CN1712450B - Thermally stable polycarbonate compositions - Google Patents
Thermally stable polycarbonate compositions Download PDFInfo
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- CN1712450B CN1712450B CN 200510082375 CN200510082375A CN1712450B CN 1712450 B CN1712450 B CN 1712450B CN 200510082375 CN200510082375 CN 200510082375 CN 200510082375 A CN200510082375 A CN 200510082375A CN 1712450 B CN1712450 B CN 1712450B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
Abstract
A thermoplastic polycarbonate composition characterized by improved thermal stability is disclosed. The composition comprises at least one sulfur-containing organic acid ester and may also contain degradation products of the ester. The compositions of the invention are suitable for the production of moldings and extrudates.
Description
Technical field
The present invention relates to thermoplastic poly carbonic ether, relate to thermally stabilized polycarbonate composition particularly.
Background technology
The production method of polycarbonate is known in the document, and in a lot of applications description is arranged:
Carry out the production of polycarbonate about utilizing interfacial polycondensation or melt transesterification technology, can reference, for example " Schnell ", the chemistry of polycarbonate and physics, superpolymer summary (Polymer Reviews), the 9th volume, Interscience publishes, New York, London, Sydney 1964, pp33 ff. and superpolymer summary (Polymer Reviews), the tenth volume, " utilizing interface and solution method condensation polymer ", Paul W.Morgan, Interscience publishes, New York 1965, chapter 8,325 pages, also can be with reference to EP-A 971790.
When being exposed to high temperature, polycarbonate needs that stablizer prevents to decolour, the chemical reaction and the DeR of additive.In treating processes subsequently, the polycarbonate that is used for optical applications especially may be exposed to high temperature.And this high temperature can generate disadvantageous monomer by DeR, polycarbonate molecular weight is descended, or caused the chemical reaction (for example being incorporated in the poly chain) of additive, has a negative impact thereby perhaps cause degraded additives that additive is renderd a service.
Known available organo phosphorous compounds for example phosphine (US 4 092 288 B) or phosphite (JP 54036363 A) increases thermostability.Same known salt, for example Si Wan Ji Phosphonium, ammonium salt and Witco 1298 Soft Acid, single acid esters of the acid of sulfur atom-containing (as the positive butyl ester of toluenesulphonic acids (JP 08-059975 A)) or the acid in addition that increases stability.
The organophosphorus thermo-stabilizer that adds in the polycarbonate generally is the hundreds of ppm order of magnitude.Yet, especially be used for the polycarbonate of optical applications, need to add minimum additive.Its objective is in order to suppress that unnecessary particle generates or casting problem during foundry pattern, simultaneously in order to guarantee that material has whole superperformance.
For consideration economically, only the additive with minute quantity is favourable.
Under high temperature and high density, for example in industrial measuring process to stablizer, the corrodibility of the ester of free acid and easy fracture is a unfavorable factor.It is favourable using the stablizer of not compromising to the device fabrication material, can prevent particle, metallic cation and safety defect like this.The ester of most free acid and easy fracture is high-volatile, and this makes that to keep quencher (quencher constantly is incorporated in the melt) constant and carry out the absolute Measurement difficulty more that becomes.
Another shortcoming of a lot of acid esters stablizers is a large amount of free acids of they very fast generations.Excessive free acid catalysis polycarbonate and for example reaction of separating agent of other additives perhaps when polycarbonate is in molten state, even promote the reversed reaction of polycarbonate and phenol to produce diphenyl carbonate.On the other hand, a small amount of unnecessary and the acid of ester bonded are very useful, and their can discharge free acid very lentamente under the situation of being heated at the polycarbonate of stabilization in the following process process.They have increased the thermostability of polycarbonate.
Therefore, target is to seek the thermo-stabilizer of polycarbonate.This thermo-stabilizer only need add amount seldom, non-corrosiveness, and low volatility, easily dissolving simultaneously, and can make an addition in inert solvent or the whole technology intrinsic component.In addition, this thermo-stabilizer should not be in and produces a lot of excessive free acids in the polycarbonate, so that prevent the degraded of polycarbonate and the generation of carbonate, and the reaction between inhibition polycarbonate and the additive.The substitute is, preferably can produce free acid lentamente.If this stablizer does not form all possible free acid when mixing polycarbonate and in the step subsequently, this is particularly advantageous so.Therefore, after the polycarbonate granulation, for example in the process of foundry pattern, this stablizer can continue to play a role (comprising that the institute that is exposed to heat brings into play long-acting by discharging free acid continuously in steps).
Summary of the invention
Disclose a kind of thermoplastic compounds that contains polycarbonate, the characteristics of this composition are the thermostabilitys with improvement.Described composition comprises the organic acid acetic of at least a sulfur-bearing and can further contain the degradation product of described ester.Composition of the present invention is applicable to makes moulded parts and extrudate.
Description of drawings
Surprisingly, the organic acid esters of sulfur-bearing combines required characteristic evenly, thereby is suitable for very much making the Merlon thermostabilization. For example, these heat stabilizers unexpectedly just lentamente with discharge corresponding free acid interimly. In addition, they have intrinsic low volatility, even the time of staying prolongs, they also are evaporated from polycarbonate melt hardly.
Even under high temperature and high concentration, the metal material that these stabilizing agents use routine does not have corrosivity yet, for example, 1.4571 or 1.4541 (Stahlschl ü ssel 2001, Stahlschl ü ssel Wegst GmbH publishes, Th-Heuss-Stra β e 36, D-71672Marbach) and the nickel-base alloy of C type, 2.4605 or 2.4610 (Stahlschl ü ssel 2001 for example, Stahlschl ü ssel Wegst GmbH publishes, Th-Heuss-Stra β e 36, D-71672Marbach).
Because in the polycarbonate stabilization procedures, generally can not predict whether stablizer has integrated required character rightly, for example low volatility, in technology in the solvent that uses solvability, non-corrosiveness and discharge acid lentamente, therefore, this makes us being surprised especially.
Therefore, the invention provides the thermostability with improvement and contain polycarbonate and the composition of the organic acid acetic of sulfur-bearing.The present invention also provides moulded parts and the extrudate of being made by the polycarbonate compositions of modification.Wherein, composition can contain the degradation product of these esters extraly.
According to the present invention, preferred appropriate thermal stablizer is the organic acid acetic of at least a sulfur-bearing, and described organic acid acetic has the various of the group of being selected from down:
A) formula (I)
In the formula
R
1Represent hydrogen or C independently
1-C
20Alkyl is preferably represented C
1-C
8Alkyl is more preferably represented unsubstituted C
1-C
6Alkyl is represented C best
1-C
4Alkyl, wherein alkyl can be replaced by halogen, especially represents hydrogen or methyl;
R
2And R
3Represent hydrogen or C independently of each other
1-C
6Base, C
4-C
30Alkyl carboxyl is preferably represented C
1-C
4Alkyl, C
6-C
25Alkyl carboxyl is more preferably represented C
8-C
20Alkyl carboxyl is especially represented hydrogen, C
17Alkyl carboxyl or C
15Alkyl carboxyl, or the following group of representative
In the formula
R
1Definition as mentioned above;
M represents 0 or 1 independently of each other,
N represents between the 0-8, and preferably an integer between the 0-6 especially represents 0,1 or 2;
B) formula (II)
In the formula
R
1Definition as mentioned above;
A represents hydrogen or C independently
1-C
12Alkyl is preferably represented C
1-C
8Alkyl is more preferably represented ethyl, propyl group or butyl;
L represents 2 or 3;
C) formula (III)
In the formula
R
1Definition as mentioned above;
D) formula (IV)
In the formula
R
1With the definition of n as mentioned above;
R
1Represent C
4-C
30Alkyl carboxyl is preferably represented C
6-C
25Alkyl carboxyl is more preferably represented C
8-C
20Alkyl carboxyl is represented C particularly
17Alkyl carboxyl or C
15Alkyl carboxyl or represent the following formula group
In the formula
R
1Definition as mentioned above;
E) formula V, (VI), (VIIa), (VIIb), (Ib), (IVa)
In the formula
R
1With the definition of n as mentioned above;
Q represents between the 0-10, preferably between the 1-8, and the integer between the 1-5 especially;
R
5And R
6Independent hydrogen or the C of representing
1-C
20Alkyl is preferably represented C
1-C
8Alkyl is more preferably represented C
1-C
6Alkyl is represented C best
1-C
4Alkyl, wherein alkyl can be replaced by halogen, especially represents hydrogen or methyl;
R
11Represent hydrogen or two-(C independently
1-C
4) alkylamino, preferably represent hydrogen or dimethylamino; With
F) formula (VIII)
In the formula
R
1With the definition of A as mentioned above;
G) formula (IX)
In the formula
R
1With the definition of m as mentioned above;
H) formula (X)
In the formula
R
1With the definition of A as mentioned above;
I) formula (XI)
In the formula
R
1With the definition of A as mentioned above.
Prepreerence is to meet formula (Ia) to (If), (IIIa), (IVb), (Va), (Vb) and thermo-stabilizer (IXa):
According to the present invention, these thermo-stabilizers can add separately in the polymer melt, with the form adding of any mixture or several different mixtures.According to the present invention, these thermo-stabilizers can with free acid for example ortho-phosphoric acid add mixture.
According to the present invention, the organic acid acetic of sulfur-bearing can be produced with ordinary method, for example, prepare (referring to Organikum from benzene sulfonyl chloride (benzene sulfonic acid chloride) or toluene sulfonyl chloride (toluene sulfonic acid chloride) with alcoholysis method with corresponding polyvalent alcohol, Wiley-VCH Verlag, the 20 edition, Weinheim, p606/1999).
