CN1033094C - Preparation of carbonic acid esters from dihydroxydiphenylcycloalkane - Google Patents

Abstract

The present invention relates to dihydroxydiphenylcycloalkanes of the formula (I) in which R<1> and R<2>, independently of one another, are hydrogen, halogen, C1-C8-alkyl, C5-C6-cycloalkyl, C6-C10-aryl or C7-C12-aralkyl, m is an integer from 4 to 7, R<3> and R<4>, independently of one another and individually selectable for each X, are hydrogen or C1-C5-alkyl, and X is carbon, with the proviso that, on at least one atom X, R<3> and R<4> are simultaneously alkyl, to the use of the diphenols of the formula (I) for the preparation of high-molecular-weight polycarbonates.

Description

Use the method that dihydroxy-phenyl cycloalkane prepares polycarbonate

The dihydroxy-phenyl cycloalkane that the present invention relates to application formula (I) prepares the high molecular aromatic polycarbonate:

R wherein ¹And R ²Represent hydrogen, halogen, preferably chlorine or bromine, C independently of each other ₁-C ₈Alkyl, C ₅-C ₆Cycloalkyl, C ₅-C ₁₀Aryl, preferably phenyl, and C ₇-C ₁₃Aralkyl, preferably phenyl C ₁-C ₄Alkyl, particularly benzyl, m are 4～7 integers, preferably 4 or 5, and R ³And R ⁴, can select respectively for each X, represent hydrogen or C independently of each other ₂-C ₆Alkyl, X represents carbon, but the R on an atom X at least ³And R ⁴Be alkyl.Preferably on 1 or 2 atom X, particularly only on 1 atom X, R ³And R ⁴Be alkyl.Best alkyl is a methyl.X atom on the alpha-position of the C atom (C-1) that phenylbenzene replaces preferably is not that dialkyl group replaces, and preferably dialkyl group replacement of the X atom on β-position of C-1.Especially, an X atom on β-position of C-1 is that dialkyl group replaces, and at the β of C-1 ¹An X atom the on-position is that monoalkyl replaces.More particularly, the present invention relates in cycloaliphatic radical, to contain the dihydroxy-phenyl-cyclohexanes of 5 and 6 ring C atoms (m=4 or 5 in formula (I)), for example corresponding to the bis-phenol of following formula With

1,1-pair-(4-hydroxy phenyl)-3,3,5-trimethyl-cyclohexane (formula (II)) is good especially.

Can adopt currently known methods to pass through to make corresponding to the dihydroxyl phenylbenzene cycloalkanes of formula (I) corresponding to the phenol of formula V with corresponding to the condensation of the ketone of formula (VI).

Wherein X, R ¹, R ², R ³, R ⁴With the regulation in the definition cotype (I) of m.

Phenol corresponding to formula V is that the known method that maybe can adopt oneself to know makes (for cresols and xylenol, referring to for example Ullmanns Encyklop  dieder technischen chemie, the 4th revision and added edition, 15 volumes, 61～77 pages, Verlag chemie, Weinheim/NewYork, 1978; For chlorinated phenol, referring to UllmannsEncyklop  die der technischen Chemie, the 4th edition, Verlag Chemie, 1975,9 volumes, 573～582 pages; And for alkylphenol, referring to Ullmanns Encyklop  die dertechnischen Chemie, the 4th edition, Verlag Chemie1979,18 volumes, 199-214 page or leaf).

The example of suitable phenol corresponding to formula V is phenol, Ortho Cresol, m-cresol, 2,6-xylenol, 2-chlorophenol, 3-chlorophenol, 2,6-chlorophenesic acid, 2-cyclohexylphenol, 2,6-phenylbenzene phenol and 2-methane.

Ketone corresponding to formula (VI) is known (referring to for example BeilsteinsHandbuch der Organischen Chemie, 7 volumes, the 4th edition, Springer-Verlag, Berlin, 1925 and corresponding ancillary volume 1～4, (1975) 1488,1492 pages of J.Am.Soc.79 volumes, United States Patent (USP) 2,692,289; J.Chem.Soc., (1954), 2186～2192 and J.Org.Chem.38 volume, (1973), 4431～4435 pages, J.Am.Chem.Soc.87, (1965), 1353～1364 pages).For example at " Organikum ", the 15th edition, 1977, VEB-Deutscher Verlag derWissenschaften, Berlin, a kind of as having introduced on 698 pages corresponding to preparation method the ketone of formula (VI).

Following is the example of known ketone corresponding to formula (VI): 3, the 3-cyclopentanone dimethyl, 3, the 3-dimethylcyclohexanon, 4, the 4-dimethylcyclohexanon, 3-ethyl-3-methyl-cyclopentanone, 2,3,3-trimethylammonium cyclopentanone, 3,3,4-trimethylammonium cyclopentanone, 3,3-dimethyl suberone, 4,4-dimethyl suberone, 3-ethyl-3-methylcyclohexanone, 4-ethyl-4-methylcyclohexanone, 2,3, the 3-trimethylcyclohexanone, 2,4, the 4-trimethylcyclohexanone, 3,3, the 4-trimethylcyclohexanone, 3,3, the 5-trimethylcyclohexanone, 3,4, the 4-trimethylcyclohexanone, 2,3,3,4-tetramethyl-ring pentanone, 3,3,5-trimethylammonium suberone, 3,5,5-trimethylammonium suberone, 5-ethyl-2,5-dimethyl suberone, 2,3,3,5-tetramethyl-ring heptanone, 2,3,5,5-tetramethyl-ring heptanone, 3,3,5,5-tetramethyl-ring heptanone, 4-ethyl-2,3,4-trimethylammonium cyclopentanone, 3-ethyl-4-sec.-propyl-3-methyl-cyclopentanone, 4-sec-butyl-3, the 3-cyclopentanone dimethyl, 2-sec.-propyl-3,3,4-trimethylammonium cyclopentanone, 3-ethyl-4-sec.-propyl-3-methylcyclohexanone, 4-ethyl-3-sec.-propyl-4-methylcyclohexanone, 3-sec-butyl-4, the 4-dimethylcyclohexanon, 2-butyl-3,3,4-trimethylammonium cyclopentanone, 2-butyl-3,3, the 4-trimethylcyclohexanone, 4-butyl-3,3, the 5-trimethylcyclohexanone, 3-isohexyl-3-methylcyclohexanone and 3,3,8-trimethylammonium cyclooctanone.

Following is the example of ketone preferably:

With

In order to prepare bisphenols, every mole of ketone (VI) relatively, the consumption of phenol (V) is generally 2～10 moles, is preferably 2.5～6 moles.Reaction times is 1～100 hour preferably.This reaction is usually at 100～2000kPa (1～20 crust) and preferably under the pressure of 100～1000kPa (1～10 crust), in-30 ℃～300 ℃ and preferably-15 ℃～carry out under 150 ℃ the temperature.

This condensation is carried out in the presence of an acidic catalyst usually, and these an acidic catalysts are mixtures of hydrogenchloride, hydrogen bromide, hydrogen fluoride, boron trifluoride, aluminum chloride, zinc dichloride, titanium tetrachloride, tin tetrachloride, Phosphorates phosphorus Halides, Vanadium Pentoxide in FLAKES, phosphoric acid, concentrated hydrochloric acid or sulfuric acid and acetate and diacetyl oxide for example.Also can use acid ion exchangers.

In addition, can be by adding for example C of co-catalyst ₁～C ₁₈Alkanethiol, hydrogen sulfide, thiophenol, thioic acid sulfoacid and dialkyl sulfide quicken this reaction, and its consumption is 0.01～0.4 moles/mole ketone, particularly 0.05～0.2 moles/mole ketone.

This condensation can be carried out under the condition of solvent or in the presence of inert solvent (for example aliphatic series or aromatic hydrocarbon, hydrochloric ether) not having.

Though, during water in used catalyzer can not association reaction, use dewatering agent always favourable for the transformation efficiency that obtains, also play at catalyzer under the situation of dewatering agent effect, do not need to use independent dewatering agent.

Suitable dewatering agent is for example diacetyl oxide, zeolite, Tripyrophosphoric acid and Vanadium Pentoxide in FLAKES.

Therefore, the present invention also relates to a kind of preparation method of the dihydroxy-phenyl cycloalkane corresponding to formula (I) R wherein ¹And R ²Represent hydrogen, halogen independently of each other, preferably chlorine or bromine, C ₁-C ₈Alkyl, C ₅-C ₆Cycloalkyl, C ₈-C ₁₀Aryl, preferably phenyl and C ₇-C ₁₂Aralkyl, preferably phenyl C ₁-C ₄Alkyl, particularly benzyl.M is 4～7 integer, preferably 4 or 5, and R ³And R ⁴, can select respectively for each X, represent hydrogen or C independently of each other ₁-C ₆Alkyl, X represents carbon, but the R at least one atom X ³And R ⁴Be alkyl, it is characterized in that, in the presence of an acidic catalyst, and can be in the presence of co-catalyst and/or solvent and/or dewatering agent,-30 ℃～300 ℃ preferably-15 ℃～150 ℃ temperature and the pressure of 100～1000kPa (1～10 crust) under, at (V): mol ratio (VI) is under 2: 1～10: 1 preferably 2.5: 1～6: 1 the condition, will react corresponding to the phenol of formula V and ketone corresponding to formula (VI) R wherein ¹And R ²Definition cotype (I) in regulation, Wherein X, m, R ³And R ⁴Definition cotype (I) in regulation.

In formula (I), better be on 1 or 2 atom X and only be more preferably on 1 atom X R ³And R ⁴It all is alkyl.Though also can use the C of ethyl or line style or branching ₃-C ₆Alkyl, but alkyl is a methyl preferably.X atom on the alpha-position of the C atom (C-1) that phenylbenzene replaces preferably is not that dialkyl group replaces, and the X atom on the β position of C-1 preferably dialkyl group replace.More particularly, an X atom on the β position of C-1 is that dialkyl group replaces, and an X atom on β ' position of C-1 is the monoalkyl replacement.

In some cases, this reaction is not quite identical, can generate several different products, so at first desired compound must be emanated from mixture.For the detail of this condensation, can be with reference to Schnell, Chemistry and physicsOf polycarbonates, Interscience publishers, New York 1964.In some cases, can control this reaction, be about to desired compound precipitation or crystallization, come out thereby make it be easier to segregation by selecting appropriate catalyst and reaction conditions in such a way.

