CN105873981A

CN105873981A - Method of adding a catalyst in a melt polymerization process and the polycarbonate polymerized therefrom

Info

Publication number: CN105873981A
Application number: CN201480059545.8A
Authority: CN
Inventors: 伊格纳西奥·维克·费尔南德斯; 乔治·A·加西亚·阿古多; 阿龙·戴维·博尔亚尔斯基
Original assignee: Individual
Current assignee: Individual
Priority date: 2013-10-28
Filing date: 2014-10-28
Publication date: 2016-08-17
Also published as: WO2015063686A3; WO2015063686A2; EP3063203A2; KR20160079772A

Abstract

In an embodiment, a process of preparing a reduced activity first catalyst comprises preparing an aqueous solution I comprising a first catalyst I; preparing an aqueous solution I comprising a first catalyst II; combining the solution I and the solution II to form a solution III comprising the reduced activity first catalyst. In another embodiment, a process of preparing a polycarbonate comprises polymerizing reactants in the presence of a catalyst comprising one or both of the reduced activity first catalyst and a second catalyst, wherein the second catalyst is one or both of a high temperature second catalyst or a second catalyst with a reduced metal content.

Description

The method adding catalyst in melt polymerization process and the poly-carbon being polymerized by it Acid esters

Technical field

The application relates to melt polymerization and Merlon prepared therefrom.

Background technology

Dihydroxy compounds that melt polycarbonate method is based in melt stage and carbonate source Successive reaction.This reaction can occur in a series of reactor, wherein, catalyst, temperature, The common effect of vacuum and stirring makes monomer reaction and removes byproduct of reaction with transfer reaction balance And make polymer chain grow.Common in melt polymerization the Merlon of preparation be by with carbon The reaction of acid diphenyl (DPC) and derived from those of bisphenol-A (BPA).This reaction is permissible By tetramethyl ammonium hydroxide (TMAOH) (its can add before being introduced to the first polymerized unit to Monomer mixture) and NaOH (NaOH) (its can add to the first reactor or first reaction After the upstream of device and monomer blender) catalysis.In addition to main polymerisation, having one is The side reaction of row, it is reset (commonly referred to Fries rearrangement by the chain causing branched polymer backbone (Fries rearrangement)) composition.Especially, find in bisphenol-A melt polycarbonate Fries species are structure A, B and C esters type.

A. linear fries (straight chain fries, Linear Fries):

B. side chain fries:

C. acid fries

Fries reaction is to be caused by the common effect of base catalyst, temperature and the time of staying, its The Merlon making melted preparation is the most branched compared with interfacial polycarbonate, because their system Standby temperature is relatively low.

Owing to the highly-branched level (side chain level, branching level) in resin is to Merlon Engineering properties (such as, impact strength) can have negative effect, and due in Fries rearrangement Chromogen (color solid, color body) can be related at some intermediate species formed during process Formation, need the polycondensation catalyst with more preferable selectivity (less fries promotion).

Summary of the invention

There is disclosed herein ester exchange catalyst, melt polycarbonate and the method for preparation.

In embodiments, preparation is dropped the method for SA first catalyst and is included, preparation comprises the The aqueous solution I of one catalyst I；Preparation comprises the aqueous solution of the first catalyst II, and (aqueous solution contains The aqueous solution, aqueous solution) I；And combine (combination, combining) solution I and solution II comprises the solution III dropping SA first catalyst with formation.

In another embodiment, preparation is dropped the method for SA first catalyst and is included, preparation bag Aqueous solution I containing NaOH；Preparation comprises KH₂PO₄Aqueous solution II；And binding soln I and molten It is SA containing KNaHPO that liquid II comprises fall with formation₄The solution III of the first catalyst, wherein, The mol ratio of Na Yu K is 0.5 to 2.

In embodiments, melt polymerization dihydroxy chemical combination during melt polymerization process is included in polymerized unit Thing and carbonate products are to form Merlon, wherein, melt polymerization and include according to aforementioned right Solution III and the second catalyst according to any one of requirement add to melt polymerization process, wherein, Merlon has the branching level less than or equal to 900ppm.

In another embodiment, melt poly-in the presence of melt polymerization process is included in carbon monoxide-olefin polymeric Conjunction dihydroxy compounds and carbonate products are to form Merlon, wherein, and carbon monoxide-olefin polymeric bag Containing the second catalyst, it comprises TPPA, TPPP or containing one or both combination aforesaid, its In, Merlon has the branching level less than or equal to 900ppm.

In yet, at carbon monoxide-olefin polymeric during melt polymerization process is included in polymerized unit In the presence of melt polymerization dihydroxy compounds and carbonate products to form the Merlon of polymerization, its In, carbon monoxide-olefin polymeric comprises the second catalyst, and wherein, the second catalyst comprises metallic compound, Wherein, this metal comprises at least one in sodium, potassium and caesium, wherein, if this compound comprises sulphur Acid sodium, the amount of sodium is 0 to 1690ppm；If this compound comprises cesium sulfate, the amount of caesium is 0 To 275ppm；If this compound comprises NaOH, the amount of sodium is 0 to 35ppm；If should Compound comprises potassium hydroxide, and the amount of potassium is 0 to 50ppm；If this compound comprises cesium hydroxide, The amount of caesium is 0 to 140ppm；It is based on the weight of the second catalyst, wherein, the poly-carbonic acid of polymerization Ester has the branching level less than or equal to 900ppm.

Above and other feature is illustrated by detailed description below.

Detailed description of the invention

Melt polycarbonate polymerization can be by the first and second catalyst, such as NaOH and TMAOH Combination is catalyzed respectively.In addition to main polymerisation, there is a series of side reaction, the most not In this reset, it is made up of the chain rearrangement product causing branched polymer backbone.It has been found that By using the combination of the first and second different catalyst, branching level can be based on Merlon Gross weight less than or equal to 5000 parts by weight every million (ppm), particularly less than 2000 Ppm, more specifically less than or equal to 900ppm, more specifically less than or equal to 750ppm, more Especially less than or equal to 410ppm, specifically less than or equal to 300ppm.Especially, They find when the first catalyst comprises and by NaOH, KOH, Cs₂CO₃Or combinations thereof institute group The first catalyst become is compared, and has the activity and relatively low selective the of reduction to Fries rearrangement One catalyst, such as KNaHPO₄Time, then can reduce branched.

The activity reduced as used in this article refers to the fact, i.e. at identical reaction condition, And the sodium in the first catalyst being made up of NaOH with by KNaHPO₄First catalyst of composition In the molar equivalent of sodium identical in the case of, KNaHPO₄Catalyst, with NaOH catalyst phase Ratio will have the activity of reduction in melt polymerization.The branched of reduction is so as used in this article The fact, the most such as by KNaHPO₄The SA catalyst of fall as defined above of composition, with The first catalyst being made up of NaOH is compared and will be caused the branched Merlon with reduction.

Generally, SA first catalyst of this fall is not used in the melt polymerization of Merlon, because SA first catalyst of fall is used to mean in some stages (particularly at the second reactor In), the amount of (unreacted) monomer free in reactive material is compared with during the pure NaOH of use High.The monomer concentration increased, together with high temperature (be greater than or equal to 50 DEG C) with low pressure is (such as Cause under vacuo) monomer increased by tower top (overhead) system loss, cause reactant The notable change of mol ratio, and therefore can have the end-blocking to product (end cap, end cap) ratio The impact of rate, causes inconsistent product.

About the second catalyst, generally TMAOH is used as second in the melt polymerization of Merlon Ester exchange catalyst.It should be noted that as used in this article first and second are not offered as melted poly- Addition sequence in conjunction, but for distinguishing two kinds of catalyst.Second catalyst of this TMAOH is Thermal sensitivity, and due at elevated temperatures, especially in the temperature more than or equal to 175 DEG C Lower fast degradation, the most only some times in the first polymerized unit are active.In order to reduce By the loss of monomer of overhead system, applicant have further found that, when dropping SA first catalysis When agent is used in combination with high temperature the second catalyst and non-temperature sensitive the second catalyst TMAOH, this catalysis Agent will improve the extent of reaction of polymerisation starting stage, with the final extent of reaction increasing monomer.As " high temperature the second catalyst " used herein refers to the degraded having degradation temperature more than TMAOH Second catalyst of temperature.Have been found that and use the second catalyst of being only made up of TMAOH Melt polymerization is compared, under identical reaction conditions, and the height in melt polymerization (temperature is gradually increased) Temperature the second catalyst is active under the longer time.Such as, compare under identical reaction condition The second catalyst being made up of TMAOH, high temperature the second catalyst is at a temperature of 150 to 260 DEG C With more than or equal under the pressure of 100mbara, the melt polymerization of Merlon keeps activity Time increases.High temperature the second catalyst can comprise tetraphenylphosphoniacetate acetate (TPPA), phenol tetraphenyl (tetraphenylphosphonium phenolate) (TPPP) or comprise one or both combination aforementioned.

Also find, may reside in the second catalyst and (such as, comprise in TPPA and TPPP Kind or high temperature second catalyst of two kinds) in the existence of alkali metal salt can increase in Merlon Branching level.Have been found that and depend on metal species (M) (i.e. sodium, potassium and caesium) and they phases The gegenion (counter ion, counter ion) (i.e. chlorine, bromine and sulfuric acid) closed, alkali metal salt chemical combination Thing can have different amounts of impact to Fries reaction.Hence, it can be determined that the class of metallic compound Type, and then can adjust the amount of the metal of existence.Be there is the alkali metal reducing concentration by use First catalyst of salt compound and the second catalyst, the branched of Merlon can be based on poly-carbonic acid The gross weight of ester less than or equal to 900ppm, especially less than or equal to 750ppm, particularly Ground is less than or equal to 410ppm, specifically less than or equal to 300ppm.

Such as, the second catalyst can comprise one or more of the following: based on the second catalyst Gross weight, a) less than or equal to the sodium of 2000ppm, especially less than or equal to 1,675ppm Sodium, the sodium of especially less than or equal to 500ppm, more specifically less than or equal to 100ppm Sodium, the specifically sodium less than or equal to 30ppm；B) caesium less than or equal to 500ppm, The especially less than or equal to caesium of 300ppm, the caesium of more specifically less than or equal to 135ppm；With And c) less than or equal to the potassium of 100ppm, the potassium of especially less than or equal to 45ppm.

Such as, the second catalyst can comprise alkali metal compound, if wherein this compound comprises sulphur Acid sodium, gross weight based on the second catalyst, the amount of sodium can be less than or equal to 1,690ppm, Especially less than or equal to 1,670ppm；If this compound comprises cesium sulfate, based on the second catalysis The gross weight of agent, the amount of caesium can be less than or equal to 275ppm, and especially less than or equal to 252 ppm；If this compound comprises NaOH, gross weight based on the second catalyst, the amount of sodium can To be less than or equal to 35ppm, especially less than or equal to 29ppm；If this compound comprises Potassium hydroxide, gross weight based on the second catalyst, the amount of potassium can be less than or equal to 50ppm, Especially less than or equal to 43ppm, if this compound comprises cesium hydroxide, based on the second catalyst Gross weight, the amount of caesium can be less than or equal to 140ppm, especially less than or equal to 132 ppm；Or comprise one or more combination aforesaid.