Polycarbonate can pass through melt transesterification technology or interfacial polycondensation explained hereafter.By melt transesterification explained hereafter fragrance oligomerization carbonic ether or polycarbonate is known in the document, and description is arranged in following document: for example, and superpolymer science pandect, the tenth phase (1969), the chemistry of polycarbonate and physics, superpolymer summary, H.Schnell, the 9th phase, John Wiley and Sons, Inc. (1964) and DE-C 10 31512, US-A3,022,272, US-A 5,340,905 and US-A 5,399,659.
According to this technology, under the assistance of suitable catalyzer and optional other additives, the aroma dihydroxy compound in melt with carbonic diester generation transesterify.
Plant designing shown in the WO 02/,077 067 can be used for this implementation of processes.
The dihydroxyl aryl compound that is applicable to polycarbonate production has formula (XII)
HO-Z-OH (XII)
In the formula, Z is the aromatic base that contains 6-30 carbon atom, and it can contain one or more aromatic nucleus, can be substituted, and can contain aliphatic series or cycloaliphatic groups or alkylaryl or impurity atoms as associative key (binding links).
The example of dihydroxyl aryl compound is: dihydroxyphenyl, dihydroxybiphenyl, two (hydroxyphenyl) alkane, two (hydroxyphenyl) cycloalkanes, two (hydroxyphenyl) aralkyl, two (hydroxyphenyl) ether, two (hydroxyphenyl) ketone, two (hydroxyphenyl) sulfide, two (hydroxyphenyl) sulfone, two (hydroxyphenyl) sulfoxide, 1,1 '-two (hydroxyphenyl) diisopropyl benzenes and cycloalkylation and ring halogenated compound.
These and other suitable dihydroxyl aryl compounds have description in following patent description or document, for example, and US Patent specification 2 970 131,2 991 273,2 999 835,2 999 846,3 028 365,3 062 781,3 148 172,3 271 367,3 275 601,4 982 014, German patent specification 1 570 703,2 063 050,2 036 052,2 211 956,3 832 396, French Patent specification sheets 1 561 518, disquisition " Interscience publishes; New York 1964, p28 ff for H.Schnell, the chemistry of polycarbonate and physics; P102ff " and " D.G.Legrand, J.T.Bendler, polycarbonate Science and Technology handbook, Marcel Dekker, New York 2000, p72ff ".
Preferential dihydroxyl aryl compound for example is: Resorcinol, 4,4 '-dihydroxybiphenyl, two-(4-hydroxyphenyl) methane, two-(3,5-dimethyl-4-hydroxyphenyl) methane, two-(4-hydroxyphenyl) biphenyl methane, 1,1-two-(4-hydroxyphenyl)-1-diphenylphosphino ethane, 1,1-two-(4-hydroxyphenyl)-1-(1-naphthyl) ethane, 1,1-two-(4-hydroxyphenyl)-1-(2-naphthyl) ethane, 2,2-two-(4-hydroxyphenyl) propane, 2,2-two-(3-methyl-4-hydroxyphenyl) propane, 2,2-two-(3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-two-(4-hydroxyphenyl)-1-phenylpropyl alcohol alkane, 2,2-two-(4-hydroxyphenyl) HFC-236fa, 2,4-two-(4-hydroxyphenyl)-2-methylbutane, 2,4-two-(3,5-dimethyl-4-hydroxyphenyl)-the 2-methylbutane, 1,1-two-(4-hydroxyphenyl) hexanaphthene, 1,1-two-(3,5-dimethyl-4-hydroxyphenyl) hexanaphthene, 1,1-two-(4-hydroxyphenyl)-4-methylcyclohexane, 1,1-two-(4-hydroxyphenyl)-3,3, the 5-trimethyl-cyclohexane, 1,3-two-[2-(4-hydroxyphenyl)-2-propyl group] benzene, 1,1 '-two-(4-hydroxyphenyl)-3-diisopropyl benzene, 1,1 '-two-(4-hydroxyphenyl)-4-diisopropyl benzene, 1,3-two-[2-(3,5-dimethyl-4-hydroxyphenyl)-2-propyl group] benzene, two-(4-hydroxyphenyl) ethers, two-(4-hydroxyphenyl) sulfide, two-(4-hydroxyphenyl) sulfones, two-(3,5-dimethyl-4-hydroxyphenyl) sulfones and 2,2 ', 3,3 '-tetrahydrochysene-3,3,3 ', 3 '-tetramethyl--1,1 '-spiral shell two-[1H-indenes]-5,5 '-glycol.
Particularly preferred dihydroxyl aryl compound is: Resorcinol, 4,4 '-dihydroxybiphenyl, two-(4-hydroxyphenyl) ditanes, 1,1-two-(4-hydroxyphenyl)-1-phenylethane, two-(4-hydroxyphenyl)-1-(1-naphthyl) ethane, two-(4-hydroxyphenyl)-1-(2-naphthyl) ethane, 2,2-two-(4-hydroxyphenyl) propane, 2,2-two-(3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-two-(4-hydroxyphenyl) hexanaphthene, 1,1-two-(3,5-dimethyl-4-hydroxyphenyl) hexanaphthene, 1,1-two-(4-hydroxyphenyl)-3,3, the 5-trimethyl-cyclohexane, 1,1 '-two-(4-hydroxyphenyl)-3-diisopropyl benzene and 1,1 '-two-(4-hydroxyphenyl)-4-diisopropyl benzene.
Most preferably: 4,4 '-dihydroxybiphenyl, 2,2-two-(4-hydroxyphenyl) propane and two-(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane.
Can utilize a dihydroxyl aryl compound to form same polycarbonate, or several dihydroxyl aryl compound form Copolycarbonate.
Except dihydroxyl aryl monomeric compound, low-molecular-weight mainly is the oligomerization carbonic ether that has hydroxyl terminal groups, also can be used as initial compounds.
The dihydroxyl aryl compound can utilize together with the monohydroxy aryl compound of residual quantity.The dihydroxyl aryl compound can be produced by the monohydroxy aryl compound.Perhaps, low-molecular-weight oligomerization carbonic ether can utilize together with the monohydroxy aryl compound of residual quantity, and the latter is eliminated in the oligomer production process.The residual quantity of monohydroxy aryl compound can reach in 20%, preferably is in 10%, and preferably is in 5%, is 2% with interior (for example referring to EP-A 1 240 232) best.
As other all raw materials, chemicals and the synthetic middle auxiliary substance that adds, used dihydroxyl aryl compound also can pollute by impurity synthetic by himself, that produce when handling or storing, though this does not wish to take place, thereby purpose is to use purified starting material, chemicals and auxiliary substance as far as possible.
The suitable diaryl carbonate that reacts with the dihydroxyl aryl compound has following formula (XIII):
In the formula, R, R ' and R " be identical or different and represent hydrogen, ramose C arbitrarily independently of each other
1-C
34Alkyl, C
7-C
34Alkylaryl or C
6-C
34Aryl, R also can represent-COO-R " ', wherein R " ' represent hydrogen, ramose C arbitrarily
1-C
34Alkyl, C
7-C
34Alkylaryl or C
6-C
34Aryl.
The example of such diaryl carbonate for example is: dipheryl carbonate base ester, tolyl benzol carbonate and carbonic acid two (tolyl) ester, 4-ethyl phenyl phenyl carbonic ether, two-(ethylphenyl) carbonic ethers, 4-n-propyl phenyl benzol carbonate, two-(4-n-propyl phenyl) carbonic ethers, 4-isopropyl phenyl benzol carbonate, two-(4-isopropyl phenyl) carbonic ethers, 4-n-butylphenyl benzol carbonate, two-(4-n-butylphenyl) carbonic ethers, 4-isobutyl phenenyl benzol carbonate, two-(4-isobutyl phenenyl) carbonic ethers, 4-tert-butyl-phenyl benzol carbonate, two-(4-tert-butyl-phenyl) carbonic ethers, 4-n-pentyl phenyl benzol carbonate, two-(4-n-pentyl phenyl) carbonic ethers, 4-n-hexyl phenyl benzol carbonate, two-(4-n-hexyl phenyl) carbonic ethers, 4-iso-octyl phenyl carbonic ether, two-(4-iso-octyl phenyl) carbonic ethers, 4-n-nonyl phenyl carbonic ether, two-(4-n-nonyl phenyl) carbonic ethers, 4-cyclohexyl phenyl benzol carbonate, two-(4-cyclohexyl phenyl) carbonic ethers, 4-(1-methyl isophthalic acid-styroyl) benzol carbonate, two-[4-(1-methyl isophthalic acid-styroyl) phenyl] carbonic ethers, phenylbenzene-4-base carbonic ether, two-(phenylbenzene-4-yl) carbonic ethers, 4-(1-naphthyl) phenyl carbonic ether, 4-(2-naphthyl) phenyl carbonic ether, two-[4-(1-naphthyl) phenyl] carbonic ethers, two-[4-(2-naphthyl) phenyl] carbonic ethers, 4-Phenoxyphenyl benzol carbonate, two-(4-Phenoxyphenyl) carbonic ethers, 3-pentadecyl phenyl carbonic ether, two-(pentadecyl phenyl) carbonic ethers, 4-trityl phenyl carbonic ether, two-(4-trityl phenyl) carbonic ethers, cresotinic acid benzol carbonate (methyl salicylate phenyl carbonate), two-(cresotinic acid) carbonic ethers, ethyl Whitfield's ointment benzol carbonate, two-(ethyl Whitfield's ointment) carbonic ethers, n-propyl Whitfield's ointment benzol carbonate, two-(n-propyl Whitfield's ointment) carbonic ethers, normal-butyl Whitfield's ointment benzol carbonate, two-(normal-butyl Whitfield's ointment) carbonic ethers, isobutyl-Whitfield's ointment benzol carbonate, two-(isobutyl-Whitfield's ointment) carbonic ethers, tertiary butyl Whitfield's ointment benzol carbonate, two-(tertiary butyl Whitfield's ointment) carbonic ethers, two-(phenylsalicylic acid) carbonic ether and two-(benzyl Whitfield's ointment) carbonic ether.
