CN107266671A - Melt polymerization makrolon is quenched - Google Patents

Abstract

The application is related to the quenching of melt polymerization makrolon.In embodiments, melt polymerization process includes：Melt polymerization thing to be to form makrolon in the presence of carbon monoxide-olefin polymeric, wherein, carbon monoxide-olefin polymeric includes catalyst；Quencher compositions are added to makrolon, wherein, quencher compositions include quencher；Makrolon is guided to extruder.

Description

Melt polymerization makrolon is quenched

The application is the Chinese patent of entitled " quenching of melt polymerization makrolon " that the applying date is on October 16th, 2014 Apply for No.201480058466.5 divisional application.

Technical field

The application be related to quenching (cold shock, quenching, quenching) in melt polymerization process and quencher (cold shock agent, suddenly Cryogen, quencher).

Background technology

In the melt polymerization process of polymerization makrolon, quencher can be added to reduce fused catalyst (melt Catalyst activity).

The catalytic preparation preparation that the B1 of EP 2 540 758 are related to melt polymerization device system and added using the later stage is poly- The method of carbonic ester, the catalytic preparation, which has, to be scattered in the liquid carrier system for preferably including the water less than 10wt% Melt transesterification catalyst.Said preparation preferably includes the liquid with phenol and cosolvent (cosolvent, cosolvent) and carried System is united.Melt transesterification catalyst can be present in preparation with 50ppm to 60,000ppm scope.

The A2 of EP 0 955 768 are related to the method for preparing aromatic polycarbonate resin.Disclose fragrant adoption carbon The preparation of acid ester resin, " in such a situa-tion, i.e., the reactant mixture in pipeline (molten reaction mixture is passed through by it) Flowing velocity be particular value or higher, the viscosity-average molecular weight of reactant mixture is 1,000 or higher, reactant mixture Overall average retention time is no longer than 3 hours, and the wall temperature of pipeline (molten reaction mixture is passed through by it) is set higher than in pipeline instead Answer the temperature of mixture, melt polycondensation reaction complete 2 hours within add catalyst deactivator (passivator, Deactivation agent), and enter by using with the specific filter for retaining particle diameter under specific pressure differential Row filtering ... "

The A of JP 2,003 335853 are related to aromatic/aliphatic copolycarbonate resin composition, and it is by making aromatic series Carbonic diester, aliphatic dihydroxy compounds and aromatic dihydroxy compound are subjected to melt polymerization to make in the presence of a catalyst Standby aromatic/aliphatic Copolycarbonate (A), and after catalyst inactivation (passivation, deactivate), make copolymerization carbonic acid Ester (A) is melted and kneaded in extrusion step with other at least one resins (B) and prepared.

The improved method for adding quencher is desired.

The content of the invention

There is disclosed herein the method for adding quencher.

In embodiments：Melt polymerization process includes：Melt polymerization thing is with shape in the presence of carbon monoxide-olefin polymeric Into makrolon, wherein, the carbon monoxide-olefin polymeric includes catalyst；Quencher compositions are added to makrolon, wherein, should Quencher compositions include quencher；Makrolon is guided to extruder.

In embodiments, melt polymerization process includes：In at least two polymerized units, exist in carbon monoxide-olefin polymeric Lower melt polymerization thing to form makrolon, wherein, carbon monoxide-olefin polymeric include α catalyst, wherein, α catalyst is included Alkali metal and/or source of alkaline earth metal；Liquid-carrier and quencher is combined in quenching agent container to form quencher combination Thing；Quencher compositions are added to makrolon under the pressure more than or equal to 2 bars；Any tool is being added to makrolon Before the additive for having reactive OH groups or reactive ester group, quencher compositions are mixed with makrolon and is more than or waits In the period of 5 seconds；Filter makrolon；And guide makrolon to extruder.

