperature and high density condition, for example can take place under the situation of industry measurement inhibitor.With regard to the angle of safety, better be to use the inhibitor that can not influence described device materials, to prevent particle, metallic cation and deficiency.And, (under the melt polycarbonate situation) volatilization under the unit that is used for removing residual monomer condition commonly used of most quencher, and under the situation that is metered into the melt polycarbonate melt flow stream, volatilize.If from removing residual monomer under the high-temperature vacuum condition in the relatively long residence time, then can lose a large amount of quenchers, the efficient of quencher can reduce greatly like this.Under continuously stirring, quencher is constant and be metered into neatly in the melt flow stream, and this must carry out, but because high volatile volatile becomes difficulty more.After degassing step in, component that is added such as phosphoric acid also will be separated from polycarbonate together with other volatiles, and can concentrate in device, because of corrosion causes device impaired.When in the isolating component (comprising the component that suppresses catalyst activity) adding apparatus loop again, can also estimate the disadvantageous effect that reaction is carried out.For example, the catalysis quencher can add in the polycarbonate preparation processes again, thus the carrying out of inhibited reaction.In extracting the isolated compound vapo(u)rization system, also exist corrosion-damaged.

Described in WO 00 07799, though little to the volatility of the quaternary salt of substituted benzenesulfonic acid, because its solubleness of depositing in the solvent for use is low, so they significant disadvantage occurs.Deposit among the WO 00 07799, they must be dispersed in the water by the complicated operations process, are convenient to metering.From the angle of industry, the constant suspension that is metered into minute quantity is very difficult continuously.The preferred solvent that uses be interpreted as water and in described technology the inherent solvent, as phenol.

Another shortcoming of many acid esters quenchers is a large amount of free acids of they too fast generations.Excessive acid meeting catalysis for example, the reaction between polycarbonate and the additive, or even promote the reversed reaction of polycarbonate and phenol to discharge diphenyl carbonate.On the other hand, some are in demand for the ester bond excessive acids, and they can discharge free acid when being heated very slowly in the polycarbonate process of further processing quencher.They have improved the thermal load amount of polycarbonate.

Therefore as can be known from prior art, the objective of the invention is to find the inhibitor that is used for quencher polycarbonate catalytically active impurities, described inhibitor is not corrosive, and volatility is low and be dissolved in easily simultaneously in the described method in the inherent solvent, is convenient to measure in described solvent.Similarly, described inhibitor should not produce relatively excessive greatly free acid in polycarbonate, to avoid polycarbonate generation DeR, forms carbonic ether, perhaps suppresses the reaction of they and additive.The substitute is needs slowly to produce free acid.Especially require described inhibitor should in the process that adds polycarbonate and any later step, not be completed into all possible free acid.In this way, show active in after the polycarbonate granulation of quencher, further processing as injection molded process once more.

Summary of the invention

The improvement of the melt transesterification method that is used to prepare polycarbonate is disclosed.Described improvement is to add in the technology between isoviscous therein reactor and the high viscosity reactor bridging ester of the acid of at least a organic sulfur-containing.

Detailed Description Of The Invention

Now, be surprisingly found out that the ester of the acid of organic sulfur-containing combines required performance evenly, be very suitable for suppressing the catalytically active impurities in polycarbonate-based.Surprisingly, this stablizer only slowly and stage by stage discharges corresponding free acid.And their volatility own are low, even also seldom be evaporated from polycarbonate melt under the long relatively residence time.Surprisingly, even under high temperature and high density condition, described stablizer can not corrode metal commonly used, as 1.4571 or 1.4541 (Stahlschlussel 2001Verlag:Stahlschlussel Wegst GmbH, Th-Heuss-Stra β e 36, D-71672 Marbach) and C type Ni base alloy, as 2.4605 or 2.4610 (Stahlschlussel 2001 Verlag:Stahlschlussel Wegst GmbH, Th-Heuss-Stra β e 36, D-71672 Marbach).

Owing to can not predict usually in the catalytically active impurities that in inhibition is polycarbonate-based whether described inhibitor is with the comprehensive required performance of correct mode, as low volatility, in the intrinsic solvent of technology solubleness, can not corrode and slowly discharge acid, this point especially makes us feeling surprised.

Therefore, the invention provides the method for preparing polycarbonate, it is characterized in that, between medium-viscosity and high viscosity reactor, add the ester of the acid of organic sulfur-containing.

The application that the present invention also provides the ester of the acid of organic sulfur-containing to prepare the catalytically active impurities in the polycarbonate in inhibition by the melt transesterification method.

The preferred inhibitor that the present invention is suitable for is one or more esters of the acid of organic sulfur-containing, is selected from:

(a) compound shown in the general formula (I):

In the formula, substituent R 1 is represented hydrogen or C1-C20-alkyl independently of each other, better is the C1-C8-alkyl, especially better is unsubstituted C1-C6-alkyl, C1-C4 alkyl very preferably, and alkyl is optional to be replaced by halogen, especially hydrogen or methyl,

R2 and R3 represent hydrogen or C1-C6 alkyl, C4-C30-alkyl carboxyl independently of each other, better are C1-C4-alkyl, C6-C25-alkyl carboxyl, especially better be C8-C20-alkyl carboxyl, especially hydrogen, C17-alkyl carboxyl or C15-alkyl carboxyl or

Group shown in R2 and R3 are expressed as follows:

In the formula, R1 has above-mentioned implication, and subscript m represents 0 or 1 independently of each other,

N represents the integer of 0-8, better is the integer of 0-6, especially 1,1 or 2,

M=0 or 1;

B) compound shown in the general formula (II):

In the formula, R1 has above-mentioned implication, and substituent A is represented hydrogen or C1-C12-alkyl independently of each other, better is the C1-C8-alkyl, especially better is ethyl, propyl group or butyl,

I represents 2 or 3;

(c) compound shown in the general formula (III):

In the formula, R1 has above-mentioned implication;

(d) compound shown in the general formula (IV):

In the formula, R1 and n have above-mentioned implication,

R4 represents the C4-C30-alkyl carboxyl, better is the C6-C25-alkyl carboxyl, especially better is the C8-C20-alkyl carboxyl, especially C17-alkyl carboxyl or C15-alkyl carboxyl, or the following group of expression:

In the formula, R1 has above-mentioned implication; And

(e) compound shown in logical formula V, (VI), (VIIa), (VIIb), (Ib), (Iva):

In the formula, R1 and n have above-mentioned implication,

Q represents the integer of 0-10, better is 1-8,1-5 especially,

R5 and R6 represent hydrogen or C1-C20-alkyl independently of each other, are preferably the C1-C8-alkyl, especially are preferably the C1-C6-alkyl, preferred C1-C4-alkyl, and alkyl can be replaced by halogen, especially hydrogen or methyl;

Substituent R 11 is represented hydrogen or two-(C1-C4)-alkylamino independently of each other, better is hydrogen or dimethylamino; And

(f) compound shown in the general formula (VIII):

In the formula, R1 and A have above-mentioned implication; And

(g) compound shown in the general formula (IX):

In the formula, R1 and m have above-mentioned implication; And

(h) compound shown in the general formula (X):

In the formula, R1 and A have above-mentioned implication; And

(i) compound shown in the general formula (XI):

In the formula, R1 and A have above-mentioned implication.