Preferential biaryl compound is: dipheryl carbonate base ester, 4-tert-butyl-phenyl benzol carbonate, two-(4-tert-butyl-phenyl) carbonic ether, phenylbenzene-4-base carbonic ether (di-(biphenyl-4-yl) carbonate), two-(phenylbenzene-4-yl) carbonic ethers, 4-(1-methyl isophthalic acid-styroyl) phenyl carbonic ether and two-[4-(1-methyl isophthalic acid-styroyl) phenyl] carbonic ether.
Particularly preferably be: dipheryl carbonate base ester.
Diaryl carbonate can utilize together with the monohydroxy aryl compound of residual quantity.The dihydroxyl aryl compound can be produced by the monohydroxy aryl compound.The residual quantity of monohydroxy aryl compound can reach in 20%, preferably is in 10%, more preferably is in 5%, is in 2% best.
With respect to the dihydroxyl aryl compound, the general consumption of diaryl carbonate is 1.02 to 1.30mol, preferably is 1.04 to 1.25mol, more preferably is 1.06 to 1.22mol, is 1.06 to 1.20mol every mole of dihydroxyl aryl compounds best.Also can utilize the mixture of above-mentioned diaryl carbonate.
Produce used diaryl carbonate if the monohydroxy aryl compound is not used in, this monohydroxy aryl compound can be used to control extraly or modify end group so.It is shown in following general formula (XIV):
In the formula, R, R ' and R " identical with the definition that provides in the formula (XIII), supplementary condition are: R can not be hydrogen in this formula, but R ' and R " can be hydrogen.
Such monohydroxy aryl compound is, for example: the 1-methylphenol, 2-methylphenol or 3-methylphenol, 2, the 4-xylenol, the 4-ethylphenol, 4-n-propyl phenol, the 4-isopropyl-phenol, 4-normal-butyl phenol, 4-isobutyl-phenol, the 4-tert.-butyl phenol, 4-n-pentyl phenol, 4-n-hexyl phenol, the 4-isooctyl phenol, 4-n-nonyl phenol, 3-pentadecyl phenol, 4-hexanaphthene phenol, 4-(1-methyl isophthalic acid-styroyl) phenol, the 4-phenylphenol, the 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.
Preferably 4-tert.-butyl phenol and 3-pentadecyl phenol.
The boiling point of selected monohydroxy aryl compound should be higher than the boiling point of the monohydroxy aryl compound that is used for producing used diaryl carbonate.The monohydroxy aryl compound can add in any time of reaction process.Joining day preferably is when the beginning of reaction or in any time of reaction process.With respect to the dihydroxyl aryl compound, the ratio of monohydroxy aryl compound can be 0.2-20mol%, more preferably 0.4-10mol%.
End group also can be modified by mixing diaryl carbonate, wherein generates the boiling point of the monohydroxy aryl compound of this diaryl carbonate, is higher than the boiling point of the monohydroxy aryl compound that generates the diaryl carbonate that accounts for main component.Diaryl carbonate equally, herein can add in any time of reaction process.The suitable joining day is when the beginning of reaction or in any time of reaction process.With respect to used diaryl carbonate total amount, the ratio of the diaryl carbonate that one hydroxy aryl compound boiling point is higher can be 1-40mol%, preferably 1-20mol%, more preferably 1-10mol%.
Known basic catalyst in the document, such as the oxyhydroxide and the oxide compound of basic metal and alkaline-earth metal, and ammonium salt Huo phosphonium salt (hereinafter referred to as salt), can in the melt transesterification process of producing polycarbonate, be used as catalyzer.Qi Shi phosphonium salt of salt You preferably being used to synthesizes.Zhong De phosphonium salt of the present invention has following general formula (XV):
In the formula, R
7-10Can be identical or different C
1-C
10Alkyl, C
6-C
14Aryl, C
7-C
15Arylalkyl or C
5-C
6Cycloalkyl is preferably methyl or C
6-C
14Aryl, especially methyl or phenyl; And X-can be a negative ion, such as hydroxyl, sulfate radical, bisulfate ion, bicarbonate radical, carbonate or halogen ion, and chlorion or have alkylide or the arylide of formula-OR preferably, R can be C in the formula
6-C
14Aryl, C
7-C
15Arylalkyl or C
5-C
6Cycloalkyl, preferably phenyl.
Preferred catalyzer is tetraphenylphosphonium chloride, tetraphenylphosphoniphenolate oxyhydroxide and tetraphenylphosphoniphenolate phenates, and wherein the tetraphenylphosphoniphenolate phenates is particularly preferred.
With respect to 1mol dihydroxyl aryl compound, the suitable consumption of catalyzer is 10
-8To 10
-3Mol, more preferably consumption is 10
-7To 10
-4Mol.
Other catalyzer can use with salt separately or as co-catalyst, accelerates the speed of polycondensation.
They comprise the basic salt of basic metal and alkaline-earth metal, for example, and the oxyhydroxide of lithium, sodium, potassium, alcoholate and aromatic oxide, the preferably oxyhydroxide of sodium, alcoholate or aromatic oxide.Most preferably sodium hydroxide and sodium phenylate also have 2, the disodium salt of 2-two-(4-hydroxyphenyl) propane.
Calculate with sodium, with respect to the polycarbonate that generates, individually or the consumption of the alkali salt of basic metal that uses as co-catalyst and alkaline-earth metal be 1-500ppb, preferably be 5-300ppb, be 5-200ppb best.
The alkali salt of basic metal and alkaline-earth metal can use in oligomerization carbonic ether production process, promptly when synthetic beginning or add before polycondensation, to suppress unnecessary less important reaction.
Also can before polycondensation, replenish the catalyzer that adds identical or different kind.
Catalyzer is added in the solution, deleterious excessive concentration when preventing to measure.Solvent is the original compound that just exists in system and the technology, for example, and dihydroxyl aryl compound, diaryl carbonate or monohydroxy aryl compound.The monohydroxy aryl compound is especially suitable, changes easily because one skilled in the art will appreciate that dihydroxyl aryl compound and diaryl carbonate, and temperature improves a little and will degrade, especially under the effect of catalyzer.This has influence on the quality of polycarbonate.In the industrialization ester exchange process of producing polycarbonate, preferred compound is a phenol.When producing with the mixed crystal form, the available phenol of preferred catalyzer tetraphenylphosphoniphenolate phenates (tetraphenyl phosphonium phenolate) separates, and therefore on logic, phenol also is good selection.
Thermoplastic poly carbonic ether can be expressed as formula (XVI)
In the formula
R, R ', R " identical with Z with the definition that formula (X III) and (X II) provide.
X is a repeated structural unit, and its value has determined the size of polycarbonate molecular weight.
Group
As a complete group in the formula (XVI), also can be H, and can be different in both sides.
The average molecular mass of polycarbonate is generally 15,000 to 40,000, be preferably 17,000 to 36,000, more preferably be 17,000 to 34,000, wherein, according to Mark-Houwing dependency (correlation), average molecular mass is measured (J.M.G.Cowie by relative viscosity, Chemie undPhysik der synthetischen Polymeren, Vieweg Lehrbuch, Braunschweig/Wiesbaden, 1997,235 pages).
Positively charged ion and anionic content are extremely low in the polycarbonate.In each case, the basic metal of existence and alkaline earth metal cation concentration are lower than 60ppb, preferably＜and 40ppb, more preferably＜20ppb (calculating) with sodium ion, these positively charged ions can derive from impurity or Lai Yuan Yu phosphonium salt and the ammonium salt in the starting material.Other ions, for example, Fe, Ni, Cr, Zn, Sn, Mo, Al ion or its similar ion can be present in the starting material, also may be by the factory building device with material corrosion or corrosion and produce.This type of ionic total content is less than 2ppm, preferably is less than 1ppm, more preferably is less than 0.5ppm.
But there are (for example, muriate, vitriol, carbonate, phosphoric acid salt, phosphite and oxalate etc.) in mineral acid and organic acid negatively charged ion equivalent.
Therefore, purpose is to obtain minimum possible amount, and this can only realize by the starting material with highest purity.The starting material of this purity can obtain by purifying process, for example, and recrystallization, distillation, redeposition and washing etc.
Can carry out branch branching to polycarbonate on demand.For polycarbonate production, suitable branch's agent is a compound known, and they have three or more functional groups, more preferably is the compound that three or more hydroxyls are arranged.
The compound ions that available contains three or more phenolic hydroxyls is, Phloroglucinol, 4 for example, 6-dimethyl-2,4,6-three-(4-hydroxyphenyl) heptene-2,4,6-dimethyl-2,4,6-three-(4-hydroxyphenyl) heptane, 1,3,5-three-(4-hydroxyphenyl) benzene, 1,1,1-three-(4-hydroxyphenyl) ethane, three-(4-hydroxyphenyl) phenylmethane, 2,2-two-[4,4-two-(4-hydroxyphenyl) cyclohexyl] propane, 2,4-two-(4-hydroxyphenyl sec.-propyl) phenol and four-(4-hydroxyphenyl) methane.
Some other trifunctional compound: 2,4-resorcylic acid, trimesic acid, cyanuryl chloride (cyanuric chloride) and 3,3-two (3-methyl-4-hydroxyphenyl)-2-oxo-2,3-indoline.
The agent of preferred branch is: 3, and 3-two-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-indoline and 1,1,1-three-(4-hydroxyphenyl) ethane.