In embodiments, melt polymerization process includes：In at least two polymerized units, exist in carbon monoxide-olefin polymeric Under, melt polymerization thing to form makrolon, wherein, carbon monoxide-olefin polymeric include α catalyst, wherein, α catalyst is included Alkali metal and/or source of alkaline earth metal；Quencher is melted to form quencher compositions, wherein, quencher compositions are free of Carrier；Quencher compositions are added to makrolon；Filter makrolon；And guide makrolon to extruder.

In embodiments, melt polymerization process includes：Melt polymerization thing is with shape in the presence of carbon monoxide-olefin polymeric Into makrolon, wherein, carbon monoxide-olefin polymeric only includes beta catalyst, wherein, beta catalyst includes quaternary ammonium compound, quaternary phosphine chemical combination Thing includes foregoing at least one combination；Quencher compositions are added to makrolon, wherein, quencher compositions Include quencher；And guide makrolon to extruder.

In embodiments, the method for addition solid quencher compositions includes：Makrolon is fed to extruder；Will Quencher compositions are added to makrolon, wherein, quencher compositions are solid quencher compositions；And to poly- carbonic acid Ester is added before any reactive additive, and quencher compositions are mixed into the period more than or equal to 5 seconds with makrolon, Wherein, reactive additive has reactivity OH groups or reactive ester group；Wherein, makrolon is the poly- carbonic acid of melting Ester.

Described above and further feature is illustrated by the following drawings and embodiment.

Brief description of the drawings

Referring now to accompanying drawing, they are exemplary embodiments, and wherein similar key element is with same reference Label is represented.

The method that Fig. 1 shows addition quencher compositions.

Embodiment

Applicant develops the quencher in quencher compositions and to be added to makrolon with liquid and/or solid form Melt polymerization process in improved method.

" makrolon " 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 containing aryl moieties and its surplus, alicyclic or fragrant Fragrant race.Each R¹Can be C_6-30Aromatic group, i.e., containing at least one aryl moieties.R¹Formula HO-R can be derived from¹- The aromatic dihydroxy compound of OH, especially formula (2)：

HO–A¹–Y¹–A²–OH (2)

Wherein, A¹And A²In be each monocyclic divalent aryl group and Y¹It is by A¹With A²The singly-bound of separation or with one The bridge linkage group of individual or multiple atoms.One atom can be by A¹With A²Separate.Especially, each R¹Can be derived from formula (3) Bis-phenol

Wherein R^aAnd R^bIt is halogen, C independently of one another_1-12Alkoxy or C_1-12Alkyl；And p and q are 0 independently of one another To 4 integer.It should be understood that when p or q is less than 4, the valence link of each carbon of ring is filled by hydrogen.Equally in formula (3), X^a It is the bridged group for the aromatic group for connecting two hydroxyl substitutions, wherein, bridged group and each C₆The hydroxyl of arylene group Base substituent is arranged at C with ortho position, meta or contraposition (particularly aligning) each other₆In arylene group.Bridged group X^aCan be with 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 non-annularity, aromatic series or non-aromatic, and can further include hetero atom, such as halogen, oxygen, nitrogen, sulphur, silicon or Phosphorus.C_1-18Organic group is arranged to be connected to its C₆Arylene group is each attached to C_1-18Organic bridging group Common alkylidene radical carbon or different carbon.Each p and q can be 1, and R^aAnd R^bCan be individually C_1-3Alkyl group, especially Ground methyl, is placed in the meta of the oh group of each arylene group.

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

X^aCan be C_1-18Alkylidene, C_3-18Cycloalkylidene, the C of fusion_6-18Cycloalkylidene or formula-B¹-G-B²- group, Wherein, B¹And B²It is same or different C_1-6Alkylidene and G is C_3-12Ring alkylidene radical (cycloalkylidene) or C_6-16 Arlydene.For example, X^aCan be the substituted C of formula (4)_3-18Ring alkylidene radical

