CN105683243A - Melt polymerization polycarbonate quenching - Google Patents

Abstract

In an embodiment, a melt polymerization process comprising: melt polymerizing reactants in the presence of a catalyst composition to form polycarbonate, wherein the catalyst composition comprising a catalyst; adding a quencher composition to the polycarbonate, wherein the quencher composition comprises a quencher; directing the polycarbonate to an extruder.

Description

Melt polymerization Merlon quencher

Technical field

The application relates to the quencher (cold shock is quenched, quenching) in melt polymerization process and quencher (cold shock agent, quenchant, quencher).

Background technology

In the melt polymerization process of polymerization Merlon, it is possible to add quencher to reduce the activity of fused catalyst (meltcatalyst).

EP2540758B1 relates to melt polymerization device system and the catalytic preparation method of preparing Merlon using the later stage to add, and this catalytic preparation has and is scattered in the melt transesterification catalyst preferably included less than in the liquid carrier system of the water of 10wt%. Said preparation preferably includes the liquid carrier system with phenol and cosolvent (cosolvent, cosolvent). Melt transesterification catalyst can be present in preparation with the scope of 50ppm to 60,000ppm.

EP0955768A2 relates to prepare the method for aromatic polycarbonate resin. disclose the preparation of aromatic polycarbonate resin, " in such a situa-tion, namely the flowing velocity of the reactant mixture in pipeline (molten reaction mixture by its by) is particular value or higher, the viscosity-average molecular weight of reactant mixture is 1, 000 or higher, the grand mean retention time of reactant mixture was no longer than 3 hours, the temperature that the wall temperature of pipeline (molten reaction mixture by its by) is set higher than in pipeline reactant mixture, addition catalysqt deactivation agent (passivator within 2 hours is completed at melt polycondensation reaction, deactivationagent), and by using the filter with specific reservation particle diameter to be filtered under specific pressure differential ... "

JP2003335853A relates to aromatic/aliphatic copolycarbonate resin compositions, it is by making aromatic carbonate diester, aliphatic dihydroxy compounds and aromatic dihydroxy compound stand melt polymerization in the presence of a catalyst to prepare aromatic/aliphatic Copolycarbonate (A), and in catalysqt deactivation (passivation, deactivate), after, make Copolycarbonate (A) melt with at least one other resins (B) and knead in extrusion step and be prepared.

The method of the improvement adding quencher is desired.

Summary of the invention

There is disclosed herein the method for adding quencher.

In embodiments: melt polymerization process includes: under carbon monoxide-olefin polymeric exists, melt polymerization thing is to form Merlon, and wherein, this carbon monoxide-olefin polymeric comprises catalyst; Quencher compositions is added into Merlon, and wherein, this quencher compositions comprises quencher; Merlon is guided to extruder.

In embodiments, melt polymerization process includes: at least two polymerized unit, and under carbon monoxide-olefin polymeric exists, melt polymerization thing is to form Merlon, wherein, carbon monoxide-olefin polymeric comprises α catalyst, and wherein, α catalyst comprises alkali metal and/or source of alkaline earth metal; In conjunction with liquid-carrier and quencher to form quencher compositions in quencher container; Quencher compositions is added into Merlon under the pressure more than or equal to 2 bars; Before add any additive with reactive OH group or reactive ester group to Merlon, quencher compositions is mixed with Merlon the time period more than or equal to 5 seconds; Filter Merlon; And Merlon is guided to extruder.

In embodiments, melt polymerization process includes: at least two polymerized unit, under carbon monoxide-olefin polymeric exists, melt polymerization thing is to form Merlon, and wherein, carbon monoxide-olefin polymeric comprises α catalyst, wherein, α catalyst comprises alkali metal and/or source of alkaline earth metal; Melted quencher is to form quencher compositions, and wherein, quencher compositions is without carrier; Quencher compositions is added into Merlon; Filter Merlon; And Merlon is guided to extruder.

In embodiments, melt polymerization process includes: under carbon monoxide-olefin polymeric exists, melt polymerization thing is to form Merlon, wherein, carbon monoxide-olefin polymeric only comprises beta catalyst, wherein, beta catalyst comprises quaternary ammonium compound, quaternary compound or comprises aforesaid at least one combination; Quencher compositions is added into Merlon, and wherein, quencher compositions comprises quencher; And Merlon is guided to extruder.

In embodiments, the method adding solid quencher compositions includes: Merlon is fed to extruder; Quencher compositions is added into Merlon, and wherein, quencher compositions is solid quencher compositions; And before adding any reactive additive to Merlon, quencher compositions is mixed with Merlon the time period more than or equal to 5 seconds, wherein, reactive additive has reactive OH group or reactive ester group; Wherein, Merlon is melted Merlon.

Described above and further feature is illustrated by the following drawings and detailed description of the invention.

Accompanying drawing explanation

Referring now to accompanying drawing, they are illustrative of embodiment, and wherein similar key element represents with same reference number.

Fig. 1 illustrates the method adding quencher compositions.

Detailed description of the invention

Applicant develops the method for the improvement being added in the melt polymerization process of Merlon with liquid and/or solid form by the quencher in quencher compositions.

" Merlon " used herein refers to the polymer of the structure carbonate unit of the repetition with formula (1)

Wherein, R¹At least the 60% of group sum is aliphatic, alicyclic or aromatic series containing aryl moieties and its surplus. Each R¹Can be C_6-30Aromatic group, namely contains at least one aryl moieties. R¹Can derived from formula HO-R¹The aromatic dihydroxy compound of-OH, especially formula (2):

HO–A¹–Y¹–A²–OH(2)

Wherein, A¹And A²In each be monocyclic divalent aromatic yl group and Y¹It is by A¹With A²The singly-bound separated or the bridge linkage group with one or more atom. One atom can by A¹With A²Separate. Especially, each R¹Can derived from the bis-phenol of formula (3)

Wherein R^aAnd R^bIt is halogen, C independently of one another_1-12Alkoxyl or C_1-12Alkyl; And p and q is the integer of 0 to 4 independently of one another. Should be understood that, when p or q is less than 4, the valence link of each carbon of ring is filled by hydrogen. Same in formula (3), X^aIt is the bridged group connecting the aromatic group that two hydroxyls replace, wherein, bridged group and each C₆The hydroxyl substituent of arylene group is arranged at C with ortho position, a position or para-position (particularly para-position) each other₆In arylene group. Bridged group X^aCan be singly-bound ,-O-,-S-,-S (O)-,-S (O)₂-,-C (O)-or C_1-18Organic group. C_1-18Organic bridging group can be ring-type or acyclic, aromatic series or non-aromatic, and can comprise hetero atom further, such as halogen, oxygen, nitrogen, sulfur, silicon or phosphorus. C_1-18Organic group is arranged to be connected to its C₆Arylene group is each attached to C_1-18The common alkylidene radical carbon of organic bridging group or different carbon. Each p and q can be 1, and R^aAnd R^bC can be individually_1-3Alkyl group, especially methyl, be placed in position between the oh group of each arylene group.

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

X^aCan be C_1-18Alkylidene, C_3-18Cycloalkylidene, the C condensed_6-18Cycloalkylidene or formula-B¹-G-B²-group, wherein, B¹And B²It is identical or different C_1-6Alkylidene and G are C_3-12Ring alkylidene radical (cycloalkylidene) or C_6-16Arlydene. Such as, X^aCan be the C of the replacement of formula (4)_3-18Ring alkylidene radical

Wherein, R^r、R^p、R^q, and R^tVarious is hydrogen, halogen, oxygen or C independently_1-12Hydrocarbyl group; Q be the oxygen of direct bond, carbon or bivalence, sulfur or-N (Z)-, wherein, Z is hydrogen, halogen, hydroxyl, C_1-12Alkyl, C_1-12Alkoxyl or C_1-12Acyl group; R is 0 to 2, and t is 1 or 2, q is 0 or 1, and k is 0 to 3, and condition is R^r、R^p、R^q, and R^tAmong at least two connect together alicyclic, the aromatic series or heteroaromatic rings that are to condense. Should be understood that, when condensed ring is aromatic series, the ring shown in formula (4) will have unsaturated carbon-carbon bond when ring is to condense. When k is 1 and i is 0, the ring as shown in formula (4) contains 4 carbon atoms; When k is 2, as contained 5 carbon atoms at the ring shown in formula (4); And when k is 3, this ring contains 6 carbon atoms. Two adjacent group (such as, R^qAnd R^tConnect together) fragrance group group and R can be formed^qAnd R^tConnect together and can form aromatic group and R^rAnd R^pConnect together and can form the second aromatic group. Work as R^qAnd R^tConnect together formation aromatic group time, R^pCan be double bond oxygen atom, i.e. ketone.

Bis-phenol, wherein, X^aIt is the ring alkylidene radical of formula (4), it is possible to contain the Merlon of phthalimidine carbonic ester (phthalimidinecarbonate) unit of formula (1a) for preparation

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

Wherein, R⁵It is hydrogen, alternatively by up to 5 C_1-6Alkyl, or C_1-4The phenyl that alkyl replaces. In formula (1b), R⁵Can be hydrogen, methyl or phenyl, particularly phenyl. Carbonate unit (1b), (wherein, R⁵It is phenyl) can derived from 2-phenyl-3, double; two (4-hydroxy phenyl) phthalimidine of 3'-is (also referred to as 3, double; two (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 carbonate unit of formula (1c) and (1d)

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

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

Wherein, R^aAnd R^bIt is C independently of one another_1-12Alkyl, R^gIt is C_1-12Alkyl, p and q is 0 to 4 independently of one another, and t is 0 to 10. Each R^aAnd R^bIn at least one can be placed in ring and pitched position between base bridged group. R^aAnd R^bCan be C independently of one another_1-4Alkyl, R^gIt is C_1-4Alkyl, p and q is individually 0 or 1, and t is 0 to 5. R^a、R^bAnd R^gCan being individually methyl, p and q can be individually 0 or 1, and t can be 0 or 3, and particularly 0.

Derived from bis-phenol (3) (wherein, X^aIt is replacement or non-substituted C_3-18Ring alkylidene (4)) other examples of bisphenol carbonate unit include the adamantyl units of formula (1f) and the fluorenyl unit of formula (1g)

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

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

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

Some illustrative examples of specific dihydroxy compounds include following: 4,4' dihydroxy diphenyl, 1,6-dihydroxy naphthlene, 2,6-dihydroxy naphthlene, double, two (4-hydroxy phenyl) methane, double, two (4-hydroxy phenyl) diphenyl methane, double, two (4-hydroxy phenyl)-1-naphthyl methane, double, two (4-hydroxy phenyl) ethane of 1,2-, double, two (4-the hydroxy phenyl)-1-diphenylphosphino ethane of 1,1-, 2-(4-hydroxy phenyl)-2-(3-hydroxy phenyl) propane, double, two (4-hydroxy phenyl) phenylmethane, double, two (4-hydroxyl-3-bromophenyl) propane of 2,2-, double, two (hydroxy phenyl) Pentamethylene. of 1,1-, 1,1-bis(4-hydroxyphenyl)-cyclohexane, double, two (4-hydroxy phenyl) isobutene. of 1,1-, double, two (4-hydroxy phenyl) cyclododecane of 1,1-, double, two (4-the hydroxy phenyl)-2-butylene of trans-2,3-, double, two (4-hydroxy phenyl) diamantane (obsolete) of 2,2-, α, α '-bis-(4-hydroxy phenyl) toluene, double, two (4-hydroxy phenyl) acetonitrile, 2,2-(3-ethyl-4-hydroxy phenyl) propane, 2,2-(3-n-pro-pyl-4-hydroxy phenyl) propane, 2,2-(3-isopropyl-4-hydroxy phenyl) propane, double, two (3-sec-butyl-4-hydroxy phenyl) propane of 2,2-, double, two (3-tert-butyl-hydroxy phenyl) propane of 2,2-, double, two (3-cyclohexyl-4-hydroxy phenyl) propane of 2,2-, double, two (3-pi-allyl-4-hydroxy phenyl) propane of 2,2-, double, two (3-methoxyl group-4-hydroxy phenyl) propane of 2,2-, double, two (4-hydroxy phenyl) HFC-236fa of 2,2-, double, two (4-hydroxy phenyl) ethylene of the chloro-2,2-of 1,1-bis-, double, two (4-hydroxy phenyl) ethylene of the bromo-2,2-of 1,1-bis-, double, two (5-phenoxy group-4-hydroxy phenyl) ethylene of the chloro-2,2-of 1,1-bis-, 4,4'-dihydroxy benaophenonel, double, two (4-the hydroxy phenyl)-2-butanone of 3,3-, double, two (4-the hydroxy phenyl)-1,6-acetyl butyryl of 1,6-, ethylene glycol bis (4-hydroxy phenyl) ether, double, two (4-hydroxy phenyl) ether, double, two (4-hydroxy phenyl) sulfur ether, double, two (4-hydroxy phenyl) sulfoxide, double, two (4-hydroxy phenyl) sulfone, double, two (4-hydroxy phenyl) fluorenes of 9,9-, 2,7-dihydroxy pyrene, 6,6'-dihydroxy-3,3,3'3'-tetramethyl spiral shell (double, two) indane (" the full bis-phenol of spirobindene "), double, two (4-hydroxy phenyl) Phthalide (phthalimide) of 3,3-, 2,6-dihydroxy dibenzo-p-dioxin, 2,6-dihydroxy thianthrene, 2,7-dihydric phenol flavin, 2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxy dibenzofurans, 3,6-dihydroxy dibenzothiophenes, with 2,7-dihydroxy carbazole, resorcinol, the resorcinol compound replaced, such 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., catechol, hydroquinone, replace hydroquinone, as 2-methylnaphthohydroquinone, 2-ethyl hydroquinone, 2-propyl group hydroquinone, 2-butylhydroquinone, TBHQ, 2-pheny lhydro quinone, 2-cumyl hydroquinone, 2,3,5,6-duroquinols, 2,3,5,6-tetra-tert hydroquinone, 2,3,5,6-tetrafluoro hydroquinone, 2,3,5,6-tetra-bromohydroquinones etc. or comprise combination at least one in aforementioned dihydroxy compounds.