With respect to the dihydroxyl aryl compound, the consumption of branch's agent is normally 0.02 to 3.6mol%.
Producing polycarbonate with ester exchange process can carry out continuously or in batches.In case dihydroxyl aryl compound, diaryl carbonate also have other optional compounds to be in molten state, reaction has just begun under the condition that suitable catalyzer exists.Along with the rising of temperature and the decline of pressure,, in suitable equipment, carry out permutoid reaction or molecular weight is increased, up to reaching required final state by removing (drawing off) monohydroxy aryl compound.The type of end group and concentration are subjected to following factor affecting: for example, and the ratio of dihydroxyl aryl compound and diaryl carbonate; Owing to evaporating the diaryl carbonate (this full-scale plant by technology type or production polycarbonate is determined) that loses; The optional compound (as high boiling monohydroxy aryl compound) that adds.
Which kind of carry out in which way at device for the type of technology and essence and technology, all without limits.
And for the transesterification reaction between the reactant of dihydroxyl aryl compound and diaryl carbonate and other any optional addings, its temperature, pressure and catalyzer all do not have special restriction.Reaction is carried out if selected temperature, pressure and catalyzer allow melt transesterification, and needn't remove the monohydroxy aryl compound fast, and so any condition all is possible.
The temperature of whole technological process is generally at 180 to 330 ℃, and absolute pressure is between 15 crust (bar) and 0.01 crust.
Usually select continuous processing, because it has superiority aspect quality product.
The distinguishing feature of the continuous production processes of polycarbonate is, reactant in one or more dihydroxyl aryl compounds and diaryl carbonate, other addings, when existing with catalyzer, after the precondensation, do not removing under the formed monohydroxy aryl compound situation, can by the rising gradually of temperature and the decline gradually of pressure, make molecular weight reach required level in several reactive evaporation device stages subsequently.
Corresponding to technological process, equipment, instrument and the reactor that is suitable for each independent reaction evaporator stage is respectively heat exchanger, decompressing unit, separator, post, vaporizer, steel basin and reactor or other business equipment, the residence time of necessity when these business equipment can be provided at selected temperature and pressure.Selected instrument must be allowed necessary heat input, and its structure makes it can deal with the melt viscosity that increases continuously.
All equipment all passes through pump, pipe and valve and is connected with another one equipment.Very naturally, for avoiding the unnecessary residence time, the pipeline between all unit should be lacked as far as possible, and the radian of pipeline should be low as far as possible.Must meet the outside and be matching requirements technology, limiting condition and chemical devices.
For implementing preferred continuous processing, reactant or melted together, perhaps solid dihydroxyl aryl compound is dissolved in the diaryl carbonate melt, perhaps diaryl carbonate is dissolved in dihydroxyl aryl compound melt, perhaps two kinds of raw-material melt-mixing are preferably two kinds of starting material and directly mix aborning.Raw-material independent melt, especially dihydroxyl aryl compound melt, its residence time should be short as far as possible.On the other hand because with independent starting material relatively, raw-material mixture fusing point is lower, so the mixture of melt can stop the longer time and not influence quality product under corresponding more low temperature.
Then, catalyzer preferentially is dissolved in phenol, mixes, and melt is heated to temperature of reaction then.Industrial, with 2,2-two-(4-hydroxyphenyl) propane and dipheryl carbonate base ester are produced in the technology of PC, and starting temperature is 180 to 220 ℃, is preferably 190 to 210 ℃, is 190 ℃ best.In the residence time is 15 to 90 minutes, when being preferably 30 to 60 minutes, under the situation of the hydroxy aryl compound of not removing generation, just can set up molecular balance.Reaction can under atmospheric pressure be carried out, perhaps because technical reason can carry out adding to depress.Preferred absolute pressure is 2 to 15 crust in the industrial premises.
Melted blend is extracted in first vacuum chamber, and the pressure of first vacuum chamber is set at 100 to 400 crust, more preferably is 150 to 300 crust.Then, melted blend is heated to temperature in again immediately under pressure same in the suitable instrument.In decompression procedure, the hydroxy aryl compound of generation and the monomer that still exists are evaporated together.Under identical pressure and temperature, after stopping 5 to 30 minutes in the subsider (can randomly carry out pump circulation), reaction mixture is extracted in second vacuum chamber, the pressure of second vacuum chamber is 50 to 200mbar, more preferably be 80 to 150mbar, under suitable containers and identical pressure, be heated to 190 to 250 ℃ then, being preferably 210 to 240 ℃, more preferably is 210 to 230 ℃.The monomer of hydroxy aryl compound of Sheng Chenging and still existence is evaporated together equally, herein.Under identical pressure and temperature, after stopping 5 to 30 minutes in the subsider (can randomly carry out pump circulation), reaction mixture is extracted in the 3rd vacuum chamber, the pressure of the 3rd vacuum chamber is 30 to 150mbar, more preferably be 50 to 120mbar, under suitable containers and identical pressure, be heated to 220 to 280 ℃ immediately then, being preferably 240 to 270 ℃, more preferably is 240 to 260 ℃.The monomer of hydroxy aryl compound of Sheng Chenging and still existence is evaporated together equally, herein.Under identical pressure and temperature, after stopping 5 to 20 minutes in the subsider (can randomly carry out pump circulation), reaction mixture is extracted in another vacuum chamber, the pressure of this vacuum chamber is 5 to 100mbar, is preferably 15 to 100mbar, more preferably is 20 to 80mbar, then under suitable containers and identical pressure, being heated to 250 to 300 ℃ immediately, being preferably 260 to 290 ℃, more preferably is 260 to 280 ℃.The monomer of hydroxy aryl compound of Sheng Chenging and still existence is evaporated together equally, herein.
In the present embodiment as an example, the number in stage is 4, but also can change between 2 to 6 stages.If the number in stage changes, temperature and pressure should be done to adjust to produce suitable result accordingly so.In these stages, the relative viscosity that oligomerization carbonate reaches is between 1.04 and 1.20, is preferably 1.05 to 1.15, more preferably is 1.06 to 1.10.
Under the pressure and temperature identical with last flash distillation/evaporation stage, after stopping 5 to 20 minutes in the subsider (can randomly carry out pump circulation), the few carbonic ether of Chan Shenging enters into disc type or basket reactor by this way, continuing condensation at 250 to 310 ℃, be preferably 250 to 290 ℃, more preferably is 250 to 280 ℃, pressure is 1 to 15mbar, be preferably 2 to 10mbar, the residence time is 30 to 90 minutes, is preferably 30 to 60 minutes.Product reaches relative viscosity 1.12 to 1.28, is preferably 1.13 to 1.26, more preferably is 1.13 to 1.24.
The melt that leaves this reactor is adjusted to required final viscosity or molecular weight in another disc type or basket reactor.Temperature is 270 to 330 ℃ herein, is preferably 280 to 320 ℃, more preferably is 280 to 310 ℃, and pressure is 0.01 to 3mbar, is preferably 0.2 to 2mbar, and the residence time is 60 to 180 minutes, is preferably 75 to 150 minutes.Relative viscosity is adjusted to the desired level of specified application, and normally 1.18-1.40 is preferably 1.18-1.36, more preferably is 1.18-1.34.
The function of these two basket reactors can be comprehensively in a basket reactor.
The steam of each operation stage is extracted immediately, collects and handles.In order to obtain highly purified product from the material that reclaims, this treating processes is normally distilled.For example, can be with reference to German patent specification 10100
404 (corresponding to United States Patent (USP) 6,703,473, the document is incorporated herein by reference).From economy and ecological view, clearly, the monohydroxy aryl compound that is eliminated should be recovered and separate its purest form.The monohydroxy aryl compound can be directly used in produces dihydroxyl aryl compound or diaryl carbonate.
The characteristics of disc type or basket reactor are the surfaces that they provide a very big continuous renewal, and the vacuum and the long residence time.The geometry of disc type or basket reactor is according to the design of the melt viscosity of product.For example, the reactor of describing among DE 44 47 422C2 and the EP A 1 253 163, or the duplex reactor of describing among the WO A99/28 370, all be fit to (respectively corresponding to United States Patent (USP) 5,779,986; 6,630,563 and 6,329,495, these documents are incorporated herein by reference).
Few carbonic ether (even the very low few carbonic ether of molecular weight) and those synthetic polycarbonate transport by the screw pump of toothed gear pump, various designs or the positive-displacement pump of particular design usually.
Especially the material that is fit to be used for to produce this kind equipment, reactor, pipe, pump and part is the stainless steel of Cr Ni (Mo) 18/10 class, 1.4571 or 1.4541 (Stahlschl ü ssel 2001 for example, Stahlschl ü ssel Wegst GmbH delivers, Th-Heuss-Stra β e 36, D-71672Marbach) with based on the C type alloy of Ni, for example, 2.4605 or 2.4610 (Stahlschl ü ssel 2001, Stahlschl ü ssel Wegst GmbH delivers, Th-Heuss-Stra β e 36, D-71672Marbach).Stainless steel can be used for the processing temperature about 290 ℃, and Ni base alloy can be used for being higher than about 290 ℃ processing temperature.