Wherein, R^r、R^p、R^qAnd R^tVarious is independently hydrogen, halogen, oxygen or C_1-12Hydrocarbyl group；Q be direct bond, carbon or Oxygen, sulphur or the-N (Z) of divalence-, wherein, Z is hydrogen, halogen, hydroxyl, C_1-12Alkyl, C_1-12Alkoxy or C_1-12Acyl group；R is 0 To 2, t be 1 or 2, q be 0 or 1, and k is 0 to 3, and condition is R^r、R^p、R^qAnd R^tAmong at least two connect together be fusion Alicyclic, aromatic series or heteroaromatic rings.It should be understood that when condensed ring is aromatic series, the ring shown in formula (4) is in ring There to be unsaturated carbon-carbon bond in the case of fusion.When k is 1 and i is 0, the ring as shown in formula (4) contains 4 carbon originals Son；When k is 2, the ring as shown in formula (4) contains 5 carbon atoms；And when k is 3, the ring contains 6 carbon atoms.Two Individual adjacent group is (for example, R^qAnd R^tConnect together) fragrance group group, and R can be formed^qAnd R^tConnecting together to form Aromatic group and R^rAnd R^pThe second aromatic group can be formed by connecting together.Work as R^qAnd R^tConnect together to form aromatic series base During group, R^pCan be double bond oxygen atom, i.e. ketone.

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

Wherein, R^a、R^b, p and q such as formulas (3), R³It is C independently of one another_1-6Alkyl, j is 0 to 4, and R⁴It is hydrogen, C_1-6Alkane Base, or replace or non-substituted phenyl, for example, by up to 5 C_1-6Alkyl-substituted phenyl.For example, phthalimidine carbon Acid esters unit is formula (1b)

Wherein, R⁵It is hydrogen, alternatively by up to 5 C_1-6Alkyl, or C_1-4Alkyl-substituted phenyl.In formula (1b), R⁵Can To be hydrogen, methyl or phenyl, particularly phenyl.Carbonate unit (1b), (wherein, R⁵Phenyl) can derived from 2- phenyl- 3,3'- double (4- hydroxy phenyls) phthalimidines (double (4- the hydroxy phenyls) -2- phenyl 1-isoindolinones of also referred to as 3,3-, or N- phenyl phenolphthalein bis-phenol (" PPPBP ")).

Such other bisphenol carbonate repeat units are formula (1c) and the isatin carbonate unit of (1d)

Wherein, R^aAnd R^bIt is C independently of one another_1-12Alkyl, p and q are 0 to 4 independently of one another, and RⁱIt is C_1-12Alkyl, Alternatively by 1 to 5 C_1-10Alkyl-substituted phenyl, or alternatively by 1 to 5 C_1-10Alkyl-substituted benzyl.Each R^aAnd R^b Can be 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)) bisphenol carbonate unit Other examples including formula (1e) the alkyl substitution bis-phenol that bridges of cyclohexylidene base

Wherein, R^aAnd R^bIt is C independently of one another_1-12Alkyl, R^gIt is C_1-12Alkyl, p and q are 0 to 4 independently of one another, and t It is 0 to 10.Each R^aAnd R^bIn at least one can be placed in the meta that ring has pitched base bridged group.R^aAnd R^bCan be each only It is on the spot C_1-4Alkyl, R^gIt is C_1-4Alkyl, p and q are individually 0 or 1, and t is 0 to 5.R^a、R^bAnd R^gCan be individually methyl, p Can be individually 0 or 1 with q, and t can be 0 or 3, particularly 0.

Derived from bis-phenol (3) (wherein, X^aIt is substitution or non-substituted C_3-18Ring alkylidene (4)) bisphenol carbonate list Other examples of member 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 are 1 to 4 independently of one another.Each R^aAnd R^bIn At least one can be placed in the meta of 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 be individually methyl, p and q are individually 0 or 1, and when p and q are 1, methyl The meta that ring alkylidene radical bridges group can be placed in.Carbonic ester containing unit (1a) to (1g), which is used to prepare, has higher glass Change transition temperature (Tg) and the makrolon of higher heat distortion temperature.

Formula HO-R¹- OH other useful dihydroxy compounds 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, the C of halogen substitution_1-10Alkane Base, C_6-10Aryl or the C of halogen substitution_6-10Aryl, and n is 0 to 4.Halogen is typically bromine.