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

Merlon herein is to be prepared by the melt polymerization of bis-phenol and carbonate precursor. Exemplary carbonate precursor includes carbonyl halide, such as carbonyl bromide or phosgene (phosgene), double; two haloformate (such as the bischloroformates of bisphenol-A, hydroquinone ethylene glycol, neopentyl glycol etc.) of dihydroxy compounds, and diaryl carbonate. Combination at least one in the carbonate precursor comprising aforementioned type can also be used. Diaryl carbonate can be the dipheryl carbonate base ester of dipheryl carbonate base ester or the activation on each aryl with electron-withdrawing substituent, such as double; two (4-nitrobenzophenone) carbonic ester, double; two (2-chlorphenyl) carbonic ester, double; two (4-chlorphenyl) carbonic ester, double; two (methyl salicyl) carbonic ester, double; two (4-methyl carboxyl phenyl) carbonic ester, double; two (2-acetylbenzene) carboxylate, double; two (4-acetylbenzene) carboxylate or comprise aforementioned at least one combination.

This polymerization can occur under branching agent exists. The example of these branching agents includes containing the multifunctional organic compound selected from least three kinds of following functional groups: hydroxyl, carboxyl, carboxylic acid anhydrides, haloformyl, and the mixture of aforementioned functional groups. This branching agent includes aromatic series three acyl halide, for instance three acid chlorides of formula (20):

Wherein, Z is halogen, C_1-3Alkyl, C_1-3Alkoxyl, C_7-12Aryl alkylene, C_7-12Alkyl arylene or nitro, and z is 0 to 3; Three-fortified phenol of formula (21)

Wherein, T is C_1-20Alkyl, C_1-20Alkoxyl, C_7-12Aralkyl or C_7-12Alkaryl, Y is halogen, C_1-3Alkyl, C_1-3Alkoxyl, C_7-12Aralkyl, C_7-12Alkaryl or nitro, s is 0 to 4.

The specific example of branching agent include trimellitic acid, trimellitic anhydride, inclined benzene three acyl chlorides, three-p-hydroxybenzene ethane, formula (22) isatin-bis--phenol,

Trisphenol TC (1; 3; 5-tri-((p-hydroxybenzene) isopropyl) benzene), trisphenol PA (4 (4 (1; double; two (the p-hydroxybenzene)-ethyl of 1-) bis (alpha, alpha-dimethylbenzyl) base) phenol), 4-chloroformyl phthalic anhydride, trimesic acid and benzophenone tetrabasic carboxylic acid.

In melt polymerization process, Merlon can pass through under ester exchange catalyst exists, and makes the dihydroxy reactants of molten condition and carbonate precursor coreaction prepare. This reaction can at typical polymerization unit, as continuous-stirring reactor (CSTR), plug flow reactor, line wet type polymerizer (wire-wettingfallpolymerizer), free-falling polymerizer, horizontal (horizontal, horizontal) polymerizer, scraped film type polymerizer, Banbury mixer (BANBURYmixer), single screw rod or double screw extruder, or include one or more combination aforementioned carries out. By distilling, from frit reaction thing, remove Volatile monohydric phenol, and polymer is separated as molten residue. Melt polymerization can be carried out with discontinuous method (batchprocess) or continuation method. In either case, the melt polymerization conditions of use can include (independent, distinct) stage of reaction that two or more are different. Such as, polymerization can include oligomerization (oligomerization) stage, wherein, initial dihydroxy aromatic compounds and diaryl carbonate are converted into oligomeric polycarbonate, and second stage of reaction, also referred to as polymerization stage, wherein, the oligomeric polycarbonate formed in oligomerization stage is converted into high-molecular-weight polycarbonate. Oligomerization stage can include one or more, and especially 2 or multiple, more particularly 2 to 4 oligomerization unit (such as 2 to 4 continuous stirring grooves). When 2 or more oligomerization unit are contacted and are existed, can occur from a unit to the next one temperature increase or pressure reduce one or both. Polymerization stage can include one or more, 2 or multiple especially, more particularly 2 polymerized units (such as 2 horizontal or line wets type polymerizer). Polymerization stage can include one or more polymerized unit, and it can by polycarbonate polymerization extremely, for instance 20,000 to 50,000 daltonian molecular weight. After forming Merlon, then can by polycarbonate compositions quencher alternatively and at devolatilization (devolatilization, devolatization) devolatilization (elimination volatile ingredient in unit, 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 and the time of staying to reduce the concentration of lower-molecular-weight component (as having lower than those of 1,000 daltonian molecular weight). Oligomerization unit is defined to cause that polycarbonate oligomer has less than or equal to 8 in this article, the oligomerization unit of 000 daltonian number-average molecular weight, and polymerized unit is defined to generation and has the polymerized unit of the Merlon more than 8,000 daltonian number-average molecular weights in this article. It is noted that while use less than or equal to 8,000 dalton at this to limit the molecular weight obtained in oligomerization stage, skilled addressee readily understands that, described molecular weight is used for limiting oligomerization stage, wherein, the molecular weight of oligomer can more than 8,000 dalton. " segmentation " polymeric reaction condition may be used for continuous polymerization system, wherein, initial monomer is oligomeric in the first reaction vessel, and, the oligomeric polycarbonate formed wherein is continuously delivered to one or more downstream reactor, wherein, oligomeric polycarbonate is converted into high-molecular-weight polycarbonate. Generally, in the oligomeric stage, the oligomeric polycarbonate of generation has 1,000 to 7,500 daltonian number-average molecular weights.In one or more polymerization stages subsequently, the number-average molecular weight (Mn) of Merlon can increase extremely, for instance 8,000 to 25,000 dalton (use polycarbonate standards), 13,000 to 18,000 dalton especially.

Generally, do not use solvent in the method, and reactant dihydroxy aromatic compounds and diaryl carbonate are in molten condition. Reaction temperature can be 100 to 350 degrees Celsius (DEG C), especially, and 180 to 310 DEG C. The pressure of reaction starting stage may be at atmospheric pressure, super-atmospheric pressure or is depressed into the pressure of pressure limit of 15 holders from air, and at after-stage, is in the pressure of decline, for instance 0.2-15 holds in the palm. Similarly, polymerization can occur in a series of aggregation container, and it each can individually have temperature and/or the vacuum of increase. Such as, oligomerization stage can occur at 100 to 280 DEG C, especially at the temperature of 140 to 240 DEG C, and polymerization stage can occur at 240 to 350 DEG C, especially at the temperature of 280 to 300 DEG C or 240 to 270 DEG C or 250 to 310 DEG C, wherein, the temperature in polymerization stage is more than the temperature in oligomerization stage. Response time from initial oligomeric unit to final polymerized unit is usually 0.1 to 15 hour. Final polymerized unit refers to the final polymerized unit in the melt polymerization of the last increase that molecular weight wherein occurs as used in this article. Such as, quencher after final polymerization (such as, after the weight average molecular weight (Mw) of Merlon increases the point less than or equal to 10%), and alternatively, can be added into polycarbonate resin before any melt filtration.

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

Polymerization stage subsequently of oligomeric stage can include being polymerized in one or two polymerized unit. First polymerized unit can at 240 to 350 DEG C, especially at the temperature of 260 to 310 DEG C and under the pressure of 1 to 10 millibar. Second polymerized unit can at 240 to 350 DEG C, especially under the pressure at the temperature of 260 to 300 DEG C with less than or equal to 5 millibars. Merlon can after final polymerization devolatilization.

After final aggregation container (polymerized unit also referred to as final), polymer can guide to reactor, extrusion, stand to filter in fondant filter, or includes one or more combination aforementioned. Before or after it should be noted that fondant filter may be located at extruder. Such as, the melt polymerization process for preparing polycarbonate compositions may include that melt polymerization dihydroxy reactants and carbonate products are to produce molten reaction products; Quencher molten reaction products; The fondant filter of any extruder upstream filters molten reaction products; Introduce additive alternatively to form mixture; And extrude this mixture to form polycarbonate compositions. Similarly, the melt polymerization process for preparing polycarbonate compositions may include that melt polymerization dihydroxy reactants and carbonate products are to produce molten reaction products; Introduce quencher compositions and optional additive is used for forming mixture; And extrude this mixture to form polycarbonate compositions.

The catalyst prepared for the melt transesterification polymerization of Merlon can include α and/or beta catalyst. Beta catalyst is ester exchange catalyst that is generally volatile and that degrade at elevated temperatures. Therefore, beta catalyst can use in the low temperature polymerization stage earlier (such as, oligomeric period). α catalyst is usual ratio beta catalyst more thermal-stable and not volatile ester exchange catalyst, and therefore can using in whole ester exchange reaction, whole ester exchange reaction included in oligomeric period, and after oligomerization, such as in aggregation container, in the course of the polymerization process.

α catalyst can comprise alkali metal and/or source of alkaline earth metal, for instance, it is to provide the catalyst of alkali metal and/or source of alkaline earth metal. These ion sources include alkali metal hydroxide, such as Lithium hydrate, sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxide, such as magnesium hydroxide and calcium hydroxide. Other possible source of alkali and alkaline earth metal ions ion includes the salt (such as EDTA tetrasodium salt, and EDTA magnesium disodium salt) of the correspondence of the corresponding salt (such as sodium acetate) of carboxylic acid and the derivant of ethylenediaminetetraacetic acid (EDTA). Other α ester exchange catalysts include alkali metal or the alkali salt of carbonic acid, such as Cs₂CO₃、NaHCO₃, and Na₂CO₃Deng the alkali metal alkaline earth metal salt of, non-volatile inorganic acid, such as NaH₂PO₃、NaH₂PO₄、Na₂HPO₃、KH₂PO₄、CsH₂PO₄、Cs₂HPO₄Deng, or the salt-mixture of phosphoric acid, such as NaKHPO₄、CsNaHPO₄、CsKHPO₄Deng. At least one combination comprised in any Above-mentioned catalytic agent can be used.