Especially preferred formula (Ia)-(If), (IIIa), (IVb), (Va), (Vb) and (IXa) shown in inhibitor:

Inhibitor of the present invention can be separately or is added polymer melt with the form of any appropriate mixture or multiple different mixtures.Also can and the form of mixtures of free acid (as tosic acid or ortho-phosphoric acid) add inhibitor of the present invention.The preparation method of the bridging ester of the acid of organic sulfur-containing of the present invention can be according to ordinary method by for example carrying out (seeing Organikum with suitable multi-group alcohol's alcoholysis Phenylsulfonic acid chlorine or toluenesulphonic acids chlorine, Wiley-VCH Verlag, the 20th edition, Weinheim, the 606th page/1999).

For example prepare described polycarbonate according to the melt transesterification method.The known in the literature method for preparing aromatics oligomerization carbonic ether or polycarbonate according to the melt transesterification method, and at Encyclopedia of PolymerScience, the 10th volume (1969), Chemistry and Physics of Polycarbonates, PolymerReviews, H.Schnell, the 9th volume, John Wiley and Sons, Inc. (1964) and in DE-C1031512, US-A3022272, US-A5340905 and US-A 5399659, description is arranged.

In this method, aromatic dihydroxy compound carries out transesterify by appropriate catalyst and optional other additive and carbonic diester class in melt.

In order to carry out described method, can use for example type of device described in the WO 02/07767 (corresponding U.S. Patent application 2004526839,2002177684 and 2004143088, its reference in content is incorporated in this).

Be used to prepare polycarbonate-based suitable dihydroxyl aryl compound and be shown in the general formula (XII) those:

HO-Z-OH (XII)

In the formula, Z is the aromatic group with 6-30 carbon atom, and it can comprise one or more aromatic kernels, can be substituted, and can comprise aliphatic series or alicyclic group or alkaryl or heteroatoms as the bridging part.

The example of dihydroxyl aryl compound is dihydroxy-benzene class, dihydroxybiphenyl class, two-(hydroxy phenyl)-alkane, two-(hydroxy phenyl) naphthenic hydrocarbon, two-(hydroxy phenyl)-aromatic hydrocarbons, two-(hydroxy phenyl)-ether, two-(hydroxy phenyl)-ketone, two-(hydroxy phenyl)-thioether, two-(hydroxy phenyl)-sulfone, two-(hydroxy phenyl)-sulfoxide, 1,1 '-two-(hydroxy phenyl)-di-isopropyl-benzene class and the ring on carry out alkylation and halogenated compound.

At for example U.S. Patent application 2970131,2991273,2999835,2999846,3028365,3062781,3148172,3271367,3275601,4982014, German patent specification 1570703,2063050,2036052,2211956,3832396, the 28th page of French Patent specification sheets 1561518 and monograph " H.Schnell; Chemistry and Physics of Polycarbonates; Interscience Publishers; New York1964 ", these and other suitable dihydroxyl aryl compound has been described among the 102nd page and " D.G.Legrand; J.J.Bendler; Handbook ofPolycarbonate Science and Technology; 2000, the 72 pages of Marcel Dekker New York ".

Preferred dihydroxyl aryl compound for example is a Resorcinol, 4,4 '-dihydroxybiphenyl, two-(4-hydroxy phenyl)-methane, two-(3,5-dimethyl-4-hydroxy phenyl)-methane, two-(4-hydroxy phenyl)-phenylbenzene-methane, 1,1 '-two-(4-hydroxy phenyl)-1-phenyl-ethane, 1,1 '-two-(4-hydroxy phenyl)-1-(1-naphthyl)-ethane, 1,1 '-two-(4-hydroxy phenyl)-1-(2-naphthyl)-ethane, 2,2 '-two-(4-hydroxy phenyl)-propane, 2,2 '-two-(3-methyl-4-hydroxy phenyl)-propane, 2,2 '-two-(3,5-dimethyl-4-hydroxy phenyl)-propane, 2,2 '-two-(4-hydroxy phenyl)-1-phenyl-propane, 2,2 '-two-(4-hydroxy phenyl)-hexafluoro-propane, 2,2 '-two-(4-hydroxy phenyl)-2-methyl-butane, 2,4 '-two-(3,5-dimethyl-4-hydroxy phenyl)-2-methyl-butane, 2,4 '-two-(3,5-dimethyl-4-hydroxy phenyl)-2-methyl-butane, 1,1 '-two-(4-hydroxy phenyl)-hexanaphthene, 1,1 '-two-(3,5-dimethyl-4-hydroxy phenyl)-hexanaphthene, 1,1 '-two-(4-hydroxy phenyl)-4-methyl-cyclohexyl alkane, 1,1 '-two-(4-hydroxy phenyl)-3,3,5-trimethylammonium-hexanaphthene, 1,3-two-[2-(4-hydroxy phenyl)-2-propyl group]-benzene, 1,1 '-two-(4-hydroxy phenyl)-3-di-isopropyl-benzene, 1,1 '-two-(4-hydroxy phenyl)-4-di-isopropyl-benzene, 1,3-two-[2-(3,5-dimethyl-4-hydroxy phenyl)-the 2-propyl group]-benzene, two-(4-hydroxy phenyl) ethers, two-(4-hydroxy phenyl) thioethers, two-(4-hydroxy phenyl)-sulfone, two-(3,5-dimethyl-4-hydroxy phenyl)-sulfone and 2,2 ', 3,3 '-tetrahydrochysene-2,2,3 ', 3 '-tetramethyl--1,1 '-spiral shell two-[1H-indenes]-5,5 '-glycol.