Example is the preparation of the bis-phenol of formula (II) A.1

Under 28～30 ℃, 7.5 moles of (705 gram) phenol and 0.15 mole of (30.3 gram) one of dodecyl mercaptans adding are equipped with in 1 liter of round-bottomed flask of agitator, dropping funnel, thermometer, reflux exchanger and gas inlet pipe, and saturated with dried HCl gas.Be added in the solution of top gained with the drips of solution of 3 hours times with 1,5 mole of (210 gram) dihydro-isophorone (3,3,5-3-methyl cyclohexanol-1-ketone) and 1.5 moles of (151 gram) phenol, HCl gas continues by this reaction soln.After intact, logical again HCl gas 5 hours.This mixture was at room temperature reacted 8 hours.Remove excessive phenol by steam distillation then.Residue extracts secondary with sherwood oil (60-90) heat, with dichloromethane extraction once, filters.Product: 370 grams, Mp:205-207 ℃.

Example is the preparation of the bis-phenol of formula (II) A.2

Under 28～30 ℃, with 1692 gram (18 moles) phenol, 60.6 gram (0.3 mole) dodecyl mercaptans and 420 gram (3 moles) dihydro-isophorones (3,3,5-3-methyl cyclohexanol-1-ketone) adds in the device that is stirring that agitator, thermometer, reflux exchanger and gas inlet pipe be housed.Under 28～30 ℃, will do HCl gas and introduce this solution 5 hours.This mixture was reacted about 10 hours down at 28～30 ℃.When ketone has transformed 95% (measuring with GC), 2.5 premium on currency are added in this reaction mixture, and the pH value is transferred to 6 by adding 45%NaOH solution.This reaction mixture stirred one hour down at 80 ℃, cooled off 25 ℃ then.The water decant is come out, and remaining resistates washes with water under 80 ℃ and waters.The gained crude product is leached, extract secondary, use the dichloromethane extraction secondary again, filter then with normal hexane heat.This resistates dimethylbenzene recrystallization secondary.Product: 753 gram fusing points: 209～211 ℃.

Example is the preparation of the bis-phenol of formula (II) A.3

Under 30 ℃, with 564 gram (6 moles) phenol, 10.8 gram (0.12 mole) butyl sulfhydryl and 140 gram (1 mole) dihydro-isophorones (3,3,5-3-methyl cyclohexanol-1-ketone) add and be equipped with in the device that is stirring of agitator, thermometer, reflux exchanger and gas inlet pipe.Under this temperature, add 44 gram 37%HCl.This reaction mixture was 28～30 ℃ of following stir abouts 70 hours.When ketone has transformed 95% (measuring with GC), 2 premium on currency are added in this reaction mixture, and the pH value is transferred to 6 by adding 45%NaOH solution.This reaction mixture stirs down at 80 ℃ and was chilled to 25 ℃ then in 1 hour.The water decant is come out, and remaining resistates washes with water under 80 ℃.The gained crude product is leached, and extract secondary, use the methylbenzene extraction secondary again, filter down at 30 ℃ then with hexane heat.Product: 205～208 ℃ of 253 gram fusing points.

Example is formula (Ib) (R A.4 ¹And R ²=CH ₂) the preparation of bis-phenol

Under 35 ℃, with 2196 gram (18 moles) 2,6-xylenol, 38.2 gram (0.36 mole) β-Qiu Jibingsuans and 420 gram (3 moles) dihydro-isophorones (3,3,5-3-methyl cyclohexanol-1-ketone) add and be equipped with in the device that is stirring of agitator, thermometer, reflux exchanger and gas inlet pipe.Under 35 ℃, will do HCl gas and feed this solution 5 hours.This mixture was reacted about 10 hours down at 28～30 ℃.When ketone has transformed 95% (measuring with GC), 2.5 premium on currency are added in this reaction mixture, and the pH value is transferred to 6 by adding 45%NaOH solution.This reaction mixture stirred 1 hour down at 80 ℃, was chilled to room temperature then.The water decant is come out, and remaining resistates washes with water under 60 ℃.The gained crude product is leached, and extract three times, filter then with normal hexane heat.Product: 856 gram fusing points: 236～238 ℃.

Example is the preparation of the bis-phenol of formula (III) A.5

Adopt the method A.2 identical with example, use 3 mole 3, the 3-dimethylcyclohexanon replaces 3 moles of dihydro-isophorones.The fusing point of this product is 190～201 ℃.

The bis-phenol of formula of the present invention (I) is particularly suitable for preparing the high-molecular-weight thermoplastic polycarbonate, and the characteristics of this polycarbonate are the superperformances that has high heat resistance and have other.

The bis-phenol that the purpose of this invention is to provide application formula (I) prepares the method for high-molecular-weight thermoplastic aromatic polycarbonate.

Can use single bis-phenol, in the case, obtain homo-polycarbonate, also can use several bis-phenols, in this case, obtain Copolycarbonate corresponding to formula (I) corresponding to formula (I).

In addition, when preparation high-molecular-weight thermoplastic aromatic polycarbonate, also can with corresponding to the bis-phenol of formula (I) with other bis-phenol for example those (bis-phenol of V (VII) mixes use corresponding to formula OH-Z-OH.

Other suitable bis-phenol corresponding to formula OH-Z-OH (VII) is those, wherein Z is the aryl that contains 6～30 C atoms, it can contain one or more virtue nuclears, it can replace, and can contain aliphatic group or the cycloaliphatic radical except that those cycloaliphatic radicals corresponding with formula (I) or as the heteroatoms of bridge joint.

Example corresponding to the bis-phenol of formula (VII) is quinhydrones, Resorcinol, dihydroxybiphenyl, two (hydroxy phenyl) alkane, two (hydroxy phenyl) naphthenic hydrocarbon, two (hydroxy phenyl) thioether, two (hydroxy phenyl) ether, two (hydroxy phenyl) ketone, two (hydroxy phenyl) sulfone, two (hydroxy phenyl) sulfoxide, α, and α '-two (hydroxy phenyl) diisopropyl benzene and ring thereof are by halogenated compound.

These and other suitable bis-phenol is introduced in following patent and document, and for example United States Patent (USP) 3,028, and 365,2,999,835,3,148,172.3,275,601,2,991,273,3,271,367,3,062,781,2,970,131 and 2,999,846; Germany's prospectus 1570703,2063050,2063052,22110956, the book of French Patent 1561518 and Schnell " Chemistry and physics ofPolycarbonates ", Interscience publishers, New York, 1964.

Other bis-phenol is for example 4 preferably, 4 '-dihydroxybiphenyl, 2, two (4-hydroxy phenyl) propane of 2-, 2, two (4-the hydroxy phenyl)-2-methylbutanes of 4-, 1, the 1-bis(4-hydroxyphenyl) cyclohexane, α, α '-two (4-hydroxy phenyl) is to diisopropyl benzene, 2, two (3-methyl-4-hydroxy phenyl) propane of 2-, 2, two (the 3-chloro-4-hydroxy phenyl) propane of 2-, two (3,5-dimethyl-4-hydroxy phenyl) methane, 2,2-two (3,5-dimethyl-4-hydroxy phenyl) propane, two (3,5-dimethyl-4-hydroxy phenyl) sulfone, 2, two (3,5-dimethyl-4-the hydroxy phenyl)-2-methylbutanes of 4-, 1,1-two (3,5-dimethyl-4-hydroxy phenyl) hexanaphthene, α, α '-two (3,5-dimethyl-4-hydroxy phenyl) is to diisopropyl benzene, 2,2-two (3,5-two chloro-4-hydroxy phenyls) propane and 2, two (3, the 5-two bromo-4-hydroxy phenyls) propane of 2-.

The good especially bis-phenol corresponding to formula (VII) is for example 2, two (4-hydroxy phenyl) propane, 2 of 2-, 2-two (3,5-dimethyl-4-hydroxy phenyl) propane, 2, two (3, the 5-two chloro-4-hydroxy phenyls) propane, 2 of 2-, 2-two (3,5-two bromo-4-hydroxy phenyls) propane and 1, two (4-hydroxy phenyl) cyclohexanes of 1-.

2, two (4-hydroxy phenyl) propane of 2-are good especially.

These other bis-phenol can use separately also and can mix use mutually.

Corresponding to the bis-phenol of formula (I) and spendable other bis-phenol for example corresponding to the mol ratio of those bis-phenols of formula (VII) be by 100% (mole) (I) and 0% (mole) other bis-phenol to 2% (mole) (I) with 98% (mole) other bis-phenol, be preferably by 100% (mole) (I) and 0% (mole) bis-phenol to 5% (mole) (I) with 95% (mole) other bis-phenol, be more preferably by 100% (mole) (I) and 0% (mole) other bis-phenol to 10% (mole) (I) and 90% (mole) other bis-phenol, best is by 100% (mole) (I) with 0% (mole) other bis-phenol to 20% (mole) (I) with 80% (mole) other bis-phenol.

Can adopt any currently known methods that is used to prepare polycarbonate to be prepared corresponding to the high-molecular-weight polycarbonate of the bis-phenol of formula (I) (can in conjunction with other bis-phenol).Various bis-phenols interconnect can be statistical also can be block.

Therefore, the present invention also relates to a kind of by the known method for preparing polycarbonate, the method that preferably prepares the macromolecular thermoplastic aromatic polycarbonate by bis-phenol, available chain terminator and available branching agent by interfacial polycondensation, wherein based on the integral molar quantity of used bis-phenol, the consumption of the bis-phenol of formula (I) is 100% (mole)～2% (mole), it better is 100% (mole)～5% (mole), be more preferably 100% (mole)～10% (mole), preferably 100% (mole)～20% (mole).

If used branching agent, it is measured also seldom, and they are known substances, better is that 0.05～2.0% (mole) is (based on the trifunctional of the amount of used bis-phenol or more than the compound of trifunctional, particularly those contain the compound of three or three above phenolic hydroxyl groups.The branching agent that contains three or three above phenolic hydroxyl groups comprises Phloroglucinol, 4,6-dimethyl-2,4,6-three (4-hydroxy phenyl) hept-2-ene", 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, two (4-hydroxy phenyl) cyclohexyl of 4-) propane, 2, two (the 4-hydroxy phenyl sec.-propyl) phenol of 4-, 2,6-pair (2-hydroxyl-5 '-methyl-benzyl)-the 4-methylphenol, 2-(4-hydroxy phenyl)-2-(2, the 4-dihydroxy phenyl) propane, the former terephthalate of six (4-(4-hydroxy phenyl sec.-propyl) phenyl), four (4-hydroxy phenyl) methane, four (4-(4-hydroxy phenyl sec.-propyl) phenoxy group) methane and 1,4-pair (4 ', 4 " the dihydroxyl trityl group) benzene.