Possible beta catalyst can comprise quaternary ammonium compound, quaternary phosphonium compound or include aforesaid at least one combination. Quaternary ammonium compound can be structure (R⁴)₄N⁺X^-Compound, wherein, each R⁴It is identical or different, and is C_1-20Alkyl, C_4-20Cycloalkyl or C_4-20Aryl; And X^-It is organic or inorganic anion, for instance hydroxyl, halogen ion (halogenide, halide), carboxylate radical, sulfonate radical, sulfate radical, formate, carbonate or bicarbonate radical. The example of quaternary organic ammonium compounds includes tetramethylammonium hydroxide, tetrabutylammonium hydroxide, acetic acid tetramethylammonium, tetramethyl-ammonium formate, acetic acid tetrabutylammonium and comprises aforementioned at least one combination. Commonly used is Tetramethylammonium hydroxide. Quaternary compound can be structure (R⁵)₄P⁺X^-Compound, wherein, each R⁵It is identical or different, and is C_1-20Alkyl, C_4-20Cycloalkyl or C_4-20Aryl; And X^-It is organic or inorganic anion, for instance hydroxyl, phenolate (phenolate ions, phenoxide), halogen ion, carboxylate radical (such as acetic acid or formic acid), sulfonate radical, sulfate radical, formate, carbonate or bicarbonate radical. Wherein, X^-It is multivalent anions, such as carbonate or sulfate radical, it should be appreciated that positive charge and negative charge in quaternary ammonium and season structure are properly balanced. Such as, at R²⁰To R²³It is individually methyl and X^-When being carbonic acid, it should be understood that X^-Represent 2 (CO₃ ^-2). The example of organic quaternary compound includes tetramethylphosphonihydroxide hydroxide base, acetic acid tetramethyl, formic acid tetramethyl, tetrabutylphosphoniuhydroxide hydroxide, tetrabutylphosphoniuacetate acetate (TBPA), tetraphenylphosphoniacetate acetate (tetraphenylphosphoniacetate acetate, tetraphenylphosphoniumacetate, TPPA), tetraphenyl benzene oxidatoin (TPPP) and include aforesaid at least one combination. Catalyst can comprise TBPA. Catalyst can comprise TPPP.

The α used and the amount of beta catalyst can based on the total mole numbers of the dihydroxy compounds for polyreaction. When relating to beta catalyst (such as, microcosmic salt) with for the ratio of all dihydroxy compounds of polyreaction time, conveniently refer to the molal quantity of the catalyst of the dihydroxy compounds of every mole, represent the molal quantity mole total amount divided by dihydroxy compounds every kind be present in reactant mixture independent of catalyst. Ester exchange catalyst can enough to provide 1 × 10^-8To 1 × 10^-5, especially 1 × 10^-7To 8 × 10^-6, more particularly 3 × 10^-7To 2 × 10^-6Mole catalyst/use aromatic dihydroxy compound molal quantity amount use. α catalyst can enough to provide 1 × 10^-2To 1 × 10^-8Mole, especially 1 × 10^-4To 1 × 10^-7Mole metal/use dihydroxy compounds molal quantity amount use. The amount of beta catalyst (such as organic ammonium or microcosmic salt) can be 1 × 10^-2To 1 × 10^-5, especially 1 × 10^-3To 1 × 10^-4Mole/reactant mixture in total mole of dihydroxy compounds. The amount of α catalyst can less than the amount of the beta catalyst adding polyreaction. Can also be useful in some melt polymerization process with acid compound quencher ester exchange catalyst and any active catalyst residue after being polymerized. From melt polymerization, remove relict catalyst and/or quencher after polymerization and other non-volatile residue can also be useful in some melt polymerization process.

Merlon is it may be that such as have 21800 daltonian weight average molecular weight and have the bisphenol-a polycarbonate of fluidity of molten (ASTMD1238,300 DEG C, 2.16kg) of 24 to 32g/10min.

Merlon can have by ASTMD1238 at 300 DEG C, 4 to the 40g/10min measured under 1.5kg, for instance the fluidity of molten of 4.5 to 15g/10min. Merlon can have by ASTMD1238 at 250 DEG C, the fluidity of molten of 5 to the 15g/10min measured under 1.5kg.

In the melted preparation of the Merlon of the present invention, it is possible to add quencher compositions in one or more positions to reduce the activity of catalyst, for instance reduce or suppress the activity of α catalyst. Quencher compositions comprises quenching agent (quenchingagent) (in this article also referred to as quencher (quencher)). Such as, quencher can comprise sulphonic acid ester, such as formula R₁SO₃R₂Alkyl sulfonic ester, wherein, R₁It is hydrogen, C₁-C₁₂Alkyl, C₆-C₁₈Aryl or C₇-C₁₉Alkaryl, and R₂It is C₁-C₁₂Alkyl, C₆-C₁₈Aryl or C₇-C₁₉Alkaryl. The example of alkyl sulfonic ester includes benzene sulfonate, p-toluenesulfonic esters, tosylate, EBSA ester, n-butylbenzene sulphonic acid ester, octyl benzene sulfonic acid ester and phenyl benzene sulphonic acid ester, methyl p-toluenesulfonic esters, ethyl p-toluenesulfonic esters, normal-butyl p-toluenesulfonic esters, octyl group p-toluenesulfonic esters and phenyl p-toluenesulfonic esters. Sulphonic acid ester can comprise alkyl benzenesulfonates (alkyl p-toluenesulfonic esters, alkyltosylate), such as normal-butyl tosylate (normal-butyl p-toluenesulfonic esters, n-butyltosylate). Sulphonic acid ester can with 0.1 to 10 percentage by volume (vol%) of the cumulative volume based on quencher compositions, and 0.1 to 5vol% especially, more particularly the amount of 0.5 to 2vol% is present in quencher compositions.

Quencher can comprise borate (such as B (OCH₃)₃、B(OCH₂CH₃)₃With B (OC₆H₆)₃), Firebrake ZB, boron phosphate, aluminium stearate, aluminium silicate, zirconium carbonate, C₁-C₁₂Alkoxide zirconium, hydroxy carboxylic acid zirconium, gallium phosphide, gallium antimonide, germanium oxide, C₁-C₃₂Organic germanium compounds, C₄-C₃₂Four organic group stannum tin compounds, C₆-C₃₂Six organic group tin compound (such as [(C₆H₆O)Sn(CH₂CH₂CH₂CH₃)₂]₂O)、Sb₂O₃, stibium oxide, C₁-C₃₂Alkyl antimony, bismuth oxide, C₁-C₁₂Alkyl bismuth, zinc acetate, zinc stearate, C₁-C₃₂Alkoxytitanium and titanium dioxide, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, boric acid, hydrochloric acid, hydrobromic acid, sulphuric acid, sulfurous acid, adipic acid, Azelaic Acid, dodecylic acid, L-AA, aspartic acid, benzoic acid, formic acid, acetic acid, citric acid, glutamic acid, salicylic acid, nicotinic acid, fumaric acid, maleic acid, oxalic acid, benzenesulfinic acid, C₁-C₁₂Dialkylsulfates (such as, dimethyl sulfate and dibutyl sulfate), formula (R^aSO₃ ^-)(PR^b ₄)⁺Sulfonate, wherein, R^aIt is hydrogen, C₁-C₁₂Alkyl, C₆-C₁₈Aryl or C₇-C₁₉Alkaryl and each R^bIt is hydrogen, C independently₁-C₁₂Alkyl, C₆-C₁₈Aryl, formula A¹-(Y¹-SO₃X¹)_mSulfonic acid, wherein, A¹It is the C with m valency₁-C₄₀Hydrocarbyl group, Y¹It is singly-bound or oxygen atom, X¹It is formula-CR¹⁵R¹⁶R¹⁷Second or tertiary alkyl groups, the metal cation of monovalent, ammonium cation (such as NR^b ₃ ⁺, wherein, each R^bIt is hydrogen, C independently₁-C₁₂Alkyl or C₆-C₁₈Aryl) or (such as PR^b ₄ ⁺, wherein, each R^bIt is hydrogen, C independently₁-C₁₂Alkyl 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 be hydrogen atom, and m is the integer of 1 to 4, and condition is to work as Y¹When being singly-bound, the X of the amount of all of m¹Can not be the metal cation of monovalent, formula⁺X²-A²-Y¹-SO₃ ^-Compound, wherein, A²It is divalent hydrocarbyl mission,⁺X²Be second, uncle or quaternary ammonium cation or second (such as, uncle or season 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-C₄₀Alkyl,⁺X³It is second, uncle or quaternary ammonium cation (such as, NR^b ₃ ⁺, wherein, each R^bIt is hydrogen, C independently₁-C₁₂Alkyl or C₆-C₈Aryl) or second, uncle or season cation (such as, PR^b ₄ ⁺, wherein, each R^bIt is hydrogen, C independently₁-C₁₂Alkyl or C₆-C₈Aryl), R is the C of unit price₁-C₄₀Alkyl, n are the integers of 2 to 4, and Y¹It is singly-bound or oxygen atom, formula A⁵-Ad¹-A⁴-(Ad²-A⁵)_lCompound, wherein, A⁵It is the C of unit price or bivalence₁-C₄₀Alkyl, A⁴It is the C of bivalence₁-C₄₀Alkyl, Ad¹And Ad²It is chosen from-SO independently of one another₂-O-SO₂-、-SO₂-O-CO-and-CO-O-SO₂-anhydride group, and l is 0 or 1, and condition is when l is 0 ,-(Ad²-A⁵)_lIt is hydrogen atom or A⁴And A⁵Between key, wherein, A⁵It is divalent hydrocarbyl mission or singly-bound, there is formula R_aR_bN-A-SO₃R_cSulfamate, wherein, R_aAnd R_bIt is hydrogen, C independently of one another₁-C₁₂Alkyl, C₆-C₂₂Aryl, C₇-C₁₉Alkaryl or R_aAnd R_bAromatic series or non-aromatic heterocyclic compound (such as pyrrole radicals, pyridine radicals, pyrimidine radicals, pyrazinyl, carbazyl, quinolyl, imidazole radicals, piperazinyl, azoles base, thiazolyl, pyrazolyl, pyrrolinyl, indyl, purine radicals, pyrrolidinyl etc.), R is formed either individually or in combination with N_cIt is hydrogen, and A is C₁-C₁₂Alkyl, C₆-C₂₂Aryl or C₇-C₁₉Alkaryl (such as, compound, such as N-(2-hydroxyethyl) piperazine-N'-3-propane sulfonic acid, Isosorbide-5-Nitrae-piperazine double; two (ethyl sulfonic acid) and 5-dimethylamino-1-naphthyl sulphonic acids), formula R_aR_bR_cN⁺-A-SO₃ ^-Ammonium sulphonic acid ester, wherein, R_a、R_bIt is hydrogen, C independently of one another₁-C₁₂Alkyl, C₁-C₁₂Aryl, C₇-C₁₉Alkaryl or R_aAnd R_bAromatic series or non-aromatic heterocyclic compound is formed (such as either individually or in combination with N, pyrrole radicals, pyridine radicals, pyrimidine radicals, pyrazinyl, carbazyl, quinolyl, imidazole radicals, piperazinyl, azoles base, thiazolyl, pyrazolyl, pyrrolinyl, indyl, purine radicals, pyrrolidinyl etc.), R_cIt is hydrogen and A is C₁-C₁₂Alkyl, C₆-C₂₂Aryl or C₇-C₁₉Alkaryl, sulfonated polystyrene, acrylic acid methyl ester .-sulfonated phenylethylene copolymer and comprise aforementioned at least one combination.

Quencher compositions can add with solid or liquid form. When being in liquid form, quencher compositions is passable, for instance added by add-on system. Add-on system can include the first rotary drum (cylinder, drum); Buffering drum (dsah-pot, bufferdrum); Dosing pump; Filter; Syringe or include one or more combination aforementioned, wherein, one or two of the first rotary drum and buffering drum can include agitator and/or heating system. For example, it is possible to quencher and liquid-carrier are added the first rotary drum and are subsequently adding buffering drum. Can by liquid quencher compositions from buffering drum by be arranged in polymerized unit, reactor, transmission line, blender and extruder one or more in infusion appliance be injected to paradigmatic system. Quencher compositions pump can be controlled by main dispensing loop (maindistributionloop) to dosing pump, wherein can monitor the interpolation of quencher compositions constantly or intermittently with effusion meter. This pump may further include the controller of the amount monitoring and adjusting the quencher compositions to polymerized unit for automatization's effusion meter. More than or equal to 2 bars, 3 bars can be specifically greater than or equal to, more particularly under the pressure of 3 to 100 bars, liquid quencher compositions is being added into Merlon. Again may be by the liquid jet (spraying, spray) is added liquid quencher compositions in solid polycarbonate substrate. Liquid quencher compositions can be filtered before it adds paradigmatic system.