Such as, the second catalyst can comprise alkali metal compound, and wherein, the amount of sodium may be greater than Or equal to 1ppm, or more than or equal to 30ppm, or more than or equal to 100ppm；The amount of caesium can To be greater than or equal to 10ppm, or more than or equal to 30ppm, or more than or equal to 50ppm； The amount of potassium may be greater than 0ppm, or more than or equal to 10ppm；Or comprise aforesaid one or many The combination planted, wherein, the amount of metal weight based on the second catalyst.

" Merlon " means the carbonic ester with the repetitive structure of formula (1) as used in this article The polymer of unit

Wherein, R¹At least the 60% of group sum is aliphatic, alicyclic ring containing aryl moieties and its surplus Race or aromatic series.Each R¹Can be C_6-30Aromatic group, i.e. contains at least one aromatic series portion Point.R¹Can be derived from formula HO-R^1-The aromatic dihydroxy compound of OH, especially formula (2):

HO–A¹–Y¹–A²–OH(2)

Wherein, A¹And A²It is individually monocyclic divalent aromatic group and Y¹It is by A¹With A²The list separated Key or there is the bridged group of one or more atom.One atom can be by A¹With A²Separate.Special Not, each R¹Can be derived from the bis-phenol of formula (3)

Wherein, R^aAnd R^bIt is halogen, C independently of one another_1-12Alkoxyl or C_1-12Alkyl；And p and q It is the integer of 0 to 4 independently of one another.Should be appreciated that when p or q is less than 4, each carbon of ring Valence mumber filled by hydrogen.Same in formula (3), X^aIt is to connect two hydroxyl substituted aromatic series bases The bridged group of group, wherein, bridged group and each C₆The hydroxyl substituent of arylene group is each other It is arranged in C with o-, m-or p-(particularly to)₆In arylene group.Bridged group X^aCan be Singly-bound ,-O-,-S-,-S (O)-,-S (O)₂-,-C (O)-or C_1-18Organic group.C_1-18Organic bridging Group can be ring-type or acyclic, aromatic series or non-aromatic, and can additionally comprise such as halogen The hetero atom of element, oxygen, nitrogen, sulphur, silicon or phosphorus.C can be arranged_1-18Organic group is so that being connected to Its C₆Arylene group is each attached to C_1-18The common alkylidene carbon of organic bridging group or not Same carbon.Each p and q can be 1, and R^aAnd R^bC can be individually_1-3Alkyl group, Methyl especially, is arranged in the meta of the oh group of each arylene group.

X^aCan be substituted or unsubstituted formula-C (R^c)(R^d)-C_3-18Ring alkylidene radical, C_1-25Alkylidene Base, wherein, R^cAnd R^dIt is hydrogen, C independently of one another_1-12Alkyl, C_1-12Cycloalkyl, C_7-12Aralkyl Base, C_1-12Miscellaneous alkyl or ring C_7-12Heteroarylalkyl, or formula-C (=R^e)-group, wherein, R^eIt is two Valency C_1-12Hydrocarbyl group.Such group includes methylene, cyclohexyl methene base, ethidine (ethylidene), new pentylidene base (neopentylidene) and isopropylidene (isopropylidene), And 2-[2.2.1]-dicyclo pitches base (bicycloheptylidene), cyclohexylidene base heptan (cyclohexylidene), cyclopentylidene base (cyclopentylidene), cyclododecane fork base And adamantylidene base (adamantylidene) (cyclododecylidene).

X^aCan be C_1-18Alkylidene, C_3-18Cycloalkylidene, the C condensed_6-18Cycloalkylidene or formula -B¹-G-B²-group, wherein, B¹And B²It is same or different C_1-6Alkylidene and G are C_3-12Ring alkylidene radical (cycloalkylidene) or C_6-16Arlydene.Such as, X^aCan be formula (4) Substituted C_3-18Ring alkylidene radical

Wherein, R^r、R^p、R^qAnd R^tIt is hydrogen, halogen, oxygen or C independently of one another_1-12Hydrocarbyl group；Q Be the oxygen of Direct Bonding, carbon or divalence, sulphur or-N (Z)-, wherein, Z be hydrogen, halogen, hydroxyl, C_1-12Alkyl, C_1-12Alkoxyl or C_1-12Acyl group；R is 0 to 2, and t is 1 or 2, and q is 0 or 1, And k is 0 to 3, condition is R^r、R^p、R^qAnd R^tAt least two connects together the alicyclic ring being to condense Race, aromatic series or heteroaromatic rings.Should be appreciated that when condensed ring is aromatic series, shown in formula (4) Ring there is in the case of this ring is to condense unsaturated carbon-bond with carbon.When k is 1 and i is 0, The ring as shown in formula (4) contains 4 carbon atoms；When k is 2, as shown in formula (4) Ring contain 5 carbon atoms；And when k is 3, this ring contains 6 carbon atoms.Two adjacent Group (such as, R^qAnd R^tConnect together) fragrance group group, and R can be formed^qAnd R^t Connect together and can form aromatic group and R^rAnd R^pConnect together and can form the second aromatic series base Group.Work as R^qAnd R^tConnect together formation aromatic group time, R^pCan be double bond oxygen atom, i.e. ketone.

Bis-phenol, wherein, X^aIt is the ring alkylidene radical of formula (4), may be used for preparation containing formula (1a) The Merlon of phthalimidine carbonic ester (phthalimidine carbonate) unit

Wherein, R^a、R^b, p and q such as formula (3), R³It is C independently of one another_1-6Alkyl, j is 0 to 4, And R⁴It is hydrogen, C_1-6Alkyl, or substituted or unsubstituted phenyl, such as, by up to 5 Individual C_1-6The substituted phenyl of alkyl.Such as, phthalimidine carbonate unit is formula (1b)

Wherein, R⁵It is hydrogen, alternatively by up to 5 C_1-6Alkyl, or C_1-4The substituted phenyl of alkyl.? In formula (1b), R⁵Can be hydrogen, methyl or phenyl, particularly phenyl.Carbonate unit (1b), (wherein, R⁵It is phenyl) can phthalimidine be (also derived from 2-phenyl-3,3'-double (4-hydroxy phenyl) It is referred to as 3, double (4-the hydroxy phenyl)-2-phenyl 1-isoindolinone of 3-, or N-phenyl phenolphthalein bis-phenol (“PPPBP”))。

Other bisphenol carbonate repetitive such is the isatin carbonic acid of formula (1c) and (1d) Ester units

Wherein R^aAnd R^bIt is C independently of one another_1-12Alkyl, p and q is 0 to 4 independently of one another, and RⁱIt is C_1-12Alkyl, alternatively by 1 to 5 C_1-10The substituted phenyl of alkyl, or alternatively by 1 To 5 C_1-10The substituted benzyl of alkyl.R^aAnd R^bCan be individually methyl, p and q can be respective It is 0 or 1 independently, and RⁱIt is C_1-4Alkyl or phenyl.

Derived from bis-phenol (3) (wherein, X^aIt is substituted or unsubstituted C_3-18Ring alkylidene radical (4)) Other examples of bisphenol carbonate unit include that the alkyl of cyclohexylidene base bridge joint of formula (1e) replaces double Phenol

Wherein, R^aAnd R^bIt is C independently of one another_1-12Alkyl, R^gIt is C_1-12Alkyl, p and q is each independent Ground is 0 to 4, and t is 0 to 10.Each R^aAnd R^bIn at least one can be arranged in ring Pitch the meta of base bridged group.R^aAnd R^bCan be C independently of one another_1-4Alkyl, R^gIt is C_1-4 Alkyl, p and q is individually 0 or 1, and t is 0 to 5.R^a、R^bAnd R^gFirst can be individually Base, p and q can be individually 0 or 1, and t can be 0 or 3, particularly 0.

Derived from bis-phenol (3) (wherein, X^aIt is substituted or non-substituted C_3-18Ring alkylidene) Other examples of bisphenol carbonate unit include adamantyl units and the fluorenes of formula (1g) of formula (1f) Base unit

Wherein, R^aAnd R^bIt is C independently of one another_1-12Alkyl, and p and q be 1 to 4 independently of one another. Each R^aAnd R^bIn at least one can be arranged in the meta of ring alkylidene radical bridged group.R^aAnd R^b Can be C independently of one another_1-3Alkyl, and p and q can be individually 0 or 1；Especially, R^a、 R^bCan be individually methyl, p and q is individually 0 or 1, and when p and q is 1, methyl can To be arranged in the meta of ring alkylidene radical bridge joint group.Carbonic ester containing unit (1a) to (1g) is used In preparation, there is higher glass transition temperature (Tg) and the Merlon of higher heat distortion temperature.

Formula HO-R¹Other useful dihydroxy compounds of-OH include the aromatic series dihydroxy of formula (6) Based compound

Wherein, R^hIt is halogen atom, C independently of one another_1-10Hydrocarbyl group such as C_1-10Alkyl, halogen substiuted C_1-10Alkyl, C_6-10Aryl or the C of halogen substiuted_6-10Aryl, and n is 0 to 4.Halogen leads to It it is often bromine.

Some illustrative examples of specific dihydroxy compounds include following: 4,4' dihydroxy diphenyl, 1,6-dihydroxy naphthlene, 2,6-dihydroxy naphthlene, double (4-hydroxy phenyl) methane, double (4-hydroxy phenyl) diphenyl Double (4-hydroxy phenyl) ethane of methane, double (4-hydroxy phenyl)-1-naphthyl methane, 1,2-, double (the 4-hydroxyl of 1,1- Base phenyl)-1-diphenylphosphino ethane, 2-(4-hydroxy phenyl)-2-(3-hydroxy phenyl) propane, double (4-hydroxy phenyls) Double (4-hydroxyl-3-bromophenyl) propane of phenylmethane, 2,2-, 1,1-double (hydroxy phenyl) pentamethylene, 1,1- Double (4-hydroxy phenyl) isobutene of bis(4-hydroxyphenyl)cyclohexane, 1,1-, double (4-hydroxy phenyl) ring of 1,1- Double (4-hydroxy phenyl) adamantane of double (4-the hydroxy phenyl)-2-butylene of dodecane, trans-2,3-, 2,2-, α, α '- Double (4-hydroxy phenyl) toluene, double (4-hydroxy phenyl) acetonitrile, 2,2-(3-ethyl-4-hydroxy phenyl) propane, Double (the 3-of 2,2-(3-n-pro-pyl-4-hydroxy phenyl) propane, 2,2-(3-isopropyl-4-hydroxy phenyl) propane, 2,2- Sec-butyl-4-hydroxy phenyl) propane, double (3-tert-butyl-hydroxy phenyl) propane of 2,2-, double (the 3-ring of 2,2- Hexyl-4-hydroxy phenyl) propane, double (3-pi-allyl-4-hydroxy phenyl) propane of 2,2-, double (the 3-methoxy of 2,2- Base-4-hydroxy phenyl) propane, double (4-hydroxy phenyl) HFC-236fa of 2,2-, double (the 4-hydroxyl of the chloro-2,2-of 1,1-bis- Phenyl) ethene, double (4-hydroxy phenyl) ethene of the bromo-2,2-of 1,1-bis-, the double (5-phenoxy group-4-of the chloro-2,2-of 1,1-bis- Hydroxy phenyl) ethene, 4,4'-dihydroxy benaophenonel, double (4-the hydroxy phenyl)-2-butanone of 3,3-, 1,6-be double (4-hydroxy phenyl)-1,6-acetyl butyryl, ethylene glycol bis (4-hydroxy phenyl) ether, double (4-hydroxy phenyl) ether, Double (the 4-of double (4-hydroxy phenyl) thioether, double (4-hydroxy phenyl) sulfoxide, double (4-hydroxy phenyl) sulfone, 9,9- Hydroxy phenyl) fluorenes, 2,7-dihydroxy pyrene, 6,6'-dihydroxy-3,3,3'3'-tetramethyl spiral shell (double) indane (" spiral shell Two indane bis-phenols "), double (4-hydroxy phenyl) phthalimide of 3,3-, 2,6-dihydroxy dibenzo- P-dioxin, 2,6-dihydroxy thianthrene, 2,7-dihydric phenol flavine, 2,7-dihydroxy-9,10-dimethyl Azophenlyene, 3,6-dihydroxy dibenzofurans, 3,6-dihydroxy dibenzothiophenes and 2,7-dihydroxy carbazole, Resorcinol, substituted resorcinol compound, as oreinol diphenol, 5-ethyl resorcinol, 5-propyl diphenol, 5-butyl resorcinol, 5-tert-butyl resorcin, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5,6-tetrabromo resorcinol etc.；Adjacent benzene two Phenol；Quinhydrones；Substituted quinhydrones, such as 2-methylnaphthohydroquinone, 2-ethyl hydroquinone, 2-propyl group quinhydrones, 2-fourth Base quinhydrones, TBHQ, 2-pheny lhydro quinone, 2-cumyl quinhydrones, 2,3,5,6-duroquinol, 2,3,5,6-tetra-tert quinhydrones, 2,3,5,6-tetrafluoro quinhydrones, 2,3,5,6-tetra-bromohydroquinone etc..Or comprise aforementioned The combination of at least one in dihydroxy compounds.

