CN105873981A - Method of adding a catalyst in a melt polymerization process and the polycarbonate polymerized therefrom - Google Patents
Method of adding a catalyst in a melt polymerization process and the polycarbonate polymerized therefrom Download PDFInfo
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- CN105873981A CN105873981A CN201480059545.8A CN201480059545A CN105873981A CN 105873981 A CN105873981 A CN 105873981A CN 201480059545 A CN201480059545 A CN 201480059545A CN 105873981 A CN105873981 A CN 105873981A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
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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
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 C6-30Aromatic group, i.e. contains at least one aromatic series portion
Point.R1Can be derived from formula HO-R1-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, RaAnd RbIt is halogen, C independently of one another1-12Alkoxyl or C1-12Alkyl;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), XaIt 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 XaCan be
Singly-bound ,-O-,-S-,-S (O)-,-S (O)2-,-C (O)-or C1-18Organic group.C1-18Organic 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 arranged1-18Organic group is so that being connected to
Its C6Arylene group is each attached to C1-18The common alkylidene carbon of organic bridging group or not
Same carbon.Each p and q can be 1, and RaAnd RbC can be individually1-3Alkyl group,
Methyl especially, is arranged in the meta of the oh group of each arylene group.
XaCan be substituted or unsubstituted formula-C (Rc)(Rd)-C3-18Ring alkylidene radical, C1-25Alkylidene
Base, wherein, RcAnd RdIt is hydrogen, C independently of one another1-12Alkyl, C1-12Cycloalkyl, C7-12Aralkyl
Base, C1-12Miscellaneous alkyl or ring C7-12Heteroarylalkyl, or formula-C (=Re)-group, wherein, ReIt is two
Valency C1-12Hydrocarbyl 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).
XaCan be C1-18Alkylidene, C3-18Cycloalkylidene, the C condensed6-18Cycloalkylidene or formula
-B1-G-B2-group, wherein, B1And B2It is same or different C1-6Alkylidene and G are
C3-12Ring alkylidene radical (cycloalkylidene) or C6-16Arlydene.Such as, XaCan be formula (4)
Substituted C3-18Ring alkylidene radical
Wherein, Rr、Rp、RqAnd RtIt is hydrogen, halogen, oxygen or C independently of one another1-12Hydrocarbyl group;Q
Be the oxygen of Direct Bonding, carbon or divalence, sulphur or-N (Z)-, wherein, Z be hydrogen, halogen, hydroxyl,
C1-12Alkyl, C1-12Alkoxyl or C1-12Acyl 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 Rr、Rp、RqAnd RtAt 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, RqAnd RtConnect together) fragrance group group, and R can be formedqAnd Rt
Connect together and can form aromatic group and RrAnd RpConnect together and can form the second aromatic series base
Group.Work as RqAnd RtConnect together formation aromatic group time, RpCan be double bond oxygen atom, i.e. ketone.
Bis-phenol, wherein, XaIt 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, Ra、Rb, p and q such as formula (3), R3It is C independently of one another1-6Alkyl, j is 0 to 4,
And R4It is hydrogen, C1-6Alkyl, or substituted or unsubstituted phenyl, such as, by up to 5
Individual C1-6The substituted phenyl of alkyl.Such as, phthalimidine carbonate unit is formula (1b)
Wherein, R5It is hydrogen, alternatively by up to 5 C1-6Alkyl, or C1-4The 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 RaAnd RbIt is C independently of one another1-12Alkyl, p and q is 0 to 4 independently of one another, and
RiIt is C1-12Alkyl, alternatively by 1 to 5 C1-10The substituted phenyl of alkyl, or alternatively by 1
To 5 C1-10The substituted benzyl of alkyl.RaAnd RbCan be individually methyl, p and q can be respective
It is 0 or 1 independently, and RiIt is C1-4Alkyl or phenyl.
Derived from bis-phenol (3) (wherein, XaIt is substituted or unsubstituted C3-18Ring 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, RaAnd RbIt is C independently of one another1-12Alkyl, RgIt is C1-12Alkyl, p and q is each independent
Ground is 0 to 4, and t is 0 to 10.Each RaAnd RbIn at least one can be arranged in ring
Pitch the meta of base bridged group.RaAnd RbCan be C independently of one another1-4Alkyl, RgIt is C1-4
Alkyl, p and q is individually 0 or 1, and t is 0 to 5.Ra、RbAnd RgFirst 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, XaIt is substituted or non-substituted C3-18Ring alkylidene)
Other examples of bisphenol carbonate unit include adamantyl units and the fluorenes of formula (1g) of formula (1f)
Base unit
Wherein, RaAnd RbIt is C independently of one another1-12Alkyl, and p and q be 1 to 4 independently of one another.