When being in solid form, quencher compositions can comprise quencher and optional solid carrier, for instance polycarbonate powder, wherein, polycarbonate powder can comprise, for instance, it is in melt polycarbonate and/or the interfacial polycarbonate of powder type as described in this article. When being in solid form, solid quencher compositions is only passable, for instance with masterbatch or by spraying to being directly added into extruder and/or downstream in solid polycarbonate substrate. Similarly, solid quencher compositions can pass through feeder, for instance feed screw (feed screw, screwfeeder) adds. Especially, the method for adding solid quencher compositions can include melt polycarbonate pelletize to form Merlon; Merlon is fed to extruder; Solid quencher compositions is added into Merlon; And quencher compositions was mixed the time period more than or equal to 5 seconds with Merlon before adding any reactive additive to Merlon, wherein, reactive additive has reactive OH group or reactive ester group. Melt polycarbonate before solid quencher compositions can added.

Solid quencher compositions can comprise 0.1 to the 100wt% of the gross weight based on solid quencher compositions, especially the quencher of 10 to 99wt%.

When being in liquid form, quencher compositions can comprise liquid-carrier. Liquid-carrier can comprise low boiling point solvent, so that the boiling point of low boiling point solvent is less than the boiling point of the quencher being present in quencher compositions. Such as, if quencher comprises butyl tosylate, then low boiling point solvent can have the boiling point less than 140 DEG C. Low boiling point solvent can be when the temperature and pressure of extruder, for instance does not substantially react with Merlon under high-temperature vacuum. Low boiling point solvent can be able to dissolve quencher. Low boiling point solvent can comprise dimethylbenzene, toluene, benzene, ethylbenzene, methyl phenyl ethers anisole, chlorobenzene, and comprises one or more combination aforementioned. Low boiling point solvent can comprise water, organic solvent (such as acetone), or comprises one or both combination aforementioned.

Liquid-carrier can comprise high boiling solvent so that the boiling point of high boiling solvent is more than or equal to the boiling point of the quencher being present in quencher compositions. Such as, if quencher comprises butyl p-toluenesulfonate, then low boiling point solvent can have the boiling point more than or equal to 140 DEG C. High boiling solvent can comprise the compound being present in melt polymerization. Such as, in the melt polymerization of bisphenol A polycarbonate, high boiling solvent can comprise diphenyl carbonate, phenol, bisphenol-A, polycarbonate oligomer, bisphenol-a derivative, propylene carbonate (propylene glycol carbonate, propylenecarbonate) or comprise one or more combination aforementioned.

If low boiling point solvent and high boiling solvent both exist, then they can dissolve each other each other. In quencher compositions, low boiling point solvent can be 4:1 to 1:4, especially 2:1 to 1:2, more particularly 1.5:1 to 1:1.5 with the ratio of high boiling solvent. Similarly, quencher compositions can without liquid-carrier.

Liquid quencher compositions can comprise with 0.1 to the 99wt% of the gross weight based on liquid quencher compositions, 1 to 50wt% especially, more particularly the quencher of 1 to 20wt%.

Similarly, quencher compositions can without carrier. Such as, quencher compositions can include quencher, additive, and does not have carrier; For example, it is possible to be made up of quencher and optional additive. Quencher can add as melted (namely melting) quencher. When quencher compositions is without carrier, quencher compositions can comprise the quencher of 0.1 to the 100wt% of the gross weight based on carrier-free quencher compositions.

Quencher with 5 weight portions (ppm) more than or equal to every million parts of the total amount based on Merlon, can be specifically greater than or equal to the amount of 10ppm and add. Quencher can with the total amount based on Merlon less than or equal to 5ppm, the amount being especially less than or equal to 10ppm adds. Quencher compositions can be added polymerized unit so that quencher is with 0.5 to the 15ppm of the gross weight based on Merlon, and 1 to 10ppm especially, more particularly 1.5 to 5ppm, specifically the amount of 1.5 to 3ppm adds. Likewise it is possible to quencher compositions is added into polymerized unit so that with 5 to the 10ppm of the gross weight based on Merlon, the amount of 6 to 8ppm adds quencher especially. Likewise it is possible to addition quencher so that quencher or derivatives thereof is with 0.1 to 50 times, and the amount of the catalyst of the use of 0.5 to 30 times of every neutralization equivalent exists especially.

Quencher compositions can add the one or more positions in the melted preparation of Merlon. Such as, quencher compositions can add polymerized unit upstream, be directly added into polymerized unit (such as in porch, in the charging aperture of side, in outlet or include one or more combination aforementioned), the downstream of polymerized unit, add be not polymerized the reactor of Merlon, extruder upstream, be directly added into extruder (such as, at the feed throat place of extruder, in the charging aperture of side, in outlet or include one or more combination aforementioned), the downstream of extruder or include one or more combination aforementioned. When adding the upstream of extruder, it is possible to quencher compositions is added the upstream of final polymerized unit and/or adds among final polymerized unit and/or after final polymerized unit. Quencher compositions can be added among final polymerized unit. Quencher compositions can be added the outlet of the first polymerized unit, the outlet of the second polymerized unit, reactor between final polymerized unit and extruder, extruder or include one or more combination aforementioned. Likewise it is possible to a certain amount of quencher compositions is added and/or after one or more stage feeding polymerization unit and/or among final extruder. For example, it is possible to quencher compositions is added after initial polymerization unit, then can add fresh catalyst, and other quencher can be added after polymerization further.

Polymerization can include parallel polymerization and (be polymerized parallel, parallelpolymerization) part (section, section), wherein, parallel polymerization refers to and polycarbonate flow is divided into 2 or more stream, it hereafter can or can without undergoing identical polymerizing condition (namely they can reach different molecular weight, has addition different additive etc. therein). For example, it is possible to prepare Merlon in the Part I of polymerization process; Can be two or more stream by the flow point comprising Merlon and guide to 2 or more parallel operation line. Such as, method can include polymerization Merlon in a series of oligomeric polymerized unit; Can be two kinds of stream: A and B by the flow point that the oligomeric stage discharges, wherein, A stream be guided to polymerized unit A and B stream is guided to polymerized unit B. Similarly, method can include polymerization Merlon in a series of oligomeric unit, is polymerized subsequently in a series of polymerized unit; The flow point that can be discharged by polymerization stage is two kinds of stream: A and B, wherein, guides A stream to extruder A, and guides B stream to extruder B. Similarly, method can include polymerization Merlon in a series of oligomeric unit, is polymerized subsequently in a series of polymerized unit; The flow point that can be discharged by the first polymerized unit is two plume: A and B, wherein, is guided by A stream to the second polymerized unit A and guides B stream to the second polymerized unit B. In any aforementioned circumstances, it is possible to quencher compositions is added into stream A and B one or two, wherein, quencher compositions can be identical or different. Those skilled in the art can easily be contemplated to other embodiments including more than two concurrent flow and the embodiment wherein separately flowed in different positions.

When quencher compositions being added into polymerized unit and/or extruder, quencher compositions is passable, such as mix alternatively by Henschel mixer (Henschelmixer), and introduce to feeder, such as gravity-feeder, and then pass through feeder, as side feeder is fed to polymerized unit and/or extruder and/or is directly fed in the feed throat of extruder.

When quencher compositions being added into the connection stream connecting first module and second unit, the connection stream of the quencher compositions then comprising addition can pass through, such as set up turbulent flow (line mixer (on-line mixing device, in-linemixer)), such as it is arranged in the static mixer containing the pipeline connecting stream and/or holds the mixer unit rotating oar, for instance the static mixer mixing in continuously stirred groove. Mixing can occur 0.3 to 5 minute, for instance 0.5 to 3 minute, for instance 1 to 2 minute. It is added into connection stream likewise it is possible to do not mixed by quencher compositions.

After polycarbonate compositions is formed, namely can add quencher compositions after extrusion and/or melt filteration. Such as, after preparing polycarbonate compositions, it is possible to polycarbonate compositions and quencher compositions are existed, for instance mixing in line mixer, bitubular agitator etc., and then pelletize. Likewise it is possible to first by polycarbonate compositions pelletize and then can introduce quencher compositions. Can pass through, for instance flowing or injection, with solid or liquid form, quencher compositions be added on polycarbonate pellet and can mix with pellet in such as melt kneading machine alternatively. In this case, it is possible to after introducing quencher compositions, introduce additive. Such as, granular (pelletized) Merlon, for instance without the granular Merlon of additive, it is possible to be combined with quencher compositions and antioxidant and/or releasing agent can be subsequently adding.

Can by polycarbonate compositions devolatilization to remove low-molecular-weight (as having less than or equal to those of 1,000 daltonian molecular weight). Devolatilization can occur in polymerized unit (such as, in polymerized unit), in reactor, in extruder, in blender or in including one or more combination aforementioned. Merlon can quencher before devolatilization. For example, it is possible to quencher is added extruder upstream and/or is directly added into extruder, it is possible to by extruder devolatilization, it is possible to add additive.

It should be noted that and some water can be added extruder 4 with devolatilization polycarbonate compositions. The amount of the water that can introduce can be 0.1 to the 10wt%, 0.3 to 5wt% especially of the gross weight based on polycarbonate compositions.

Fig. 1 illustrates the method that quencher compositions is added into paradigmatic system. Especially, Fig. 1 illustrates, quencher compositions can pass through one or more quencher stream 40-50 and add, and wherein quencher stream 40-50 can be liquid quencher stream and quencher stream 46-50 can be solid quencher stream. For example, it is possible to quencher stream 40 to be added into stream 20, and can then stream 20 be mixed alternatively in blender 10; Quencher stream 42 can being added into reactor unit 2, wherein, reactor unit 2 can be one or more of the first aggregation container, middle aggregation container, final aggregation container and the post-reactor being positioned at final aggregation container; Quencher stream 44 can be added into aggregated flow 22, and can then aggregated flow 22 be mixed alternatively in blender 10; Quencher stream 46 can be added into extruder 4 by extruder feed throat 8; Quencher stream 48 can be added into extruder 4 by surveying charging aperture 12; And quencher stream 50 can be added extrudate flow 24 and can mix in blender 10 alternatively. Extrudate flow 24 can be fed to fondant filter 6 to form polycarbonate compositions stream 26. Blender 10 is it may be that such as line mixer, turbulent flow or continuously stirred unit. It should be noted that fondant filter 6 can be equally located on the upstream of extruder 4 and can add quencher compositions before or after this fondant filter. It should also be noted that, although stream 42,56 and 58 is illustrated into the corresponding side of container, it is readily appreciated that these streams can enter container in any suitable position.

Fig. 1 additionally illustrates the method for the polycarbonate compositions that quencher compositions is added into further pelletize. Especially, Fig. 1 illustrates that can pass through one or more quencher stream 52-58 adds quencher compositions, and wherein, quencher stream 52-58 can be solid quencher stream or liquid quencher stream. For example, it is possible to quencher stream 52 is added into optional blender 14, wherein, optional blender 14 is it may be that such as line mixer, turbulent flow or continuously stirred unit (such as twin-barrel extruder); Can by quencher stream 56, for instance add comminutor 16 at the feed throat place of comminutor; Can by quencher stream 58, for instance by by quencher compositions injection to the pellet formed, being added into pelletize stream 30. Although it should be noted that quencher stream 56 and 58 is illustrated into the corresponding side of container, it is readily appreciated that these streams can enter container in any suitable position. Indicating in accompanying drawing, stream 40,44 and 26 includes for other potential processes, such as the mark of the position of the polymerized unit being likely to occur, transmitting step and purifying step.