The specific example of the bisphenol compound of formula (3) includes 1,1-double (4-hydroxy phenyl) methane, 1,1- Double (4-hydroxy phenyl) propane of double (4-hydroxy phenyl) ethane, 2,2-(hereinafter " bisphenol-A " or " BPA "), double (4-hydroxy phenyl) butane of 2,2-, double (4-hydroxy phenyl) octane of 2,2-, double (the 4-hydroxyl of 1,1- Base phenyl) propane, double (4-hydroxy phenyl) normal butane of 1,1-, double (the 4-hydroxy-2-methyl phenyl) propane of 2,2-, Double (the 4-hydroxy-tert-butyl phenyl) propane of 1,1-, 3,3-double (4-hydroxy phenyl) phthalimidine, 2-phenyl Double (4-hydroxy phenyl) phthalimidine (PPPBP) of-3,3-and double (the 4-hydroxy-3-methyl phenyl) ring of 1,1- Hexane (DMBPC).The combination of at least one comprised in aforementioned dihydroxy compounds can also be used. Merlon can be derived from the straight chain homopolymer of bisphenol-A, wherein, A¹And A²It is individually Asia Phenyl and Y¹It it is the isopropylidene in formula (3).

Merlon herein is by bis-phenol and carbonate precursor (also referred to as carbonate products) Melt polymerization prepare.Exemplary carbonate precursor includes carbonyl halide, such as carbonyl bromide or phosgene (phosgene), double haloformate of dihydroxy compounds (such as bisphenol-A, hydroquinones ethylene glycol, The bischloroformates of neopentyl glycol etc.) and diaryl carbonate.Can also use and comprise aforementioned type The combination of at least one in carbonate precursor.Diaryl carbonate can be dipheryl carbonate base ester or often There is the dipheryl carbonate base ester of the activation of electron-withdrawing substituent, such as double (4-nitrobenzophenone) carbon on individual aryl Acid esters, double (2-chlorphenyl) carbonic ester, double (4-chlorphenyl) carbonic ester, double (methyl salicyl) carbonic ester, Double (4-methyl carboxyl phenyl) carbonic ester, double (2-acetylphenyl) carboxylate, double (4-acetylphenyls) Carboxylate or comprise at least one combination aforementioned.

In melt polymerization process, Merlon can make to melt by the presence of ester exchange catalyst The dihydroxy reactants melting state is prepared with carbonate precursor coreaction.This reaction can be typically Polymerization unit, as continuous-stirring reactor (CSTR), plug flow reactor (plug flow reactor), Line wet fall type polymerizer (wire wetting fall polymerizer), free-falling polymerizer, horizontal poly- Clutch (horizontal focusing clutch, horizontal polymerizer), scraped film type polymerizer, Banbury banburying Machine (BANBURY mixer), single screw rod or double screw extruder, or include aforesaid one or many The combination planted is carried out.By distillation, from frit reaction thing, remove Volatile monohydric phenol, and will be poly- Compound separates as molten residue.Melt polymerization can be carried out with discontinuous method or continuation method.? Under either case, the melt polymerization conditions of use can include that two or more are different (independent, Distinct) stage of reaction.Such as, polymerization can include oligomerization stage, wherein, by initial two Hydroxy aromatic compound and diaryl carbonate are converted into oligo-ester carbonate, and second stage of reaction, Also referred to as polymerization stage, wherein, is converted into height by the oligo-ester carbonate formed in oligomerization stage Molecular weight polycarbonate.Oligomerization stage can include 1 or multiple, especially 2 or more, More particularly 2 to 4 oligomerization unit (such as, 2 to 4 continuously stir groove).When 2 or In the presence of more oligomerization unit series winding, can occur that temperature increases from a unit to the next one Or pressure reduce in one or both.Polymerization stage can include 1 or multiple, especially 2 or More, more particularly 2 polymerized units (such as, 2 horizontal or line wet fall type polymerizer).Poly- The conjunction stage can include one or more polymerized unit, and it can by polycarbonate polymerization extremely, such as 20,000 to 50,000 daltonian molecular weight.After forming Merlon, then can be by poly-carbonic acid The quencher alternatively of ester composition devolatilization in devolatilization (devolatilization, devolatization) unit Sending out (removing volatile ingredient, devolatilize), wherein, the molecular weight of Merlon does not dramatically increase (such as, molecular weight does not increase more than 10 percetages by weight (wt%)), and use temperature, pressure Power and the time of staying are to reduce lower-molecular-weight component (as having less than 1,000 daltonian molecular weight Those) concentration.To be defined to cause polycarbonate oligomer to have little for oligomerization unit in this article In or equal to 12,000 dalton or 8, the oligomerization unit of 000 daltonian number-average molecular weight, and And polymerized unit is defined to generation and has daltonian more than 12,000 dalton or 8,000 in this article The polymerized unit of the Merlon of number-average molecular weight.Although it should be noted that to use at this and being less than or equal to 12000 dalton or 8000 dalton are to limit the molecular weight obtained in oligomerization stage, this area Skill will readily appreciate that, described molecular weight is used for limiting oligomerization stage, wherein, and oligomer Molecular weight can be more than 12000 dalton or 8000 dalton." segmentation " polymeric reaction condition can For continuous polymerization system, wherein, initial monomer is oligomeric in the first reaction vessel, and, The oligo-ester carbonate wherein formed is continuously delivered to one or more downstream reactor, wherein, oligomeric Merlon is converted into high-molecular-weight polycarbonate.Generally, in the oligomeric stage, generation oligomeric Merlon has 1,000 to 7,500 daltonian number-average molecular weights.One or more subsequently In polymerization stage, the number-average molecular weight (Mn) of Merlon can increase to, such as 8,000 to 25,000 dalton (use polycarbonate standards), 13,000 to 18,000 dalton especially.

Generally, the most do not use solvent, and reactant dihydroxy compounds and carbonation Compound is in molten condition.Reaction temperature can be 100 to 350 degrees Celsius (DEG C), especially 180 To 310 DEG C.Pressure in the reaction starting stage may be at atmospheric pressure, super-atmospheric pressure or from air Being depressed into the pressure of 150 torr scopes, especially, atmospheric pressure is to 15 torr, and the stage later, It is in the pressure of decline, such as 0.2-15 torr or 2 to 150 torr.Similarly, polymerization can occur In a series of aggregation container, it can the most individually have temperature and/or the vacuum of increase.Such as, Oligomerization stage can occur at 100 to 280 DEG C, especially at a temperature of 140 to 240 DEG C, And polymerization stage can occur at 240 to 350 DEG C, especially 280 to 300 DEG C or 240 to At a temperature of 270 DEG C or 250 to 310 DEG C, wherein, the temperature in polymerization stage is more than oligomerization Temperature in stage.From the reaction time of initial oligomerization unit to final polymerized unit can be 0.1 to 15 hour.The most final polymerized unit refers to wherein last dividing Final polymerized unit in the melt polymerization that son amount increases.For example, it is possible to by quencher (quenchant, Quencher) after final polymerization, (such as, the Mw increase at Merlon is less than or equal to After the point of 10%), and alternatively, added to polycarbonate resin before any melt filtration.

Similarly, oligomeric can occur more than or equal to 100 millibars of absolute pressures (mbara) Under pressure, or the oligomeric at least two oligomerization unit that can include, wherein, the first oligomeric unit can Oligomeric can have 15 to 90mbara having the pressure more than or equal to 100mbara and second Pressure, wherein, the first oligomeric unit is in the second oligomeric unit upstream, and wherein one or more are oligomeric Before unit may be located at described polymerized unit, middle or afterwards.

Polymerization stage subsequently of oligomeric stage can be included in one or two polymerized unit polymerization.The One polymerized unit may be at 240 to 350 DEG C, especially at a temperature of 260 to 310 DEG C and 1 to Under the pressure of 10 millibars.Second polymerized unit may be at 240 to 350 DEG C, especially 260 to At a temperature of 300 DEG C and less than or equal under the pressure of 5 millibars.Merlon can gather at final Devolatilization after conjunction.

After final aggregation container (the most final polymerized unit), polymer can introduce To reactor, extrusion, stand to filter in fondant filter, or include one or more group aforementioned Close.Before or after it should be noted that fondant filter may be located at extruder.Such as, it is used for preparing poly- The melt polymerization process of carbonate composition may include that melt polymerization dihydroxy reactants and carbonic ester Compound is to produce molten reaction products；Quencher molten reaction products；Melting in any extruder upstream Body filter filters molten reaction products；Introduce additive alternatively to form mixture；And squeeze Go out this mixture to form polycarbonate compositions.Similarly, for preparing polycarbonate compositions Melt polymerization process may include that melt polymerization dihydroxy reactants and carbonate products are molten to produce Melt product；Introduce quencher compositions and optional additive is used for forming mixture；And This mixture is extruded to form polycarbonate compositions after filtration.