Polycarbonate also can be used the interfacial polycondensation explained hereafter.This technology has different descriptions in the literature, wherein for example, and Schnell, " chemistry of polycarbonate and physics ", the superpolymer summary, the 9th volume, Interscience publishes, New York, London, Sydney 1964,33-70 page or leaf; D.C.Prevorsek, B.T.Debona and Y.Kesten, joint study center, chemical company of alliance, Morrison town, west, knob pool 07960: " synthesizing of Copolycarbonate ", superpolymer science magazine, polymer chemistry version, the 18th volume, (1980) "; The 75-90 page or leaf; D.Freitag, U.Grigo, P.R.M ü ller, N.Nouvertne ', BAYER AG, " polycarbonate ", superpolymer science and engineering pandect, the 11st volume, second edition, 1988,651-692 page or leaf and Drs.U.Grigo, K.Kircher and P.R..M ü ller " polycarbonate ", Becker/Braun, Kunststoff-Handbuch, the 3/1st volume, polycarbonate, poly-acetal, polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992,118-145 page or leaf and EP-A0 517 044 and many other patent applications.
According to this technology, the disodium salt of the bis-phenol in the alkaline aqueous solution (or suspension) (or mixture of multiple bis-phenol), its phosgenation occurs in inert organic solvents or the solvent mixture.Inert organic solvents or solvent mixture form second phase.What generate mainly is present in few carbonic ether in the organic phase, and under the assistance of suitable catalyzer, polycondensation is the high-molecular weight polycarbonate and is dissolved in the organic phase.Last organic phase is separated, and polycarbonate is separated by various treatment steps.
In this technology, moisture, the sodium hydroxide that uses, the water of one or more bis-phenols, wherein, with respect to the total content of bis-phenol, to calculate with free bis-phenol rather than sodium salt, the concentration of this aqueous solution may be for 1 to 30wt%, be preferably 3 to 25wt%, more preferably be 3 to 8wt%, this is greater than 45,000 polycarbonate to molecular weight.Less than 45,000 polycarbonate, then is 12 to 22wt% for molecular weight.Concentration is higher, may need to control solution temperature.Be used for dissolving the sodium hydroxide of bis-phenol can solid or the solution form use.The concentration of sodium hydroxide solution is subjected to the control of bis-phenol strength of solution, but is generally 5 to 25wt%, and preferably is 5 to 10wt%, perhaps selects the higher solution of concentration dilute with water again for use.In dilution subsequently, the sodium hydroxide solution of use is 15 to 75wt%, is preferably 25 to 55wt%, can randomly carry out temperature control.The alkali content of every mole of bis-phenol is decided by the structure of bis-phenol to a great extent, but be generally 0.25 moles base per mole bis-phenol to 5.00 moles base per mole bis-phenol, be preferably 1.5-2.5 moles base per mole bis-phenol, when dihydroxyphenyl propane is unique bis-phenol, the 1.85-2.15 mol alkali.If use more than a kind of bis-phenol, they can dissolve together.Yet, dissolves various phenol individually in mutually and in solution, measure individually at the highly basic of the best, or they are added in the reaction together is favourable.The dissolving bis-phenol also is favourable in having added rare bisphenolate salt solution of alkali but not in the sodium hydroxide solution.Dissolution process can be from solid bis-phenol (usually with sheet or granular form), or begins with the fused bis-phenol.Mercury electrode technology or so-called membrane process can be used to produce used sodium hydroxide or sodium hydroxide solution.These two kinds of technologies all have very long applicating history, and those skilled in the art are very familiar to them.The sodium hydroxide solution that membrane process is produced is more desirable.
The aqueous solution of Chan Shenging and contain the organic phase phosgenation together of polycarbonate solvent by this way, wherein said solvent is inert to reactant and forms second phase.
In introducing the process of phosgene or afterwards, as long as have phosgene or its direct secondary species in the reaction soln, chloro-formic ester just can measure bis-phenol.
In alkaline medium, be a thermopositive reaction with bis-phenol photoreactive gas polycarbonate synthesis, thereby carry out at-5 ℃ to 100 ℃, preferably 15 ℃ to 80 ℃, carry out under 25 to 65 ℃ the temperature best, this depends on solvent or mixed solvent, may carry out under superpressure.
Be applicable to that the bis-phenol example that the present invention produces polycarbonate is: for example Resorcinol, Resorcinol, dihydroxybiphenyl, two (hydroxyphenyl) alkane, two (hydroxyphenyl) cycloalkanes, two (hydroxyphenyl) sulfide, two (hydroxyphenyl) ether, two (hydroxyphenyl) ketone, two (hydroxyphenyl) sulfone, two (hydroxyphenyl) sulfoxide, α, α '-two (hydroxyphenyl) diisopropyl benzene, and alkylide, cycloalkylation thing, ring halogenide.
Bis-phenol preferably is: 4,4 '-dihydroxybiphenyl, 2,2-two-(4-hydroxyphenyl)-1-phenylpropyl alcohol alkane, 1,1-two-(4-hydroxyphenyl) phenylethane, 2,2-two-(4-hydroxyphenyl) propane, 2,4-two-(4-hydroxyphenyl)-2+ methylbutane, 1,1-two-(4-hydroxyphenyl)-m/p-diisopropyl benzene, 2,2-two-(3-methyl-4-hydroxyphenyl) propane, two-(3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-two-(3,5-dimethyl-4-hydroxyphenyl) propane, two-(3,5-dimethyl-4-hydroxyphenyl) sulfones, 2,4-two-(3,5-dimethyl-4-hydroxyphenyl)-the 2-methylbutane, 1,1-two-(3,5-dimethyl-4-hydroxyphenyl)-m/p-diisopropyl benzene and 1,1-two-(4-hydroxyphenyl)-3,3, the 5-trimethyl-cyclohexane.
Particularly preferred bis-phenol is 4,4 '-dihydroxybiphenyl, 1,1-two-(4-hydroxyphenyl) phenylethane, 2,2-two-(4-hydroxyphenyl) propane, 2,2-two-(3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-two-(4-hydroxyphenyl) hexanaphthene and 1,1-two-(4-hydroxyphenyl)-3,3, the 5-trimethyl-cyclohexane.
These and other suitable bis-phenols have description in following patent or document, US-A 2 999 835, and 3 148172,2 991 273,3 271 367,4 982 014 and 2 999 846, the disclosed application 1 570 703 of Germany, 2,063 050,2 036 052,2 211 956 and 3 832 396, French Patent specification sheets 1 561 518, disquisition " H.Schnell; the chemistry of polycarbonate and physics; Interscience publishes, New York 1964, p28 ff; P102 ff " and " D.G.Legrand, J.T.Bendler, polycarbonate Science and Technology handbook, Marcel Dekker, New York 2000, p72 ff ".
For same polycarbonate, only use a kind of bis-phenol.For Copolycarbonate, use several bis-phenols.Though should use purified as far as possible starting material, the bis-phenol of Shi Yonging herein adds chemical and additional substances in synthetic as other, may be synthetic by himself, the impurity handling and produce during storage pollutes.
Organic phase also can be made of the mixture of a kind of solvent or several solvents.The suitable solvent is hydrochloric ether (aliphatics and/or an aromatic series), is preferably the mixture of methylene dichloride, trieline, 1, vinyl trichloride, chlorobenzene and these materials.Also can utilize aromatic hydrocarbon, for example benzene, toluene, neighbour// right-dimethylbenzene or aromatic oxide are such as methyl-phenoxide, they can individually or mix ground, use extraly or with hydrochloric ether.Another synthetic example uses the solvent that does not dissolve the polycarbonate that only expands.Therefore the precipitation agent of polycarbonate can use together with solvent.In this case, also can use the solvent that is soluble in the aqueous phase, such as tetrahydrofuran (THF), 1,3/1,4-diox or 1, the 3-dioxolane, and partner's thing (partner) of solvent forms second organic phase.
The two-phase that forms reaction mixture is mixed together to add fast response.This process need provides energy by shearing, promptly with pump or stirrer, or utilizes the static mixing tank, or forms turbulent flow with nozzle and/or baffle plate.These measures also can be united use, often are to reuse in one period or use by a graded.The water screw of anchor type, MIG stirrer etc. are more suitable agitators, for example at " the technical chemistry pandect " of Ullmann, and the 5th edition, the type described in the B2 volume, p251ff.Using rotary pump, often is that 2 to 9 grades stage pump is more suitable.The nozzle and/or the baffle plate that use are perforated retainer, tapered tube, Venturi meter or lefos nozzle.
The phosgene of introducing can be gas or liquid form, or is dissolved in the solvent.With respect to the total amount of used bis-phenol, used excessive phosgene is 3 to 100mol%, is preferably 5 to 50mol%.In this case, during phosgene metering and afterwards, by interpolation sodium hydroxide solution or corresponding bis-phenol solution disposable or repeatedly, the pH value of water can be alkaline, suitable is 8.5 to 12, and after adding catalyzer, the pH value of water should be between 10 to 14.The temperature of phosgenation process is 25 to 85 ℃, is preferably 35 to 65 ℃.According to used solvent, also can under superpressure, carry out.
Phosgene can directly be counted the mixture of described organic phase and water, and perhaps before two-phase was mixed, all or part phosgene was counted the phase in the two-phase, and this mixes with corresponding other one mutually mutually then.In addition, all or part of phosgene can count a round-robin shunting (splitstream) of synthetic mixture, circulation before this shunting contains two-phase solvent and is preferably in the catalyzer adding.In another example, water mixes with the organic phase that contains phosgene, stops 1 second to 5 minutes, is preferably 3 seconds to 2 minutes.Afterwards, join in the above-mentioned circulation shunting.Perhaps, water directly mixes in above-mentioned circulation shunting with the organic phase that contains phosgene.In all these examples, must detect the pH scope, can select disposable or repeatedly add sodium hydroxide solution or corresponding bisphenolate salt solution.Similarly, can come the holding temperature scope randomly by cooling or diluted reaction mixture.
Polycarbonate is synthetic can be undertaken by continuous or batch mode.Therefore, reaction can be carried out in stirred tank reactor, tubular flow reactor, pump circulation reactor or a series of steel basin, and perhaps these reactors are in conjunction with utilization.Herein, the whipping device of above-mentioned utilization is that before, water does not separate with organic phase in order to ensure finishing (promptly not containing any saponifiable chlorine from phosgene or chloro-formic ester) in the synthetic mixture reaction.