Some other trifunctional compound is 2,4-resorcylic acid, 1,3,5-benzenetricarboxylic acid, cyanuryl chloride and 3, two (3-methyl-4-the hydroxy phenyl)-2-oxygen-2 of 3-, 3-indoline.

Monofunctional compound can conventional concentration be used as chain terminator, adopts known mode to adjust the molecular weight of polycarbonate (a).Suitable compound is for example phenol, tert.-butyl phenol or other C ₁=C ₇The phenol that alkyl replaces.A spot of phenol corresponding to formula (VIII) is particularly suitable for being used for adjusting molecular weight, Wherein R is the C of branching ₃And/or C ₉Alkyl.In alkyl R, CH ₃Proton percentage in the-group is 47～89%, and CH-and CH ₂Proton percentage in the-group is 53～11%.R better is in the ortho position of OH group and/or contraposition, and the upper limit of ortho position component preferably 20%.Consumption based on these chain terminators of amount of used bis-phenol is generally 0.5～10% (mole), is preferably 1.5～8% (moles).

Polycarbonate of the present invention can adopt known mode to be prepared, preferably adopt interface fasculation method (referring to H.Schnell " Chemistry and physicsof Polycarbonates ", Polymer Reviews, Vol.IX, 33 reach afterwards some pages or leaves, Interscience Publ., 1964).In the method, will be dissolved in the alkali aqueous phase corresponding to the bis-phenol of formula (I).In order to prepare Copolycarbonate, use mixture corresponding to the bis-phenol of formula (I) and other bis-phenol (for example corresponding to formula (VII) bis-phenol) with other bis-phenol.In order to adjust molecular weight, for example can add chain terminator corresponding to formula (VIII).Then a kind of inertia, preferably the solubilized polycarbonate organic solvent in the presence of, carry out this reaction by the method for interfacial polycondensation with phosgene.Temperature of reaction is 0～40 ℃.

Available branching agent (preferably 0.05～2% (mole)) can add the alkali aqueous phase with bis-phenol in beginning, also can add in the form with its solution in organic solvent before the phosgenation.

Except that the bis-phenol and available other bis-phenol (VII) of formula (I), also can use the list and/or the bischloroformates of these bis-phenols, they add with the form of the solution in organic solvent.Measure the used chain terminator and the amount of branching agent by molar weight then corresponding to the bisphenolate salt resistates of formula (I) and available formula (VII).Under the situation of using chloro-formic ester, the amount of phosgene can adopt known method suitably to reduce.

The organic solvent that is suitable for chain terminator and branching agent that can be suitable for selecting for use and chloro-formic ester is the mixture of the mixture of methylene dichloride, chlorobenzene, acetone, acetonitrile and these solvents, particularly methylene dichloride and chlorobenzene for example.Used chain terminator also dissolves in the identical solvent with branching agent.

The organic phase of interfacial polycondensation can form with for example mixture of methylene dichloride, chlorobenzene and methylene dichloride and chlorobenzene.

As the buck phase, for example can use the NaOH aqueous solution.

Preparing polycarbonate of the present invention by interface fasculation method can adopt catalyzer such as tertiary amine, particularly aliphatic tertiary amine for example tributylamine or triethylamine carry out catalysis with the method for routine.Molar weight based on used bis-phenol.Catalyst consumption can be 0.05～10% (mole).This catalyzer can phosgenation begin preceding or phosgenation process in addition phosgenation add later on.

Polycarbonate of the present invention reclaims with known method.

High molecular of the present invention, thermoplastic aromatic polycarbonate also can be by known homogeneous phase methods, so-called " pyridine method " and by replacing the melt transesterification process of phosgene to be prepared with for example dipheryl carbonate base ester.In this case, polycarbonate of the present invention also separates in a known manner.

Adopt its molecular weight of polycarbonate Mw (weight-average molecular weight is measured with gel chromatography after the calibration in advance) of method gained of the present invention to be preferably at least 10000 gram/moles, good especially is 10000～300000 gram/moles.With polycarbonate of the present invention during as injectable plastic material, molecular weight is that 20000～80000 gram/moles are good especially.With polycarbonate of the present invention during as cast film, molecular weight Mw is that 100000～250000 gram/moles are good especially.In order to prepare cast film, the molecular weight Mw of polycarbonate of the present invention is preferably 25000～150000 gram/moles.Polycarbonate of the present invention can be linear or branching; Based on the diphenol of formula (I), they are homo-polycarbonate or Copolycarbonate.

Therefore, the present invention also relates to its Mw (weight-average molecular weight) and be at least 10000 gram/moles, be preferably 10000～300000 gram/moles, being more preferably (under the situation that injection moulding is used) is high molecular, the thermoplastic aromatic polycarbonate of 20000～80000 gram/moles, and it contains the bifunctional carbonate structural unit corresponding to formula (Ia)

Wherein X, R ¹, R ², R ³, R ⁴With the middle defined of the definition cotype (I) of m, total amount based on bifunctional carbonate structural unit in this polycarbonate is 100% (mole), the amount of this structural unit is 100% (mole)～2% (mole), be preferably 100% (mole)～5% (mole), more preferably 100% (mole)～1010% (mole) is preferably 100% (mole)～20% (mole).

Polycarbonate of the present invention contains other bifunctional carbonate structural unit, and for example corresponding to those structural units of formula (VIIa), its content should be able to make can complement to 100% (mole) in each case.

Promptly the total amount based on bifunctional carbonate structural unit in the polycarbonate of every kind of situation is 100% (mole), the amount of this structural unit is 0% (mole) (being included)～98% (mole) (being included), be preferably 0% (mole)～95% (mole), more preferably 0% (mole)～90% (mole) is preferably 0% (mole)～80% (mole).

Substantially be known on and in following patent literature, be described based on the polycarbonate of cyclic aliphatic bis-phenol, for example european patent application 164476, German prospectus 3345945 and 2063052, French Patent 1427998, WO8000348, belgian patent 785189.They usually have quite high second-order transition temperature, but other important physicals all is not enough as UV stable and heat-resistant aging.

Shockingly find, as described,, can make the polycarbonate that has high heat resistance and other superperformance new the time by the bis-phenol of adding formula of the present invention (I).This is particularly suitable for the polycarbonate based on bis-phenol (I) (wherein m is 4 or 5), and is particularly suited for the polycarbonate of the bis-phenol of formula (Ib).

R wherein ¹And R ²Have the definition of being given in the formula (I) independently of each other, be more preferably representative hydrogen.

Therefore, the present invention preferentially relates to the polycarbonate of in corresponding to the structural unit of formula (Ia) m=4 or 5, relates more specifically to those and contains unitary polycarbonate shown in the formula (Ic)

R wherein ¹And R ²Definition cotype (Ia) in regulation, but hydrogen preferably.

These are based on formula (Ib) (R wherein ¹And R ²Hydrogen preferably) polycarbonate of bis-phenol also demonstrates high UV stable and good melt flowability shown in except their high heat resistance.

In addition, can particularly corresponding to the bis-phenol of formula (VII), change the performance of this polycarbonate effectively by other bis-phenol of combination.

Reclaim with known method by the prepared polycarbonate of method of the present invention, the organic phase that is soon generated in the interfacial polycondensation process is separated, it is washed neutrality and does not contain ionogen, then it is for example separated with particle form in the evaporation forcing machine.

Generally be used for the additive of thermoplastic poly carbonic ether such as stablizer, releasing agent, pigment, fireproofing agent, static inhibitor, filler and strongthener can before the polycarbonate processing of the present invention or after, add in this polycarbonate with the amount of using always.

More particularly, can add for example carbon black, graphite, diatomite, kaolin, clay, CaF ₂, CaCO ₃, aluminum oxide, glass fibre, BaSO ₄And mineral dye is as filler and nucleating agent, and for example stearin, pentaerythritol tetrastearate and trimethylolpropane tris stearate are as releasing agent.

Polycarbonate of the present invention can be processed into moulded product for example will be with the isolating polycarbonate extruding pelletization of currently known methods, by injection moulding the pellet of gained is processed into various goods with known method then, can process after adding above-mentioned additive.

Polycarbonate of the present invention can be processed into moulded work, be used for so far still in any Application Areas of using known polycarbonate, promptly be used as coverture and lustering agent at electric field and construction field, when needing high heat resistance and good processing characteristics simultaneously, promptly be like this when needing the complex assemblies of high heat resistance particularly.

Other purposes of polycarbonate of the present invention is as follows: A. is as the optical data recording element, as compact disk:

The working method of this recording element is known (referring to for example: J.Hennig, Lecture at the symposium on " NewPolymers " in Bad Nauheim on 14/15.4.1980 " polymers as substrates for opticaldisc memories " or philips techn.Rev.33,178-180,1973, NO.7 and 33,186-189,1973NO.7).B. be used to make safe pane.

The thickness of safe pane is generally 2mm～10mm, and can use

SiO _x(wherein x is 1 or 2) steam coating perhaps can be with the glass pane glass

Glass uses together.As known to, safe pane the building, traffic and boat

Empty many aspects are essential, and can be used as protective layer and safety helmet.C. as the raw material that coats with lacquer.D. be used to prepare blow-molded article (referring to for example United States Patent (USP) 2964794).E. be used to prepare transparent wallboard, particularly for example be used to cover buildings such as railway station, greenhouse

Hollow wallboard with means of illumination.F. be used to prepare foam materials (referring to for example DE-AS1,031,507).G. be used to prepare long filament and wire rod (referring to for example DE-AS1,137,167 and DE

-OS1,785,137)。H. as the translucent plastic that contains glass fibre, be used for lighting use (referring to for example DE

-OS1,544,920)。I. it is articles injection-moulded to be used to prepare miniature precision, for example mirror holder.For this purpose, used poly-

Carbonic ether has the glass fibre of certain content and can contain and accounts for gross weight about 1%

The MoS of (weight) ₂(referring to for example DE-OS2,344,737).K. be used to prepare the camera lens of the parts of opticinstrument, particularly photographic camera and kinematograph

(referring to for example DE-OS2,701,173).L. as photoconductive carrier, in particular as light-guide material (EP-OS referring to how about

0089801)。M. as the electrically insulating material of electric conductor.O. as the solid support material of organic photoconductor.P. be used to prepare light fixture, for example headlight or optical scattering disk.