Polymerization process can include parallel polymerization (being polymerized parallel, parallel polymerization) Partly (section, section), wherein, parallel polymerization refers to be divided into polycarbonate flow 2 or more Multiple streams, hereafter it may or may not stand identical polymerizing condition, and (i.e. they can reach different Molecular weight, there is the different additive etc. being added thereto).For example, it is possible in polymerization process Part I is prepared Merlon；Can by the flow point comprising Merlon be two or more stream also Guide to 2 or more parallel operation line.Such as, method can be included in a series of oligomeric Polymerized unit is polymerized Merlon；Can be two kinds of stream: A and B by the flow point that the oligomeric stage discharges, Wherein, A stream is guided to polymerized unit A and B stream is guided to polymerized unit B.Similarly, Method can be included in a series of oligomeric unit polymerization Merlon, subsequently in a series of polymerization Unit is polymerized；The flow point that can be discharged by polymerization stage is two kinds of stream: A and B, is wherein flowed by A Guide to extruder A and B stream is guided to extruder B.Similarly, method can be included in one The oligomeric unit of series is polymerized Merlon, is polymerized in a series of two polymerized units subsequently； The flow point that can be discharged by the first polymerized unit is two kinds of stream: A and B, wherein, is guided extremely by A stream B stream is also guided to the second polymerized unit B by the second polymerized unit A.In any aforementioned circumstances, Can be by one or two in quencher compositions addition to stream A and B, wherein, quencher group Compound can be same or different.Those skilled in the art can easily be contemplated to other and include The embodiment of more than two concurrent flow, and the embodiment wherein separately flowed in different positions.

Catalyst can comprise the first catalyst, such as, drop SA first catalyst.Catalyst can To comprise the second catalyst, such as high temperature the second catalyst.Catalyst can comprise the gold with reduction Belong to the second catalyst of salinity, such as, there is high temperature second catalyst of the metal salt concentrations of reduction. Catalyst can be to comprise one or more combination aforesaid.

First catalyst comprises alkali metal or source of alkaline earth metal.Therefore the first catalyst be typically than The second more heat-staple ester exchange catalyst of catalyst, and therefore can be in whole ester exchange reaction In, during oligomerization, after oligomerization, such as in aggregation container, in the course of the polymerization process Use.It is found by the applicant that by using SA first catalyst of fall can reduce branched degree. Drop SA first catalyst and comprise the first catalyst I and the product of the second catalyst II.The One catalyst I comprises alkali metal or source of alkaline earth metal, wherein, is present in the first catalyst I Alkali metal ion and the total amount herein referred to as " the first element " of alkaline-earth metal ions, wherein, First element is the total amount that lithium, sodium, potassium, caesium, rubidium, magnesium, calcium and strontium are present in the first catalyst I. These ion guns include alkali metal hydroxide, such as lithium hydroxide, NaOH, barium hydroxide, hydrogen Strontium oxide strontia and potassium hydroxide, and alkaline earth metal hydroxide, such as magnesium hydroxide and calcium hydroxide.Its Alkali metal or source of alkaline earth metal that he is possible include that the corresponding salt of carboxylic acid is (such as sodium acetate, acetic acid Potassium, lithium acetate, calcium acetate, barium acetate, magnesium acetate and strontium acetate) and ethylenediamine tetra-acetic acid (EDTA) Derivative (such as EDTA tetrasodium salt and EDTA magnesium disodium salt).First catalyst I can comprise The alkali metal of carbonic acid or alkali salt, such as Cs₂CO₃, sodium acid carbonate (NaHCO₃), sodium carbonate (Na₂CO₃), saleratus, lithium bicarbonate, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, carbon Acid hydrogen strontium, potassium carbonate, lithium carbonate, calcium carbonate, brium carbonate, magnesium carbonate, strontium carbonate etc..First urges Agent I can comprise lithium stearate, odium stearate, strontium stearate, potassium stearate, hydroxyl boric acid (hydroxyborate) lithium, hydroxyl Boratex, phenoxy group Boratex, Sodium Benzoate, Potassium Benzoate, Lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphoric acid hydrogen two lithium, the disodium salt of bisphenol-A, double The di-potassium of phenol A and the dilithium salt of bisphenol-A, the sodium salt of phenol, the sylvite of phenol, the lithium of phenol Salt or comprise one or more combination aforementioned.First catalyst I can include comprising aforesaid one Or the combination of multiple first catalyst I.

First catalyst II comprises non-volatile inorganic acid, and wherein, term as used in this article is " non- Volatility " mean be there is no estimable steam under melt polymerization conditions by the catalyst of this acid preparation Pressure.The example of non-volatile acid compound includes phosphorous acid, phosphoric acid, sulfuric acid, metal " oxyacid ", Oxyacid such as germanium, antimony, niobium etc..The salt of non-volatile acid includes the alkali metal salt of phosphorous acid；Phosphorous The alkali salt of acid；The alkali metal salt of phosphoric acid；The alkali salt of phosphoric acid, the alkali metal salt of sulfuric acid, The alkali metal salt of the alkali salt of sulfuric acid, metal oxygen-containing acid and the alkali salt of metal oxygen-containing acid. The specific example of the salt of non-volatile acid includes NaH₂PO₃、NaH₂PO₄、Na₂HPO₄、 KH₂PO₄、CsH₂PO₄、Cs₂HPO₄、NaKHPO₄、NaCsHPO₄、KCsHPO₄、Na₂SO₄、 NaHSO₄、NaSbO₃、LiSbO₃、KSbO₃、Mg(SbO₃)₂、Na₂GeO₃、K₂GeO₃、Li₂GeO₃、 MgGeO₃、Mg₂GeO₄With the combination comprising one or more compounds aforesaid.First catalyst II comprises the second element, wherein, the second element equal to the alkali metal come from the first catalyst II from Son, alkaline-earth metal ions and the total amount of metal ion, such as sodium, potassium, caesium, lithium, antimony, magnesium and germanium.

Drop SA first catalyst can comprise be derived from NaOH the first catalyst I and KH₂PO₄The KNaHPO of the first catalyst II₄.Drop SA first catalyst can have 0.5 to 2, especially 0.7 to 1.5, especially 0.8 to 1.2 the first element and the second element (example As from NaOH Na with from KH₂PO₄K) mol ratio.

Two kinds of solution of the first catalyst I and the first catalyst II can be included respectively by preparation, molten Liquid I and solution II prepare SA first catalyst of fall.Solution I can be by being catalyzed first Agent I is dissolved in water preparation.Solution I can be more than 30 DEG C, specifically greater than or equal to 40 DEG C Rising at a temperature of prepare.After preparation solution I, solution I can be cooled to 20 to 30 DEG C, The temperature of 20 to 25 DEG C especially.Solution I can comprise the 0.1 to 60 of gross weight based on solution The first catalyst I of wt%, especially 1 to 50wt%, more particularly 1 to 40wt%.Such as, Solution I by combining the water of 1 liter and can comprise 50 to 3000 grams, 800 to 950 grams especially The solution of 40 to 60wt% of the first catalyst I prepare.

Solution II can be by being dissolved in water preparation by the first catalyst II.Solution II can comprise 0.1 to the 40wt% of gross weight based on solution II, 1 to 30wt% especially, more particularly 1 The first catalyst II to 20wt%.Solution II can comprise in 20 liters of water, and such as 100 to 4000 Gram, the first catalyst II of 1500 to 2000 grams especially.

Fall SA (decrement, reduced) can be comprised to be formed with binding soln I and solution II The solution III of the first catalyst.Can alternatively volumetric soiutions III with confirm this solution comprise 0 to 20,000,100 to 10, the first free catalyst II of 000ppm especially, such as free KH₂PO₄, wherein, the first free catalyst II refer to not with the first catalyst I complexing and Remain on the amount of the first catalyst II in solution.Solution III can be directly added to melt polymerization Or can dilute before interpolation.Solution III, the most after the dilution, can comprise based on solution III 0.1 to the 50wt% of gross weight, especially the fall of 0.5 to 30wt% SA (decrement, Reduced) the first catalyst.For example, it is possible to by 500 to 4,000kg, especially 1,000 to 1,500kg Water adding to adding solution III before polymerized unit.

Based on entering the 10 of polymerized unit, 000 to 20,000kg/h, especially 12,000 to 15,000 Total monomer charging (that is, reaction-ure feeding) of kg/h and 5,000 to 9, the 000 of entrance polymerized unit Total bisphenol-A feed rate of the dihydroxy monomers of kg/h, solution III enters the charging speed of polymerized unit Rate can be 0.1 to 10,1 to 5 kg/hr especially (kg/h).Such as, based on 14,200kg/h Total monomer charging (wherein the monomer feed of 7250kg/h is dihydroxy monomers), solution III enter The flow velocity of polymerized unit can be 0.1 to 10kg/h, especially 1 to 5kg/h, more particularly 2 to 3kg/h.Solution III can add monomer stream to form catalyst stream and this catalyst stream is added polymerization Unit.Likewise it is possible to solution III to be added any stage of polymerization, such as monomer mixed cell Upstream and/or be directly added into and/or afterwards；And/or the upstream of polymerized unit and/or be directly added into and/ Or afterwards (after such as, adding first stage oligomeric unit and/or final polymerized unit).

Second ester exchange catalyst (the also referred to as second catalyst) is generally degraded also at elevated temperatures Lose their activity.Therefore such as the second ester can be used in the oligomeric stage in the low temperature polymerization stage Exchange catalysts.Second catalyst include quaternary ammonium compound, quaternary compound or include aforesaid at least A kind of combination.

It has been found that high temperature the second catalyst, such as, comprise the one or two of TPPA and TPPP The second catalyst planted may be used for the melt polymerization of Merlon to improve the anti-of polymerization starting stage Answer degree, with the final loss of monomer reduced by overhead system (overhead system), such as Maybe (it is added without first when polymerization does not contains the first catalyst when using and dropping SA first catalyst Catalyst) time.High temperature the second catalyst can comprise tetraphenylphosphoniacetate acetate, phenol tetraphenyl or bag Containing one or both combination aforesaid.High temperature the second catalyst can comprise TPPP.High temperature second Catalyst can comprise TPPA.

Second catalyst can comprise quaternary ammonium compound, and it can be structure (R⁴)₄N⁺X^-Compound, The most each R⁴It is same or different, and is C_1-20Alkyl, C_4-20Cycloalkyl or C_4-20Virtue Base；And X^-It is organic or inorganic anion, such as hydroxyl, halogen ion (halide ion, halide), Carboxylate radical, sulfonate radical, sulfate radical, formate, carbonate or bicarbonate radical.Quaternary organic ammonium compounds Example include tetramethylammonium hydroxide, tetrabutylammonium hydroxide, acetic acid tetramethylammonium, tetramethyl-ammonium formate, second Acid tetrabutylammonium and comprise at least one combination aforesaid.High temperature the second catalyst can be without quaternized Compound, such as, high temperature the second catalyst can not contain TMAOH.