The required simple function chain terminator that is used to regulate molecular weight, for example phenol or alkylphenol, especially phenol, the p-tert.-butyl phenol, isooctyl phenol, cumyl phenol, the mixture of chloro-formic ester or monocarboxylic acid chloride or these chain terminators, can add in the reaction with one or more bis-phenols, perhaps put adding any time at synthetic, supplementary condition are: also have phosgene or chloroformic acid end group in the reaction mixture, and under the situation as chain terminator, in the polymer that generates, also have enough phenol end groups with acid chloride and chloro-formic ester.Chain terminator adds after being preferably in phosgenation, but will not add before having the residue phosgene and also not adding catalyzer.Chain terminator can add before catalyzer, add together or parallel adding with catalyzer.
Any stand-by branch's agent or the mixture of branch's agent all add in the same manner, but are to add before chain terminator traditionally.The conventional acid chloride that trisphenol, quaternary phenol (quaternary phenol), tricarboxylic acid or tetracarboxylic acid are arranged that uses, the perhaps mixture of polyphenol or acid chloride.
Some available, the examples of compounds that contains three or more phenolic hydroxyl group are: for example,
Phloroglucinol,
4,6-dimethyl-2,4,6-three-(4-hydroxyphenyl) heptene-2,
4,6-dimethyl-2,4,6-three-(4-hydroxyphenyl) heptene,
1,3,5-three-(4-hydroxyphenyl) benzene,
1,1,1-three-(4-hydroxyphenyl) ethane,
Three-(4-hydroxyphenyl) phenylmethanes,
2,2-two-[4,4-two-(4-hydroxyphenyl) cyclohexyl] propane,
2,4-two-(4-oxybenzene sec.-propyl) phenol,
Four-(4-hydroxyphenyl) methane.
Some other trifunctional compound comprises 2,4-resorcylic acid, trimesic acid, cyanuryl chloride and 3,3-two-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-indoline.
The agent of preferred branch is 3,3-two-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-indoline and 1,1,1-three-(4-hydroxyphenyl) ethane.
The catalyzer of using during interfacial polycondensation is synthetic is: tertiary amine, especially triethylamine, Tributylamine, trioctylamine, N-ethylpiperidine, N-methyl piperidine, N-i/n-propyl group piperidines, quaternary ammonium salt be the oxyhydroxide/muriate/bromide/hydrosulphuric acid salt/a tetrafluoro borate of tetrabutyl quaternary ammonium/tetrabutyl benzyl quaternary ammonium/tetraethyl-quaternary ammonium for example; With respect to ammonium compound De phosphonium compounds.Ammonium compound herein is with the compound that phosphonium compounds is referred to as.
As the typical catalyzer of interfacial polycondensation technology, these compounds have description in the literature, can buy to obtain, and be well known to those skilled in the art.In synthetic, these catalyzer can separately or mix, add together or successively, also can add before phosgenation; But add after phosgenation is preferred, unless compound or its mixture are used as catalyzer (it is preferred adding in this case) before phosgenation.
One or more catalyzer can integral body join in the inert solvent (in particular for the solvent of polycarbonate production), perhaps with tertiary amine as quaternary ammonium salt (with acid (preferred mineral acid, especially in the time of the salt that forms hydrochloric acid)), catalyzer adds with aqueous solution form.If add more than one the catalyzer or the part of adding catalyzer total amount, can use various metering method in different places and time naturally so.
With respect to the mole number of the bis-phenol that uses, the total amount of the catalyzer of use is 0.001 to 10mol%, is preferably 0.01 to 8mol%, more preferably is 0.05 to 5mol%.
Introduce after the phosgene, and before randomly adding branch's agent (if branch's agent does not add together with bisphenolate salt), chain terminator and catalyzer, it is favourable that organic phase and water are mixed.It is favourable after each the adding such churning time being arranged.If stirring is arranged, then churning time can be between 10 seconds to 60 minutes, preferably 30 seconds to 40 minutes suitable, more preferably be 1 to 15 minute.
After reaction finishes,, be separated to having two-phase at least and containing the reaction mixture of the chloro-formic ester of trace (being lower than 2ppm) at the most.All or part of alkaline water can be used as water and is returned to the polycarbonate building-up process, or is used for wastewater treatment.Separated and the recirculation of solvent and catalyzer when wastewater treatment.In another treating processes, after organic impurity (especially solvent and polymer residue) is separated, and can salt be separated out and be used for the electrolysis of chloro-alkali by for example adding after sodium hydroxide solution sets up specific pH, water can randomly turn back to building-up process simultaneously.
Now, contain the pollution that polymeric organic phase must be removed all alkali, ion or catalyzer.Even but, still can contain very a spot of alkaline water through after one or more treating processess, contain catalyzer (being generally tertiary amine).These treating processess can wherein can add water at all or some separation phases by making organic phase through subsider, stirred tank reactor, distiller or separator or its combination, can use active or the passive type whipping device.
Through after the water roughing out with alkalescence, organic phase Diluted Acid Washing one or many, described acid can be mineral acid, carboxylic acid, hydroxycarboxylic acid and/or sulfonic acid.Preferably inorganic acid aqueous solution, especially hydrochloric acid, phosphorous acid and phosphoric acid or these sour mixtures.These sour concentration should be between 0.001-50wt%, are preferably 0.01-5wt%.
Organic phase is also with deionized water or distilled water repetitive scrubbing.At each independently after the washing stage, the separation of organic phase (can randomly separate) with aqueous portion, be by subsider, stirred tank reactor, distiller or separator or its combination, wherein between each stage of washing, can add water, and can use active or the passive type whipping device.
Acid (especially being dissolved in the acid of the solvent that is used for polymer solution) can add between these washing stages or after the washing.Herein, preferably hydrogen chloride gas, phosphorous acid, phosphoric acid or these sour mixtures.
After the last separable programming, the polymer solution of the purifying that obtains in this way should contain and be less than 5wt%, preferably is less than 1wt%, is less than the water of 0.5wt% best.
Polymer and solution separating can be made solvent evaporation with heating, vacuum or heat-carrying gas.Other separation method also has crystallization and precipitation.
If remove solvent by distillation, optional overheated and expand (expansionn), thereby realize that the concentrated of polymer solution separates with polymeric, this just is called " flash process (flash process) " so, see " Thermische Trennverfahren ", 1,988 114 pages of VCH Verlagsanstalt; If heat-carrying gas and the solution that will evaporate spray together, so just be called " spray steaming/spray is done ", see Vauck, " Grundoperationen chemischer Verfahrenstechnik ", Deutscher Verlag f ü rGrundstoffindustrie 2000, the 11 editions, 690 pages.All these technologies all have in patent documentation and textbook to be described and is well known to those skilled in the art.
If solvent is removed by heating (distillation) or other industrial more effective flash process, so just can obtain the polymer melt of high density.Known to flash process in, polymer solution is in the temperature that is heated to above boiling point under the standard atmosphere pressure under the excessive slightly pressure repeatedly, then, these expand down with respect to the pressure (such as normal pressure) that standard atmosphere pressure superheated solution reduces in container.Advantageously, should guarantee that enriching stage (in other words, the temperature stage of superthermal process) is unlikely to long, should select the process of a secondary to level Four.
Residual solvent can be removed from the polymer melt of high density in the following manner: remove from melt with the steam forcing machine directly that (BE-A 866 991, EP-A 0 411 510, US-A 4 980 105, DE-A 33 32065), film evaporator (EP-A 0 267 025), falling-film evaporator, strand vaporizer or friction fine and close (EP-A 0,460 450), wherein can randomly add separating agent (for example nitrogen or carbonic acid gas), or with vacuum (EP-A 003996, EP-A 0 256 003, US-A 4 423 207), also can from solid phase, remove solvent (US-A 3 986 269, and DE-A 2 053 876) by crystallization (DE-A 3 429 960) with by baking subsequently.
Preferably by the direct spinning (spinning) and the granulation subsequently of melt, or utilize melt extruder to obtain particle, wherein in melt extruder, melt is spun in air or in the liquid (normally water).If the use forcing machine can add additive before forcing machine, and can randomly use the auxiliary extruder in static agitator or the forcing machine.
For injection, polymer solution (can randomly heating after) under reduced pressure is directed onto in the container, perhaps under normal pressure with the carrier gas (as nitrogen, argon gas and water vapour) of heating, spray in the container by nozzle.In two kinds of methods,, can obtain the powder (lower concentration) or the thin slice (high density) of polymer based on the concentration of polymer.The residue of solvent must randomly be removed as mentioned above.By mix forcing machine and subsequently spinning can obtain the particle of polymer.In this process, also can add additive to unit or extrusion machine itself on every side.Because the apparent density of powder and thin slice is low, therefore usually must be before extruding earlier the compacting of polymer powder.
By adding the polycarbonate precipitation agent, polymer can from washed and spissated polycarbonate be precipitated out and become crystallization.At this, only add a spot of precipitation agent during beginning, and to reserve for some time between the precipitation agent of different batches be favourable adding.Use various precipitation agent then better.For example, hydrocarbon compound, especially heptane, iso-octyl hexanaphthene also have alcohols such as methyl alcohol, ethanol, Virahol can be used as precipitation agent at this.
Sedimentary process normally is added to polymer solution in the precipitation agent lentamente. in this case, yet use methyl alcohol, ethanol, Virahol usually. and, hexanaphthene or ketone such as acetone also can be used as precipitation agent.
The material that obtains like this is processed to particle (as above described like that to carburation by spraying technology) and can randomly adds additive.