Especially preferred dihydroxyl aryl compound is a Resorcinol, 4,4 '-dihydroxybiphenyl, two-(4-hydroxy phenyl)-phenylbenzene-methane, 1,1 '-two-(4-hydroxy phenyl)-1-phenyl-ethane, two-(4-hydroxy phenyl)-1-(1-naphthyl)-ethane, two-(4-hydroxy phenyl)-1-(2-naphthyl)-ethane, 2,2 '-two-(4-hydroxy phenyl)-propane, 2,2 '-two-(3,5-dimethyl-4-hydroxy phenyl)-propane, 1,1 '-two-(4-hydroxy phenyl)-hexanaphthene, 1,1 '-two-(3,5-dimethyl-4-hydroxy phenyl)-hexanaphthene, 1,1 '-two-(4-hydroxy phenyl)-3,3,5-trimethylammonium-hexanaphthene, 1,1 '-two-(4-hydroxy phenyl)-3-di-isopropyl-benzene and 1,1 '-two-(4-hydroxy phenyl)-4-di-isopropyl-benzene.

It is most preferred that 4,4 '-dihydroxybiphenyl, 2,2 '-two-(4-hydroxy phenyl)-propane and two-(4-hydroxy phenyl)-3,3,5-trimethylammonium-hexanaphthene.

Can use a kind of dihydroxyl aryl compound to form the homo-polycarbonate class, perhaps use different dihydroxyl aryl compounds to form Copolycarbonate.

Also can use low-molecular-weight mainly be the end capped oligo-ester carbonate class of OH-end group as raw material, replace dihydroxyl aryl compound monomer.

Also described dihydroxy compound can used, the monohydroxy aryl compound (described dihydroxyl aryl compound is made by the monohydroxy aryl compound) that wherein has residual content perhaps can use low-molecular-weight oligo-ester carbonate class to separate the monohydroxy aryl compound of having removed residual content in preparation oligopolymer process.The residual content of described monohydroxy aryl compound at the most 20% better is at the most 10%, especially better is at the most 5%, preferably 2% (seeing for example EP-A-1240232) at the most.

Other raw material, chemical reagent and auxiliary substance that adds in the synthetic system is the same as all, used dihydroxyl aryl compound can be by the contaminating impurity from itself synthetic method, transportation and storage, though suitable purified as far as possible raw material, chemical reagent and the auxiliary substance of using.

The diaryl carbonate that is suitable for reacting with the dihydroxyl aryl compound is those shown in the general formula (XIII):

In the formula, R, R ' and R " identical or different, represent hydrogen, optional C1-C34 branched-chain alkyl aryl or C6-C34-aryl independently of each other; R also represents-COO-R " ', R " ' expression hydrogen, optional C1-C34 branched-chain alkyl, C7-C34-alkylaryl or C6-C34-aryl.

Suitable diaryl carbonate for example is a dipheryl carbonate base ester, carbonic acid aminomethyl phenyl-phenylester and carbonic acid two (aminomethyl phenyl) ester, carbonic acid 4-ethylphenyl-phenylester, carbonic acid two-(4-ethylphenyl) ester, carbonic acid 4-n-propyl phenyl-phenylester, carbonic acid two-(4-n-propyl phenyl) ester, carbonic acid 4-isopropyl phenyl-phenylester, carbonic acid two-(4-isopropyl phenyl) ester, carbonic acid 4-n-butylphenyl-phenylester, carbonic acid two-(4-n-butylphenyl) ester, carbonic acid 4-isobutyl phenenyl-phenylester, carbonic acid two-(4-isobutyl phenenyl) ester, carbonic acid 4-tert-butyl-phenyl-phenylester, carbonic acid two-(4-tert-butyl-phenyl) ester, carbonic acid 4-n-pentyl phenyl-phenylester, carbonic acid two-(4-n-pentyl phenyl) ester, carbonic acid 4-n-hexyl phenyl-phenylester, carbonic acid two-(4-n-hexyl phenyl) ester, carbonic acid 4-iso-octyl phenyl-phenylester, carbonic acid two-(4-iso-octyl phenyl) ester, carbonic acid 4-n-nonyl phenyl-phenylester, carbonic acid two-(4-n-nonyl phenyl) ester, carbonic acid 4-cyclohexyl phenyl-phenylester, carbonic acid two-(4-cyclohexyl phenyl) ester, carbonic acid 4-(1-methyl isophthalic acid-phenylethyl)-phenyl-phenylester, carbonic acid two-[4-(1-methyl isophthalic acid-phenylethyl)-phenyl] ester, carbonic acid biphenyl-4-base phenylester, carbonic acid two-(biphenyl-4-yl) ester, carbonic acid 4-(1-naphthyl)-phenyl-phenylester, carbonic acid 4-(2-naphthyl)-phenyl-phenylester, carbonic acid two-[4-(1-naphthyl)-phenyl] ester, carbonic acid two-[4-(2-naphthyl)-phenyl] ester, carbonic acid 4-Phenoxyphenyl-phenylester, carbonic acid two-(4-Phenoxyphenyl) ester, carbonic acid 3-pentadecyl phenyl-phenylester, carbonic acid two-(3-pentadecyl phenyl) ester, carbonic acid 4-trityl phenyl-phenylester, carbonic acid two-(4-trityl phenyl) ester, carbonic acid bigcatkin willow acid methyl phenylester, carbonic acid two (Whitfield's ointment methyl) ester, carbonic acid Whitfield's ointment ethyl phenyl ester, carbonic acid two (Whitfield's ointment ethyl) ester, carbonic acid Whitfield's ointment n-propyl phenyl ester, carbonic acid two (Whitfield's ointment n-propyl) ester, carbonic acid Whitfield's ointment isopropyl phenyl ester, carbonic acid two (Whitfield's ointment sec.-propyl) ester, carbonic acid Whitfield's ointment n-butylphenyl ester, carbonic acid two (Whitfield's ointment normal-butyl) ester, carbonic acid Whitfield's ointment isobutyl phenenyl ester, carbonic acid two (Whitfield's ointment isobutyl-) ester, the carbonic acid TBS tert butyl phenyl salicylate, carbonic acid two (the Whitfield's ointment tertiary butyl) ester, carbonic acid two-(Whitfield's ointment phenyl) ester and carbonic acid two-(Whitfield's ointment benzyl) ester.

The preferred aryl groups compound is dipheryl carbonate base ester, carbonic acid 4-tert-butyl-phenyl-phenylester, carbonic acid two-(4-tert-butyl-phenyl) ester, carbonic acid biphenyl-4-base phenylester, carbonic acid two-(biphenyl-4-yl) ester, carbonic acid 4-(1-methyl isophthalic acid-phenylethyl)-phenyl-phenylester, carbonic acid two-[4-(1-methyl isophthalic acid-phenylethyl)-phenyl] ester.

Especially preferred is dipheryl carbonate base ester.