Second catalyst can comprise quaternary compound, and it can be structure (R⁵)₄P⁺X^-Compound, Wherein, each R⁵It is same or different, and is C_1-20Alkyl, C_4-20Cycloalkyl or C_4-20 Aryl；And X^-It is organic or inorganic anion, such as hydroxyl, benzene oxygen root, halogen ion (halogen Ion, halide, halide), carboxylate radical (such as acetic acid or formic acid), sulfonate radical, sulfate radical, first Acid group, carbonate or bicarbonate radical.Wherein, X^-It is multivalent anions, such as carbonate or sulfate radical, Should be appreciated that the positive charge in quaternary ammonium and season structure and negative electrical charge are properly balanced.Such as, exist R²⁰To R²³It is individually methyl and X^-When being carbonic acid, it should be understood that X^-Represent 2 (CO₃ ^-2).Organic season The example of compound includes tetramethylphosphonihydroxide hydroxide base, acetic acid tetramethyl, formic acid tetramethyl, hydrogen The oxidation tetrabutyl, tetraphenylphosphoniacetate acetate, phenol tetraphenyl (tetraphenylphosphonium phenolate, tetraphenyl Phosphonium phenoxide) (TPPP), acetic acid tetraethyl, acetic acid tetrapropyl, acetic acid four Butyl, acetic acid four pentyl, acetic acid four hexyl, acetic acid four heptyl, acetic acid four octyl group, Acetic acid four decyl, acetic acid four-dodecyl, acetic acid tetramethylphenyl, benzoic acid tetramethyl, Benzoic acid tetraethyl, benzoic acid tetrapropyl, benzoic acid tetraphenyl, formic acid tetraethyl, first Acid tetrapropyl, formic acid tetraphenyl, propionic acid tetramethyl, propionic acid tetraethyl, propionic acid tetrapropyl , butyric acid tetramethyl, butyric acid tetraethyl and butyric acid tetrapropyl, and comprise aforesaid at least A kind of combination.

Second catalyst, such as high temperature the second catalyst, can be with the aqueous solution, such as with 10 to 80 The aqueous solution of high temperature second catalyst of wt%, especially 30 to 50wt%, such as 40wt% adds To polymerized unit.

The first catalyst used and the amount of the second catalyst can be based on the dihydroxies for polymerisation The total mole number of based compound.When relating to the second catalyst of polymerisation and all dihydroxies During the ratio of compound, convenient for the sake of refer to the molal quantity of molal quantity/dihydroxy compounds of catalyst, meaning Refer to that the molal quantity of catalyst is divided by the single dihydroxy compounds of every kind be present in reactant mixture Mole total amount.Can be enough to provide 1 × 10^-8To 1 × 10^-5, especially 1 × 10^-7To 8 × 10^-6, More particularly 3 × 10^-7To 2 × 10^-6Mole the rubbing of aromatic dihydroxy compound of catalyst/use The amount of your number uses ester exchange catalyst.

Can be enough to provide 1 × 10^-2To 1 × 10^-8Mole, especially 1 × 10^-4To 1 × 10^-7Mole The amount of the molal quantity of the dihydroxy compounds of metal/use uses the first catalyst, such as, drop SA First catalyst, wherein, metal can be Na.Second catalyst (such as, TPPA and/or TPPP) Amount can be 1 × 10^-2To 1 × 10^-7, especially 1 × 10^-3To 1 × 10^-7Mole/reactant mixture in two Total mole of hydroxy compounds, the molal quantity of such as 50 micromolar second catalyst/dihydroxy monomers. The amount of the second catalyst (such as TPPA and/or TPPP) can be 0.1 to 100 microequivalent (μ eq), 5 μ eq to 90 μ eq especially, and more particularly 20 μ eq to 80 μ eq (in other words, 2 × 10^-5 To 8 × 10^-5Mole) total mole of dihydroxy compounds in/reactant mixture, such as 50 micromoles The molal quantity of the second catalyst/dihydroxy monomers.

By acid compound quencher ester exchange catalyst and any active catalyst residual after being polymerized Thing can also be useful in some melt polymerization process.Remove from melt polymerization after polymerization Relict catalyst and/or quencher and other non-volatile residue in some melt polymerization process also Can be useful.

First catalyst can be added polymerization in any stage of polymerization, such as monomer mixed cell Upstream and/or be directly added into and/or afterwards；And/or the upstream of polymerized unit and/or be directly added into and/or Afterwards (after such as, adding first stage polymerized unit and/or the second stage of reaction polymerized unit). Second catalyst can be in monomer mixed cell upstream and/or be directly added into and/or afterwards；And/or first Stage polymerization unit upstream and/or be directly added into and/or add afterwards to polymerized unit.

Before melt polymerization, the second catalyst can be added to catalyst tank.At catalyst tank, Second catalyst persistently can be guided to monomer mixed cell from catalyst tank.When the second catalyst Amount is reduced to, during the amount of e.g., less than or equal to 15wt%, and can be by the second catalyst of new amount Add to catalyst tank.Likewise it is possible to add the second catalyst in interval adds step.

One or more steps in this method can be automated by the step of pre-programmed, such as, urge Agent adds step, quencher adds step, guide step etc..

In the melted preparation of the Merlon of the present invention, quencher can be added in one or more positions Agent composition is to reduce the activity of catalyst.Quencher compositions comprises quenching agent (quenching Agent) (quencher (quencher) it is also referred to as in this article).Such as, quencher can comprise sulphur Acid esters, such as formula R₁SO₃R₂Alkyl sulfonic ester, wherein, R₁It is hydrogen, C₁-C₁₂Alkyl, C₆-C₁₈ Aryl or C₇-C₁₉Alkaryl, and R₂It is C₁-C₁₂Alkyl, C₆-C₁₈Aryl or C₇-C₁₉Alkane Aryl.The example of alkyl sulfonic ester includes benzene sulfonate, p-methyl benzenesulfonic acid ester, tosylate, second Benzene sulfonate, n-butylbenzene sulphonic acid ester, octyl benzene sulfonic acid ester and phenyl benzene sulphonic acid ester, methyl are to toluene Sulphonic acid ester, ethyl p-methyl benzenesulfonic acid ester, normal-butyl p-methyl benzenesulfonic acid ester, octyl group p-methyl benzenesulfonic acid ester and Phenyl p-methyl benzenesulfonic acid ester.Sulphonic acid ester can comprise alkyl benzenesulfonates (alkyl p-methyl benzenesulfonic acid ester, Alkyl tosylate) such as normal-butyl tosylate (normal-butyl p-methyl benzenesulfonic acid ester, n-butyl tosylate).Sulphonic acid ester can be with 0.1 to 10 volume basis of cumulative volume based on quencher compositions Number (vol%), the amount of 0.1 to 5vol% especially, more particularly 0.5 to 2vol% is present in sudden Go out in agent composition.

Quencher can comprise borate (such as B (OCH₃)₃With B (OCH₂CH₃)₃With B(OC₆H₆)₃), Firebrake ZB, boron phosphate, aluminum stearate, alumina silicate, zirconium carbonate, C₁-C₁₂Alcoxyl Change zirconium, hydroxycarboxylic acid zirconium, gallium phosphide, gallium antimonide, germanium oxide, C₁-C₃₂Organic germanium compounds, C₄-C₃₂ Four organic group tin tin compounds, C₆-C₃₂Six organic group tin compounds are (such as [(C₆H₆O)Sn(CH₂CH₂CH₂CH₃)₂]₂O)、Sb₂O₃, antimony oxide, C₁-C₃₂Alkyl antimony, oxidation Bismuth, C₁-C₁₂Alkyl bismuth, zinc acetate, zinc stearate, C₁-C₃₂Alkoxytitanium and titanium dioxide, phosphorus Acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, boric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, Asia Sulfuric acid, adipic acid, azelaic acid, dodecylic acid, L-AA, aspartic acid, benzoic acid, first Acid, acetic acid, citric acid, glutamic acid, salicylic acid, nicotinic acid, fumaric acid, maleic acid, oxalic acid, benzene Sulfinic acid, C₁-C₁₂Dialkylsulfates (such as dimethyl suflfate and dibutyl sulfate), formula (R^aSO₃ ^-)(PR^b ₄)⁺Sulfonate, wherein, R^aIt is hydrogen, C₁-C₁₂Alkyl, C₆-C₁₈Aryl or C₇-C₁₉Alkaryl and each R^bIt is hydrogen, C independently₁-C₁₂Alkyl, C₆-C₁₈Aryl, formula A¹-(Y¹-SO₃X¹)_mSulfonic acid, wherein, A¹It is the C with m valency₁-C₄₀Hydrocarbyl group, Y¹It is singly-bound or oxygen atom, X¹It is formula-CR¹⁵R¹⁶R¹⁷Secondary or tertiary alkyl groups, the gold of monovalent Belong to cation, ammonium cation (such as NR^b ₃ ⁺, the most each R^bIt is hydrogen, C independently₁-C₁₂Alkyl Or C₆-C₁₈Aryl) or (such as PR^b ₄ ⁺, wherein, each R^bIt is hydrogen, C independently₁-C₁₂Alkane Base or C₆-C₁₈Aryl), wherein, R¹⁵It is hydrogen atom or the alkyl group with 1 to 5 carbon atom, R¹⁶It is hydrogen atom, phenyl group or the alkyl group with 1 to 5 carbon atom, and R¹⁷With R¹⁵Identical or different, and have and R¹⁵Identical definition, condition is R¹⁵、R¹⁶And R¹⁷In Two can not be hydrogen atom, and m is the integer of 1 to 4, and condition is to work as Y¹When being singly-bound, institute The X of the amount of some m¹Can not be the metal cation of monovalent, formula⁺X²-A²-Y¹-SO₃ ^-Compound, Wherein, A²It is divalent hydrocarbyl mission,⁺X²It it is ammonium cation secondary, tertiary or quaternary or secondary (such as, tertiary or quaternary Cation, and Y¹It is singly-bound or oxygen atom, formula A³-(⁺X³)_n·(R-Y¹-SO₃ ^-)_nCompound, Wherein, A³It is the C with n valency₁-C₄₀Hydrocarbyl group,⁺X³It it is ammonium cation (example secondary, tertiary or quaternary As, NR^b ₃ ⁺, wherein, each R^bIt is hydrogen, C independently₁-C₁₂Alkyl or C₆-C₁₈Aryl) or secondary, Tertiary or quaternary cation (such as, PR^b ₄ ⁺, wherein, each R^bIt is hydrogen, C independently₁-C₁₂Alkyl Or C₆-C₁₈Aryl), R is the C of unit price₁-C₄₀Alkyl, n is the integer of 2 to 4, and Y¹It is Singly-bound or oxygen atom, formulaCompound, wherein, A⁵It is unit price or divalence C₁-C₄₀Hydrocarbyl group, A⁴It is the C of divalence₁-C₄₀Hydrocarbyl group, Ad¹And Ad²Independently of one another It is selected from-SO₂-O-SO₂-、-SO₂-O-CO-and-CO-O-SO₂-anhydride group, andIt is 0 Or 1, condition is to work asWhen being 0,It is hydrogen atom or A⁴And A⁵Between key, wherein, A⁵It is divalent hydrocarbyl mission or singly-bound, there is formula R_aR_bN-A-SO₃R_cSulfamate, wherein, R_aAnd R_bIt is hydrogen, C independently of one another₁-C₁₂Alkyl, C₆-C₂₂Aryl, C₇-C₁₉Alkaryl or R_a And R_bAromatic series or non-aromatic heterocyclic compound (such as pyrroles is formed either individually or in combination with N Base, pyridine radicals, pyrimidine radicals, pyrazinyl, carbazyl, quinolyl, imidazole radicals, piperazinyl, azoles Base, thiazolyl, pyrazolyl, pyrrolinyl, indyl, purine radicals, pyrrolidinyl etc.), R_cIt is Hydrogen, and A is C₁-C₁₂Alkyl, C₆-C₁₈Aryl or C₇-C₁₉(such as, compound is such as alkaryl N-(2-hydroxyethyl) piperazine-N'-3-propane sulfonic acid, 1,4-piperazine double (ethyl sulfonic acid) and 5-dimethylamino-1- Naphthyl sulphonic acids), formula R_aR_bR_cN⁺-A-SO₃ ^-Ammonium sulphonic acid ester, wherein, R_a、R_bBe independently of one another hydrogen, C₁-C₁₂Alkyl, C₁-C₁₂Aryl, C₇-C₁₉Alkaryl or R_aAnd R_bEither individually or in combination with N Form aromatic series or non-aromatic heterocyclic compound (such as pyrrole radicals, pyridine radicals, pyrimidine radicals, pyrazine Base, carbazyl, quinolyl, imidazole radicals, piperazinyl, oxazolyl, thiazolyl, pyrazolyl, pyrroles Quinoline base, indyl, purine radicals, pyrrolidinyl etc.), R_cIt is hydrogen and A is C₁-C₁₂Alkyl, C₆-C₁₈Aryl or C₇-C₁₉Alkaryl, sulfonated polystyrene, methyl acrylate-sulfonated phenylethylene copolymerization Thing and comprise at least one combination aforesaid.