According to other technology, make precipitation and crystallized product or amorphous solid granular product crystalline method, be to heat to be lower than second-order transition temperature when making it, and then concentrate the higher molecular weight of generation by one or more polycarbonate precipitation agent steam.For oligomer, different end group (phenol and stopping of chain end group) can be arranged, this process is stated to solid phase and is concentrated.
Thermo-stabilizer
In case polycarbonate has reached required molecular weight, preferably add the thermo-stabilizer of formula of the present invention (I) to (XI).The static vortex mixer or other vortex mixers (as extrusion machine) that can uniform mixing add composition all are fit to mixture heat stablizer effectively.Under one situation of back, by being used for the auxiliary extrusion machine of polymer melt, thermo-stabilizer is added in the main polymer flow, also can add other material simultaneously, for example releasing agent (releasingagent).
Independent thermo-stabilizer of the present invention or mixture each other or several different mixture can be added in the polymer melt.The thermo-stabilizer mixture of the present invention that has free sulfonic derivative such as Phenylsulfonic acid or toluenesulphonic acids also can add.
The fusing point of thermo-stabilizer preferably is higher than 30 ℃, be higher than 40 ℃ better, be higher than 50 ℃ especially good.Boiling point preferably is higher than 150 ℃ under 1mbar (millibar), be higher than 200 ℃ better, be higher than 230 ℃ especially good.
According to the present invention, with respect to polycarbonate, the ester that contains the acid of organosulfur can be lower than the amount use of 100ppm, and it is then better to be lower than 50ppm, and it is especially good to be lower than 30ppm, and it is best to be lower than 15ppm.
Preferable use is thermo-stabilizer or its mixture of 0.5ppm at least, and 1ppm is better, preferably 1.5ppm.Especially, the consumption of thermo-stabilizer is 2 to 10ppm with respect to polycarbonate.
Thermo-stabilizer also can be fit to do the additive of stablizer such as Phenylsulfonic acid or benzene methanesulfonic acid with for example former phosphoric acid of free acid or other and be mixed together and add.The amount of free acid or other stablizers (with respect to polycarbonate) is maximum 20ppm, and preferable maximum 10ppm especially 0 arrive 5ppm.
In the present invention, without limits to the adding form that contains organic vitriolic ester.Of the present inventionly contain machine vitriolic ester or its mixture can be used as solid (powder just), liquid or join in the polymer melt as melt.Another adding method is to use masterbatch (preferable with polycarbonate), and it also can contain other additives, as other stablizers or releasing agent.
Preferable with the liquid form adding ester that contains the acid of organosulfur of the present invention.Because add-on is very low, the solution of preferable use ester of the present invention.
Suitable solvent is that those can not disturb this technology, chemically inertia and type of solvent that can very fast evaporable.
Suitable examples of solvents comprises that boiling point under all normal pressures is 30 to 300 ℃, preferred 30-250 ℃, preferred 30-200 ℃ organic solvent especially, also has water-comprise crystal water.The compound that is present in each technology is preferred.The amount that depends on any residue that may stay of the scope for the treatment of the requirement that produces product can not reduce quality.
Except water, solvent has alkane, cycloalkanes, aromatics, and these also can be substituted.Substituting group can be the aliphatic series of various combination, alicyclic or aromatic group, and halogen or hydroxyl.Heteroatoms (as Sauerstoffatom) also can be aliphatic, alicyclic or family's group in conjunction with connecting, wherein, these groups can be identical also can be different.Other solvents also can be ketone and organic acid ester and cyclic carbonate ester.Thermo-stabilizer also can be dissolved in the Zerol, and adds with this form.
Except water, also has for example Skellysolve A, normal hexane, normal heptane and its isomer, chlorobenzene, methyl alcohol, ethanol, propyl alcohol, propyl carbinol and its isomer, phenol, adjacent-,-, right-cresylol, acetone, ether, DIMETHYL GLYOXIME, polyoxyethylene glycol, polypropylene glycol, ethyl acetate, ethylene carbonate and propylene carbonate.
Water, phenol, propylene carbonate, ethylene carbonate and toluene are suitable for polycarbonate processing more.
More preferably be water, phenol and propylene carbonate.
Under free sulfonic and some situation the sulfonic acid of esterification and and alcohols produce to the degraded product of the thermo-stabilizer of (XI) as formula of the present invention (I).
In order to change its performance, also can with the polycarbonate of gained with mix at the additive of the known routine of the known function of polycarbonate molding Composition Aspects after adding inhibitor because of it according to the present invention.These additives can increase the service life (as hydrolysis or the degraded stablizer), improve colour stability (as heat and ultra-violet stabilizer), convenient processing (, flowing) with reference to agent as releasing agent, improve performance characteristic (as anti-electrostatic), improve fire resistance, influence outward appearance (as organic dye, pigment) or make the character of polymkeric substance adapt to specified pressure (impact modifier, the fine grinding mineral, fiber, quartz, glass and carbon fiber).All these can combine by any way, with the character of adjusting and obtaining to want.These additives and filler are existing to be described, as " Plastic Additives ", R.Gachter and H.Muller, Hanser Publishers 1983.
These additives can join in the polymer melt separately or with any mixture or several different form of mixtures with filler, also can directly add after the fusing bead when isolating polymer or in so-called mix stages.
These additives and filler or its mixture can be with solid (powder just), and perhaps the form of melt joins in the polymer melt.Another adding mode is with masterbatch or transfers the mixture of additive masterbatch or the mixture of additive.
These materials are preferably joining in the middle of the final polycarbonate in conventional elements, and still, as requested, they also can add in other stages of polycarbonate production process.
Suitable additive has the additive handbook of describing as plastics, John Murphy, Elsevier, Oxford 1999 or plastics additive handbook, Hans Zweifel, Hanser, Munich2001 as an example in the literature.
Other citable examples of applications comprises following (but not limiting theme of the present invention):
1. shatter proof glass, this is at a lot of construction areas, the vehicles and aircraft, and the eye-protection glasses of the helmet all needs.
2. film
3. blow-molded article (with reference to US-A 2 964 794), for example 1 to 5 gallon water bottles.
4. semitransparent thin film as solid film or particularly bilayer film, for example is used for hiding buildings such as platform, greenhouse and means of illumination.
5. optical digital storage media, audio frequency CD CD, CD erasable optical disk CD-R (W), DVD CD DCDs, DVD erasable optical disk DVD-R (W), minidisk and corresponding expansion equipment.
6. traffic lamp room and road sign.
7. has the porous plastics that opens or closes with the selectivity printable surface.
8. line and electric wire (with reference to DE-A 11 37 167)
9. means of illumination randomly uses glass fibre in translucent portion.
10. the translucent medium that contains barium sulfate and/or titanium dioxide and/or zirconium white or organic poly acrylate rubber (EP-A 0 634 445, and EP-A 0 269 324) is used for producing translucent and the scattering of light moulded parts.
11. accurate instrument used for injection, as fixer, camera lens fixer for example; Contain glass fibre and selectivity added the molybdenumdisulphide of 1-10wt% (with respect to all not body form) polycarbonate optionally be used for this purposes.
12. optical device components, particularly photography camera lens and film camera (DE-A 27 01 173).
13. optical media, particularly optical cable (EP-A 0 089 801) and photoconductive fiber.
14. cable, junctor kernel, the insulating material of plug-in connector and electrical condenser.
15. wireless telephony case.
16. socket device.
17. the upholder of organic photoconductor.
18. lamp, head lamp, diverging lens or endoscope.
19. medicine equipment, as oxygenator, dialysis machine.
20. tableware, as bottle, pottery and chocolate mould.
21. in the application of trolley part, for example glazing or with ABS as beam.
22. the pole of sports goods such as slalom, skiing leather boots clip.
23. household goods, as kitchen basin, washbowl, mailbox.
24. fence, for example electrical network pavilion.
25. the household electrical appliance, as toothbrush, blower, coffee-maker, machine tool is as the machine of drilling, runner milling, planing machine and saw.
26. washing machine manhole appendix.
27. eye-protection glasses, sun glasses, optical correction glasses and camera lens.
28. lampshade.
29. packing film.
30. chip cartridges, chip carrier, silicon wafer film magazine.
31. the cage of other purposes such as Dutch door or pass animal.
Embodiment
Below these embodiment be used for illustrating of the present invention, but be not used in restriction the present invention.
Embodiment
Relative solution viscosity is to measure in methylene dichloride with the concentration of 5 grams per liters under 25 ℃.
Phenolic hydroxyl content is measured by IR.For this reason, measured 2 gram polymers 50 milliliters of dichloromethane solutions and absolute dichloromethane at 3582cm
-1The absorbance difference at place.
The analysis of measuring residual monomer is described as follows:
Sample dissolution precipitates in methylene dichloride and with acetone/methanol.The polymer that precipitates is separated, and filtrate is concentrated to small volume.Residual monomer is quantitative assay in 0.04% phosphoric acid-acetonitrile with reverse-phase chromatography in the solvent strength gradient.Detect with UV-light.
Bis-phenol (BPA), phenol and diphenyl carbonate (DPC) detect in this way.
Term GMS is meant the mixture of Zoomeric acid monoglyceride and stearic acid monoglyceride.
Total GMS content is by free GMS (GMS
Free), carbonic acid GMS (GMS-CO
3) and bonded GMS composition.The latter uses subtraction.
Hydrochloric acid adjust pH to 1 is used in the hydrolysis under 80 ℃ of alkaline conditions of part sample then.Extract this solution, dry extract then with t-butyl methyl ether.After the derivatize, at the enterprising promoting the circulation of qi analysis of hplc of the capillary column that is connecting flame ionization detector.Use the inherent standard product to carry out quantitative analysis, and draw total GMS content.