Some illustrative examples of specific dihydroxy compounds include following：4,4' dihydroxy diphenyl, 1,6- dihydroxy Naphthalene, 2,6- dihydroxy naphthlenes, double (4- hydroxy phenyls) methane, double (4- hydroxy phenyls) diphenyl methanes, double (4- hydroxy phenyls) -1- Double (4- hydroxy phenyls) ethane of naphthyl methane, 1,2-, double (4- the hydroxy phenyls) -1- diphenylphosphino ethanes of 1,1-, 2- (4- hydroxy phenyls) - Double (4- hydroxyl -3- bromophenyls) propane of 2- (3- hydroxy phenyls) propane, double (4- hydroxy phenyls) phenylmethanes, 2,2-, 1,1- are double Double (4- hydroxy phenyls) isobutenes of (hydroxy phenyl) pentamethylene, 1,1-bis(4-hydroxyphenyl)-cyclohexane, 1,1-, the double (4- of 1,1- Hydroxy phenyl) cyclododecane, double (4- the hydroxy phenyls) -2- butylene of trans- 2,3-, 2,2- double (4- hydroxy phenyls) adamantane, α, α ' - Double (4- hydroxy phenyls) toluene, double (4- hydroxy phenyls) acetonitriles, 2,2- (3- ethyl -4- hydroxy phenyls) propane, 2,2- (3- positive third Base -4- hydroxy phenyls) propane, 2,2- (3- isopropyl -4- hydroxy phenyls) propane, 2,2- double (3- sec-butyl -4- hydroxy phenyls) Double (3- tert-butyl-hydroxy phenyls) propane of propane, 2,2-, double (3- cyclohexyl -4- hydroxy phenyls) propane of 2,2-, 2,2- are double Double (3- methoxyl group -4- hydroxy phenyls) propane of (3- pi-allyl -4- hydroxy phenyls) propane, 2,2-, 2,2- are double (4- hydroxy phenyls) Double (4- hydroxy phenyls) ethene of HFC-236fa, the chloro- 2,2- of 1,1- bis-, the bromo- 2,2- of 1,1- bis- double (4- hydroxy phenyls) ethene, 1,1- Double (5- phenoxy group -4- hydroxy phenyls) ethene of two chloro- 2,2-, 4,4'- dihydroxy benaophenonels, 3,3- double (4- hydroxy phenyls) - Double (4- hydroxy phenyls) ethers of double (4- the hydroxy phenyls) -1,6- acetyl butyryls of 2- butanone, 1,6-, ethylene glycol, double (4- hydroxy phenyls) ethers, Double (4- hydroxy phenyls) fluorenes of double (4- hydroxy phenyls) thioethers, double (4- hydroxy phenyls) sulfoxides, double (4- hydroxy phenyls) sulfones, 9,9-, 2,7- dihydroxy pyrene, 6,6'- dihydroxy -3,3,3'3'- tetramethyls spiral shell (double) indane (" the full bis-phenol of spirobindene "), the double (4- of 3,3- Hydroxy phenyl) phthalide (phthalimide), 2,6- dihydroxy dibenzo-p- dioxin, 2,6- dihydroxy thianthrene, 2,7- dihydroxies Base phenoxanthein, 2,7- dihydroxy -9,10- dimethylphenazines, 3,6- dihydroxy dibenzofurans, 3,6- dihydroxy dibenzo thiophenes Fen and 2,7- dihydroxy carbazole, resorcinol, the resorcinol compound of substitution, such as oreinol diphenol, 5- ethyl resorcinols Diphenol, 5- propyls diphenol, 5- butyl resorcinol, 5- tert-butyl resorcins, 5- phenyl resorcinol, 5- cumyl isophthalic Diphenol, 2,4,5,6- tetrafluoros resorcinol, 2,4,5,6- tetrabromo resorcinols etc.；Catechol；Quinhydrones；Substituted quinhydrones, such as 2- methylnaphthohydroquinones, 2- ethyl hydroquinones, 2- propyl group quinhydrones, 2- butylhydroquinones, TBHQ, 2- pheny lhydro quinones, 2- cumyl hydrogen Quinone, 2,3,5,6- duroquinols, 2,3,5,6- tetra-terts quinhydrones, 2,3,5,6- tetrafluoros quinhydrones, the bromohydroquinones of 2,3,5,6- tetra- Deng.Or include the combination of at least one of foregoing dihydroxy compounds.