Quencher add step can include, to Merlon add any reactive additive it Before, quencher compositions is more than or equal to the Merlon mixing being polymerized the time period of 5 seconds, its Middle reactive additive has reactive OH group or reactive ester group.As it is used in the present context, When relating to " reactive " or " reactive group ", such as, there is reactive OH^-Group or reactivity During ester group, described reactivity is for Merlon.

Can additionally this Merlon melted preparation one or more positions add additive.Example As, additive can be added the upstream of polymerized unit, be directly added into polymerized unit and (such as, entering At Kou, in the charging aperture of side, in outlet, or include one or more combination aforesaid), The downstream of polymerized unit, not in the reactor of polymerization Merlon, the upstream of extruder, directly add Enter extruder (such as, at the feed throat of extruder, in the charging aperture of side, in outlet, or Including one or more combination aforesaid), the downstream of extruder or include aforesaid one or more Combination.Additive can be added as the part of quencher compositions, maybe can be individually added into. Additive can add with molten condition or can add after the Merlon of extrusion is remelted.Can Additive is filtered before adding polymerized unit.

Additive can comprise, such as impact modifier, flow ability modifying agent, filler (such as, particle Polytetrafluoroethylene (PTFE) (PTFE), glass, carbon, mineral or metal), reinforcing agent (such as, glass Fiber), antioxidant, heat stabilizer, light stabilizer, ultraviolet (UV) reagent (e.g., UV Light stabilizer and UV absorbing additives), plasticizer, lubricant, mould release (as releasing agent (as Glycerin monostearate, stearic acid pentaerythritol ester, glyceryl tristearate, stearyl stearate Deng)), antistatic additive, antifoggant, antimicrobial, colouring agent (such as, dyestuff or pigment), Skin effect additive, stable radiation agent, fire retardant, the anti-dripping agent (benzene of such as PTFE encapsulation Ethylene-propylene lonitrile copolymer (TSAN)) or comprise one or more combination aforesaid.Such as, The combination of heat stabilizer, releasing agent and UV light stabilizing agent can be used.Generally, can use the most Know the additive of effective amount.Such as, the total amount of compositions of additives (except any impact modifier, Filler or reinforcing agent) can be 0.001 to 10.0 percetage by weight (wt%), or 0.01 to 5wt%, The gross weight of the polymer being each based in the composition of polymerization.This polymerization can branching agent exist or Occurring in the case of not existing, in other words, this method can comprise maybe can add step without branching agent.

Merlon can have, and as used the sample that 3.2 millimeters (mm) are thick, uses ASTM D1003-00, program B, use CIE standard illuminant C, with one way vision determine more than 90% Light transmission.Therefore, when the composition of quencher has such light transmission, it is herein referred to as " optical-grade " composition.

Merlon can have according to ASTM D1238-04 300 DEG C and the load of 1.2 kilograms Lower mensuration less than or equal to 50 cubic centimetres/10 minutes (cc/10min), especially 3 to 30cc/10 The fluidity of molten of min.

Merlon can have by ASTM D1238-04 at 300 DEG C, measures under 1.2kg 40 grams/10 minutes (g/10min), such as 4.5 to 15g/10min's or 15 to 35g/10min Fluidity of molten.Merlon can have by ASTM D1238-04 at 250 DEG C, under 1.5kg The fluidity of molten of 5 to the 15g/10min measured.

Merlon is it may be that such as bisphenol-a polycarbonate, and it has 20,000 to 40,000 road Er Dun (use polycarbonate standards), such as 21,800 daltonian weight average molecular weight and 24 to The fluidity of molten of 32g/10min (ASTM D1238-04,300 DEG C, 2.16kg).

Merlon can have gross weight based on Merlon less than or equal to 1200ppm, special Not less than or equal to 900ppm, especially less than or equal to 750ppm, specifically it is less than Or the branching level equal to 410ppm.

Merlon can have more than or equal to 60%, and specifically greater than or equal to 70%, particularly The ground End-cap levels more than or equal to 80%, wherein, End-cap levels is the end group by non-hydroxyl group Sum divided by end group (such as, derived from those of DPC plus comprising those of-OH group) Sum and be multiplied by 100 and determine.

There is provided the following example so that this melt polymerization process to be described.These embodiments be merely illustrative and It is not intended to material, condition or the method ginseng being limited to the device prepared according to the disclosure wherein provide Number.

Embodiment

In continuous fusion Merlon device (factory, plant), carry out melt polymerization, wherein, incite somebody to action The DPC of BPA and 55.1kg/h of 58.7kg/h feeds to the most continuously stirred preparing tank (formulation tank).Preparing tank runs at atmospheric pressure and 170 DEG C.By rubbing of 75 micromole TPPA/BPA You add preparing tank by number.In the case of operating with TBPA, with 50 micromolar TBPA/BPA The ratio of molal quantity complete it and add, as the ultimate density in preparing tank.

Then by row's outflow pump of preparing tank to the most continuously stirred the first reactor, its at 257 DEG C and Run under the vacuum of 180 millibars (mbar) to remove byproduct of reaction phenol.In washer (washing Tower, scrubber) in persistently distillation containing phenol and the steam of unreacted monomer BPA and DPC Phase, wherein, regulation reflux ratio is so that tower top (column head) temperature is 127 DEG C, to obtain height The phenol of purity.Unreacted BPA and DPC charging is returned in the first reactor.In order to make up In the phenol tower top stream of neighbouring reactor (reactor that i.e. will appear from, forthcoming reactor) DPC loses, and adds other DPC stream to the first reactor with 1.8kg/h.Will be real at each Execute the aqueous stream (current, aqueous stream) of the first catalyst limited in example with ml/min (mL/min) flow velocity adds the first reactor.

Then by row's outflow pump of the first reactor to the second continuously stirred reactor, it is at 280 DEG C Run with under the vacuum of 37mbar.The higher viscosity flowed due to this, uses gear pump by defeated for this stream Delivering to polymeric part, wherein, two horizontal focusing clutchs of series connection are used for reaching final polymer viscosity. First polymerizer runs under the vacuum of 300 DEG C and 2.5 to 3.0mbar.Remove phenol and pass through Glasses (spectacle) type blade (blade) runs to provide with 20 rpms (rpm) and stirs continuously Mix.Then by polymer flow pump to the second polymerizer, it runs at 1.0-1.5mbar and 302 DEG C. Second polymerizer has grid type (lattice-type) agitator run with 8rpm.Then will be poly- Compound from the second polymerizer charging to 6 final extruders of twin-screw (length/diameter (L/D)=21, D=44mm), wherein, barrel temperature is arranged on 300 DEG C and rotating speed is 100rpm.

Embodiment 1-4

The Merlon of embodiment 1-4 uses and drops SA KNaHPO₄First catalyst and having Second polymerization catalyst of the high temperature TPPA of different metals and gegenion level.Measure catalyst In the metal of varying level and gegenion and by the branching level of acquisition and illustrating in Table 1. BDL represents detectable below horizontal.

Comparing embodiment 1 and embodiment 2 and 3, table 3 shows that molecular weight is similar, but implements Branching level in example 2 and 3 adds about 300ppm.Sum it up, table 1 shows relatively low Sodium, causes the relatively low branching level less than 720ppm in the presence of as hydroxide.

Given below is some embodiments of the disclosure.

Embodiment 1: a kind of prepare the method dropping SA first catalyst, including: preparation bag Aqueous solution I containing the first catalyst I；Preparation comprises the aqueous solution I of the first catalyst II, and optional Make solution II cool down；Solution I and solution II are combined and comprises SA first catalysis of fall to be formed The solution III of agent, wherein, the first catalyst I comprises element I and the second catalyst II comprises element II, and wherein, the mol ratio of Na Yu K is 0.5 to 2.

Embodiment 2: a kind of prepare the method dropping SA first catalyst, including: preparation bag The aqueous solution I of the first catalyst I containing NaOH；Preparation comprises KH₂PO₄The first catalyst II Aqueous solution II；And binding soln I and solution II comprise containing KNaHPO to be formed₄Reduction The solution III of the first catalyst of activity, wherein, the mol ratio of Na Yu K is 0.5 to 2.

Embodiment 3: according to the method according to any one of aforementioned embodiments, wherein, described in rub Your ratio is 0.7 to 1.5 or 0.8 to 1.2.

Embodiment 4: according to the method according to any one of aforementioned embodiments, farther include by Other water adds to solution III.

Embodiment 5: according to the method for embodiment 4, wherein, this interpolation adds 500 to 4,000 The other water of kg.

Embodiment 6: according to the method any one of aforementioned embodiments, wherein, solution II is 20 The water risen comprises the first catalyst II of 100 to 4,000 grams.

Embodiment 7: according to the method any one of aforementioned embodiments, wherein, solution II is 20 The water risen comprises the first catalyst II of 1,500 to 2,000 grams.

Embodiment 8: according to the method any one of aforementioned embodiments, wherein, solution I is 1 The solution of the 50wt% of the water risen comprises the first catalyst I of 50 to 3,000 grams.

Embodiment 9: according to the method any one of aforementioned embodiments, wherein, solution I is 1 The solution of the 50wt% of the water risen comprises the first catalyst I of 800 to 950 grams.

Embodiment 10: according to the method any one of aforementioned embodiments, wherein, in solution III The level of the first free catalyst II is 0 to 20,000ppm.

Embodiment 11: according to the method for embodiment 10, wherein, level is 100 to 10,000 ppm。

Embodiment 12: according to the method any one of aforementioned embodiments, farther includes to titrate molten Liquid III is to measure free KH₂PO₄Level.

Embodiment 13: a kind of melt polymerization process, including: melt polymerization dihydroxy in polymerized unit Based compound and carbonate products are to form Merlon, and wherein, melt polymerization includes according to front State the solution III any one of claim and the second catalyst adds to melt polymerization process, wherein, Merlon has the branching level less than or equal to 900ppm.

Embodiment 14: according to the method for embodiment 5, wherein, melt polymerization farther includes to add Entering the second catalyst, wherein, the second catalyst comprises containing TPPA, TPPP or containing aforesaid one Kind or high temperature second catalyst of the combination of two kinds.

Embodiment 15: a kind of melt polymerization process, including: melt in the presence of carbon monoxide-olefin polymeric Polymerization dihydroxy compounds and carbonate products are to form Merlon, wherein, carbon monoxide-olefin polymeric Comprise containing TPPA, TPPP or containing one or both the second catalyst of combination aforesaid, its In, Merlon has the branching level less than or equal to 900ppm.