High molecular aromatic polycarbonate of the present invention can be used in particular for preparing film.The thickness of this film be 1～1500 micron better, be 10～900 microns good especially.

The film of gained can carry out single shaft or biaxial stretch-formed with known method, and stretch ratio is preferably 1: 1.5～and 1: 3.

This film can be prepared by the currently known methods of preparation film, for example by flat film die polymer melt is extruded, and uses film blow molding machine blowing, deep-draw or curtain coating.For curtain coating, be to make the strong solution of polymkeric substance in suitable solvent curtain coating on a dull and stereotyped base, evaporating solvent, the film that will form unloads from base then.

This film stretches with known method on known machine, and service temperature is that room temperature extremely still can not make polymer malt viscosity reduce too many temperature, and general top temperature is about 370 ℃.

For by the curtain coating thin films, the strong solution of polycarbonate in suitable solvent can be poured on the horizontal surface, keep this horizontal surface to be under the temperature of room temperature～150 ℃, simultaneously with solvent evaporation.Also the strong solution of this polycarbonate can be poured on the density of its density greater than this polycarbonate solution, can be not miscible and do not dissolve on the liquid of this polycarbonate with used solvent, after this solution diffusion, obtain this film by evaporating the used solvent of polycarbonate and also can evaporating highdensity liquid.

Film of the present invention at high temperature has extra high dimensional stability, and many gas tables are revealed selective permeability.Therefore, they can be advantageously used for gas-permeable membrane.

Can certainly come together to prepare laminated film with them and other plastics film; Basically all known films all are suitable for as second film, and this depends on later application of laminated film and final performance.The THIN COMPOSITE gland of two or more films can be prepared as follows, and for example each film is comprised that polycarbonate film of the present invention is stacked together mutually, presses them together under the high temperature that is determined by each film softening temperature then.Also can use known film coextrusion process.

In fact, the preparation of this laminated film can be at first with known fortune method or prepare the film of each component with the method for above-mentioned control optimum temps.Then under without any the situation of big degree of stretch still the film of heat place under the common temperature, this temperature is preferably room temperature～370 ℃.Then with each film through roller combine and together the short period of time as pressing.For this purposes, can use 2 * 10 ⁵～5 * 10 ⁷The pressure of handkerchief (2～500 crust).This method can not undertaken by other film that this polycarbonate is formed with more than one yet; In this case, other film is for example at first to use the known so far method group can be together.Under above-mentioned pressure, force together then with this polycarbonate film.

This film or laminated film also can uniform films, the form of combined films or asymmetric membrane, with known method preparation with use.These films, film or laminated film can be equatorial, can form various geometrical shape-round shapes, sphere or tubular hollow piece, or also can be tubular fibres.These moulded partss can prepare with currently known methods.

According to contemplated application, the various polymkeric substance that exemplify below can be used for preparing film, contain the laminated film of polycarbonate film of the present invention with preparation.Also can make laminated film air-locked and that its dimensional stability increases than prior art when being heated according to purposes, perhaps those when being heated dimensional stabilizing and make its breathable laminated film by other film in the suitable selection laminated film.

The polymkeric substance that makes the film compound film of inventing with water is as described below.These polymkeric substance are called component (b).The thermoplastic resin that is suitable for as component (b) is following two kinds: b1) amorphous thermoplastic resin, preferably those second-order transition temperatures are greater than 40 ℃ more preferably 60 ℃～220 ℃ resin, and b2) thermoplastic resin of partial crystallization, preferably those fusing points are greater than 60 ℃ more preferably 80 ℃～400 ℃ resin.Be used for components b) elastomerics be b3) second-order transition temperature is lower than 0 ℃, be preferably to be lower than-10 ℃ and more preferably-15 ℃～140 ℃ polymkeric substance.

Amorphous thermoplastic resin b1) example is following all kinds of amorphous polymer; Polycarbonate, polymeric amide, polyolefine, polysulfones, polyketone, thermoplastic ethylene's based polyalcohol be polymethyl acrylate or the homopolymer of aromatic vinyl compound, the multipolymer of aromatic vinyl compound or the vinyl monomer-grafted polymkeric substance of rubber for example, polyethers, polyimide, thermoplastic polyurethane, aromatic polyester (carbonic ether) and liquid crystalline polymers.

The example of crystalline thermoplastic resin (b2) be aliphatic polyester, poly arylidene thio-ester and at b1) resin of partial crystallization in the listed down above-mentioned thermoplastic resin.

Elastomerics b3) example be various rubber for example ethylene-propylene rubber(EPR), polyisoprene, chloroprene rubber, polysiloxane, atactic polypropylene(APP), diene, alkene and acrylic elastomer and natural rubber, styrene-butadiene block copolymer, ethene and vinyl acetate between to for plastic or with the multipolymer of (methyl) acrylate, elasticity polyurethane (except that at b1) or b2) the listed down thermoplastic resin), and its polymers of elasticity polycarbonate-polyether block.

Amorphous thermoplastic resin b1) particularly except that other polycarbonate those of the present invention.These other polycarbonate can be homo-polycarbonate, also can be Copolycarbonate, and can be linear and branching.The good especially bis-phenol that is suitable for polycarbonate is dihydroxyphenyl propane (2, two (4-hydroxy phenyl) propane of 2-).

These other thermoplastic poly carbonic ether is known.

The molecular weight Mw (weight-average molecular weight is passed through gel permeation chromatography in tetrahydrofuran (THF)) of these other thermoplastic poly carbonic ether is 10000～300000, is preferably 12000～150000.

As components b), these thermoplastic poly carbonic ethers can use separately also can mix use.

Components b for preparation mixture of the present invention), other thermoplastic resin also is the aliphatic thermoplastic polyester preferably, be more preferably polyalkylene terephthalates, promptly for example based on ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol and 1, those esters of the two methylol hexanaphthenes of 4-.

The molecular weight of these polyalkylene terephthalates (Mw) is 10000～80000.This polyalkylene terephthalates can be used known method, is for example made (referring to for example United States Patent (USP) 2,647 by transesterification by dimethyl terephthalate ester and corresponding diol, 885,2,643,989,2,534,028,2,578,660,2,742,494,2,901,466).

Other thermoplastic resin also comprises polyamide thermoplastic preferably.

Suitable polyamide thermoplastic is the polymeric amide of various partial crystallizations, especially polymeric amide-6, polymeric amide-6,6, and the copolyamide based on these two kinds of components of partial crystallization.Other suitable polyamide thermoplastic is the polymeric amide of partial crystallization, wherein acid constituents completely or partially comprises (except that hexanodioic acid or hexanolactam) terephthalic acid and/or m-phthalic acid and/or suberic acid and/or sebacic acid and/or nonane diacid and/or dodecanedioic acid and/or hexanodioic acid and/or cyclohexane diacid, wherein diamine components is completely or partially by between especially and/or terephthaldehyde's base diamines and/or hexamethylene-diamine and/or 2,2,4-and/or 2,4,4-trimethylhexamethylenediamine and/or isophorone diamine and/or 1, the 4-diaminobutane, and wherein these compositions generally are known (referring to for example Encyclopedia of polymers in prior art, Vol.11,315 pages etc.).

Other suitable polyamide thermoplastic is completely or partially by the lactan that contains 6～12 carbon atoms, the polymeric amide of the partial crystallization of also available one or more above-mentioned starting ingredients preparations.

The polymeric amide of good partial crystallization is polymeric amide-6 and polymeric amide-6,6 or the copolyamide that contains a small amount of (can up to about 10% (weight)) other common component especially.

Suitable polymeric amide also has the following amorphous polyamides that makes, for example by diamines such as hexamethylene-diamine, decamethylene diamine, 2,2,4-and 2,4, the 4-trimethylhexamethylenediamine, between or terephthaldehyde base diamines, two (4-aminocyclohexyl) methane, 4,4 '-and 2,2 '-mixture of diamino-dicyclohexyl methane, 2, two (4-aminocyclohexyl) propane of 2-, 3,3 '-dimethyl-4,4 '-the diamino dicyclohexyl) methane, 3-amino-ethyl-3,5,5-trimethylcyclohexyl amine, 2, two (amino methyl) norbornanes of 5-, 2, two (amino methyl) norbornanes of 6-.1, the mixture of 4-diaminomethyl hexanaphthene and these diamines and dicarboxylic acid such as oxalic acid, hexanodioic acid, nonane diacid, decane dicarboxylic acid, heptadecane dicarboxylic acid, 2,2,4-trimethyladipic acid, 2,4, the polycondensation of the mixture of 4-trimethyladipic acid, m-phthalic acid and terephthalic acid and these diacid.Therefore, comprise that also the amorphous copolyamide that the polycondensation by several above-mentioned diamines and/or dicarboxylic acid makes also comprises with omega-amino-carboxylic acid such as omega-amino-caproic acid, omega-amino-undeeanoic acid or omega-amino-laurostearic acid, or the copolyamide of its lactan preparation.

Specially suitable amorphous thermoplastic polymeric amide is by m-phthalic acid, hexamethylene-diamine and other diamines for example 4,4 '-diamino-dicyclohexyl methane, isophorone diamine, 2,2,4-and 2,4,4-trimethylhexamethylenediamine, 2,5-and/or 2, two (amino methyl) norbornanes of 6-prepared those; By m-phthalic acid, 4 and ω-hexanolactam prepared those; By m-phthalic acid, 3,3-dimethyl-4 and omega-lauric lactam prepared those; And by terephthalic acid and 2,2,4-and 2,4, the isomer mixture of 4-trimethylhexamethylenediamine prepared those.

Replace to use pure 4,4 ＇-diamino-dicyclohexyl methane, also can use the mixture 70～99% (mole) 4 of the diamino-dicyclohexyl methane of the position isomerism of forming by following component, 4 '-the diamino isomer, 1～30% (mole) 2,4 '-the diamino isomer, 0～2% (mole) 2,2 '-the diamino isomer

And the diamines that can select the corresponding higher condensation that the diaminodiphenyl-methane by the hydrogenation technical grade makes for use.