Also can use described biaryl compound, wherein exist under the condition of monohydroxy aryl compound of residual content (described biaryl compound is made by the monohydroxy aryl compound).The residual content of described monohydroxy aryl compound at the most 20% better is at the most 10%, especially better is at the most 5%, preferably at the most 2%.

For every mole of dihydroxyl aryl compound, the consumption of described diaryl carbonate is generally 1.02-1.30mol, better is 1.04-1.25mol, especially better is 1.06-1.22mol, especially preferred 1.06-1.20mol.Also can use the mixture of above-mentioned diaryl carbonate.

In order to control or change described end group, can also use the monohydroxy aryl compound that is not used in the used diaryl carbonate of preparation.Described monohydroxy aryl compound is represented by following general formula (XIV):

In the formula, R, R ' and R " have the implication shown in general formula (XIII), its prerequisite is that R can not be H, though R ' and R " can be H.

This monohydroxy aryl compound for example is 1-, 2-or 3-methylphenol, 2, the 4-xylenol, the 4-ethylphenol, 4-n-propyl phenol, 4-isopropyl-phenol, 4-normal-butyl phenol, the 4-isopropyl-phenol, 4-tert.-butyl phenol, 4-n-pentyl phenol, 4-n-hexyl phenol, the 4-isooctyl phenol, 4-n-nonyl phenol, 3-pentadecyl phenol, the 4-cyclohexylphenol, 4-(1-methyl isophthalic acid-phenylethyl)-phenol, 4-phenylphenol, 4-phenoxy phenyl, 4-(1-naphthyl)-phenol, 4-(2-naphthyl)-phenol, 4-trityl phenol, wintergreen oil, salicylic ether, the Whitfield's ointment n-propyl, isopropyl salicylate, butyl salicylate, isonefolia, the Whitfield's ointment tert-butyl ester, salol and benzyl salicylate.

Preferred 4-tert.-butyl phenol, 4-isooctyl phenol and 3-pentadecyl phenol.

Suitable monohydroxy aryl compound is its boiling point than high those of used monohydroxy aryl compound in the preparation diaryl carbonate.Described monohydroxy aryl compound can be in reaction process any the time add.More fortunately reaction beginning or in reaction process any appropriate add constantly.In the dihydroxyl aryl compound, the ratio of free monohydroxy aryl compound can be 0.2-20 mole %, better is 0.1-10 mole %.

Described end group also can change by using diaryl carbonate simultaneously, and the boiling point of its basic monohydroxy aryl compound is than the basic monohydroxy aryl compound height of the main diaryl carbonate that uses.In this article, described diaryl carbonate can be in reaction process adds any the time.More fortunately reaction beginning or in reaction process any appropriate add constantly.In used diaryl carbonate total amount, the ratio with diaryl carbonate of more high boiling basic monohydroxy aryl compound is 1-40 mole %, better is 1-20 mole %, especially better is 1-10 mole %.

Prepare that used catalyzer is a known basic catalyst in the document in the polycarbonate-based melt transesterification method, for example oxyhydroxide of basic metal and alkaline-earth metal and oxide compound, and ammonium salt Huo phosphonium salt are called salt hereinafter.In synthetic, better use salt, especially better Shi phosphonium salt.Zhong De phosphonium salt of the present invention is those shown in the general formula (XV):

In the formula, R7-10 can be identical or different, be C1-C10-alkyl, C6-C14-aryl, C7-C15-arylalkyl or C5-C6-cycloalkyl, better be methyl or C6-C14-aryl, especially better be methyl or phenyl, X-can be a negatively charged ion, as hydroxide radical, sulfate radical, bisulfate ion, bicarbonate radical, carbonate or halide-ions, it better is chlorion, or the alkoxyl group shown in alkyl or the general formula-OR, in the formula, R can be C6-C14-aryl, C7-C15-arylalkyl or C5-C6-cycloalkyl, better is phenyl.

Preferred catalyzer is tetraphenylphosphonium chloride, hydroxide tetraphenylphosphoniphenolate and tetraphenylphosphoniphenolate phenates, the phenates of especially preferred tetraphenylphosphoniphenolate.

In 1 mole of dihydroxyl aryl compound, above-mentioned catalyst consumption better is 10 ^-8To 10 ^-3Mol especially better is 10 ^-7To 10 ^-4Mol.

Can use other catalyzer separately, perhaps and salt (as co-catalyst) use together, to improve polycondensation speed.

These catalyzer comprise the alkali reaction salt of basic metal and alkaline-earth metal, as oxyhydroxide, alkoxide and the aryl oxide of lithium, sodium and potassium, better are oxyhydroxide, alkoxide and the aryl oxides of sodium.Most preferably sodium hydroxide and sodium phenylate, and 2, the disodium salt of 2-two-(4-hydroxy phenyl)-propane.

Calculating as sodium and polycarbonate forming, the amount of the alkali reaction salt of basic metal and alkaline-earth metal (use separately or use as co-catalyst) is 1-500ppb, better suitable 5-300ppb, preferably 5-200ppb.

In the process of preparation oligo-ester carbonate, can use the alkali reaction salt of basic metal and alkaline-earth metal, promptly when synthetic beginning, perhaps in the polycondensation preceding adding that is about to begin, in order to suppress disadvantageous secondary reaction.

Also can before polycondensation, add the same type of magnitude of recruitment or dissimilar catalyzer.

The adding of described catalyzer can be carried out in solution, to avoid occurring deleterious excessive concentration in metering process.Described solvent is an inherent compound in system and the technology, for example dihydroxyl aryl compound, diaryl carbonate or monohydroxy aryl compound.Especially preferred is the monohydroxy aryl compound, and this is because the known dihydroxyl aryl compound of those skilled in the art and diaryl carbonate under high-temperature slightly, especially change easily under catalyst action and decompose.Therefore unfavorable to the quality of described polycarbonate.In the ester exchange method of industrial important preparation polycarbonate, preferred compound is a phenol.Phenol is also suitable, and this is because the phenates of catalyzer tetraphenylphosphoniphenolate crystalline mixture as phenol in preparation process separates.

Described thermoplastic poly carbonic ether class is shown in general formula (XVI):

In the formula, R, R ' and R " and Z have general formula (IX) or (VIII) described implication,

X is a structural repeat unit, it is characterized in that the molecular weight of polycarbonate.

Group in the general formula (XVI) (group as a whole)

Also can be H, can be different in its both sides.

The weight-average molecular weight of described polycarbonate is generally 1500-40000, better be 17000-36000, especially better be 17000-34000, described weight-average molecular weight is determined (J.M.G.Cowie by the Mark-Houwing relational expression by relative viscosity, Chemie und Physik der syntherischen polymeren, ViewegLehrbuch, Braunschweig/Wiesbaden, 1997, the 25 pages).