Embodiment 16: a kind of melt polymerization process, including: poly-in the presence of carbon monoxide-olefin polymeric Close the dihydroxy compounds of melt polymerization in unit and carbonate products to form the poly-carbonic acid of polymerization Ester, wherein, carbon monoxide-olefin polymeric comprises the second catalyst；Wherein, the second catalyst comprises metallization Compound.Metal comprises at least one in sodium, potassium and caesium.If compound comprises sodium sulphate, sodium Amount is 0 to 1,690ppm.If compound comprises cesium sulfate, the amount of caesium is 0 to 275ppm. If compound comprises NaOH, the amount of sodium is 0 to 35ppm.If compound comprises hydroxide Potassium, the amount of potassium is 0 to 50ppm.If compound comprises cesium hydroxide, the amount of caesium is 0 to 140 ppm.All of concentration value weight based on the second catalyst.Polymerization Merlon have less than or Branching level equal to 900ppm.

Embodiment 17: according to the method for embodiment 16, wherein, the second catalyst comprise containing TPPA, TPPP or containing one or both high temperature second catalyst of combination aforementioned.

Embodiment 18: according to the method any one of embodiment 15-17, wherein, is polymerized into one Step includes adding according to the solution III any one of embodiment 1-12.

Embodiment 19: according to the method any one of embodiment 13-18, wherein, branching level Less than or equal to 750ppm.

Embodiment 20: according to the method any one of embodiment 13-19, wherein, Merlon End-cap levels more than or equal to 60%.

Embodiment 21: according to the method any one of embodiment 13-20, wherein, be aggregated in 0 Occur in the presence of the quaternary ammonium compound of wt%.

Embodiment 22: according to the method any one of embodiment 14-21, wherein, the second catalysis Agent comprises tetraphenylphosphoniacetate acetate, or is substantially made up of tetraphenylphosphoniacetate acetate, or by tetraphenylphosphoniacetate acetate Composition.

Embodiment 23: according to the method any one of embodiment 14-21, comprises phenol tetraphenyl , or be substantially made up of phenol tetraphenyl, or be made up of phenol tetraphenyl.

Embodiment 24: according to the method any one of embodiment 14-23, wherein, with 1 × 10^-2 To 1 × 10^-5Or 1 × 10^-3To 1 × 10^-4Mole/the total molal quantity of dihydroxy compounds adds second Catalyst.

Embodiment 25: according to the method any one of embodiment 13-14 and 18-24, wherein, With 1 × 10^-2To 1 × 10^-8Or 1 × 10^-4To 1 × 10^-7Mole/amount of the total mole number of dihydroxy compounds Add the first catalyst.

Embodiment 26: according to the method any one of embodiment 13-14 and 18-25, wherein, Solution III adds polymerized unit occur with the speed of 0.1 to 10kg/h.

Embodiment 27: according to the method any one of embodiment 13-14 and 18-26, wherein, Add and include solution III being added to monomer stream to form catalyst stream and to add catalyst stream to poly- Close unit.

Embodiment 28: according to the method any one of embodiment 13-27, wherein, polymerization includes Oligomeric oligomer in the oligomeric stage including oligomeric unit, and on the polymerization rank including polymerized unit Polymeric oligomers in Duan, and further include at alternatively and reactant is added to monomer before polymerization Mixed cell.

Embodiment 29: according to the method for embodiment 28, farther includes to add the second catalyst Enter the upstream of oligomeric unit, and/or after being directly added into oligomeric unit, and/or oligomeric unit.

Embodiment 30: according to the method any one of embodiment 28-29, farther includes One catalyst adds the upstream of oligomeric unit, and/or is directly added into oligomeric unit, and/or oligomeric unit Afterwards.

Embodiment 31: according to the method any one of embodiment 28-30, farther includes One catalyst adds the upstream of polymerized unit, and/or is directly added into polymerized unit, and/or polymerized unit Afterwards.

Embodiment 32: according to the method any one of embodiment 28-31, farther includes One or both addition monomer mixed cell upstreams in two catalyst and the first catalyst, and/or directly After adding monomer mixed cell, and/or monomer mixed cell.

Embodiment 33: according to the method any one of embodiment 28-32, wherein, oligomeric unit Including 1 to 4 oligomeric unit.

Embodiment 34: according to the method for embodiment 33, wherein, in oligomeric unit one or Multiple is continuously stirred groove.

Embodiment 35: according to the method any one of embodiment 28-34, wherein, polymerized unit Including 1 to 4 polymerized unit.

Embodiment 36: according to the method for embodiment 35, wherein, in polymerized unit one or Multiple include horizontal polymerizer and/or line wet fall type polymerizer.

Embodiment 37: according to the method any one of embodiment 13-36, wherein, Merlon It it is bisphenol A polycarbonate.

Embodiment 38: according to the method any one of embodiment 13-37, wherein, is polymerized into one Step includes adding quencher compositions, and wherein, quencher compositions comprises quencher.

Embodiment 39: according to the method for embodiment party 38, wherein, quencher compositions comprise based on The sulphonic acid ester of 1 to the 10ppm of the Merlon of 100 parts.

Embodiment 40: according to the method any one of embodiment 38-39, wherein, quencher group Compound comprises the phosphorous acid of 1 to the 10ppm of Merlon based on 100 parts.

Embodiment 41: according to the method any one of embodiment 38-40, wherein, quencher group Compound comprises sulphonic acid ester and the Asia of 2 to 5ppm of 2 to the 5ppm of Merlon based on 100 parts Phosphoric acid.

Embodiment 42: according to the method any one of embodiment 38-41, wherein, quencher group Compound comprises toluenesulfonic acid N-butyl.

Embodiment 43: according to the method any one of embodiment 38-42, wherein, quencher group Compound comprises the quencher of 1 to the 7ppm of Merlon based on 100 parts.

Embodiment 44: according to the method any one of embodiment 38-43, wherein, quencher group Compound comprises the quencher of 1.5 to the 3ppm of Merlon based on 100 parts.

Embodiment 45: according to the method any one of embodiment 38-44, wherein, quencher bag Containing the difunctional compound with acid or acid ester moiety and amine moiety.

Embodiment 46: according to the method any one of embodiment 38-45, wherein, quencher is combined Thing includes the compound of following formula: R_a R_b R_c N⁺-A-SO₃ ^-, wherein, R_a、R_bBe independently of one another hydrogen, C₁-C₁₂Alkyl, C₁-C₁₂Aryl or C₁-C₁₈Alkaryl；R_cIt is hydrogen；R_aAnd R_bAlone or in combination Heterocycle structure is formed with N；And A is C₁-C₁₂Alkyl, C₁-C₁₂Aryl or C₁-C₁₈Alkaryl.

Embodiment 47: according to the method any one of embodiment 38-46, wherein, adds quencher Agent composition includes being injected on Merlon quencher compositions.

Embodiment 48: according to the method any one of embodiment 38-47, further include to Before Merlon adds any additive with reactive OH group or reactive ester group, will Merlon mixes the time period more than or equal to 5 seconds with quencher compositions, and optionally, incites somebody to action One or both in reactive additive add Merlon and are added by non-reacted additive poly- Carbonic ester, wherein, non-reacted additive is without reactive OH group or reactive ester group.

Embodiment 49: according to the method any one of embodiment 38-48, wherein, quencher group Compound comprises non-reacted additive.

Embodiment 50: according to the method any one of embodiment 38-49, wherein, quencher group Compound comprises the quencher of 0.1 to 100wt% or 10 to 99wt%.

Embodiment 51: according to the method any one of embodiment 38-50, wherein, quencher group Compound is liquid quencher compositions.

Embodiment 52: according to the method any one of embodiment 38-51, wherein, quencher group Compound comprises heat stabilizer.

Embodiment 53: according to the method any one of embodiment 38-52, further include at and add Enter and introduce additive after quencher compositions, and wherein, additive comprise alternatively releasing agent and UV reagent.

Embodiment 54: according to the method any one of embodiment 38-53, wherein, adds quencher Agent composition includes being injected on Merlon quencher compositions.

Embodiment 55: according to the method any one of embodiment 38-54, farther include, Before adding quencher compositions, quencher is added to quencher container (quencher vessel) To form quencher compositions.

Embodiment 56: according to the method any one of embodiment 38-55, further include at and add Add and filter quencher compositions and/or additive before.

Embodiment 57: according to the method any one of embodiment 38-56, wherein, adds quencher Agent composition occurs more than or equal to 2 bars, or more than or equal to 3 bars, or the pressure of 3 to 100 bars Under power.

Embodiment 58: farther include to guide to extruder Merlon, wherein, solid is sudden Agent of going out adds to extruder.

Embodiment 59: according to the method any one of embodiment 13-58, farther includes to add Additive, it comprises antioxidant, releasing agent, UV reagent, fire retardant alternatively or comprises aforementioned The combination of one or more.

Embodiment 60: according to the method any one of embodiment 13-59, wherein, between method is Have a rest method.

Embodiment 61: according to the method any one of embodiment 13-60, wherein, by reactant Add to polymerized unit with the speed of 10,000 to 20,000kg/h.

Embodiment 62: according to the method any one of embodiment 14-61, wherein, urges second Agent adds to polymerized unit as the aqueous solution, and wherein, the concentration of the aqueous solution is gross weight based on solution Second catalyst of 30 to the 50wt% of amount.

Embodiment 63: according to the method any one of embodiment 13-62, wherein, melted poly- Branching agent it is added without before, during or after conjunction.

Embodiment 64: according to the method any one of embodiment 13-62, wherein, adds branched Agent.

Embodiment 65: according to the method any one of embodiment 63-64, wherein, branching agent bag Containing trimellitic acid, trimellitic anhydride, inclined benzene three acyl chlorides, three-p-hydroxybenzene ethane, formula (22) Isatin-bis--phenol,

(4 (4 (1,1-is double (right for trisphenol TC (1,3,5-tri-((p-hydroxybenzene) isopropyl) benzene), trisphenol PA Hydroxy phenyl)-ethyl) bis (alpha, alpha-dimethylbenzyl) base) phenol), 4-chloroformyl phthalic anhydride, benzene equal Three acid and benzophenone tetrabasic carboxylic acids or comprise one or more combination aforesaid.

Embodiment 66: according to the method any one of embodiment 13-65, farther includes Two catalyst and optional water added to the second catalyst tank before melt polymerization；And urge second Agent persistently guides from the second catalyst tank adds to monomer mixed cell or interval adds step Second catalyst.

Embodiment 67: according to the method for embodiment 66, farther include, when the second catalyst Amount when being reduced to 15wt%, the second catalyst of new amount is added to the second catalyst tank.

Embodiment 68: according to the method for embodiment 13-67, wherein, one or more steps is (sequencing, programmed) step of programming in automation process.

Embodiment 69: according to the method any one of embodiment 13-68, wherein, melt polymerization It is included in melt polymerization Merlon in a series of first stage oligomeric unit；To discharge the first stage Flow point be A stream and B flow, by A stream guide to second stage polymerized unit A and by B stream guide To second stage polymerized unit B；Or melt polymerization gathers in a series of first stage oligomeric unit Carbonic ester, is then polymerized in a series of second stage polymerized unit, final second stage is gathered The flow point closing unit discharge is A stream and B stream, by A stream guiding to extruder A and is guided by B stream To extruder B；Or melt polymerization Merlon in a series of first stage oligomeric unit, so After in a series of two second stage polymerized units be polymerized；The flow point that first polymerized unit is discharged Flow for A stream and B, A stream is guided to the second polymerized unit A and B stream is guided to the second polymerization Unit B.