The specific example of the bisphenol compound of formula (3) includes double (4- hydroxy phenyls) methane of 1,1-, double (the 4- hydroxyls of 1,1- Phenyl) ethane, double (4- hydroxy phenyls) propane (hereinafter " bisphenol-A " or " BPA ") of 2,2-, double (4- hydroxy phenyls) fourths of 2,2- Double (4- hydroxy phenyls) octanes of alkane, 2,2-, double (4- hydroxy phenyls) propane of 1,1-, 1,1- double (4- hydroxy phenyls) normal butane, 2, Double (the 4- hydroxy-2-methyls phenyl) propane of 2-, double (the 4- hydroxy-tert-butyls phenyl) propane of 1,1-, 3,3- are double (4- hydroxy phenyls) Double (4- hydroxy phenyls) phthalimidines (PPPBP) of phthalimidine, 2- phenyl -3,3- and double (the 4- hydroxy-3-methyls of 1,1- Phenyl) hexamethylene (DMBPC).The combination for including at least one of foregoing dihydroxy compounds can also be used.Makrolon Can be the straight chain homopolymer derived from bisphenol-A, wherein, A¹And A²Individually to phenylene and Y¹It is the isopropylidene in formula (2) Base.

Makrolon herein is prepared by the melt polymerization of bis-phenol and carbonate precursor.Exemplary carbonic ester Precursor includes carbonyl halide, such as carbonyl bromide or phosgene (phosgene), double haloformates (such as bisphenol-A, right of dihydroxy compounds The bischloroformates of benzenediol ethylene glycol, neopentyl glycol etc.), and diaryl carbonate.It can also use comprising aforementioned type The combination of at least one of carbonate precursor.Diaryl carbonate can be dipheryl carbonate base ester or have on each aryl The dipheryl carbonate base ester of the activation of electron-withdrawing substituent, it is such as double (4- nitrobenzophenones) carbonic esters, double (2- chlorphenyls) carbonic esters, double (4- chlorphenyls) carbonic ester, double (methyl salicyl) carbonic esters, double (4- methyl carboxyl phenyl) carbonic esters, double (2- acetylbenzenes) Carboxylate, double (4- acetylbenzenes) carboxylates include foregoing at least one combination.

The polymerization can occur in the presence of branching agent.The example of these branching agents, which includes containing, is selected from following at least three Plant the multifunctional organic compound of functional group：Hydroxyl, carboxyl, carboxylic acid anhydrides, haloformyl, and aforementioned functional groups mixing Thing.This branching agent includes three acid chlorides of the acyl halide of aromatic series three, such as formula (20)：

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

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

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

Trisphenol TC (1,3,5- tri- ((p-hydroxybenzene) isopropyl) benzene), the trisphenol PA (4 (4 (double (para hydroxybenzenes of 1,1- Base)-ethyl) bis (alpha, alpha-dimethylbenzyl) base) phenol), 4- chloroformyls phthalic anhydride, trimesic acid and benzophenone tetracarboxylic acid Acid.