The positively charged ion of described polycarbonate and anion-content are extremely low, usually less than 60ppb, better less than 40ppb, especially better less than 20ppb (calculating) with sodium ion, the positively charged ion that exists is the positively charged ion of basic metal and alkaline-earth metal, and for example as raw materials used impurity, Yi is Ji Phosphonium and ammonium salt.Have other ion in raw material, as Fe, Ni, Cr, Zn, Sn, Mo, Al ion and congeners ion thereof, perhaps they are from the material (because of wearing and tearing or corrosion) of institute's using appts.This ionic total content is less than 2ppm, better less than 1ppm, especially better less than 0.5ppm.

The negatively charged ion that exists is normal mineral acid and organic acid negatively charged ion (for example, chlorion, sulfate radical, carbonate, phosphate radical, oxalate etc.).

Therefore, require its amount the least possible, this is only to realize by the very pure raw material of use.This pure raw material is only to obtain afterwards by purifying process for example (recrystallization, distillation, once more clean after the deposition etc.).

Describedly polycarbonate-basedly can the target mode carry out branching.Suitable branching agent is the compound with three or above functional group, better is the compound with three or above hydroxyl, and these are known to the polycarbonate method.

Operable some compounds with three or above phenols hydroxyl for example are Phloroglucinols, 4,6-dimethyl-2,4,6-three (4-hydroxy phenyl)-heptene-2,4,6-dimethyl-2,4,6-three-(4-hydroxy phenyl)-heptane, 1,3,5-three-(4-hydroxy phenyl)-benzene, 1,1,1-three-(4-hydroxy phenyl)-ethane, three-(4-hydroxy phenyl)-phenylmethane, 2,2-two-(4,4-two-(4-hydroxy phenyl)-cyclohexyl)-and propane, 2,4-two-(4-hydroxy phenyl-sec.-propyl)-phenol and four-(the 4-hydroxyl is originally)-methane.

Some other trifunctional compounds are 2,4-resorcylic acid, 1,3,5-benzenetricarboxylic acid, tricyanic acid and 3,3-two-(3-methyl-4-hydroxy phenyl)-2-oxygen-2,3-indoline.

Preferred branching agent is 3,3-two-(3-methyl-4-hydroxy phenyl)-2-oxygen-2,3-indoline and 1,1,1-three-(4-hydroxy phenyl)-ethane.

The method for preparing polycarbonate according to ester exchange method can be discontinuous or successive.In case when described dihydroxyl aryl compound and diaryl carbonate (optional have other compound) existed with the form of melt, described being reflected under the condition that has suitable catalyst began.In suitable equipment and device, isolating monohydroxy aryl compound is shifted, up to reaching required final state,, improve transformation efficiency or molecular weight thus along with temperature raises and pressure decline.The ratio of the ratio by selecting dihydroxyl aryl compound and diaryl carbonate, the diaryl carbonate that loses by steam and character and the concentration that the optional compound (the monohydroxy aryl compound higher as boiling point) that adds forms end group, wherein rate of loss provides by step or the device of selecting the preparation polycarbonate.

The device that described method is carried out does not have any restriction.And, temperature, pressure and the catalyzer that is used to carry out the melt transesterification reaction between dihydroxyl aryl compound and the diaryl carbonate (and optional other add reactant) there is not particular restriction, any condition can, remove isolating monohydroxy aryl compound fast as long as selected temperature, pressure and catalyzer can make melt transesterification be reflected at.

The temperature of whole technology is generally 180-330 ℃, and described pressure is between the absolute pressure of-0.01 millibar of 15 crust.As a rule, since favourable to product quality, so select consecutive steps.

The continuation method that is used to prepare polycarbonate better has following feature: one or more dihydroxyl aryl compound and diaryl carbonates, the optional reactant that also has other adding, use catalyzer, need not to separate condensation in advance under the condition of formed monohydroxy aryl compound, the reactive evaporation stage after many, temperature progressively raises, and pressure progressively reduces, and described molecular weight reaches required level.

Device, equipment and the reactor that is used for the independent reactive evaporation device stage be heat exchanger, Pressure-relief Device, separator, distillation column, vaporizer, stirred vessel and reactor or other under selected temperature and pressure, provide must the residence time commercially available equipment.The heat conduction of the necessary energy of selected device must have the structure that is suitable for improving continuously melt viscosity.

All devices interconnect by pump, pipeline and valve.Pipeline itself between all devices should be short as far as possible, and the degree of crook of described pipeline should be as far as possible little, to avoid the residence time of unnecessary length.Should consider described outside, i.e. the problems such as technological frame condition of chemical devices installation.

In order to carry out the method for preferred consecutive steps, described reactant can melt together, perhaps the solid biaryl compound can be dissolved in the diaryl carbonate melt, perhaps the solid carbonic acid diaryl ester is dissolved in the melt of dihydroxyl aryl compound, perhaps described two kinds of raw materials form melt together.The residence time of the independent melt of described raw material, the especially residence time of dihydroxyl aryl compound should be short as far as possible.On the other hand, the mixture of melt can be placed the long period, and can be not influential to quality, and this is that the fusing point of described raw mix is lower because compare independent raw material.

Add catalyzer (better being dissolved in the phenol) then, described melt is heated to temperature of reaction.Be used for by 2, when the commercial run that 2-two-(4-hydroxy phenyl)-propane and dipheryl carbonate base ester prepare polycarbonate began, described temperature was 180-220 ℃, better is 190-210 ℃, especially better is 190 ℃.In the residence time is 15-90 minute, when better being 30-60 minute, reaches described molecular balance, need not to remove the hydroxy aryl compound of formation.Described reaction can be carried out under air atmosphere, because technical reason also can carry out under overpressure condition.In full scale plant, described preferred pressure is a 2-15 crust absolute pressure.