Suitable polyamide thermoplastic also can by partial crystallization form with mixture amorphous polyamide, wherein the amorphous polyamides component is less than the partial crystallization polyamide component.Amorphous polyamides and preparation method thereof also is known (referring to for example Ullmann, Enzyklop  die der technischenChemie, Vol.19,50 pages) in prior art.

Other thermoplastic resin b preferably) also comprises the poly arylidene thio-ester of thermoplastic linearity or branching.They have the structural unit corresponding to following general formula

R wherein ₁～R ₄Be identical or different, and represent C ₁～C ₅Alkyl, phenyl or hydrogen.This poly arylidene thio-ester also can contain the biphenyl unit.Poly arylidene thio-ester and preparation method thereof is known (referring to for example United States Patent (USP) 3,354,129 and european patent application 0171021).

Better other thermoplastic resin b) be the thermoplastic poly aryl sulfone.

The pure average molecular weight Mw of suitable polyaryl sulfone is (at CHCl ₃In pass through light scattering determining) be 1000～200000, be preferably 20000～60000.

Their some examples be with currently known methods by 4,4 '-dichloro diphenyl sulfone and bis-phenol, particularly 2, the polyaryl sulfone that two (4-hydroxy phenyl) propane of 2-make.Its weight-average molecular weight Mw is 2000～200000.

These polyaryl sulfones are known (referring to for example US-PS3,264,536; DE-AS1794171; GB-PS1,264,900; US-PS3,641,207; EP-A-0 038028; DE-OS 3601419 and DE-OS 3601420).Suitable polyaryl sulfone also can be used currently known methods branching (referring to for example DE-OS 2305413).

Other thermoplastic resin b preferably) also comprises the thermoplastic poly phenylate, preferably to poly-(2, the 6-dialkyl group) benzene oxygen.The weight-average molecular weight Mw (passing through light scattering determining in chloroform) that is applicable to polyphenylene oxide of the present invention is 2000～100,000, is preferably 20000～60000.These polyphenylene oxide are known.

Preferably can be with known method by usefulness dioxygen oxidation condensation 2 in the presence of the catalyst composition of mantoquita and tertiary amine to poly-(2, the 6-dialkyl group) benzene oxygen, 6-dialkyl group phenol and make (referring to for example DE-OS2126434 and US-PS3,306,875).

Suitable to poly-(2, the 6-dialkyl group) benzene oxygen particularly to poly-(2,6-two (C ₁～C ₄Alkyl)) benzene oxygen is for example to poly-(2, the 6-dimethyl) benzene oxygen.

Other thermoplastic resin b preferably) comprises that also aromatic-polyether ketone is (referring to for example GB-PS1,1078,234; US-PS4,010,147 and EP-OS0135938).

They contain following repeated structural unit

-O-E-O-E '-wherein-E '-be residue with two aryl ketones of two keys, and-O-E-O-is the bisphenolate salt residue with two keys.

They can be for example according to GB-PS1, and 078,234 is made by two (halogenated aryl) ketone of the alkali-metal two basic metal bisphenolate salt of formula basic metal-O-E-O-and formula hal-E '-hal (hal=halogen).A kind of two suitable basic metal bisphenolate salt are for example 2, two (4-hydroxy phenyl) propane of 2-, and a kind of suitable two (halogenated aryl) ketone are 4,4 '-two chloro benzophenones.

Other thermoplastic resin b preferably) also comprises thermoplastic ethylene's based polyalcohol.

In scope of the present invention, vinyl polymer is the homopolymer of vinyl monomer, the multipolymer and the graftomer of vinyl monomer on rubber of vinyl monomer.

Be applicable to that homopolymer of the present invention and multipolymer are that those are by vinylbenzene, alpha-methyl styrene, vinyl cyanide, methacrylonitrile, (methyl) acrylic acid C ₁～C ₁₂(ring) alkyl ester, C ₁～C ₄The polymkeric substance that vinyl carboxylates makes, the also available currently known methods of this multipolymer is made by the mixture of these vinyl monomers.

The limiting viscosity of these homopolymer or multipolymer is 0.3～1.5 deciliter/gram (measuring in toluene under 23 ℃ with currently known methods).

Suitable vinyl polymer is thermoplastic poly methacrylic acid C for example ₁～C ₄Alkyl ester is as those methacrylic acid methyl, ethyl, propyl group or butyl ester, preferably methacrylic acid methyl or ethyl ester.The homopolymer and the multipolymer that comprise these methacrylic esters.In addition, can the undersaturated copolymerisable monomer of a spot of other alkene class, for example (methyl) vinyl cyanide, (Alpha-Methyl) vinylbenzene, bromstyrol, vinyl acetate between to for plastic, vinylformic acid C be arranged copolymerization ₁～C ₃Alkyl ester, (methyl) vinylformic acid, ethene, propylene and N-vinyl pyrrolidone.

Be applicable to thermoplastic poly methacrylic acid C of the present invention ₁～C ₄Alkyl ester is known in the literature or can makes with known method in the document.

Suitable vinyl polymer also comprises vinylbenzene or alpha-methyl styrene and can contain 40% (weight) acrylate at the most or the methacrylic ester multipolymer of the vinyl cyanide of methyl methacrylate or n-butyl acrylate particularly.Must always contain styrene derivatives as monomer.The ratio of the styrene derivatives that is contained is 100～10% (weight), be preferably 90～20% (weight), and 80～30% (weight) more preferably, and they can make with the method for standard, for example free radical body, solution, suspension or letex polymerization, but the free-radical emulsion polymerization in water preferably.

Suitable graftomer be its second-order transition temperature be lower than 0 ℃ preferably be lower than-20 ℃ rubber in the presence of, the mixture by above-mentioned vinyl monomer of polymerization or vinyl monomer forms.This graftomer generally contains 1～85% (weight) and 10～80% (weight) rubber preferably.This graftomer can adopt the method for standard in solution, body or emulsion, preferably is prepared in emulsion; The mixture of vinyl monomer can simultaneously or carry out graft polymerization successively.

Suitable rubber is elastoprene and acrylic elastomer preferably.

Elastoprene is for example polyhutadiene, polyisoprene and divinyl and 35% (weight) comonomer such as vinylbenzene, vinyl cyanide, methacrylic methyl esters and vinylformic acid C at the most ₁～C ₆The multipolymer of alkyl ester.

Acrylic elastomer for example is following monomeric crosslinked granular emulsion polymer, and used monomer is vinylformic acid C ₁～C ₆Alkyl ester, particularly vinylformic acid C ₂～C ₅Alkyl ester, it also can be the mixture that contains at least 15% (weight) other unsaturated monomer and at least a multifunctional linking agent, these unsaturated monomers are just like vinylbenzene, methyl methacrylate, divinyl, ethene methyl ether, vinyl cyanide, above-mentioned linking agent is just like allyl ester, the isocyanuric acid triallyl ester of Vinylstyrene, ethylene glycol diacrylate, bisacrylamide, tricresyl phosphate allyl ester, citric acid triallyl ester, vinylformic acid and methacrylic acid, and this acrylic elastomer contains 4% (weight) cross-linking comonomer at the most.

The mixture of elastoprene and acrylic elastomer and also have the rubber of hollow (coreshell) structure also to be suitable for preparing graftomer.

For graft polymerization, this rubber must be with the form of discrete particle, exist as the form with latex.These particulate mean diameters are generally 10 nanometers～2000 nanometers.

This graftomer can be prepared with currently known methods, for example with water soluble starter such as peroxydisulfate or redox initiator, under 50～90 ℃ the temperature, the free radical emulsion graft polymerization of carrying out vinyl monomer in the presence of the rubber latex arranged.

By gel content greater than 80% (weight) median size (d ₅₀) for the emulsion grafting polymerization thing of the free yl graft polymerization on the granular high cross-linked rubber of 80-800 nanometer (diene or alkyl acrylate) preparation be preferably.

The industry abs polymer is specially suitable.

Lustrex and/or ethylenic copolymer and also be suitable by the branch mixture of polymers.

Other thermoplastic resin b preferably) also comprises thermoplastic polyurethane.These are vulcabond, are the reaction product of oligomeric and/or polyester and/or ether and one or more chain propagation agents of aliphatic series fully or mainly.These thermoplastic polyurethanes are linear basically and have the thermoplasticity processing characteristics.

These thermoplastic polyurethanes are known or can make with known method (referring to for example United States Patent (USP) 3,214,411; J.H.Saunders and K.C.Frisch, " Polyurethanes, Chemistry andTechnology ", Vol.II, 299～451 pages, Interscience Publishers, New York, 1964; With Mobay Chemical corporation " Aprocessing Hahdbook for Texin UrethaneElastoplastic Materials ", pittsburgh, PA).

The raw material that is used to prepare oligomer ester and polyester is for example hexanodioic acid, Succinic Acid, sebacic acid, suberic acid, oxalic acid, methyl hexanodioic acid, pentanedioic acid, pimelic acid, nonane diacid, phthalic acid, terephthalic acid and m-phthalic acid.

Hexanodioic acid is preferably.

The glycol that is suitable for preparing oligomer ester and polyester is an ethylene glycol, 1 for example, 2-and 1, ammediol, 1,2-, 1,3-, 1,4-, 2,3-and 2,4-butyleneglycol, hexylene glycol, two methylol hexanaphthene, glycol ether and 2,2-dimethyl propylene glycol.In addition, the i.e. ternary of 1% (mole) or more polyvalent alcohol such as TriMethylolPropane(TMP), glycerine, hexanetriol etc. can use with above-mentioned glycol at the most on a small quantity.

The hydroxyl oligomer ester of gained or the molecular weight of polyester are at least 600, and hydroxyl value is preferably about 40～150 for about 25～190, and acid number is about 0.5～2, and water content is about 0.01～0.2%.

Oligomer ester and polyester also comprise oligomeric or the polymerization lactone, as low polycaprolactone or polycaprolactone, and for example poly-carbonic acid-1 of aliphatic polycarbonate, 4-butanediol ester or poly-carbonic acid-1,6-hexylene glycol ester.

The specially suitable oligomer ester that can be used as the raw material of thermoplastic polyurethane is to be prepared by hexanodioic acid and the glycol that contains at least one primary hydroxyl.When acid number reaches 10 and preferably reach about 0.5～2 the time, stop this condensation reaction.With water that this reaction process generated simultaneously or separate later on, so that final water content is about 0.01～0.05%, be preferably 0.01～0.02 in reaction.

For example be used to prepare the oligo-ether of thermoplastic polyurethane or polyethers and be based on 1 those of 4-butyleneglycol, propylene glycol and ethylene glycol.