Additive additionally can be added in one or more positions of the melted preparation of the Merlon of the present invention. Such as, additive can be added polymerized unit upstream, be directly added in polymerized unit (such as in porch, in the charging aperture of side, in outlet or include one or more combination aforementioned), polymerized unit downstream, be not polymerized in the reactor of Merlon, extruder upstream, be directly added in extruder (such as, at the feed throat place of extruder, in the charging aperture of side, in outlet or include one or more combination aforementioned), extruder downstream or include one or more combination aforementioned. Can using additive partially adding and/or can be individually added into as quencher compositions. For example, it is possible to the quencher compositions comprising heat stabilizer to be added into Merlon, and the compositions of additives comprising releasing agent and UV reagent can be added into the compositions of quencher. Additive can be added with molten condition or can add after melting at the Merlon of extrusion. Before being added into polymerized unit, additive can be filtered.

Additive can comprise, such as impact modifier, flow ability modifying agent, filler is (such as, granule politef (PTFE), glass, carbon, mineral, or metal), reinforcing agent is (such as, glass fibre), antioxidant, heat stabilizer, light stabilizer, ultraviolet (UV) reagent (as, UV light stabilizer and UV absorbing additives), plasticizer, lubricant, release agent (as, releasing agent is (such as glyceryl monostearate, stearic acid pentaerythritol ester, glyceryl tristearate, stearyl stearate etc.)), antistatic additive, antifoggant, antifreezing agent (antifrostagent), antimicrobial, coloring agent is (such as, dyestuff or pigment), skin effect additive, stable radiation agent, fire retardant, anti-dripping agent is (such as, the SAN (TSAN) of PTFE encapsulation), or comprise one or more combination aforementioned. it is, for example possible to use the combination of heat stabilizer, releasing agent and UV light stabilizing agent. generally, the additive of commonly known effective amount can be used. such as, the total amount of compositions of additives is (except any impact modifier, filler, or reinforcing agent) can be 0.001 to 10.0 percetage by weight (wt%) of the gross weight being each based in polymeric compositions polymer, or 0.01 to 5wt%.

Heat stabilizer additive includes organic phosphite (such as, triphenyl phosphite, three-(2,6-3,5-dimethylphenyl) phosphite ester, three-(list of mixing-and two-nonyl phenyl) phosphite esters etc.), phosphonate ester (such as, dimethylbenene phosphonate etc.), phosphate ester (such as, trimethyl phosphate etc.) or comprise combination at least one in aforementioned heat stabilizer. Heat stabilizer can comprise can as IRGAPHOS^TM168 three (2,4-di-tert-butyl-phenyl) phosphate esters obtained. Heat stabilizer can comprise IRGAPHOS^TM205. Heat stabilizer is generally to use based on the amount of 0.01 to the 5wt% of the gross weight of polymer in compositions.

Term " antistatic additive " refers to and can be processed as polymer and/or be injected on material or goods to improve the monomer of conductive characteristic and overall physical properties, oligomeric or polymeric material. The example of monomeric antistatic agents includes ethoxylated amine, primary, secondary and tertiary amine, ethoxylated alcohol, alkyl sulfate, alkaryl sulfate, alkyl microcosmic salt, alkyl amino sulfate, alkylsulfonate; such as stearoyl acyl sodium sulfonate, dodecylbenzene sodium sulfonate etc., quaternary ammonium salt, quaternary ammonium polymer, imidazolidine derivatives, sorbitan ester, glycollic amide, glycine betaine etc., or comprise combination at least one in aforementioned monomer antistatic additive.

Polymer antistatic agent comprises specific polyesteramide, polyphenylene ether-polyamide (polyetheramides) block copolymer, polyetheresteramide block's copolymer, polyether ester, or polyurethane, each containing polyalkylene glycol moiety polyalkylene oxide units, such as Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol etc. This polymer antistatic agent is commercially available, for instance PELESTAT^TM6321 (Sanyo) or PEBAX^TMMH1657(Atofina)、IRGASTAT^TMP18 and P22 (Ciba-Geigy). Can serve as other polymeric material of antistatic additive is intrinsic conduction polymer, as polyaniline (can as PANIPOL^TMEB is commercially available from Panipol), polypyrrole and polythiophene (available commercially from Bayer), it keeps some their intrinsic conductivities after melt-processed at elevated temperatures. In embodiments, carbon fiber, carbon nano-fiber, CNT, white carbon black, or comprise aforementioned at least one combination and may be used for polymer composition, it contains chemistry antistatic additive so that said composition is electrostatic dissipation.

Can also there is stable radiation agent, especially, γ-stable radiation agent. γ-stable radiation agent includes alkylidene polyol, such as ethylene glycol, propylene glycol, 1,3-PD, 1,2-butanediol, BDO, meso-2,3-butanediol, 1,2-pentanediol, 2,3-pentanediols, Isosorbide-5-Nitrae-pentanediol, Isosorbide-5-Nitrae-hexanediol etc.; Cycloalkylidene polyhydric alcohol, such as 1,2-ring pentanediol, 1,2-cyclohexanediol etc.; Branched alkylen polylol, such as Pinacol (pinacol) etc., and the ring-type that replaces of alkoxyl or acyclic alkanes. Unsaturated enol can also be used, the example include 4-methyl-4-amylene-2-alcohol, 3-methyl pentene-3-alcohol, 2-methyl-4-amylene-2-alcohol, 2,4-dimethyl-4-amylene (pene)-2-alcohol and 9-decen-1-ol and there is the tertiary alcohol of the tertiary carbon that at least one hydroxyl replaces, such as 2-methyl-2,4-pentanediol (hexanediol), 2-phenyl-2-butanol, 3-hydroxy-3-methyl-2-butanone, 2-phenyl-2-butanol etc., and the ring tertiary alcohol, such as 1-hydroxyl-1-methyl-cyclohexyl alkane. The saturated carbon of the unsaturated carbon that can also be used in being connected in aromatic ring has the specific methylol aromatic compounds that hydroxyl replaces. The saturated carbon that hydroxyl replaces can be methylol groups (-CH₂OH) or its can be more complicated alkyl, such as-CR⁴HOH or-CR₂ ⁴Member in OH, wherein, R⁴It is complicated or simple hydrocarbons. Specific hydroxymethyl aromatic compound includes benzhydrol, 1,3-benzene dimethanol, benzylalcohol, 4-benzyloxybenzyl alcohol and benzyl benzylalcohol. 2-methyl-2,4-PD, Polyethylene Glycol and polypropylene glycol are frequently used for γ-stable radiation.

Toner can also be there is, such as pigment and/or dye additive. Useful pigment can include, for instance inorganic pigment, such as the metal-oxide of metal-oxide and mixing, such as zinc oxide, titanium dioxide, ferrum oxide etc.; Sulfide, such as zinc sulfide etc.; Aluminate; Sulfo group-silicic acid sodium sulfate, sodium chromate etc.; White carbon black; Zinc ferrite; Ultramarine; Organic pigment, as azo, two azos, quinacridone, naphthalene tetracarboxylic acid, flavanthrone, isoindolinone, tetrachloroisoindolinone, anthraquinone, anthrone, dioxazines, phthalocyanine and azo lake; Paratonere 101, pigment red 122, pigment red 149, paratonere 177, pigment red179, paratonere 202, pigment violet 29, pigment blue 15, pigment blue 60, pigment Green 7, pigment yellow 119, pigment yellow 147, pigment yellow 150 and pigment brown 24; Or comprise the combination of aforesaid at least one pigment.

Dyestuff is usually organic material and includes coumarine dye, such as coumarin 460 (blueness), coumarin 6 (green), Nile red etc.; Lanthanide series complex; The hydrocarbon dyestuff of hydrocarbon and replacement; Ppolynuclear aromatic hydrocarbon dyestuff; Scintillation dyes, such as azoles or two thiiazole dyes; Poly-(the C that aryl or heteroaryl replace_2-8) alkene dyestuff; Carbonyl cyanine dye; Indanthrone dyes; Phthalocyanine dye; Piperazine dyestuff; Hydroxyquinoline dye; Naphthalene tetracarboxylic acid dyestuff; Porphyrin dye; Double; two (styryl) biphenyl dyestuff; Acridine dye; Anthraquinone dye; Cyanine dye; Methine dyes; Arylmethane dyes; Azo dye; Bipseudoindoxyl dye; Thioindigo color; Diazo colours; Nitro dye; Quinoneimine dye; Aminoketone dye; Tetrazolium dye; Thiazole dye; Perylene dyes; Cyclic ketones dyestuff; Double; two benzoxazoles thiophene (BBOT); Triarylmethane dye; Thioxanthene dye; Naphthalimide dye; Lactone colouring matters; Fluorogen, as absorbed near-infrared wavelength and launching anti-stoke shift (anti-stokesshift) dyestuff etc. of visible wavelength; Luminescent dye, such as 7-amino-4-methylcoumarin; 3-(2'-benzothiazolyl)-7-diethyl amino coumarin; 2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1,3,4-diazole; 2,5-pair-(4-xenyl)-azoles; 2,2'-dimethyl-to quaterphenyl; 2,2-dimethyl-para-terpheny; 3,5,3 " ", 5 " "-tetra-terts-to quinquephenyl; 2,5-diphenyl furan; 2,5-diphenyloxazole; 4,4'-diphenyl stilbene; 4-dicyano methylene-2-methyl-6-(to dimethylaminostyryl)-4H-pyrans; 1,1'-diethyl-2,2'-carbocyanine iodide; 3,3 '-diethyl-4,4 ', 5,5 '-bisbenzothiazole three carbocyanine iodide (dibenzothiatricarbocyanineiodide); 7-dimethylamino-1-methyl-4-methoxyl group-8-azepine quinolinones-2; 7-dimethyl amido-4-methyl quinolinones-2; 2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3-ethyl-benzothiazole perchlorate; 3-diethylamino-7-diethyl imino group azophenlyene perchlorate (3-diethylamino-7-diethyliminophenoxazoniumperchlorate); 2-(1-naphthyl)-5-phenyl azoles; 2,2'-is to phenylene-bis-(5-phenyl azoles); Rhodamine 700; Rhodamine 800; Pyrene,Rubrene, coronene etc.; Or comprise combination at least one in abovementioned dyes.

Possible filler or reinforcing agent include, such as Muscovitum, clay, Anhydrite, quartz, quartzite, perlite, tripoli (tripoli), kieselguhr (diatomaceousearth), aluminium silicate (mullite), synthetic calcium silicate, fused silica, aerosil, husky (sand), boron-nitride powder, boron-silicate powder, calcium sulfate, calcium carbonate is (such as Chalk, limestone, marble, winnofil with synthesis), Talcum (includes fiber, module, needle-like, and lamella talc), wollastonite, hollow or solid glass ball, silicate ball, cenosphere, aluminosilicate or (armouring ball (armosphere)), Kaolin, the whisker of carborundum, aluminium oxide, boron carbide, ferrum, nickel or copper, the carbon fiber of continuous print and chopped or glass fibre, molybdenum sulfide, zinc sulfide, Barium metatitanate., Barium hexaferrite, barium sulfate, barite, TiO₂, aluminium oxide, magnesium oxide, granule or fiber aluminum, bronze, zinc, copper, or nickel, sheet glass, thin slice carborundum, lamellar aluminium diboride, flaky aluminum, steel disc, natural stuffing, such as wood flour, fibrous cellulose, Cotton Gossypii, Folium Agaves Sisalanae, Corchorus olitorius L., starch, lignin, shuck (the Semen arachidis hypogaeae shell ground, groundnutshell), or grain of rice shell, strengthen organic fibrous fillers, such as poly-(ether ketone), polyimides, polybenzoxazole, poly-(diphenyl sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, Polyetherimide, politef, with poly-(vinyl alcohol), and comprise combination at least one in aforementioned filler or reinforcing agent. filler and reinforcing agent can be coated with coated with promoting electric conductivity with metal material layer, or with silane surface treatment to improve adhesiveness and the dispersibility of itself and polymeric matrix. filler is used with the amount of 1 weight portion of the total composition based on 100 weight portions to 200 weight portions.