Another part sample is dissolved in the methylene dichloride and derivatize.In the separation of capillary column gas-chromatography and after, carry out qualitative detection with the inherent standard product with flame ionization detector (FID) detection.Draw the content of free GMS and carbonic acid GMS thus.
With stearic acid monoglyceride (GMS) and the carbonic acid stearic acid monoglyceride (GMS) of GC FID detection by quantitative in polycarbonate:
About 0.5 gram sample dissolution is at 5 milliliters of CH
2Cl
2In and add internal standard product (as normal alkane).In this solution, add about 5 milliliters of t-butyl methyl ether (MTBE) with the precipitation polymer.Concussion suspension is centrifugal then.The supernatant liquor that siphons away fixed volume (3 milliliters) dries in nitrogen then.Remaining material MSTFA solution (N-methyl-N-(TMS) trifluoroacetamide) silanization.The solution that leaches is analyzed with gas phase (GC) (as HP6890) chromatogram.Detect (FID) with the flame ion detector.
Material therefor:
Polycarbonate B:
Relative solution viscosity 1.201
Phenolic hydroxyl content 240ppm
DPC 80ppm
BPA 10ppm
Phenol 65ppm
GMS
Free288ppm
GMS-CO
3 ＜10ppm
Thermo-stabilizer A:
According to the present invention, thermo-stabilizer is to the influence of polycarbonate heat stability improvement, is that the long-term thermal stability with reference to polycarbonate detects.
Embodiment A
Thermo-stabilizer A's is synthetic:
Glycerine benzene sulfonyl chloride glycerine three benzene sulfonates
(molecular weight 92.10) (molecular weight 176.62) (molecular weight 512.58)
4746 gram (60 moles) pyridines that will be provided by 552.6 gram (6.0 moles) glycerine and the Aldrich that KMF provides place under the nitrogen uniform dissolution.Dropwise slowly add 3196.8 gram (18.1 moles) benzene sulfonyl chlorides, temperature can not exceed 30 to 35 ℃ therebetween.Then, mixture stirred 1 hour at 40 ℃.
Preparation:
Under the vigorous stirring, pour batch of material into a mixture very lentamente, this mixture contains 3 liters of distilled water, about 4 kg of ice and 3 liters of methylene dichloride.The temperature of this process should be above 35 ℃.
Then, organic phase precipitates in about 10 liters of methyl alcohol, and methanol wash also use in extraction, analyses till demonstration obtained purified product up to rete.
60 ℃ are dried to constant mass in vacuum drying oven.
Output: 970 gram white powders (31.54% theoretical value)
Analyze:
Fusing point m.p.81-83 ℃
1H-NMR(400MHz，TMS，CDCl
3)＝7.8ppm(m，6H)，7.7(m，3H)，7.55(m，6H)，4.75(m，1H)，4.1(d，4H)。
Embodiment 1
In forcing machine, with thermo-stabilizer A (pulvis) (the pressing polycarbonate calculates) uniform mixing (parent material) of 2.5 kilograms of polycarbonate B and 4ppm.Mixture is exposed to be pined for, and continues 10 minutes and continues 10 minutes at 360 ℃ at 340 ℃, carries out chemical analysis (table 1) then.
Comparative Examples 1
Identical with embodiment 1, difference is: add the former phosphoric acid of 3ppm to replace 4ppm thermo-stabilizer A.
Table 1
| Parent material | 340℃ | 360℃ | ||
| Relative viscosity | Embodiment 1 | 20.1 | 19.6 | 19.4 |
| Comparative Examples 1 | 20.1 | 19.7 | 19.3 | |
| GMS Free/ppm | Embodiment 1 | 288 | 60 | 69 |
| Comparative Examples 1 | 288 | ＜10 | ＜10 | |
| GMS-CO 3/ppm | Embodiment 1 | ＜10 | ＜10 | ＜10 |
| Comparative Examples 1 | ＜10 | 70 | 30 | |
| DPC Heavily fracture/ppm | Embodiment 1 | 80 | 81 | 80 |
| Comparative Examples 1 | 80 | 500 | 500 |
These embodiment prove, when being exposed to when hot, with respect to Comparative Examples 1 with phosphoric acid as stablizer, the stability of polycarbonate has increased.This embodies in the following areas: free GMS content increases GMS-CO
3Content reduce, and the rate of formation again of diphenyl carbonate DPC obviously reduces.Therefore residual monomer (DPC) content can be controlled in lower level.This is even more important for optical disc data storage and multimedia application, because when injecting polycarbonate, the monomer component of evaporation can be gone up formation coating (being called " coverage " (blading out)) at injection molding (mould), and this is disadvantageous.
Though detailed description has been done to the present invention for purposes of illustration in the front, it should be understood that these details are that those skilled in the art can change it for purposes of illustration under situation without departing from the spirit and scope of the present invention.Scope of the present invention is subjected to the restriction of claims.
Claims (8)
1. a thermoplastic composition is characterized in that, it contains the organic acid acetic of polycarbonate and sulfur-bearing, and the organic acid acetic of described sulfur-bearing is at least a compound that is selected from down group:
In the formula
R
1Represent hydrogen independently, unsubstituted or halogenated C
1-C
20Alkyl,
R
2And R
3Represent hydrogen, C independently of each other
1-C
6Alkyl or C
4-C
30Alkyl carboxyl or represent the following formula group
In the formula
R
1Definition as mentioned above,
M represents 0 or 1,
N represents 1 or 2,
R
5And R
6Represent hydrogen or C independently
1-C
20Alkyl, wherein alkyl can be replaced by halogen;
R
11Represent hydrogen or two-(C independently
1-C
4) alkylamino;
Wherein, with respect to the weight of polycarbonate, the content of described sulfur-bearing organic acid acetic is in the 100ppm.
2. composition as claimed in claim 1 is characterized in that, the organic acid acetic of sulfur-bearing is selected from following compound:
R wherein
1, R
2, R
3, m and n definition and claim 1 in identical.
3. composition as claimed in claim 1 or 2 is characterized in that R
2And R
3Represent hydrogen or C independently of each other
1-C
6Alkyl,
M represents 0;
N represents 1 or 2,
R
5And R
6Represent hydrogen or C independently
1-C
4Alkyl,
R
11Represent hydrogen.
4. composition as claimed in claim 1 is characterized in that, the organic acid acetic of described sulfur-bearing is the compound with following formula structure:
5. composition as claimed in claim 1 is characterized in that, the organic acid acetic of described sulfur-bearing is at least a compound with following formula structure that is selected from:
6. composition as claimed in claim 1 is characterized in that, with respect to the weight of polycarbonate, the content of the organic acid acetic of described sulfur-bearing is in the 50ppm.
7. composition as claimed in claim 1 is characterized in that, described composition also contains at least a degraded product of the organic acid acetic of described sulfur-bearing.
8. moulded parts or extruded product, it contains the described composition of claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE200410030664 DE102004030664A1 (en) | 2004-06-24 | 2004-06-24 | Composition, useful to prepare e.g. molded parts (optical components, foils, photometric applications, safety disks, electrical junction boxes or lamp covers), comprises a polycarbonate and an ester of organic sulfur containing acids |
| DE102004030664.8 | 2004-06-24 | ||
| DE102004057349.2 | 2004-11-27 | ||
| DE200410057349 DE102004057349A1 (en) | 2004-11-27 | 2004-11-27 | Composition, useful to prepare e.g. molded parts (optical components, foils, photometric applications, safety disks, electrical junction boxes or lamp covers), comprises a polycarbonate and an ester of organic sulfur containing acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1712450A CN1712450A (en) | 2005-12-28 |
| CN1712450B true CN1712450B (en) | 2010-05-26 |
Family
ID=35501815
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510082375 Expired - Fee Related CN1712450B (en) | 2004-06-24 | 2005-06-24 | Thermally stable polycarbonate compositions |
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|---|---|
| CN (1) | CN1712450B (en) |
| DE (1) | DE102004030664A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007059299A1 (en) | 2007-05-16 | 2008-11-20 | Entex Rust & Mitschke Gmbh | Device for processing products to be degassed |
| KR20150076650A (en) * | 2013-12-27 | 2015-07-07 | 제일모직주식회사 | Polycarbonate resin composition having improved appearance and flowability |
| KR20200090805A (en) * | 2017-12-19 | 2020-07-29 | 코베스트로 도이칠란트 아게 | Thermoplastic composition with excellent stability |
| CN114085368B (en) * | 2021-12-01 | 2023-08-11 | 万华化学集团股份有限公司 | Polycarbonate and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5668202A (en) * | 1993-08-26 | 1997-09-16 | Teijin Limited | Process for production of stabilized polycarbonate |
| EP0520805B1 (en) * | 1991-06-28 | 1999-09-01 | Ge Plastics Japan Limited | Polycarbonate production method |
| EP0753540B1 (en) * | 1995-07-12 | 2003-06-11 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition |
-
2004
- 2004-06-24 DE DE200410030664 patent/DE102004030664A1/en not_active Withdrawn
-
2005
- 2005-06-24 CN CN 200510082375 patent/CN1712450B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0520805B1 (en) * | 1991-06-28 | 1999-09-01 | Ge Plastics Japan Limited | Polycarbonate production method |
| US5668202A (en) * | 1993-08-26 | 1997-09-16 | Teijin Limited | Process for production of stabilized polycarbonate |
| EP0753540B1 (en) * | 1995-07-12 | 2003-06-11 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition |
Non-Patent Citations (1)
| Title |
|---|
| JP平8-311324A 1996.11.26 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102004030664A1 (en) | 2006-01-12 |
| CN1712450A (en) | 2005-12-28 |
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