Each RaAnd RbIn at least one can be arranged in the meta of ring alkylidene radical bridged group.RaAnd Rb
Can be C independently of one another1-3Alkyl, and p and q can be individually 0 or 1;Especially, Ra、
RbCan 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, RhIt is halogen atom, C independently of one another1-10Hydrocarbyl group such as C1-10Alkyl, halogen substiuted
C1-10Alkyl, C6-10Aryl or the C of halogen substiuted6-10Aryl, 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 C1-20Alkyl, C4-20Cycloalkyl or C4-20Virtue
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 C1-20Alkyl, C4-20Cycloalkyl or C4-20
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
(RaSO3 -)(PRb 4)+Sulfonate, wherein, RaIt is hydrogen, C1-C12Alkyl, C6-C18Aryl or
C7-C19Alkaryl and each RbIt 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 NRb 3 +, the most each RbIt is hydrogen, C independently1-C12Alkyl
Or C6-C18Aryl) or (such as PRb 4 +, wherein, each RbIt 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, NRb 3 +, wherein, each RbIt is hydrogen, C independently1-C12Alkyl or C6-C18Aryl) or secondary,
Tertiary or quaternary cation (such as, PRb 4 +, wherein, each RbIt 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 RaRbN-A-SO3RcSulfamate, wherein,
RaAnd RbIt is hydrogen, C independently of one another1-C12Alkyl, C6-C22Aryl, C7-C19Alkaryl or Ra
And RbAromatic 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.), RcIt 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 RaRbRcN+-A-SO3 -Ammonium sulphonic acid ester, wherein, Ra、RbBe independently of one another hydrogen,
C1-C12Alkyl, C1-C12Aryl, C7-C19Alkaryl or RaAnd RbEither 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.), RcIt 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: Ra Rb Rc N+-A-SO3 -, wherein, Ra、RbBe independently of one another hydrogen,
C1-C12Alkyl, C1-C12Aryl or C1-C18Alkaryl;RcIt is hydrogen;RaAnd RbAlone 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 (17)
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.
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13382432 | 2013-10-28 | ||
EP13382432.6 | 2013-10-28 | ||
EP14382151.0A EP2937371A1 (en) | 2014-04-25 | 2014-04-25 | A method of melt polymerizing polycarbonate and polycarbonates derived therefrom |
EP14382151.0 | 2014-04-25 | ||
EP14382152.8 | 2014-04-25 | ||
EP14382152.8A EP2937372B1 (en) | 2014-04-25 | 2014-04-25 | A method of melt polymerizing polycarbonate and polycarbonates derived therefrom |
PCT/IB2014/065668 WO2015063686A2 (en) | 2013-10-28 | 2014-10-28 | Method of adding a catalyst in a melt polymerization process and the polycarbonate polymerized therefrom |
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CN105873981A true CN105873981A (en) | 2016-08-17 |
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CN201480059545.8A Pending CN105873981A (en) | 2013-10-28 | 2014-10-28 | Method of adding a catalyst in a melt polymerization process and the polycarbonate polymerized therefrom |
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EP (1) | EP3063203A2 (en) |
KR (1) | KR20160079772A (en) |
CN (1) | CN105873981A (en) |
WO (1) | WO2015063686A2 (en) |
Cited By (1)
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CN112334509A (en) * | 2018-06-14 | 2021-02-05 | 科思创知识产权两合公司 | Transesterification process for the simultaneous production of at least two different types of polycarbonate in a production plant |
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WO2017081640A1 (en) * | 2015-11-13 | 2017-05-18 | Sabic Global Technologies B.V. | Impact performance modified high transparent melt polymerized polycarbonate |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101479315A (en) * | 2006-06-26 | 2009-07-08 | 沙伯基础创新塑料知识产权有限公司 | Manufacture of polycarbonates |
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US6228973B1 (en) * | 2000-06-02 | 2001-05-08 | General Electric Company | Method for preparing high molecular weight polycarbonate |
EP2692766B8 (en) * | 2012-07-30 | 2016-03-16 | SABIC Global Technologies B.V. | Continuous process for the production of melt polycarbonate |
-
2014
- 2014-10-28 WO PCT/IB2014/065668 patent/WO2015063686A2/en active Application Filing
- 2014-10-28 CN CN201480059545.8A patent/CN105873981A/en active Pending
- 2014-10-28 KR KR1020167008662A patent/KR20160079772A/en not_active Application Discontinuation
- 2014-10-28 EP EP14806084.1A patent/EP3063203A2/en not_active Withdrawn
Patent Citations (1)
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CN101479315A (en) * | 2006-06-26 | 2009-07-08 | 沙伯基础创新塑料知识产权有限公司 | Manufacture of polycarbonates |
Non-Patent Citations (1)
Title |
---|
陈思礼: "《生物化学与分子生物学实验教程》", 31 August 2012, 华中师范大学出版社 * |
Cited By (1)
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CN112334509A (en) * | 2018-06-14 | 2021-02-05 | 科思创知识产权两合公司 | Transesterification process for the simultaneous production of at least two different types of polycarbonate in a production plant |
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WO2015063686A3 (en) | 2015-12-03 |
WO2015063686A2 (en) | 2015-05-07 |
EP3063203A2 (en) | 2016-09-07 |
KR20160079772A (en) | 2016-07-06 |
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