Antioxidant includes organic phosphite, as three (nonyl phenyl) phosphite ester, three (2,4-di-tert-butyl-phenyl) phosphite ester, double; two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, Distearyl pentaerythritol; Alkylating monohydric phenol or polyphenol; The hydrocarbyl reaction product of polyphenol and diene, such as four [methylene (3,5-di-t-butyl-4-hydroxy hydrocinnamate)] methane; The butylation product of paracresol or bicyclopentadiene; Alkvlated hvdroquinones; Hydroxylated thiodiphenyl ethers; Alkylidenebisphenols; Benzyl compounds; The ester of β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid and unitary or polyhydric alcohol; The ester of β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl)-propanoic acid and unitary or polyhydric alcohol; The ester of alkylthio or thioaryl compounds, such as propane thioic acid distearyl acyl ester, propane thioic acid dilauroyl ester, thio-2 acid double tridecyl ester, octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, pentaerythrityl-four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester; The amide of β-(3,5-di-tert-butyl-hydroxy phenyl)-propanoic acid, or comprise combination at least one in aforementioned antioxidant. Antioxidant can be used with the amount of 0.01 to 0.1 weight portion of the total composition except any filler based on 100 weight portions.

UV absorbing additives includes dihydroxy benaophenonel; Hydroxybenzotriazole; Hydroxy benzo triazine; Cyanoacrylate; Oxanilide; Benzoxazinone; Salicylic acid aromatic ester; The monoesters of diphenol, such as resorcinol monobenzoate; 2-(2H-benzotriazole-2-base)-4-(1,1,3,3-tetramethyl butyl)-phenol (CYASORB^TM5411); Octabenzone (CYASORB^TM531); 2-[double; two (2,4-the 3,5-dimethylphenyl)-1,3,5-triazine-2-base of 4,6-]-5-(octyloxy)-phenol (CYASORB^TM1164); 2,2'-(1,4-phenylene) double; two (4H-3,1-benzimidazole dihydrochloride-4-ketone) (CYASORB^TMUV-3638); Poly-[(6-morpholinyl-s-triazine-2,4-two base) [2,2,6,6-tetramethyl-4-piperidyl) imino group]-hexa-methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino group], 2-hydroxyl-4-octyloxybenzophenone (UVINUL^TM3008), the 6-tert-butyl group-2-(5-chloro-2H-benzotriazole-2-base)-4-aminomethyl phenyl (UVINUL^TM3026), 2,4-di-t-butyl-6-(5-chloro-2H-benzotriazole-2-base)-phenol (UVINUL^TM3027), 2-(2H-benzotriazole-2-base) tertiary phenylphenol (UVINUL of-4,6-two^TM3028), 2-(2H-benzotriazole-2-base)-4-(1,1,3,3-tetramethyl butyl)-phenol (UVINUL^TM3029), 1,3-pair [(2' cyano group-3', 3'-diphenylacryloyl) oxygen]-2,2-pair-[2'-cyano group-3', 3'-diphenylacryloyl) oxygen] methyl }-propane (UVINUL^TM3030), 2-(2H-benzotriazole-2-base)-4-methylphenol (UVINUL^TM3033), double; two (1-methyl isophthalic acid-phenylethyl) phenol (UVINUL of 2-(2H-benzotriazole-2-base)-4,6-^TM3034), ethyl-2-cyano group-3,3-diphenylacrylate ester (UVINUL^TM3035), (2-ethylhexyl)-2-cyano group-3,3-diphenylacrylate ester (UVINUL^TM3039), double; two (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine (UVINUL of N, N'-double; two formyl-N, N'-^TM4050H), double; two-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (UVINUL^TM4077H), double; two-(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate+methyl-(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate (UVINUL^TM4092H), double; two [[(2-cyano group-3,3-diphenylacryloyl) oxygen] methyl] propane (UVINUL of double; two [(2-cyano group-3,3-diphenylacryloyl) the oxygen]-2,2-of 1,3-^TM3030); 2,2'-(1,4-phenylene) double; two (4H-3,1-benzimidazole dihydrochloride-4-ketone); Double; two [[(2-cyano group-3,3-diphenylacryloyl) oxygen] methyl] propane of double; two [(2-cyano group-3,3-diphenylacryloyl) oxygen] 2,2-of 1,3-; TINUVIN^TM234; Nano-sized inorganic material, such as titanium dioxide, cerium oxide and zinc oxide, is respectively provided with the particle diameter less than or equal to 100 nanometers; Etc., or comprise combination at least one in aforementioned UV absorbent. UV absorbent can be used with the amount based on 0.01 to 1 weight portion of the Merlon of 100 weight portions and impact modifier. The UV absorbent that can use together with polycarbonate compositions disclosed herein especially includes 2-(2H-benzotriazole-2-base)-4-(1,1,3,3-tetramethyl butyl)-phenol (such as, CYASORB^TM5411, available commercially from CytecIndustries, Inc., WoodlandPark, NewJersey) and 2,2'-(Isosorbide-5-Nitrae-phenylenes) double; two (4H-3,1-benzimidazole dihydrochloride-4-ketone) (such as CYASORB^TMUV-3638, available commercially from CytecIndustries, Inc., WoodlandPark, NewJersey), and comprise aforementioned at least one combination. UV stabilizer with 0.01 of the gross weight based on polycarbonate compositions to 1wt%, 0.1 can arrive 0.5wt% especially, and more particularly 0.15 to 0.4wt% amount exist.

Plasticizer, lubricant and/or releasing agent can also be used. There is considerable overlap among the material of these types, it includes, phthalic acid ester, such as dioctyl-4,5-epoxy radicals-hexahydrophthalic acid ester; Three-(octoxycarbonylethyl) cyanurates; Glyceryl tristearate; Two or multi-functional aromatic phosphoric ester, such as double; two (diphenyl) phosphate esters of resorcinol tetraphenyldiphosphate (RDP), double; two (diphenyl) phosphate esters of hydroquinone and bisphenol-A; Polyalphaolefin; Epoxidised soybean oil; Silicone, including silicone oil; Ester, for instance fatty acid ester, such as alkyl stearates, for instance methyl stearate, stearyl stearate, pentaerythritol tetrastearate etc.; The combination of methyl stearate and hydrophilic and Hydrophobic nonionic surfactant, including polyethylene glycol polymer, polypropylene glycol polymers, poly-(ethylene glycol-co-propylene glycol) copolymer, or comprise combination at least one in aforementioned ethylene glycol polymer, for instance the applicable methyl stearate in solvent and polyethylene glycol propylene glycol copolymers; Wax, such as Cera Flava, lignite wax, paraffin etc.

Plasticizer, lubricant and/or releasing agent can the compounds of contained (I)

Wherein, R₁、R₂, and R₃Can be identical or different, there is the hydrocarbon chain of degree of unsaturation of 8 to 20 carbon atoms and 0 to 6, wherein R₁、R₂, and R₃It is each independently selected from C₈-C₂₀Alkyl, C₈-C₂₀Haloalkyl, C₈-C₂₀Multi-haloalkyl, C₈-C₂₀Alkene and C₈-C₂₀Alkoxyl. R₁、R₂And R₃Can independently of one another from C₁₇H₃₅, or all of R₁、R₂, and R₃Can be C₁₇H₃₅. Plasticizer, lubricant and/or releasing agent can comprise glyceryl monostearate, monopalmitin, glyceryl tristearate, glyceryl tristearate, stearyl stearate or comprise one or more combination aforementioned. Aforesaid one or more can have the acid number by 2 to 20 milligrams of (mg) KOH identified below: the isopropanol of 100 milliliters (ml) adds the partial ester of 2.5 grams (g) thus dissolving this partial ester; Phenolphthalein is added into the solution of acquisition as indicator; Use the mixture that the standard potassium hydroxide solution titration of 0.1 mol/L (mol/L) obtains thus obtaining acid number (mgKOH). In the measurement of acid number, when expecting that partial ester has 1 or less acid number, it is 20g by the quantitative change of partial ester standing to measure; When expecting that partial ester has the acid number of 1 to 4, it is 10g by the quantitative change of partial ester standing to measure; And when expecting that partial ester has the acid number of 15 or higher, it is 0.5g by the quantitative change of partial ester standing to measure.

Plasticizer, lubricant and/or releasing agent can with 0.01 to 5 weight portions based on the Merlon of 100 weight portions and impact modifier, and the amount of 0.01 to 0.1 weight portion exists especially.

Useful fire retardant includes the organic compound comprising phosphorus, bromine and/or chlorine. Non-brominated and non-chlorinated phosphonium flame retardant can be preferred for the reason regulated in specific applications, for instance organophosphorus ester and the organic compound containing phosphorus-to-nitrogen bonds.

Fire retardant aromatic phosphoric ester includes triphenyl phosphate, tricresyl phosphate, isopropylation triphenyl phosphate, double, two (dodecyl) phosphate ester of phenyl, double, two (neopentyl) ester of phosphoric acid phenyl, phosphoric acid phenyl double, two (3, 5, 5'-trimethyl) ester, ethyl diphenyl ester, phosphoric acid 2-ethylhexyl two (p-methylphenyl) ester, double, two (2-ethylhexyl) the p-methylphenyl ester of phosphoric acid, tricresyl phosphate, double, two (2-ethylhexyl) phenyl ester of phosphoric acid, tricresyl phosphate (nonyl phenyl) ester, double, two (dodecyl) the p-methylphenyl ester of phosphoric acid, di(2-ethylhexyl)phosphate butyl phenyl ester, phosphoric acid 2-chloroethyl diphenyl, phosphoric acid p-methylphenyl double, two (2, 5, 5'-trimethyl) ester, with phosphoric acid 2-ethylhexyl diphenyl phosphate. two or polyfunctional aromatic series phosphorus-containing compound be also useful, it is such as double, two (diphenyl) phosphate esters of resorcinol tetraphenyldiphosphate (RDP), double, two (diphenyl) phosphate esters of hydroquinone and bisphenol-A respectively, and they oligomer and polymer homologue. flame retardant compound containing phosphorus-to-nitrogen bonds includes phosphonium chloride nitrile, phosphide amide, phosphoamide, phosphonic acid amide, phosphinic acid amide and three (sub-third pyridine base) phosphine oxide. when deployed, phosphonium flame retardant with based on the 0.1-30 weight portion of the total composition except any filler of 100 weight portions, more particularly the amount of 1-20 weight portion exists.

Halogenated material is also used as fire retardant, for instance following bis-phenol is representational: 2,2-pairs-(3,5-Dichlorobenzene base)-propane; Double; two-(2-chlorphenyl)-methane; Double; two (2,6-dibromo phenyl)-methane; 1,1-pair-(3-iodophenyl)-ethane; 1,2-pair-(2,6-Dichlorobenzene base)-ethane; Double; two (the 2-chlorine-4-iodine phenyl) ethane of 1,1-; 1,1-pair-(the chloro-4-aminomethyl phenyl of 2-)-ethane; 1,1-pair-(3,5-Dichlorobenzene base)-ethane; 2,2-pair-(3-phenyl-4-bromophenyl)-ethane; 2,6-pair-(4,6-dichloro naphthyl)-propane;-(3,5-bis-chloro-4-hydroxy phenyl)-propane double; two with 2,2-; 2,2-pair-(3-bromo-4-hydroxy phenyl)-propane. Other halogenated material include 1,3-dichloro-benzenes, Isosorbide-5-Nitrae-dibromobenzene, 1, the chloro-4-hydroxy benzenes of 3-bis-and biphenyl, as 2,2'-DCBPs, many brominations Isosorbide-5-Nitrae-two phenoxy group benzene, 2,4'-'-dibromobiphenyl, 2,4'-DCBP and decabrominated dipheny base oxide, and oligomeric and polymerization halogenated aromatic compounds, such as bisphenol-A and tetrabromobisphenol A and carbonate precursor, such as, the Copolycarbonate of phosgene. Metal synergist, for instance stibium oxide, it is also possible to use together with fire retardant. When it is present, halogen-containing flame retardant with based on 1 to 25 weight portion of the total composition except any filler of 100 weight portions, more particularly the amount of 2 to 20 weight portions exists.

Inorganic combustion inhibitor can also be used, for instance C_1-16The salt of alkylsulfonate, such as potassium perfluorobutane sulfonate (Rimar Salt), potassium perfluoroctane sulfonate, perfluorohexanesulfonic acid etamon and potassium diphenylsulfone sulfonate; Salt, such as Na₂CO₃、K₂CO₃、MgCO₃、CaCO₃, and BaCO₃, or fluoro-anion complex, such as Li₃AlF₆、BaSiF₆、KBF₄、K₃AlF₆、KAlF₄、K₂SiF₆, and/or Na₃AlF₆. When it is present, inorganic combustion inhibitor salt is with 0.01 to 10 weight portion of the total composition except any filler based on 100 weight portions, and more particularly the amount of 0.02 to 1 weight portion exists.