Polyacetal also can be considered to polyethers and can be used as polyethers use.

The number-average molecular weight Mn of this oligo-ether or polyethers (number-average molecular weight of the OH pH-value determination pH by product) should be 600～2000, is preferably 1000～2000.

Organic diisocyanate as this urethane of preparation, preferably use 4,4 '-diphenylmethanediisocyanate.It should contain be less than 5% 2,4 '-diphenylmethanediisocyanate and be less than the dimer of 2% diphenylmethanediisocyanate.In addition, represent that with HCl its acidity should be 0.005～0.2%.The following mensuration of representing with %HCl of acidity, promptly by extracting muriate in the aqueous methanol solution of vulcabond heat or in the process that water is hydrolyzed, discharging muriate, then with this extracting solution of silver nitrate solution titration of standard to obtain the wherein concentration of existing chlorion.

Also can use other vulcabond to prepare this thermoplastic polyurethane, comprise for example ethylene, ethylidene, propylidene, butylidene, 1, the 3-cyclopentylidene, 1, the 4-cyclohexylidene, 1, the 2-cyclohexylidene, 2, the 4-tolylene, 2, the 6-tolylene, to phenylene, the n-phenylene, xylylene, 1, the 4-naphthylidene, 1, the 5-naphthylidene, 4,4 '-vulcabond of biphenylene, 2,2-diphenyl propane-4,4 '-vulcabond, nitrogen benzide-4,4 '-vulcabond, sulfobenzide-4,4 '-vulcabond, two chloro-hexamethylene diisocyanates, 1,5-penta vulcabond, hexamethylene diisocyanate, 1-chlorinated benzene-2, the 4-vulcabond, the furfuryl group vulcabond.Dicyclohexyl methane diisocyanate, isophorone diisocyanate, diphenylethane vulcabond and ethylene glycol, 1, two (isocyanato-phenyl) ethers of 4-butyleneglycol etc.

Suitable chain propagation agent can contain can with the difunctionality organic compound of the active hydrogen of isocyanate reaction, for example glycol, hydroxycarboxylic acid, dicarboxylic acid, diamines and alkanolamine and water.The example of these chain propagation agents is for example hexylene glycol, trimethylene glycol and butylidene glycol, 1,4-butyleneglycol, butyleneglycol.Butynediol, xylylene glycol, 1,5-pentamethylene glycol, 1,4-phenylene bis-beta-hydroxyethyl ether, 1,3-phenylene bis-beta-hydroxyethyl ether, two (methylol) hexanaphthene, hexylene glycol, hexanodioic acid, ω-hydroxycaproic acid, thiodiglycol, 1.Propylene diamine, butylene diamine, 1,6-is diamines, cyclohexylidene diamines, phenylenediamine, toluylene diamine and xylylene diamines, diamino-dicyclohexyl methane, isophorone diamine, 3,3 '-dichlorobenzidine, 3,3 '-dinitrobenzene p-diaminodiphenyl, thanomin, aminopropanol, 2,2-dimethyl propanol amine, 3-Trans-4-Amino Cyclohexanol and to aminobenzyl alcohol.The mol ratio of oligomer ester or polyester and difunctionality chain propagation agent is 1: 1～1: 50, is preferably 1: 2～1: 30.

Except that the difunctionality chain propagation agent, also can use small amount of trifunctional or more than the chain propagation agent of trifunctional, based on the mole number of used difunctionality chain propagation agent, its consumption is about 5% (mole) at the most.

Trifunctional or be glycerine, TriMethylolPropane(TMP), hexanetriol, tetramethylolmethane and trolamine more than the example of the chain propagation agent of trifunctional.

Also can use mono-functional component, for example butanols to prepare this thermoplastic polyurethane.

Vulcabond, oligomer ester, polyester, polyethers, chain propagation agent and the mono-functional component of described structural unit as this thermoplastic polyurethane are known in the literature, also can make with known method in the document.

The preparation example of known this urethane is as can followingly carrying out

For example, oligomer ester or polyester, organic diisocyanate and chain propagation agent can be heated respectively, preferably heat is mixed then to about 50～220 ℃.Preferably earlier oligomer ester or polyester are heated respectively, mix with chain propagation agent then, at last the isocyanic ester of the mixture of gained with preheating mixed.

The starting ingredient that is used to prepare this urethane can provide powerful mixing mechanical stirrer mix with any at short notice.If early stage rise too fast of the viscosity of this mixture can reduce temperature in whipping process, also can add a small amount of (based on ester, 0.001～0.05% (weight)) citric acid etc., reduce speed of response.In order to increase speed of response, can use appropriate catalyst, for example at United States Patent (USP) 2,729, the tertiary amine described in 618.

Other thermoplastic resin so-called in addition " LC " polymkeric substance preferably.The LC polymkeric substance is the polymkeric substance that can form the liquid crystal melt.This base polymer is also referred to as " thermic ", they be enough famous (referring to for example EP-OS0131846, EP-OS0132637 and E P-OS0134959).Enumerated more reference in these documents, they have also described the mesomorphic measuring method of polymer melt.

The example of LC polymkeric substance is based on the aromatic polyester (EP-OS0131846) of commutable P-hydroxybenzoic acid, commutable and/or terephthalic acid, 2,7 dihydroxy naphthalene and other bis-phenol.Based on the aromatic polyester (EP-OS0132637) of commutable P-hydroxybenzoic acid, bis-phenol, carbonic acid and optional aromatic dicarboxylic acid with and in commutable P-hydroxybenzoic acid, 3-chloro-4-hydroxy-benzoic acid, m-phthalic acid, quinhydrones and 3,4 ' and/or 4,4 '-dihydroxybiphenyl, 3,4 '-and/or 4,4 '-dihydroxy diphenyl ether and/or 3,4 '-and/or 4,4 '-aromatic polyester (EP-OS0134959) of dihydroxyl diphenylsulfide.

This LC polymkeric substance persistence length at room temperature is 18～1300 , is preferably 25～300 , is preferably 25～150 .

A kind of polymkeric substance persistence length at room temperature is characterized under the θ condition in dilute solution the average entanglement of molecular chain (referring to for example P.J.Flory, principles ofpolymer chemistry, Cornell Univ, Press, Ithaca, New York) and the grace step-length of partly rubbing.The persistence length mensuration that can in all sorts of ways in dilute solution is for example measured by scattering of light and small-angle x-ray.After suitable preparation, persistence length also can be measured by small-angle neutron scattering with solid.Other theory and experimental technique have been done introduction in following document, " the Liquid Crystalline Order in polymers " of J.H.Wendorff for example, as A.Blumstein, Academic Press 1978,16 pages etc. and at S.M.Aharoni, Macromolecules 19, (1986), listed reference in 429 pages etc.

Other thermoplastic resin comprises aromatic polyestercarbonates preferably.

Can be used as thermoplastic resin b according to the present invention) aromatic polyester and polyestercarbonate synthetic by at least a aromatic bisphenols (suc as formula the bis-phenol of (VII)), at least a aromatic dicarboxylic acid and optional carbonic acid.Suitable aromatic dicarboxylic acid is for example phthalic acid, terephthalic acid, m-phthalic acid, tert-butyl isophthalic acid, 3,3 '-diphenyl dicarboxylic acid, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-benzophenone dicarboxylic acid, 3,4 '-benzophenone dicarboxylic acid, 4,4 '-phenyl ether dicarboxylic acid, 4,4 '-sulfobenzide dicarboxylic acid, 2, two (4-carboxyl phenyl) propane of 2-and trimethylammonium-3-phenyl indane-4,5 '-dicarboxylic acid.

In above-mentioned aromatic dicarboxylic acid, good especially terephthalic acid and/or the m-phthalic acid of being to use.

Aromatic polyester and polyestercarbonate can be used in that known method is prepared in the document of preparation polyester and polycarbonate, for example use method, the transesterification process in the melt and two-phase interface method in the homogeneous phase solution.Preferably use the transesterification process in melt, especially the two-phase interface method.

Transesterification process in melt (acetic ester method and phenylester method) is introduced in following document.For example United States Patent (USP) 3,494, and 885; 4,386,186; 4,661,580; 4,680,371 and 4,680,372; European patent application 26,120; 26,121; 26,684; 28,030; 39,845; 91,602; 97,970; 79,075; 146,887; 156,103; 234,913; 234,919 and 240,301 and German Patent 1,495,626 and 2,232,877.The two-phase interface method is introduced in following document, and for example european patent application 68,014; 88,322; 134,898; 151,750; 182,189; 219,708; 272,426; German Patent prospectus 2,940,024; 3,007,934; 3,440,020 and PolymerReviews, Volume 10, " Cond ensation polymersby Interfacial and Solution Methods ", Paul W.Morgan, Interscience publishers, New York 1965, Chapter (VIII), 325 pages, polyesters.

Generally be generally to be that diphenyl and optional dipheryl carbonate base ester with bis-phenol, aromatic dicarboxylic acid or aromatic dicarboxylic acid reacts in the phenylester method with bisphenol diacetate in the acetic ester method, cancellation phenol simultaneously, and cancellation CO when suitable ₂, to form polyester or polyestercarbonate.In the two-phase interface method, the raw material that generally is used to prepare polyester and polyestercarbonate is bis-phenol an alkali metal salt, aromatic dicarboxylic acid chloride and optional phosgene.In this condensation reaction, polyester or polyestercarbonate have been made along with the formation of alkali metal chloride.Usually.During the salt that is generated is soluble in the aqueous phase, and polyester that is generated or polyestercarbonate are present in the organic phase with the form of solution, then from wherein separating.

For preparation mixture of the present invention, be used for components b) the b3 of elastomerics preferably) be above-mentioned urethane (as long as they be elastic), can partially hydrogenated styrene-butadiene block copolymer (kratonG for example ^, a kind of shell product), the above-mentioned rubber that is used for graftomer, graftomer itself (as long as they are elastic) and elastic polycarbonate-polyether block copolymer.

These elastomericss are known.

Film or composite membrane can be flat, hollow, spheric, tubular and tubular fibre shape.These films can make by thermoforming, deep-draw, blowing etc. with currently known methods.

Film of the present invention, especially laminated film can be used for the container of for example boilproof and ovenable roasting, packages sealed container and anti-microwave oven, but this will depend on laminated film component utilized b of the present invention).