In melt polymerization process, makrolon can be by the presence of ester exchange catalyst, making the two of molten condition Hydroxy reaction is prepared with carbonate precursor coreaction.The reaction can such as continuously stir reaction in typical polymerization unit Device (CSTR), plug flow reactor, line it is wet fall type polymerizer (wire-wetting fall polymerizer), free-falling gather Clutch, horizontal (horizontal, horizontal) polymerizer, scraped film type polymerizer, Banbury mixer (BANBURY mixer), Single screw rod or double screw extruder, or including being carried out in foregoing one or more combination.By distillation, from frit reaction thing Volatile monohydric phenol is removed, and is separated polymer as molten residue.Can be with discontinuous method (batch process) Or continuation method carries out melt polymerization.In any case, the melt polymerization conditions used can include two or more not Same (independent, distinct) stage of reaction.For example, 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 poly carbonic acid Ester.Oligomerization stage can include one or more, especially 2 or multiple, more particularly 2 to 4 oligomerization unit (examples Such as 2 to 4 continuously stir groove).In the presence of 2 or more oligomerization units series windings, from a unit to it is next can To there is one or both of temperature increase or pressure reduction.Polymerization stage can include one or more, especially 2 or It is multiple, more particularly 2 polymerized units (such as 2 horizontal or line it is wet fall type polymerizer).Polymerization stage can include one or Multiple polymerized units, it can be by polycarbonate polymerization extremely, the molecular weight of such as 20,000 to 50,000 dalton.It is poly- being formed After carbonic ester, then polycarbonate compositions can be alternatively quenched and devolatilization (devolatilization, Devolatization) devolatilization (removing volatile ingredient, devolatilize) in unit, wherein, the molecular weight of makrolon Do not dramatically increase (such as molecular weight does not increase more than 10 percetages by weight (wt%)), and temperature in use, pressure and stop Time with reduce lower-molecular-weight component (as with less than 1,000 dalton molecular weight) concentration.It is low herein Poly- reaction member is defined to the oligomeric of the number-average molecular weight for causing polycarbonate oligomer to have less than or equal to 8,000 dalton Reaction member, and polymerized unit is defined to produce the poly- carbon of the number-average molecular weight with more than 8,000 dalton herein The polymerized unit of acid esters.It is noted that while herein using less than or equal to 8,000 dalton to limit oligomerization stage The molecular weight of middle acquisition, it should be readily apparent to one skilled in the art that the molecular weight is used to limit oligomerization stage, wherein, it is low The molecular weight of polymers can be more than 8,000 dalton." segmentation " polymeric reaction condition can be used for continuous polymerization system, its In, initial monomer is oligomeric in the first reaction vessel, also, the oligomeric polycarbonate formed wherein is continuously delivered to one Or multiple downstream reactors, wherein, oligomeric polycarbonate is converted into high-molecular-weight polycarbonate.Generally, in the oligomeric stage, The oligomeric polycarbonate of generation has the number-average molecular weight of 1,000 to 7,500 dalton.In one or more subsequent polymerization ranks Duan Zhong, the number-average molecular weight (Mn) of makrolon can be increased to, and such as 8,000 to 25,000 dalton (uses makrolon Standard), especially 13,000 to 18,000 dalton.

Generally, in the method without using solvent, and reactant dihydroxy aromatic compounds and diaryl carbonate at In molten condition.Reaction temperature can be 100 to 350 degrees Celsius (DEG C), especially, 180 to 310 DEG C.React the starting stage Pressure may be at atmospheric pressure, super-atmospheric pressure or the pressure of the pressure limit of 15 supports is depressed into from air, and in the rear stage, be in The pressure of decline, such as 0.2-15 are held in the palm.Similarly, polymerization can occur in a series of aggregation container, and it can be each single It is unique to have increased temperature and/or vacuum.For example, oligomerization stage can occur at 100 to 280 DEG C, especially 140 to At a temperature of 240 DEG C, and polymerization stage can occur at 240 to 350 DEG C, especially 280 to 300 DEG C or 240 to 270 DEG C or At a temperature of 250 to 310 DEG C, wherein, the temperature in polymerization stage is more than the temperature in oligomerization stage.From initial oligomeric list The reaction time of member to final polymerized unit is typically 0.1 to 15 hour.Final polymerized unit is as used in this article Refer to the final polymerized unit in the last increased melt polymerization for wherein occurring molecular weight.For example, quencher can be final Polymerization after (for example, after point of weight average molecular weight (Mw) increase less than or equal to 10% of makrolon), and can Selection of land, is added to polycarbonate resin before any melt filtration.