Described melted blend is introduced in first vacuum chamber, and its pressure is adjusted to the 100-400 millibar, better is the 150-300 millibar, is heated to temperature of reaction or feeding temperature afterwards immediately in appropriate device under uniform pressure once more.In the relief pressure process, can there be any monomer in formed hydroxy aryl compound evaporation.After in storing up cylinder, stopping 5-30 minute, choose wantonly under uniform pressure and compatible temperature and circulate, described reaction mixture is introduced second vacuum chamber, other pressure is the 50-20 millibar, it better is the 80-150 millibar, being heated to 190-250 ℃ immediately under uniform pressure afterwards in appropriate device, better is 210-240 ℃, especially better is 210-230 ℃.Here, described hydroxy aryl compound evaporates, and can not have any monomer.After in storing up cylinder, stopping 5-30 minute, choose wantonly under uniform pressure and uniform temp and circulate with pump, described reaction mixture is introduced in the 3rd vacuum chamber, its pressure is the 30-150 millibar, be preferably the 50-120 millibar, being heated to 220-280 ℃ under uniform pressure immediately in appropriate device afterwards, being preferably 240-270 ℃, especially better is 240-260 ℃.Here, described hydroxy aryl compound evaporates, and does not stay any monomer.After in storing up cylinder, stopping 5-30 minute, choose wantonly under uniform pressure and uniform temp and circulate with pump, described reaction mixture is introduced in another vacuum chamber, its pressure is the 5-100 millibar, being preferably the 15-100 millibar, especially better is the 20-80 millibar, is heated to 250-300 ℃ under uniform pressure immediately in appropriate device afterwards, being preferably 260-290 ℃, especially better is 260-280 ℃.Here, described hydroxy aryl compound evaporates, and does not stay any monomer.

In this case, the number of times in these stages changes between 2 to 6, and for example 4.If change the number of times in stage, then want the therefore described temperature and pressure of appropriate change, to obtain comparable result.The relative viscosity of the described oligo-ester carbonate that obtains in these stages is 1.04-1.20, better is 1.05-1.15, especially better is 1.06-1.10.After in storing up cylinder, stopping 5-20 minute, choose wantonly under the pressure identical and identical temperature and circulate with pump with last flash stage, the gained oligo-ester carbonate adds in disc type or the basket reactor, at 250-310 ℃, more fortunately 250-290 ℃, especially more fortunately under 250-280 ℃ at the 1-15 millibar, the pressure of 2-10 millibar concentrates down more fortunately, the residence time is 30-90 minute, better is 30-60 minute.Described product reaches relative viscosity, is 1.12-1.28, better is 1.13-1.26, especially better is 1.13-1.24.The described melt that leaves reactor reaches required final viscosity or final molecular weight in disc type or basket reactor.Described temperature is 270-330 ℃, better is 280-320 ℃, especially better is 280-310 ℃, and pressure is the 0.01-3 millibar, better is the 0.2-2 millibar, and the residence time is 60-180 minute, better is 75-150 minute.Described relative viscosity transfers to the degree of described application requiring, is 1.18-1.40, better is 1.18-1.36, especially better is 1.18-1.34.

The function of described two basket reactors also can be combined in the basket reactor.Discharge the steam of all operation stages immediately, collect and extract.This extraction is undertaken by distillation usually, to obtain highly purified recover materials.This can for example carry out according to U.S. Patent application No.10100404 (United States Patent (USP) 6706473, its reference in content is incorporated in this).From economy and ecology, be significant with the rate of recovery of the isolating monohydroxy aryl compound of high-purity forms.Described monohydroxy aryl compound can be directly used in preparation dihydroxyl aryl compound or diaryl carbonate.

The difference of described disc type or basket reactor is the long residence time, and they provide the surface area of very big continual renovation in a vacuum.With regard to geometrical shape, described disc type or basket reactor form according to the melt viscosity of described product.Suitable reactor is DE 4447422C2 and EP A 1253163 described reactors for example, or the twin shaft reactor described in the WO A 99/28370 (corresponding United States Patent (USP) 5779986,6630563 and 6329495, its reference in content is incorporated in this).

Described oligo-ester carbonate (comprising the oligo-ester carbonate that molecular weight is very low) and final polycarbonate are carried by toothed gear pump, dissimilar screw rod or special piston pump usually.

The especially suitable material that is used for preparation facilities, reactor, pipeline, pump and accessory is the stainless steel of CrNi (Mo) 18/10 type, as for example 1.4571 or 1.4541 (Stahlschlussel 2001 Verlag:Stahlschlussel Wegst GmbH, Th-Heuss-Stra β e 36, D-71672 Marbach) and the Ni of Type C base alloy, 2.4605 or 2.4610 (Stahlschlussel 2001 Verlag:Stahlschlussel Wegst GmbH for example, Th-Heuss-Stra β e 36, D-71672 Marbach).Stainless steel uses under about 290 ℃ at the most processing temperature, and Ni-base alloy uses under about 290 ℃ at the most technological temperature.

Impurity

React the polycarbonate that makes comprises catalytic activity after preparation alkaline impurities by melt transesterification.These impurity are to be brought by the unsegregated alkaline residues of the unsegregated alkaline residues of unsegregated trace impurity, heat decomposable catalyzer in the raw material or stable basic catalyst salt on the one hand.Heat decomposable catalyzer for example is interpreted as, above-mentioned salt.Heat-staple catalyzer for example is the alkali reaction salt of basic metal or alkaline-earth metal.

In order to suppress the alkaline impurities of catalytic activity, add in the polycarbonate in the time of can be with the above-mentioned inhibitor of the present invention various in each technological process.Joining day there is not any restriction.Inhibitor is generally understood as all compounds that suppress chemical kinetics in decisive mode, avoids occurring in the polymkeric substance variation that quality reduces.

Inhibitor

In case reach the molecular weight of polycarbonate requirement, better add the inhibitor shown in the general formula of the present invention (I)-(XI).In order effectively to add inhibitor, use and can produce mixed uniformly static mixer or other mixing tank, for example, forcing machine is suitable.In one situation of back, the side direction forcing machine by polymer melt joins described thermo-stabilizer and optional other material such as releasing agent on the main polymer melt fluid.

Inhibitor of the present invention can be separately or is added in the described polymer melt with the form of mutual mixture perhaps many different mixtures.In addition, also can be with inhibitor of the present invention and free sulfonic derivative, as the mixture of Phenylsulfonic acid or toluenesulphonic acids.

The fusing point of described inhibitor is better greater than 30 ℃, and better greater than 40 ℃, especially better greater than 50 ℃, the boiling point under 1 millibar is greater than 150 ℃, better greater than 200 ℃, especially better greater than 230 ℃.

In polycarbonate, the consumption of inhibitor of the present invention is less than 10ppm, better less than 50ppm, especially better less than 30ppm, preferably less than 15ppm.

Better use 0.5ppm, especially better 1ppm at least, inhibitor or the mixture of preferred 1.5ppm.Specifically, in polycarbonate, the consumption of described inhibitor is 2-10ppm.If need, they also can and free acid (for example, ortho-phosphoric acid) or other form that is suitable for the mixture of additive (for example Phenylsulfonic acid or toluenesulphonic acids) as stablizer use.The amount of free acid or other inhibitor is 20ppm at the most, and better 10ppm at the most especially is 0-5ppm.