Laminated film of the present invention can be by it is extruded and is prepared in a single stage operation with thermoplastic resin and polycarbonate of the present invention.

By the prepared film of the present invention of polycarbonate of the present invention with and can uniform films in the laminated film of the present invention of these polycarbonate (a) film, composite membrane or asymmetric membrane form are used.

In example, relative viscosity is at CH with polycarbonate ₂Cl ₂In 0.5% (weight) measured in solution.

Second-order transition temperature is measured with dsc (DSC).

Example B.1

In inert gas atmosphere, when stirring, diphenol, 33.6 gram (0.6 mole) KOH A.1 are dissolved in the 560 gram water with 31.0 gram (0.1 mole) examples.Then the solution of 0.188 gram phenol in 560 milliliters of methylene dichloride is added that 19.8 gram (0.2 mole) phosgene are introduced this well-beaten pH is 13～14 and temperature is in 21～25 ℃ the solution.Add 0.1 milliliter of ethylpyridine then, then stirred 45 minutes.The aqueous phase separation of unparalleled phenolic ester is come out,, wash organic phase with water with after the phosphoric acid acidifying. until neutral and do not contain solvent.The relative solution viscosity of this polycarbonate is 1.259.

The second-order transition temperature of finding this polymkeric substance is 233 ℃ (DSC).

Example B.2

In inert gas atmosphere, along with stirring 68.4 gram (0.3 mole) dihydroxyphenyl propanes (2, two (4-hydroxy phenyl) propane of 2-), 217.0 restrain (0.7 mole) examples bis-phenol A.3, and 336.6 gram (6 moles) KOH are dissolved in the 2700 gram water.Restrain the solution of phenol in 2500 milliliters of methylene dichloride as going into 1.88 then.It is 13～14 and temperature is in 21～25 ℃ the solution that 198 gram (2 moles) phosgene are introduced this well-beaten pH.Add 1 milliliter of ethyl piperidine then, then stirred 45 minutes.The aqueous phase separation of unparalleled phenolic ester is come out,, wash organic phase with water with after the phosphoric acid acidifying, until neutrality, and bonding solvent not.The relative viscosity of this polycarbonate is 1.336.

The second-order transition temperature of finding this polymkeric substance is 212 ℃ (DSC).

Example B.3

With the mixture of 114 gram (0.5 mole) dihydroxyphenyl propanes and 155 gram (0.5 mole) examples bis-phenols A.1 by example B.2 method react, obtain polycarbonate.

The relative solution viscosity of this polycarbonate is 1.336.

The second-order transition temperature of finding this polymkeric substance is 195 ℃ (DSC).

Example B.4

With the mixture of 159.6 gram (0.7 mole) dihydroxyphenyl propanes and 93 gram (0.3 mole) examples bis-phenols A.3 by example B.2 method react, obtain polycarbonate.

The relative solution viscosity of this polycarbonate is 1.437.

The second-order transition temperature of finding this polymkeric substance is 180 ℃ (DSC).

Example B.5

In inert gas atmosphere, 31.0 gram (0.1 mole) examples bis-phenol, 24.0 gram (0.6 mole) NaOH A.3 are dissolved in the 270 gram water along with stirring.Then the solution of 0.309 gram 4-(1.1,3, the 3-tetramethyl butyl) phenol in 250 milliliters of methylene dichloride is added.It is 13～14 and temperature is in 21～25 ℃ the solution that 19.8 gram (0.2 mole) phosgene are introduced this well-beaten pH.Add 0.1 milliliter of ethyl piperidine then, then stirred 45 minutes.The aqueous phase separation of unparalleled phenolic ester is come out,,, and do not contain solvent until neutrality washing organic phase later on water with the phosphoric acid acidifying.The relative solution viscosity of this polycarbonate is 1.314.

The second-order transition temperature of finding this polymkeric substance is 234 ℃ (DSC).

In order to estimate the UV stable of this new polycarbonate, be determined at mercury vapor lamp (streamline filter 305 nanometers) formation of elementary free radical when carrying out uv-radiation, and with based on 2, the polycarbonate of two (4-hydroxy phenyl) propane of 2-is compared.Find that example polycarbonate B.1 shows lower elementary free radical generating rate, so UV stable is higher.

Example B.6

In inert gas atmosphere, along with stirring 148.2 gram (0.65 moles) 2, two (4-hydroxy phenyl) propane of 2-, 108.5 gram (0.35 mole) examples bis-phenol, 336.6 gram (6 moles) KOH A.1 are dissolved in the 2700 gram water.Then the solution of 8.86 gram 4-(1,1,3, the 3-tetramethyl butyl) phenol in 2500 milliliters of methylene dichloride is added.It is 13～14 and temperature is in 21～25 ℃ the solution that 198 gram (2 moles) phosgene are introduced this well-beaten pH.Add 1 milliliter of ethyl piperidine then, and with this mixture restir 45 minutes.The aqueous phase separation of unparalleled phenolic ester is come out, after with the phosphoric acid acidifying, wash organic phase with water,, and do not contain solvent until neutrality.The relative solution viscosity of this polycarbonate is 1.20.

Example B7

In inert gas atmosphere, 3.875 kilograms of (12.5 moles) examples bis-phenol A.2 is dissolved in 6.375 kilograms of 45%NaOH and 30 premium on currency along with stirring.Add 9.43 liters of methylene dichloride, 11.3 liters of chlorobenzenes and 23.5 gram phenol then.It is 13～14 and temperature is in 20～25 ℃ the solution that 2.475 kilograms of phosgene are introduced this well-beaten pH, after adding, adds 12.5 milliliters of N-ethylpiperidines.Then with this mixture reaction 45 minutes.The aqueous phase separation of unparalleled phenolic ester is come out, and organic phase phosphoric acid acidifying is washed then until not containing ionogen and not containing solvent.Relative viscosity: 1300 second-order transition temperatures: 238 ℃.

Example B.8

Under inert gas atmosphere, 15.5 gram (0.05 mole) examples bis-phenol, 13.4 gram (0.05 mole) bis(4-hydroxyphenyl) cyclohexanes (bisphenol Z) and 24.0 gram (0.6 mole) NaOH A.3 are dissolved in 362 ml waters along with stirring.Add 0.516 gram 4-(1.1,3, the 3-tetramethyl butyl) phenol then and be dissolved in 271 milliliters of solution in the methylene dichloride.It is 13～14 and temperature is in 20～25 ℃ the solution that 19.8 gram phosgene are introduced this well-beaten pH.After adding 5 minutes, add 0.1 milliliter of N-ethylpiperidine.Then with this mixture reaction 45 minutes.The aqueous phase separation of unparalleled phenolic ester is come out, and organic phase phosphoric acid acidifying is washed then until neutral and do not contain solvent.Relative viscosity: 1.297 second-order transition temperatures: 208 ℃

Example B.9

Under natural instincts atmosphere, along with stirring with 15.5 gram (0.05 mole) examples bis-phenol A.1.17.6 the gram (0.05 mole) 4,4 '-the dihydroxyl tetraphenyl methane and 24.0 the gram (0.6 mole) NaOH be dissolved in 411 ml waters.Add 0.516 gram 4-(1,1,3, the 3-tetramethyl butyl) phenol then and be dissolved in 308 milliliters of solution in the methylene dichloride.It is 13～14 and temperature is in 20～25 ℃ the solution that 19.8 gram phosgene are introduced this well-beaten pH.After adding 5 minutes, add 0.1 milliliter of N-ethylpiperidine.Then with this mixture reaction 45 minutes.The aqueous phase separation of unparalleled phenolic ester is come out, and organic phase phosphoric acid acidifying is washed then until neutral and do not contain solvent.Relative viscosity: 212 ℃ of 1.218 second-order transition temperatures.

Example B.10

Under inert gas atmosphere, 18.3 gram (0.05 mole) examples bis-phenol and 23.6 gram (0.42 mole) KOH A.4 are dissolved in 100 ml waters along with stirring.Add 100 milliliters of methylene dichloride then.It is 13～14 and temperature is in 20～25 ℃ the solution that 17.3 gram phosgene are introduced this well-beaten pH.After adding 5 minutes, add 0.3 milliliter of N-ethylpiperidine.Then with this mixture reaction 45 minutes.The aqueous phase separation of unparalleled phenolic ester is come out, and organic phase phosphoric acid acidifying is washed then until neutral and do not contain solvent.Relative viscosity: 1.310 second-order transition temperatures: 241 ℃.

Example B11

Under inert gas atmosphere, 29.6 gram (0.1 mole) examples bis-phenol and 24.0 gram (0.6 mole) NaOH A.5 are dissolved in 370 ml waters along with stirring.Add 0.413 gram 4-(1,1,3, the 3-tetramethyl butyl) phenol then and be dissolved in 277 milliliters of solution in the methylene dichloride.It is 13～14 and temperature is in 20～25 ℃ the solution that 19.8 gram phosgene are introduced this well-beaten pH.After adding 5 minutes, add 0.1 milliliter of N-ethylpiperidine.Then with this mixture reaction 45 minutes.The aqueous phase separation of unparalleled phenolic ester is come out, and organic phase phosphoric acid acidifying is washed then until neutral and do not contain solvent.Relative viscosity: 1.370 second-order transition temperatures: 193 ℃.

Example B.12

Under inert gas atmosphere, 62.0 gram (0.2 mole) examples bis-phenol, 182.4 gram (0.8 mole) dihydroxyphenyl propanes and 240 gram (6 moles) NaOH A.1 are dissolved in 2400 ml waters along with stirring.Add 6.603 gram 4-(1,1,3, the 3-tetramethyl butyl) phenol then and be dissolved in 2400 milliliters of solution in the methylene dichloride.It is 13～14 and temperature is in 20～25 ℃ the solution that 198 gram phosgene are introduced this well-beaten pH.As intact 5 minutes later on, add 1 milliliter of N-ethylpiperidine.Then with this mixture reaction 45 minutes.The aqueous phase separation of unparalleled phenolic ester is come out, and organic phase phosphoric acid acidifying is washed then until neutral and do not contain solvent.Relative viscosity: 1.298 second-order transition temperatures: 172 ℃

Example B.13

Under inert gas atmosphere, 170.5 gram (0.55 mole) examples bis-phenol, 102.6 gram (0.45 mole) dihydroxyphenyl propanes and 240 gram (6 moles) NaOH A.3 are dissolved in 2400 ml waters along with stirring.Add 5.158 gram 4-(1,1,3, the 3-tetramethyl butyl) phenol then and be dissolved in 2400 milliliters of solution in the methylene dichloride.It is 13～14 and temperature is in 20～25 ℃ the solution that 198 gram phosgene are introduced this well-beaten pH.After adding 5 minutes, add 1 milliliter of N-ethylpiperidine.Then with this mixture reaction 45 minutes.The aqueous phase separation of unparalleled phenolic ester is come out.Organic phase phosphoric acid acidifying is washed then until neutral and do not contain solvent.Relative viscosity: 1.302 second-order transition temperatures: 203 ℃.