Embodiment 70: according to the method any one of embodiment 13-69, wherein, melt polymerization It is included under the oligomerization temperature of 100 DEG C to 280 DEG C oligomeric, and the polymerization of 250 DEG C to 310 DEG C At a temperature of be polymerized, and wherein, oligomerization temperature is less than polymerization temperature.

Embodiment 71: according to the method for embodiment 70, wherein, oligomeric is more than 100mbara Oligomeric pressure under.

Embodiment 72: according to the method any one of embodiment 70-71, wherein, oligomeric includes At first oligomerization temperature of 150 DEG C to 260 DEG C, oligomeric more than or equal to the first of 100mbara Under pressure first is oligomeric；And the second oligomerization temperature and 15 to 90 at 230 DEG C to 280 DEG C Subsequently oligomeric under the second oligomeric pressure of mbara.

Embodiment 73: according to the method any one of embodiment 70-72, wherein, polymerization includes At first polymerization temperature of 260 DEG C to 310 DEG C, then under the polymerization pressure of 1 to 10mbara One polymerization；And 260 DEG C to 300 DEG C the second polymerization temperature and less than or equal to 5mbara Polymerization subsequently under second polymerization pressure.

Embodiment 74: according to the method for embodiment 73, wherein, the first polymerization temperature is 260 DEG C To 285 DEG C；And the second polymerization temperature is 260 DEG C to 285 DEG C.

Embodiment 75: according to the method any one of embodiment 73-74, wherein, the first polymerization Temperature is 270 DEG C to 280 DEG C；And the second polymerization temperature is 270 DEG C to 280 DEG C.

Embodiment 76: according to the method any one of embodiment 73-75, wherein, polymerization is in One or more lines wet fall in type polymerizer, and polymerization temperature is 200 DEG C to 300 DEG C, and gathers Resultant pressure is less than or equal to 4mbara.

Embodiment 77: according to the method for embodiment 76, wherein, polymerization temperature be 250 DEG C extremely 280℃。

Embodiment 78: according to the method any one of embodiment 13-77, farther includes optional Ground extruder and/or in devolatilization unit devolatilization Merlon.

Embodiment 79: according to the method any one of embodiment 13-78, further includes at crowded Going out extrusion Merlon in machine, wherein, extruder is counter rotating twin screW extruder alternatively.

Embodiment 80: according to the method any one of embodiment 14-79, farther includes One reactant is introduced to blender；Melted first reactant；Then by the second reactant and the second catalysis Agent adds to monomer mixed cell, and wherein, the first reactant is selected from diaryl carbonate and dihydroxy Compound, and the second reactant is the another kind in diaryl carbonate and dihydroxy compounds.

Embodiment 81: according to the method any one of embodiment 1-80, wherein, the first catalysis Agent I comprises lithium hydroxide, NaOH, barium hydroxide, strontium hydroxide, potassium hydroxide, hydroxide Magnesium, calcium hydroxide, sodium acetate, potassium acetate, lithium acetate, calcium acetate, barium acetate, magnesium acetate, second Acid strontium, EDTA tetrasodium salt, EDTA magnesium disodium salt, Cs₂CO₃, sodium acid carbonate (NaHCO₃)、 Sodium carbonate (Na₂CO₃), saleratus, lithium bicarbonate, calcium bicarbonate, barium bicarbonate, bicarbonate Magnesium, strontium bicarbonate, potassium carbonate, lithium carbonate, calcium carbonate, brium carbonate, magnesium carbonate, strontium carbonate, hard Resin acid lithium, odium stearate, strontium stearate, potassium stearate, hydroxyl lithium borate, hydroxyl Boratex, benzene Epoxide Boratex, Sodium Benzoate, Potassium Benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, Phosphoric acid hydrogen two lithium, the disodium salt of bisphenol-A, the di-potassium of bisphenol-A and the dilithium salt of bisphenol-A, benzene The sodium salt of phenol, the sylvite of phenol, the lithium salts of phenol or comprise one or more combination aforesaid.

Embodiment 82: according to the method any one of embodiment 1-81, wherein, the first catalysis Agent II comprises NaH₂PO₃、NaH₂PO₄、Na₂HPO₄、KH₂PO₄、CsH₂PO₄、Cs₂HPO₄、 NaKHPO₄、NaCsHPO₄、KCsHPO₄、Na₂SO₄、NaHSO₄、NaSbO₃、LiSbO₃、 KSbO₃、Mg(SbO₃)₂、Na₂GeO₃、K₂GeO₃、Li₂GeO₃、MgGeO₃、Mg₂GeO₄ Or aforesaid one or more combination.

Embodiment 83: according to the method any one of embodiment 13-82, further includes at The second catalyst is added in one catalyst upstream.

Embodiment 84: according to the method any one of embodiment 14-83, wherein, with identical The second catalyst being made up of TMAOH under reaction condition is compared, the second catalyst 150 to At a temperature of 260 DEG C and more than or equal to the melt polymerization of Merlon under the pressure of 100mbara In activity time increase.

Embodiment 85: a kind of Merlon, by according to the method any one of embodiment 13-84 Formed.

Embodiment 86: according to the Merlon of embodiment 85, wherein, Merlon has greatly In or equal to 60% End-cap levels.

Generally, the present invention can alternatively include any applicable component disclosed herein, by its group Become, or be consisting essentially of.The present invention can it addition, or alternatively, prepare not contain, There is no that prior art compositions uses or additionally to realize the present invention function and/or Target any component, material, composition, adjuvant or species not necessarily.

As it is used in the present context, when relating to " reactive group ", such as there is reactive OH^-Base When group or reactive ester group, reactivity is for Merlon.

All scopes disclosed herein include end points, and these end points can combination with one another independently (such as, " up to 25wt%, or more particularly, the scope of 5wt% to 20wt% ", including end points All medians etc. in the range of " 5wt% to 25wt% ")." combine " include blend, Mixture, alloy, product etc..Additionally, term " first ", " second " etc., herein In be not offered as any order, amount or importance, and be intended to indicate that an element is different from another Element.Term " one " and " a kind of " and " being somebody's turn to do " herein do not indicate that logarithm quantitative limitation, And should be interpreted that include odd number and plural number the two, unless otherwise indicated herein or lance obvious with context Shield.Suffix " (s) " is intended to include odd number and the plural number two that this term is modified as used in this article Person, thus include that (such as, film (s) includes one or more thin for this term one or more Film).Run through " another embodiment ", " embodiment " mentioned of specification ... refer to together with this reality The element-specific (such as, characteristic, structure and/or feature) that the mode of executing describes is included herein description At least one embodiment in, and may or may not be present in other embodiment.Additionally, It should be understood that described element can be incorporated into various embodiment in any suitable manner In.This application claims on October 28th, 2013 submit to european patent application 13382432.6 with And on April 25th, 2014 submit to 14382152.8 priority, entire contents with they It is integrally joined to herein.

Although it have been described that detailed description of the invention, but applicant or others skilled in the art may The replacement expected currently without or possibly cannot predict, revises, changes, improves and essentially equivalent thing. Therefore, submit to and the accessory claim that can revise is intended to include all these replacement, revises, becomes Change, improve and essentially equivalent thing.

Claims

1. prepare the method dropping SA first catalyst, including:

Preparation comprises the aqueous solution I of NaOH；

Preparation comprises KH₂PO₄Aqueous solution II；And

Comprise containing KNaHPO to be formed in conjunction with described solution I and described solution II₄Reduction The solution III of the first catalyst of activity, wherein, the mol ratio of Na Yu K is 0.5 to 2.

Method the most according to claim 1, farther includes to add to described molten other water Liquid III.

3. according to method in any one of the preceding claims wherein, wherein, described mol ratio is 0.7 To 1.5.

4., according to method in any one of the preceding claims wherein, farther include to titrate described solution III is to measure free KH₂PO₄Level.

5. a melt polymerization process, including:

In polymerized unit, melt polymerization dihydroxy compounds and carbonate products are poly-to be formed Carbonic ester,

Wherein, described melt polymerization includes solution in any one of the preceding claims wherein III and the second catalyst add to described melt polymerization process,

Wherein, described Merlon has the branching level less than or equal to 900ppm.

Method the most according to claim 5, wherein, described melt polymerization farther includes to add Second catalyst, wherein, described second catalyst comprises containing TPPA, TPPP or contains One or both high temperature second catalyst of combination aforesaid.

7. a melt polymerization process, including:

Melt polymerization dihydroxy compounds and carbonate products in the presence of carbon monoxide-olefin polymeric To form Merlon, wherein, described carbon monoxide-olefin polymeric comprises containing TPPA, TPPP With containing one or both the second catalyst of combination aforesaid,

Wherein, described Merlon has the branching level less than or equal to 900ppm.

8. a melt polymerization process, including:

In polymerized unit in the presence of carbon monoxide-olefin polymeric melt polymerization dihydroxy compounds and Carbonate products is to form the Merlon of polymerization, wherein, described carbon monoxide-olefin polymeric bag Containing the second catalyst；

Wherein, described second catalyst comprises metallic compound, and wherein, described metal comprises At least one in sodium, potassium and caesium；

Wherein, if described compound comprises sodium sulphate, the amount of sodium is 0 to 1,690ppm； If described compound comprises cesium sulfate, the amount of caesium is 0 to 275ppm；If describedization Compound comprises NaOH, and the amount of sodium is 0 to 35ppm；If described compound comprises hydrogen Potassium oxide, the amount of potassium is 0 to 50ppm；If described compound comprises cesium hydroxide, caesium Amount be 0 to 140ppm；It is based on the weight of described second catalyst,

Wherein, the Merlon of described polymerization has the branched water less than or equal to 900ppm Flat.

Method the most according to claim 8, wherein, described second catalyst comprise containing TPPA, TPPP and containing one or both high temperature second catalyst of combination aforesaid.

10. according to the method according to any one of claim 7-9, wherein, described polymerization is wrapped further Include the solution III added according to any one of claim 1-4.

11. according to the method according to any one of claim 5-10, and wherein, described branching level is less than Or equal to 750ppm.

12. according to the method according to any one of claim 5-11, wherein, and the envelope of described Merlon End level is more than or equal to 60%.

13. according to the method according to any one of claim 5-12, wherein, described in be aggregated in 0wt% Quaternary ammonium compound in the presence of occur.

14. according to the method according to any one of claim 6-13, wherein, and described second catalyst bag Containing tetraphenylphosphoniacetate acetate.

15. according to the method according to any one of claim 6-13, wherein, and described second catalyst bag Containing phenol tetraphenyl.

16. according to the method according to any one of claim 6-15, wherein, described second catalyst with 1×10^-2To 1 × 10^-5Mole/amount of total mole of described dihydroxy compounds adds.

17. according to the method according to any one of claim 5-6 and 10-16, wherein, the first catalyst With 1 × 10^-2To 1 × 10^-8Mole/amount of total mole of described dihydroxy compounds adds.