Anti-dripping agent can be used for compositions, for instance the fluoropolymer that fibril is formed or non-protofibre is formed, such as politef (PTFE). Anti-dripping agent can by rigid copolymer, for instance SAN (SAN) encapsulates. The PTFE being encapsulated in SAN is called TSAN. Based on the gross weight of the fluoropolymer of encapsulation, TSAN comprises 50wt%PTFE and 50wt%SAN. Based on the gross weight of copolymer, SAN can comprise, for instance the styrene of 75wt% and the acrylonitrile of 25wt%. The total composition except any filler based on 100 weight portions, it is possible to use anti-drip agents with the amount of 0.1 weight portion to 10 weight portions.

The compositions of quencher can be substantially free of chlorine and bromine. " it is substantially free of chlorine and bromine " and is defined as the total weight parts based on the compositions except any filler, have less than or equal to every 1,000,000 weight portions (ppm), less than or equal to 75ppm or the bromine less than or equal to 50ppm and/or chlorinity.

The compositions of quencher can have as used sample thick for 3.2mm, uses ASTMD1003-00, program B, uses CIE standard illuminant C, the light transmission more than 90% determined with one way vision. Therefore, when the compositions of quencher has such light transmission, it is herein referred to as " optical-grade " compositions.

Embodiment 1: a kind of melt polymerization process, including: under carbon monoxide-olefin polymeric exists, melt polymerization thing is to form Merlon, and wherein, carbon monoxide-olefin polymeric comprises catalyst; Quencher compositions is added into Merlon, and wherein, quencher compositions comprises quencher; And Merlon is guided to extruder.

Embodiment 2: a kind of melt polymerization process, including: at least two polymerized unit, under carbon monoxide-olefin polymeric exists, melt polymerization thing is to form Merlon, and wherein, carbon monoxide-olefin polymeric comprises α catalyst; Combine to form quencher compositions in quencher container by liquid-carrier and quencher; Quencher compositions is added into Merlon under the pressure more than or equal to 2 bars; Before add any additive with reactive OH group or reactive ester group to Merlon, quencher compositions is mixed with Merlon the time period more than or equal to 5 seconds; And Merlon is guided to extruder.

Embodiment 3: according to the method any one of embodiment 1-2, wherein, quencher compositions comprises diphenyl carbonate.

Embodiment 4: the method according to embodiment 3, wherein, liquid-carrier comprises low boiling point solvent and/or high boiling solvent.

Embodiment 5: the method according to embodiment 4, wherein, liquid-carrier comprises low boiling point solvent and high boiling solvent, and the ratio of low boiling point solvent and high boiling solvent is 4:1 to 1:4.

Embodiment 6: according to the method any one of embodiment 3-5, wherein, liquid-carrier comprises the compound being present in melt polymerization.

Embodiment 7: according to the method any one of embodiment 3-6, wherein, liquid-carrier comprises diaryl carbonate, phenol, bisphenol-A, polycarbonate oligomer, bisphenol-a derivative, propylene carbonate or comprises one or more combination aforementioned.

Embodiment 8: according to the method any one of embodiment 3-7, wherein, liquid-carrier comprises dimethylbenzene, toluene, benzene, ethylbenzene, methyl phenyl ethers anisole, chlorobenzene or comprises one or more combination aforementioned.

Embodiment 9: according to the method any one of embodiment 3-8, wherein, liquid-carrier comprises toluene.

Embodiment 10: according to the method any one of embodiment 3-9, wherein, liquid-carrier comprises water, acetone or comprises one or more combination aforementioned.

Embodiment 11: a kind of melt polymerization process, including: at least two polymerized unit at melt polymerization thing, forming Merlon under carbon monoxide-olefin polymeric exists, wherein, carbon monoxide-olefin polymeric comprises α catalyst; Melted quencher is to form quencher compositions, and wherein, quencher compositions is without carrier; Quencher compositions is added Merlon; Merlon; And Merlon is guided to extruder.

Embodiment 12: according to the method any one of embodiment 1-11, wherein, occurs guiding to after extruder Merlon.

Embodiment 13: according to the method any one of embodiment 1-12, wherein, method is discontinuous method.

Embodiment 14: according to the method any one of embodiment 1-13, wherein, quencher compositions comprises Merlon and/or additive.

Embodiment 15: according to the method any one of embodiment 1-14, wherein, adds quencher compositions and occurs guiding to extruder Merlon.

Embodiment 16: according to the method any one of embodiment 1-15, wherein, melt polymerization includes polymerization Merlon in a series of polymerized unit, and wherein, the method adds quencher compositions after further including at one or more polymerized unit.

Embodiment 17: according to the method any one of embodiment 1-16, wherein, quencher compositions comprises sulphonic acid ester.

Embodiment 18: according to the method any one of embodiment 1-17, wherein, is added directly to extruder by quencher compositions after final polymerized unit.

Embodiment 19: the method according to embodiment 18, wherein, is added into the feed throat of extruder by quencher compositions.

Embodiment 20: according to the method any one of embodiment 18-19, wherein, is injected into quencher compositions side in the extruder in extruder feed throat downstream.

Embodiment 21: according to the method any one of embodiment 1-20, wherein, carbon monoxide-olefin polymeric comprises beta catalyst.

Embodiment 22: the method according to embodiment 21, wherein, beta catalyst comprises tetraphenylphosphoniacetate acetate.

Embodiment 23: according to the method any one of embodiment 21-22, wherein, it is more more substantial beta catalyst than α catalyst that melt polymerization includes use.

Embodiment 24: according to the method any one of embodiment 1-20, wherein, melt polymerization only uses α catalyst.

Embodiment 25: a kind of melt polymerization process, including: under carbon monoxide-olefin polymeric exists, melt polymerization thing is to form Merlon, and wherein, carbon monoxide-olefin polymeric only comprises beta catalyst; Quencher compositions is added into Merlon, and wherein, quencher compositions comprises quencher; And Merlon is guided to extruder.

Embodiment 26: according to the method any one of embodiment 1-25, wherein, quencher compositions comprises the alkyl tosylate of 1 to the 10ppm of the Merlon based on 100 parts.

Embodiment 27: according to the method any one of embodiment 1-25, wherein, quencher compositions comprises the phosphorous acid of 1 to the 10ppm of the Merlon based on 100 parts.

Embodiment 28: according to the method any one of embodiment 1-27, wherein, quencher compositions comprises the alkyl tosylate of 2 to the 5ppm of the Merlon based on 100 parts and the phosphorous acid of 2 to 5ppm.

Embodiment 29: according to the method any one of embodiment 1-28, wherein, quencher compositions comprises the positive butyl ester of p-methyl benzenesulfonic acid.

Embodiment 30: according to the method any one of embodiment 1-27, wherein, quencher compositions comprises the quencher of 1 to the 7ppm of the Merlon based on 100 parts.

Embodiment 31: according to the method any one of embodiment 1-27, wherein, quencher compositions comprises the quencher of 1.5 to the 3ppm of the Merlon based on 100 parts.

Embodiment 32: according to the method any one of embodiment 1-31, wherein, quencher comprises the difunctional compound with acid or acid ester moiety and amine moiety.

Embodiment 33: according to the method any one of embodiment 1-32, wherein, quencher compositions includes formula R_aR_bR_cN⁺-A-SO₃ ^-Compound, wherein, R_aAnd R_bIt is hydrogen, C independently of one another₁-C₁₂Alkyl, C₁-C₁₂Aryl or C₁-C₁₈Alkaryl; R_cIt is hydrogen; R_a、R_bIndividually or combination formed and there is the heterocycle structure of N; And A is C₁-C₁₂Alkyl, C₁-C₁₂Aryl or C₁-C₁₈Alkaryl.

Embodiment 34: according to the method any one of embodiment 1-33, wherein, adds a certain amount of quencher to be reduced to less than by side chain (branching, branching) or equal to 100ppm.

Embodiment 35: according to the method any one of embodiment 1-34, wherein, quencher has the pKa less than or equal to 5.

Embodiment 36: according to the method any one of embodiment 1-35, wherein, quencher has the pKa less than or equal to 3.

Embodiment 37: according to the method any one of embodiment 1-36, wherein, melt polymerization includes making reactant to wet online reaction in type polymerizer.

Embodiment 38: according to the method any one of embodiment 1-37, wherein, melt polymerization includes making reactant reaction under carbon monoxide-olefin polymeric exists, and adds other catalyst and further melt polymerization thing.

Embodiment 39: the method according to embodiment 38, further includes at and adds quencher before adding other catalyst.

Embodiment 40: according to the method any one of embodiment 38-39, adds quencher after further including at further melt polymerization thing.

Embodiment 41: according to the method any one of embodiment 1-40, farther includes to introduce an additive into Merlon.

Embodiment 42: according to the method any one of embodiment 1-41, wherein, quencher compositions comprises heat stabilizer, and introduces additive generation after adding quencher compositions, and wherein, additive comprises releasing agent and UV reagent.

Embodiment 43: according to the method any one of embodiment 41-42, wherein, introduces an additive at least one to reaction vessel, extruder and blender.

Embodiment 44: according to the method any one of embodiment 41-43, further includes at and introduces an additive into filtration additives before Merlon.

Embodiment 45: according to the method any one of embodiment 1-44, filters quencher compositions before further including at addition quencher compositions.

Embodiment 46: according to the method any one of embodiment 1-45, before further including at addition quencher compositions, by quencher compositions pump to the dosing pump controlled by main dispensing loop.

Embodiment 47: the method according to embodiment 46, wherein, dosing pump has the speed of 300 to 1550rpm.

Embodiment 48: according to the method any one of embodiment 46-47, farther includes to continue with effusion meter or intermittently monitor the quencher compositions interpolation to Merlon.

Embodiment 49: the method according to embodiment 48, farther includes controller, for automatically monitoring effusion meter and adjusting the quencher compositions amount to Merlon.

Embodiment 50: the method according to embodiment 49, wherein, speed is 500 to Isosorbide-5-Nitrae 50rpm.

Embodiment 51: according to the method any one of embodiment 1-26 and 28-48, wherein, quencher compositions comprises the phosphorous acid of 1 to the 10ppm of the Merlon based on 100 parts, and wherein, quencher compositions is to add under the flow velocity of 1 to 5kg/hr.

Embodiment 52: the method according to embodiment 50, wherein, flow velocity is 2.2 to 2.7kg/hr.

Embodiment 53: according to the method any one of embodiment 1-52, wherein, melt polymerization includes under the oligomerization temperature of 100 DEG C to 280 DEG C oligomeric, and is polymerized under the polymerization temperature of 250 DEG C to 310 DEG C, and wherein, oligomerization temperature is lower than polymerization temperature.

Embodiment 54: the method according to embodiment 53, wherein, oligomeric more than under the oligomeric pressure of 100mbara.

Embodiment 55: according to the method any one of embodiment 53-54, wherein, oligomeric includes the first oligomerization temperature at 150 DEG C to 260 DEG C, oligomeric more than or equal to first under the first of 100mbara the oligomeric pressure; And subsequently oligomeric under second oligomerization temperature of 230 DEG C to 280 DEG C and the second oligomeric pressure of 15 to 90mbara.

Embodiment 56: according to the method any one of embodiment 53-55, wherein, polymerization includes the first polymerization temperature at 260 DEG C to 310 DEG C, the first polymerization under the polymerization pressure of 1 to 10mbara; And the second polymerization temperature at 260 DEG C to 300 DEG C, with less than or equal to the polymerization subsequently under second polymerization pressure of 5mbara.

Embodiment 57: the method according to embodiment 56, 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 58: according to the method any one of embodiment 56-57, 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 59: according to the method any one of embodiment 56-58, wherein, adds quencher compositions and includes adding quencher compositions before second is polymerized.

Embodiment 60: according to the method any one of embodiment 56-59, wherein, adds quencher compositions and includes adding quencher compositions after second is polymerized.

Embodiment 61: according to the method any one of embodiment 53-54, wherein, polymerization is in one or more line and wets in type polymerizer, and polymerization temperature is 200 DEG C to 300 DEG C, and polymerization pressure is less than or equal to 4mbara.