The form that adds inhibitor of the present invention there is not any restriction.The ester of acid or its mixture that the present invention can be the organic sulfur-containing of solid (being powder), solution or melt form add in the polymer melt.The another kind of type of metering is to use masterbatch (better having polycarbonate), also comprises other additive, as other stablizer or releasing agent.

The ester of the acid of organic sulfur-containing of the present invention better adds with liquid form.Because the amount that is metered into is very little, better use the solution of bridging ester of the present invention.It is chemically inert can not disturbing the suitable solvent of described method, and can evaporate rapidly.

Suitable solvent is that boiling point is 30-300 ℃ under normal pressure, better is 30-250 ℃, especially better is all organic solvents of 30-200 ℃, and water (comprising crystal water).Better be chosen in those compounds that exist in the described concrete technology.The residue that stays can not reduce the quality of product, and this depends on the requirement of prepared product.

Except water, solvent is alkane, naphthenic hydrocarbon and aromatic substance, and they also can be substituted.Described substituting group can be aliphatic series, cyclic aliphatic or the aromatic group of various combination, and halogen or hydroxyl.Heteroatoms such as oxygen also can be the bridge portions between aliphatic series, cyclic aliphatic or the aromatic group, and described group is identical or different.Other solvent also can be ketone and organic acid ester, and cyclic carbonate.Described inhibitor also can dissolve and be metered in glyceryl monostearate.

Except water, example is Skellysolve A, normal hexane, normal heptane and isomer thereof, chlorobenzene, methyl alcohol, ethanol, propyl alcohol, butanols and isomer thereof, phenol, o-methoxycresol, m-methoxycresol, p-methoxycresol, acetone, diethyl ether, dimethyl ketone, polyoxyethylene glycol, polypropylene glycol, ethyl acetate, carbonic acid ethylidene ester and propylene carbonate.

The better solvent that is suitable for preparing polycarbonate technology is water, phenol, propylene carbonate, carbonic acid ethylidene ester and toluene.

Especially be preferably water, phenol and propylene carbonate.The sulfonic acid of free sulfonic and partial esterification forms with alcohol, as the degraded product of the inhibitor shown in the general formula of the present invention (I)-(VII).

After adding inhibitor of the present invention, also can provide the material (for example, auxiliary substance and enhancing substance) of other conventional additives and adding to be used for changing character to the gained polycarbonate.Adding additive and described adding material play and (for example increase the service life, hydrolysis or degraded stablizer), (for example improve colour stability, thermo-stabilizer and UV stabilizer), (for example simplify technology, releasing agent, glidant), (for example improve use properties, static inhibitor), improve flame retardant resistance, influence its outward appearance (for example, organic colorant, pigment) or make polymer property adapt to the effect of concrete stress requirement (impact modifier, thin inorganics, filamentary material, quartz powder, glass fibre and carbon fiber).All these materials can mix on request, to obtain required character.The material of this adding and additive be as " Plastics Additives ", R.Gachter and H.Muller, and HanserPublishers 1983 is described.

The material of these additives and adding can be in the process of isolating polymer directly or in so-called mixing step after the fusing particle, add in the polymer melt respectively or with the form of any desired mixt perhaps many different mixtures.

The material of described additive and adding or their mixture can add polymer melt with the form of solid (being powder) or melt.Another kind is metered into the masterbatch that is to use parent compound or additive or additive agent mixture.

On demand, these materials join in the final polycarbonate in the conventional equipment more fortunately, also can add in the different steps of polycarbonate technology.

Suitable additive such as Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999 or Plastics Additives Handbook Hans ZweifelHanser, Munich 2001 is described.

Following examples are used to illustrate the present invention, rather than are used to limit the present invention:

Embodiment

The relative viscosity of solution concentration with 5g/l under 25 ℃ is measured in methylene dichloride.

Measure the content that can make phenols OH by IR.For this reason, the 2g polymkeric substance is carried out in the solution of 50ml methylene dichloride and the absolute dichloromethane measurement, and determine at 3582cm ^-1Under dullness difference.

GMS is interpreted as the mixture of monopalmitin and glyceryl monostearate.

Described total GMS content is by free GMS (GMS _Free), GMS carbonic ether (GMS-CO3) and bonded GMS constitute.The latter is calculated by difference.Part sample carries out alkaline hydrolysis under 80 ℃, use hydrochloric acid to transfer to about pH1 then.Described solution extracts with t-butyl methyl ether, and dry extract.After derivatization, by at the enterprising promoting the circulation of qi analysis of hplc of the capillary column with flame ionization detector.Carry out qualitative assessment by internal standard, provide the GMS total content.

Another part sample dissolution in methylene dichloride, and is derived.In the enterprising promoting the circulation of qi phase of capillary column chromatographic separation, and after detecting with flame ionization detector (FID), carry out qualitative assessment by internal standard.Obtain the content of free GMS and GMS carbonic ether.By GC-FID glyceryl monostearate in the polycarbonate (GMS) and glycerol monostearate carbonic ether (GMS carbonic ether) are carried out quantitative analysis:

Will about 0.5g sample dissolution in 5mlCH2Cl2, and add internal standard (for example, normal alkane).About 5ml t-butyl methyl ether (MTBE) is added in this solution, to deposit described polymkeric substance.Then, with described suspension vibration and centrifugation.Use pipette to take out the quantitatively supernatant liquid of (3ml), and under nitrogen atmosphere, be concentrated into dried.Described residue carries out silylation with MSTFA solution (N-methyl-N-(trimethyl silyl)-trifluoroacetamide).Described filtering solution carries out stratographic analysis by gas-chromatography (GC, for example HP6890).Detection is undertaken by flame ionic detector.

Determine the analytical procedure of residual monomer

Sample dissolution in methylene dichloride, and is deposited by acetone/methanol once more.Separate described sedimentary polymkeric substance, and filtered liquid is concentrated.Carry out the quantitative analysis of residual monomer by reverse-phase chromatography.In the chromatogram of moving phase, gradient is the chromatogram of 0.04% phosphoric acid-acetonitrile.Detect by UV.

By this way, determine bis-phenol (BPA), phenol, tert.-butyl phenol (BUP), dipheryl carbonate base ester (DPC) and carbonic acid two BUP esters.

The material that uses:

Polycarbonate A: relative solution viscosity 1.204

The content 500ppm of phenols OH

DPC 500ppm

BPA 20ppm

Phenol 100ppm

Inhibitor A

Inhibitor B

Inhibitor C

Inhibitor of the present invention is studied by the long term thermal load of polycarbonate the effect that improves the polycarbonate thermostability.