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

Subsequent polymerization stage of oligomeric stage can be included in one or two polymerized unit and polymerize.First polymerized unit Can be at 240 to 350 DEG C, especially at a temperature of 260 to 310 DEG C and under 1 to 10 millibar of pressure.Second polymerized unit can be with At 240 to 350 DEG C, especially at a temperature of 260 to 300 DEG C and under the pressure less than or equal to 5 millibars.Makrolon can be Devolatilization after final polymerization.

After final aggregation container (also referred to as final polymerized unit), polymer can guide to reactor, extrusion, Filtering is subjected in fondant filter, or including foregoing one or more combination.Squeezed it should be noted that fondant filter can be located at Go out before or after machine.For example, can include for the melt polymerization process for preparing polycarbonate compositions：Melt polymerization dihydroxy Base reactant and carbonate products are to produce molten reaction products；It is quenched molten reaction products；In any extruder upstream Molten reaction products are filtered in fondant filter；Additive is alternatively introduced to form mixture；And extrude the mixture with Form polycarbonate compositions.Similarly, it can include for preparing the melt polymerization process of polycarbonate compositions：Melting is poly- Dihydroxy reactants and carbonate products are closed to produce molten reaction products；Introduce quencher compositions and optional additive For forming mixture；And the mixture is extruded to form polycarbonate compositions.

Catalyst prepared by the melt transesterification polymerization for makrolon can include α and/or beta catalyst.Beta catalyst It is ester exchange catalyst that is generally volatile and degrading at elevated temperatures.Therefore, beta catalyst can be low earlier Warm polymerization stage (for example, oligomeric period) uses.α catalyst is generally than beta catalyst more thermal-stable and not volatile ester Exchange catalysts, and therefore can be used in whole ester exchange reaction, whole ester exchange reaction was included in oligomeric period, with And after oligomerization, such as in aggregation container, in the course of the polymerization process.

α catalyst can include alkali metal and/or source of alkaline earth metal, for example, being to provide alkali metal and/or alkaline earth gold Belong to the catalyst of ion gun.These ion guns include alkali metal hydroxide, such as lithium hydroxide, sodium hydroxide and potassium hydroxide, And alkaline earth metal hydroxide, such as magnesium hydroxide and calcium hydroxide.Other possible sources of alkali and alkaline earth metal ions ion Corresponding salt (such as sodium of EDTA tetra- of the derivative of corresponding salt (such as sodium acetate) and ethylenediamine tetra-acetic acid (EDTA) including carboxylic acid Salt, and EDTA magnesium disodium salt).Other α ester exchange catalysts include the alkali metal or alkali salt of carbonic acid, such as Cs₂CO₃、 NaHCO₃And Na₂CO₃Deng the alkali metal alkaline earth metal salt of, non-volatile inorganic acid, such as NaH₂PO₃、NaH₂PO₄、Na₂HPO₃、 KH₂PO₄、CsH₂PO₄、Cs₂HPO₄Deng, or phosphoric acid salt-mixture, such as NaKHPO₄、CsNaHPO₄、CsKHPO₄Deng.Bag can be used Combination containing at least one of any Above-mentioned catalytic agent.