Example B.14

Under inert gas atmosphere, along with stirring with 108.5 gram (0.35 mole) examples bis-phenol A.1.148.2 gram (0.65 mole) dihydroxyphenyl propane and 240 gram (6 moles) NaOH are dissolved in 2400 ml waters.Add 6.189 gram 4-(1.1, the 3.3-tetramethyl butyl) phenol then and be dissolved in 2400 milliliters of solution in the methylene dichloride.It is 13～14 and temperature is in 20～25 ℃ the solution that 198 gram phosgene are introduced this well-beaten pH.After adding 5 minutes, add 1 milliliter of N-ethylpiperidine.Then with this mixture reaction 45 minutes.The aqueous phase separation of unparalleled phenolic ester is come, and organic phase phosphoric acid acidifying is washed until neutrality then and is not contained solvent.Relative viscosity: 1.305 second-order transition temperatures: 185 ℃.

Example C

Netstal injection moulding machine (330～350 ℃ of body temperatures) is with example Copolycarbonate and relative viscosity η B.6 _RelIt is 12 centimetres compact disk that=1.20 dihydroxyphenyl propane homo-polycarbonate prepares diameter.These two dishes are tested by using conventional comparer to measure path difference by polarization microscope in axial double refraction.The transparency is with the naked eye estimated, and second-order transition temperature DSC measures.The material path difference Tg transparency

(nanometer/millimeter) (℃) the example poly-carbon of transparent bisphenol-A+12 145 transparent acid esters B.6+13 185

Example is (preparation of film) D.1

Under 30 ℃, in continuously stirring, 20 gram examples polycarbonate B.1 is dissolved in 200 milliliters of methylene dichloride, with this solution thickening, then by this solution casting is prepared the film of 204 micron thickness on one 25 ℃ sheet glass.This film was 90 ℃ of following vacuum-dryings 4 hours.Test the ventilation property of this film then.

The mensuration of the ventilation property of polymeric film (infiltration)

Gas is described with dissolving/method of diffusion by the pressuretightness polymeric film.The characteristic constant of this method is permeability coefficient P, and it shows for given pressure difference Δ P, in regular hour t, the gas volume V of the film by known surface area F and thickness d.For stable state, can reason out following formula by the differential equation of this process of osmosis: $P=\frac{V\&CenterDot;d}{F\&CenterDot;t\&CenterDot;\mathrm{\&Delta;p}}---\left(1\right)$ In addition, the temperature and the water content of gas also depended in infiltration.

This test set comprises thermostatically controlled 2 one chamber systems.A chamber is used for holding test gas, and another chamber holds the gas of infiltration.Separate with film to be measured these two chambers.

Two chambers are evacuated to 100Pa (10 ^-3Millibar), then first Room is charged into gas.Shen Tou gas (rare gas element) increases the pressure in the permeate chamber of constant volume then, with the increase of this pressure with a pressure recorder (MKS Baratron) as the quantitative record of the function of time, pass through to reach steady state until gas.Calculate the V of normal pressure and temperature by the increase of this pressure.Consider that external air pressure is adjusted to 10 with Δ P ⁵Handkerchief.The surperficial F of this film is known.The thickness d of this film is measured with micrometer, and it is to be distributed in the independently mean value of thickness measurements of this film lip-deep ten times.

Determine permeability coefficient P with following dimension according to formula (1) by these numerical value:

Film thickness based on 1 millimeter.

Other test parameter is: temperature: 25 ± 1 ℃ of gas relative humidity: 0% result: the permeability coefficient for all gases is as follows:

O ₂：280.8

N ₂：84.5

CO ₂：2174.0

CH ₄：149.4

This film remains dimensional stabilizing under 180 ℃.

Example is (comparative example) D.2

Be that 1.28 bisphenol-a polycarbonate prepares film (thickness is 154 microns) by example 3 described methods and tests by relative viscosity.The result: the permeability coefficient to all gases is as follows

O ₂：72.0

N ₂：366.0

CO ₂：35.0

CH ₄：27.0

Under 180 ℃, the size of this film is unsettled.

Example D.3

Identical with the method for example described in D.1, be 92 microns film by 20 gram examples polycarbonate thickness B.12, test its ventilation property then.

Example D.4

Identical with the method for example described in D.1, be 95 microns film by 20 gram examples polycarbonate thickness B.13, test its ventilation property then.

Example D.5

Identical with the method for example described in D.1.By 20 gram examples polycarbonate thickness B.14 is 89.7 microns film, tests its ventilation property then.

Example D.6

With the fusion and extrude by a die head of the flat sheet that to obtain thickness be 163 microns film in a forcing machine (temperature is 360～370 ℃) of example polycarbonate B.7, test its ventilation property then.

Example D.7

In inert gas atmosphere, 31 gram (0.1 mole) examples bis-phenol and 24 gram (0.6 mole) NaOH A.1 are dissolved in 270 ml waters along with stirring.Add 250 milliliters of methylene dichloride then.It is 13～14 and temperature is in 20～25 ℃ the solution that 19.8 gram phosgene are introduced this well-beaten pH.After adding 5 minutes, add 0.1 milliliter of N-ethylpiperidine.Then with this mixture reaction 45 minutes.The aqueous phase separation of unparalleled phenolic ester is come out, and organic phase phosphoric acid acidifying is washed then until neutrality.With methylene dichloride strong solution cast film, it shows clear thorough transparency.Gpc analysis: determining molecular weight on the basis of demarcating with bisphenol-a polycarbonate.

Mw=246000, Mn=38760 permeability coefficient: infiltration gas sample N ₂O ₂CO ₂CH ₄D.3 23.9 109.2 634.9 30.2D.4,49.7 227.9 1629.5 64.3D.5,33.6 138.8 828.1 46.8D.6,78.2 400.5 2555.0 n.d.n.d: survey

Example is (laminated film) D.8

After solvent evaporation, will stack at 235 ℃ of films that prepare down according to example D1 and D2, and at medicine 2.34 * 10 ⁷The pressure of Pa (about 234 crust) was pressed 4 minutes down and under 235 ℃ the temperature together, formed the film of about 307 micron thickness.Press the same procedure of example described in D.1, testing air permeable.The result: the permeability coefficient to all gases is as follows

O ₂：208.3

CO ₂：1209.4

CH ₄：77.1

Under 180 ℃, it is stable that the size of this laminated film also remains.

Example D.9

The example polycarbonate B.14 and the laminated film of polymethylmethacrylate.With thickness is the example polycarbonate film preheating B.14 30 seconds that 130 microns polymethyl methacrylate film (PMMA) and thickness are 131 microns, then 2 * 10 ⁷Pressed together 30 seconds in 160 ℃ under the loading pressure of Pa (200 crust), form thickness and be 200 microns laminated film.Press the same procedure of example described in D.1, the ventilation property of testing this laminated film.

Example D.10

The example polycarbonate B.14 and the laminated film of polystyrene.

Be 78 microns polystyrene film (the polystyrene N168 that produces by BASFAG) with thickness and be 101 microns film preheating 30 seconds, then 2 * 10 by the thickness of example polycarbonate B.14 ⁷Pressed together 30 seconds in 160 ℃ under the loading pressure of Pa (200 crust), form thickness and be 168 microns laminated film.Press the same procedure of example described in D.1, the ventilation property of testing this laminated film.Permeability coefficient:

Infiltration gas sample N ₂O ₂CO ₂CH ₄D.9 0.7* 4.5 20.3 0.42*D.10 18.0 102.9 488.5 25.6

^*=when in the following time of situation of this laminated film, after gas is introduced measuring cell, only observe the small increase of pressure, measure later on 3 days penetration time by the penetration number that infiltration gas records.

Claims (12)

1. One kind by with phosgene carry out conventional interfacial polycondensation reaction, with phosgene carry out conventional homogeneous phase solution polycondensation or with diphenyl carbonate carry out conventional transesterification polycondensation by bis-phenol, can select chain terminator for use and can select for use branching agent to prepare the method for high molecular aromatic polycarbonate, it is characterized in that, described bis-phenol mainly is the bis-phenol by following formula (I) expression, and the consumption of formula (I) bis-phenol is the 100-2% (mole) of used bis-phenol total amount:

   

   R in the formula ¹And R ²U represents hydrogen or methyl separately,

   M is the integer of 4-7,

   R ³And R ⁴Can select respectively for each X, and represent hydrogen or methyl separately,

   X represents carbon, and condition is the R at least one X atom ³And R ⁴Be methyl.
2. 2. by the described method of claim 1, wherein used formula (I) bis-phenol is the 100-5% (mole) of bis-phenol total amount.
3. 3. by the described method of claim 2, wherein used formula (I) bis-phenol is the 100-10% (weight) of bis-phenol total amount.
4. 4. by the described method of claim 3, wherein used formula (I) bis-phenol is the 100-20% (mole) of bis-phenol total amount.
5. 5. press the described method of claim 1, the weight-average molecular weight M of wherein prepared aromatic polycarbonate _wBe at least 10000.
6. 6. by the described method of claim 1, wherein used another kind of bis-phenol is
7. 7. by the described method of claim 1, two X atoms at the alpha-position of C-1 in wherein used formula (I) bis-phenol are not that dialkyl group replaces.
8. 8. by the described method of claim 1, the β-position of the X atom of a dialkyl group replacement at C-1 arranged in wherein used formula (I) bis-phenol.
9. 9. press the described method of claim 1, the m=4 or 5 in its Chinese style (I).
10. 10. press the described method of claim 1, in its Chinese style (I) Part is

    
11. 11. by the described method of claim 1, the R in its Chinese style (I) ¹And R ²All be H.
12. 12. by the described method of claim 10, wherein R ¹And R ²Be hydrogen, used formula (I) bis-phenol is 1, two (the 4-hydroxy phenyls)-3,3 of 1-, 5-trimethylammonium cyclohexane.