Embodiment A

Inhibitor A's is synthetic:

Glycerine Phenylsulfonic acid glycerin chlorohydrin three benzene sulfonates

(MW 92.10) (MW 176.62) (MW 512.58)

552.6g (6.0mol) glycerine (KMF) and 4746g (60mol) pyridine (Aldrich) are placed nitrogen, and dissolving evenly.Drip 31968g (18.1mol) Phenylsulfonic acid chlorine, temperature can be above 30-35 ℃ in this course very slowly.Stirred 1 hour down at 40 ℃ then.

Extract

Under intense agitation, described batch of material joined very slowly in the methylene dichloride of 3 liters the ice of distilled water, 4kg and 3 liters.In adition process, temperature should be above 35 ℃.

Described then organic phase deposits in about 10 liters of methyl alcohol, and carries out suction filtration, washs with methyl alcohol, shows that up to thin-layer chromatography described product is clean.

In 60 ℃ vacuum drying oven, be dried to constant weight then.

Productive rate: 970g (31.54% theory), white powder

Analyze:

Fusing point: 81-83 ℃

1H-NMR(400MHz，TMS，CDCl3)5＝7.8ppm(m，6H)，7.7(m，3H)，7.55(m，6H)，4.75(m，1H)，4.1(d，4H)。

Embodiment 1

In the amount of used polycarbonate, among the inhibitor A adding raw material polycarbonate A with 2.5ppm, make described mixture in nitrogen and vacuum, keep inertia.Described sample is immersed in the bath that is heated to 300 ℃ in advance, and under condition of high vacuum degree, melted 20 minutes, need not to stir.As long as described sample fusing starts agitator, and removes a spot of sample.Be stirred in and carry out 2 hours, after 30,60 and 120 minutes, take out small amount of sample.

Determine the relative viscosity and the residual monomer content (table 1) of these samples.

Embodiment 2

Shown in embodiment 1, but the inhibitor B of adding 2.5ppm.

Embodiment 3

Shown in embodiment 1, but the inhibitor C of adding 2.5ppm.

Comparative Examples 1

Shown in embodiment 1, but unconstrained dose.

Comparative Examples 2

Shown in embodiment 1, but the toluenesulphonic acids ethyl ester that is to use 2.5ppm is as inhibitor.

Comparative Examples 3

Shown in embodiment 1, but the ortho-phosphoric acid that is to use 2.5ppm is as inhibitor.

With regard to the active inhibition of polycarbonate polycondensation (relative viscosity raises little in the vacuum), these embodiment show inhibitor of the present invention positively effect (with without inhibitor, use bridging inhibitor not and relatively easy evaporable acid test relatively), simultaneously effectively reduced residual monomer, shown in dipheryl carbonate base ester (DPC) embodiment.

Material 1.4571 and 2.4605 corrosive test (having added 0.41 weight % inhibitor C) is presented at 300 ℃ and keeps down and also do not demonstrate corrosion (wear rate is less than 0.01mm/a) after 600 hours in the polycarbonate.

Inhibitor of the present invention is used to suppress the active effect of polycarbonate catalyst also can be by being metered into glyceryl monostearate research.

Embodiment 4

GMS is added in the polycarbonate melt (relative viscosity is 1200) of 4600kg/ hour flow, to improve demoulding behavior.For this reason, in biaxial extruder (shaft diameter is 70mm), melt the 400kg polycarbonate pellets down at 290 ℃.46g/h inhibitor C (1ppm is in the polycarbonate fluid) is dissolved in the phenol/water mixture (90: 10), and is metered into, added polycarbonate melt by this unlimited cover by the unlimited cover of forcing machine.Immediately 1560g liquid GMS (90 ℃ of temperature of fusion) is metered in the compatible forcing machine by pipeline afterwards, enters another and open wide cover.Make some nitrogen through opening wide cover, so that the mixture inertia.The described melt that leaves forcing machine is carried by toothed gear pump, and pumps in the main melt-flow, and its temperature is 288 ℃.Mix on flow direction at the position that melt-flow is joined with static mixer immediately, this gas mixture is evenly distributed to additive in the main melt-flow.Discharge described melt then, and granulation.The value shown in the meter 2 in product.

Comparative Examples 4:

Shown in embodiment 4, but do not add inhibitor.

Table 2

	Free GMS/ppm	GMS-CO3/ppm	In conjunction with GMS/ppm
				Embodiment 4	242	35	66
Comparative Examples 4	81	239	23

Can clearly find to add the positively effect of inhibitor of the present invention free releasing agent stability in joining polymer melt the time.

Though below described the present invention in detail, it should be understood that these details only are used for illustrative purposes, under the condition that does not deviate from spirit and scope of the invention, those skilled in the art can make conversion, as long as they are in the scope of described claim.

Claims (3)

1. melt transesterification method that is used to prepare polycarbonate, described method comprises medium-viscosity reactor and high viscosity reactor, it is characterized in that, add the bridging ester of the acid of at least a organic sulfur-containing in the technology between described reactor, described bridging ester is the compound shown in the following general formula:

(a) compound shown in the general formula (I):

In the formula, substituent R ¹Represent hydrogen independently of each other or do not replace or C that halogen replaces ₁-C ₂₀-alkyl,

R ²And R ³Represent hydrogen or C independently of each other ₁-C ₆Alkyl, C ₄-C ₃₀-alkyl carboxyl, or R ²And R ³Group shown in being expressed as follows:

In the formula, R ¹Have above-mentioned implication,

The expression 0 or 1 that m is separate,

N represents the integer of 0-8;

(b) compound shown in the general formula (IV):

In the formula, R ¹Have above-mentioned implication with n,

R ⁴Expression C ₄-C ₃₀-alkyl carboxyl, or the following group of expression:

In the formula, R ¹Has above-mentioned implication; And

(c) compound shown in the logical formula V,

(d) compound shown in the general formula (VI),

(e) compound shown in the general formula (VIIa),

(f) compound shown in the general formula (VIIb),

(g) general formula (Ib) and (IVa) shown in compound:

In the formula, R ¹Have above-mentioned implication with n,

Q represents the integer of 0-10,

R ⁵And R ⁶Represent hydrogen or C independently of each other ₁-C ₂₀-alkyl

R ¹¹Represent hydrogen or two-(C independently of each other ₁-C ₄)-alkylamino.

2. the method for claim 1 is characterized in that, with respect to the weight of polycarbonate, the amount of described ester is 100ppm at the most.

3. a bridging ester that uses the acid of the described organic sulfur-containing of claim 1 suppresses in the polycarbonate method of catalytically active impurities in the melt transesterification method.