Embodiment 62: the method according to embodiment 61, wherein, polymerization temperature is 250 DEG C to 280 DEG C.

Embodiment 63: according to the method any one of embodiment 53-62, wherein, polymerization includes the first polymerized unit and second unit, and wherein, the Merlon produced in the first polymerized unit has 20,000 to 50,000 daltonian number-average molecular weight.

Embodiment 64: the method according to embodiment 63, wherein, Merlon increases its molecular weight less than or equal to 10wt% in second unit, and wherein, method further includes at devolatilization in second unit.

Embodiment 65: according to the method any one of embodiment 1-64, wherein, extruder is counter rotating twin screW extruder.

Embodiment 66: according to the method any one of embodiment 20-65, wherein, beta catalyst comprises tetraphenylphosphoniacetate acetate.

The ratio of embodiment 67: according to the method any one of embodiment 1-66, wherein, quencher and catalyst is 3:1 to 2:1.

Embodiment 68: according to the method any one of embodiment 1-67, wherein, before melt polymerization, farther includes to introduce to blender the first reactant; Melted first reactant; Then the second reactant and carbon monoxide-olefin polymeric are added into blender.

Embodiment 69: the method according to embodiment 68, wherein, the first reactant is selected from diaryl carbonate and dihydroxy compounds.

Embodiment 70, according to the method any one of embodiment 68-69, wherein, the second reactant is selected from diaryl carbonate and dihydroxy compounds.

Embodiment 71: according to the method any one of embodiment 1-70, farther includes devolatilization polycarbonate compositions.

Embodiment 72: the method according to embodiment 71, wherein, devolatilization occurs in an extruder and/or in polymerized unit.

Embodiment 73: the method according to embodiment 71-72, wherein, devolatilization occurs after quencher.

Embodiment 74: according to the method any one of embodiment 1-73, wherein, method includes the part of parallel polymerization.

Embodiment 75: the method according to embodiment 74, wherein, the part of parallel polymerization includes: be polymerized Merlon in a series of oligomeric unit; It is A stream and B stream by the flow point discharging oligomeric unit, A stream is guided to polymerized unit A and B stream is guided to polymerized unit B.

Embodiment 76: the method according to embodiment 74, wherein, the part of parallel polymerization oligomeric unit, then it is polymerized in a series of polymerized unit, it is A stream and B stream by the flow point discharging final polymerized unit, A stream is guided to extruder A and B stream is guided to extruder B.

Embodiment 77: the method according to embodiment 74, wherein, the part of parallel polymerization includes: be polymerized Merlon in a series of oligomeric unit; Then it is polymerized in a series of two polymerized units; It is A stream and B stream by the flow point discharging the first polymerized unit, A stream is guided to the second polymerized unit A and B stream is guided to the second polymerized unit B.

Embodiment 78: according to the method any one of embodiment 1-77, wherein, adds quencher compositions and includes being injected on granular Merlon quencher compositions.

Embodiment 79: a kind of melt polymerization process, including: melt polymerization Merlon, wherein, melt polymerization includes making reactant reaction under carbon monoxide-olefin polymeric exists; Merlon is guided to extruder; Balancing selection quencher compositions based on color stability, the reservation of UV reagent and hydrolytic stability; And quencher compositions is added in extruder upstream, or it is directly added into extruder, wherein, quencher compositions comprises quencher.

Embodiment 80: a kind of melt polycarbonate, is prepared by the method any one of embodiment 1-79.

Embodiment 81: according to the method any one of embodiment 1-80, wherein, Merlon is bisphenol-a polycarbonate.

Embodiment 82: according to the method any one of embodiment 1-81, wherein, pressure is more than or equal to 3 bars.

Embodiment 83: according to the method any one of embodiment 1-82, wherein, pressure is 3 bar 100 bars.

Embodiment 84: the method according to embodiment 11, wherein, quencher compositions is added into Merlon occur under the pressure more than or equal to 2 bars, and/or wherein, before add any additive with reactive OH group or reactive ester group to Merlon, quencher compositions mixes the time period occurred more than or equal to 5 seconds with Merlon.

Embodiment 85: a kind of method adding quencher compositions, including: Merlon being fed to extruder, quencher compositions is added into Merlon, wherein, quencher compositions is solid quencher compositions; And before adding any reactive additive to Merlon, quencher compositions is mixed with Merlon the time period more than or equal to 5 seconds, wherein, reactive additive has reactive OH group or reactive ester group; Wherein, Merlon is melt polycarbonate.

Embodiment 86: the method according to embodiment 85, further includes at the Merlon pelletize being polymerized before charging.

Embodiment 87: according to the method any one of embodiment 85-86, further includes at and adds the Merlon of melt polymerization before solid quencher compositions.

Embodiment 88: according to the method any one of embodiment 85-87, wherein, solid quencher compositions comprises polycarbonate powder.

Embodiment 89: according to the method any one of embodiment 85-88, wherein, quencher compositions is without carrier.

Embodiment 90: according to embodiment 1,3, method any one of 11-84, wherein, quencher compositions is solid quencher compositions.

Embodiment 91: according to the method any one of embodiment 1-90, wherein, quencher reduces the activity of catalyst.

As it is used in the present context, when relating to " reactivity " or " reactive group ", for instance having reactive OH-group group or reactive ester group, this reactivity is relative to Merlon.

Generally, the present invention can alternatively include any applicable part disclosed herein, consisting of or be substantially made up of it. The present invention can it addition, or alternatively, carry out preparing so as without, or there is no that prior art compositions uses or additionally to realizing the function of the present invention and/or target any component not necessarily, material, composition, adjuvant or species.

All scopes disclosed herein include end points, and these end points can combination with one another (such as, " up to 25wt%, or more particularly; the scope of 5wt% to 20wt% ", all intermediate values etc. including in the scope of end points and " 5wt% to 25wt% ") independently. " combination " includes blend, mixture, alloy, product etc. Additionally, term " first ", " second " etc., it is not offered as any order, amount or importance in this article, and is intended to indicate that an element is different from another element. Term " one " and " one " and " being somebody's turn to do " herein do not indicate that quantitative limitation, and should be interpreted that include odd number and plural number the two, unless otherwise indicated herein or otherwise clearly contradicted. Suffix " (s) " as used in this article is intended to include odd number and both the plural numbers that this term is modified, thus includes one or more (such as, film (s) includes one or more film) of this term. Run through " a kind of embodiment ", " another embodiment ", " embodiment " etc. that description mentions and refer to that the element-specific that describes together with this embodiment is (such as, characteristic, structure and/or feature) it is included herein at least one embodiment of description, and can exist and maybe can be not present in other embodiment. "or" means "and/or". Further, it is understood that described element can be incorporated in various embodiment in any suitable manner. Disclosed in outside wider range, more close limit or group particularly are not to give up the group of broader scope or bigger. This application claims the priority of the patent application 13382423.5 in the Europe of submission on October 23rd, 2013 and EP13382419.3, by quoting being integrally joined to them herein as proof.

Although it have been described that detailed description of the invention, but applicant or others skilled in the art not may want to up till now not or the replacement that cannot predict of possibly, amendment, change, improve and substantial equivalents. Therefore, claims that are proposed and that be likely to be modified are intended to all such replacements, amendment, change, improvement and substantial equivalents.

Claims (22)

1. a melt polymerization process, including:

In at least two polymerized unit, under carbon monoxide-olefin polymeric exists, melt polymerization thing is to form Merlon, and wherein, described carbon monoxide-olefin polymeric comprises α catalyst, and wherein, described α catalyst comprises alkali metal and/or source of alkaline earth metal;

In conjunction with liquid-carrier and quencher to form quencher compositions in quencher container;

Described quencher compositions is added into described Merlon under more than or equal to the pressure of 2 bars;

Before add any additive with reactive OH group or reactive ester group to described Merlon, described quencher compositions is mixed the time period more than or equal to 5 seconds with described Merlon;

Filter described Merlon; And

Described Merlon is guided to extruder.

2. method according to claim 1, wherein, described liquid-carrier comprises diaryl carbonate, phenol, bisphenol-A, polycarbonate oligomer, bisphenol-a derivative, propylene carbonate, dimethylbenzene, toluene, benzene, ethylbenzene, methyl phenyl ethers anisole, chlorobenzene, water, acetone or comprises one or more combination aforesaid.

3. a melt polymerization process, including:

In at least two polymerized unit, under carbon monoxide-olefin polymeric exists, melt polymerization thing is to form Merlon, and wherein, described carbon monoxide-olefin polymeric comprises α catalyst, and wherein, described α catalyst comprises alkali metal and/or source of alkaline earth metal;

Melted quencher is to form quencher compositions, and wherein, described quencher compositions is without carrier;

Described quencher compositions is added into described Merlon;

Filter described Merlon; And

Described Merlon is guided to extruder.

4. a melt polymerization process, including:

Under carbon monoxide-olefin polymeric exists, melt polymerization thing is to form Merlon, and wherein, described carbon monoxide-olefin polymeric only comprises beta catalyst, and wherein, described beta catalyst comprises quaternary ammonium compound, quaternary compound or comprises aforesaid at least one combination;

Quencher compositions is added into described Merlon, and wherein, described quencher compositions comprises quencher; And

Described Merlon is guided to extruder.

5. method according to claim 4, wherein, described beta catalyst comprises tetraphenylphosphoniacetate acetate.

6. the method adding quencher compositions, including:

Merlon is fed to extruder;

Quencher compositions is added into described Merlon, and wherein, described quencher compositions is solid quencher compositions; And

Before adding any reactive additive to described Merlon, with described Merlon, described quencher compositions being mixed the time period more than or equal to 5 seconds, wherein, described reactive additive has reactive OH group or reactive ester group;

Wherein, described Merlon is melt polycarbonate.

7. method according to claim 6, by the described Merlon pelletize of polymerization before further including at charging.

8. the method according to any one of claim 6-7, further includes at and adds the described Merlon of melt polymerization before described solid quencher compositions.

9. the method according to any one of claim 6-8, wherein, described solid quencher compositions comprises polycarbonate powder.

10. the method according to claim 4-8, wherein, described quencher compositions is without carrier.

11. according to method in any one of the preceding claims wherein, wherein, described quencher compositions comprises the alkyl tosylate of 1 to the 10ppm of the described Merlon based on 100 parts.

12. according to method in any one of the preceding claims wherein, wherein, described quencher compositions comprises the phosphorous acid of 1 to the 10ppm of the described Merlon based on 100 parts.

13. according to method in any one of the preceding claims wherein, wherein, described quencher compositions comprises the positive butyl ester of toluenesulfonic acid.

14. according to method in any one of the preceding claims wherein, wherein, melt polymerization includes making reactant to wet online reaction in type polymerizer.

15. according to method in any one of the preceding claims wherein, filter described quencher compositions before further including at the described quencher compositions of interpolation.

16. according to method in any one of the preceding claims wherein, wherein, described melt polymerization includes under the oligomerization temperature of 100 DEG C to 280 DEG C oligomeric, and wherein, described polymerization includes occurring under first polymerization temperature of 260 DEG C to 310 DEG C and first polymerization pressure of 1 to 10mbara first to be polymerized; And occur 260 DEG C to 300 DEG C the second polymerization temperature and less than or equal under second polymerization pressure of 5mbara second polymerization.

17. according to method in any one of the preceding claims wherein, wherein, quencher is 3:1 to 2:1 with the ratio of catalyst.

18. according to method in any one of the preceding claims wherein, further include at the described Merlon devolatilization making polymerization after adding described quencher compositions more than or equal to 5 seconds.

19. according to method in any one of the preceding claims wherein, wherein, add described quencher compositions to include being injected on granular Merlon described quencher compositions.

20. according to method in any one of the preceding claims wherein, wherein, described carbon monoxide-olefin polymeric comprises tetraphenylphosphoniacetate acetate.

21. according to the method described in claim 1-3 and 5-23, wherein, described melt polymerization only uses described α catalyst.

22. according to method in any one of the preceding claims wherein, wherein, described melt polymerization includes making described reactant reaction under described carbon monoxide-olefin polymeric exists, and adds reactant described in other catalyst and further melt polymerization; And add first liquid quencher before further including at the described other catalyst of interpolation.