Possible beta catalyst can be comprising quaternary ammonium compound, quaternary phosphonium compound or including foregoing at least one group Close.Quaternary ammonium compound can be structure (R⁴)₄N⁺X^-Compound, wherein, each R⁴It is same or different, and is C_1-20 Alkyl, C_4-20Cycloalkyl or C_4-20Aryl；And X^-It is organic or inorganic anion, such as hydroxyl, halogen ion (halide, Halide), carboxylate radical, sulfonate radical, sulfate radical, formate, carbonate or bicarbonate radical.The example bag of quaternary organic ammonium compounds Include tetramethylammonium hydroxide, tetrabutylammonium hydroxide, acetic acid tetramethylammonium, tetramethyl-ammonium formate, acetic acid tetrabutylammonium and comprising foregoing at least one The combination planted.What is be commonly used is TMAH.Quaternary phosphonium compound can be structure (R⁵)₄P⁺X^-Compound, its In, each R⁵It is same or different, and is C_1-20Alkyl, C_4-20Cycloalkyl or C_4-20Aryl；And X^-It is organic or nothing Machine anion, such as 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 understood that in quaternary ammonium He positive charge and negative electrical charge in quaternary phosphine structure are properly balanced.For example, in R²⁰To R²³Individually first Base and X^-When being carbonic acid, it should be understood that X^-Represent 2 (CO₃ ^-2).The example of You Ji quaternary phosphonium compounds include tetramethylphosphonihydroxide hydroxide Ji Phosphonium, Acetic acid tetramethyl phosphonium, formic acid tetramethyl phosphonium, hydroxide 4-butyl-phosphonium, acetic acid 4-butyl-phosphonium (TBPA), acetic acid tetraphenylphosphoniphenolate (four benzene Ji Phosphonium acetates, tetraphenyl phosphonium acetate, TPPA), tetraphenyl Ben Yangization Phosphonium (TPPP) and including before At least one combination stated.Catalyst can include TBPA.Catalyst can include TPPP.

The α and the amount of beta catalyst used can the total mole number based on the dihydroxy compounds for polymerisation.When relating to And beta catalyst (for example, microcosmic salt) with ratio for all dihydroxy compounds of polymerisation when, it is convenient for the sake of refer to often rub The molal quantity of the catalyst of your dihydroxy compounds, represents the molal quantity of catalyst divided by is present in every in reactant mixture Plant mole total amount of single dihydroxy compounds.Ester exchange catalyst can be with offer 1 × 10 enough^-8To 1 × 10^-5, especially Ground 1 × 10^-7To 8 × 10^-6, more particularly 3 × 10^-7To 2 × 10^-6Mole catalyst/use aromatic dihydroxy compound The amount of molal quantity use.α catalyst can be with offer 1 × 10 enough^-2To 1 × 10^-8Mole, especially 1 × 10^-4To 1 × 10^-7Mole the amount of molal quantity of dihydroxy compounds of metal/use use.Beta catalyst (such as organic ammonium or microcosmic salt) Amount can be 1 × 10^-2To 1 × 10^-5, especially 1 × 10^-3To 1 × 10^-4Mole/reactant mixture in dihydroxy compounds it is total Mole.The amount of α catalyst can be less than the amount for the beta catalyst for adding polymerisation.It is quenched after the completion of polymerization with acid compound Ester exchange catalyst and any active catalyst residue can also be useful in some melt polymerization process.After polymerization Relict catalyst and/or quencher and other non-volatile residues are removed from melt polymerization in some melt polymerization sides Can also be useful in method.

Makrolon can be, such as weight average molecular weight with 21800 dalton and with 24 to 32g/10min's The bisphenol-a polycarbonate of fluidity of molten (ASTM D1238,300 DEG C, 2.16kg).

Makrolon can have by ASTM D1238 at 300 DEG C, 4 determined under 1.5kg to 40g/10min, for example 4.5 to 15g/10min fluidity of molten.Makrolon can have by ASTM D1238 at 250 DEG C, be determined under 1.5kg 5 to 15g/10min fluidity of molten.

The present invention makrolon melting prepare in, can one or more positions add quencher compositions with The activity of catalyst is reduced, for example, reduces or suppress the activity of α catalyst.Quencher compositions include quenching agent (quenching agent) (is also referred to as quencher (quencher)) herein.For example, quencher can include sulphonic acid ester, Such as formula R₁SO₃R₂Alkyl sulfonic ester, wherein, R₁It is hydrogen, C₁-C₁₂Alkyl, C₆-C₁₈Aryl or C₇-C₁₉Alkaryl, and R₂ It is C₁-C₁₂Alkyl, C₆-C₁₈Aryl or C₇-C₁₉Alkaryl.The example of alkyl sulfonic ester includes benzene sulfonate, p-methyl benzenesulfonic acid Ester, tosylate, ethylbenzenesulfonic acid ester, n-butylbenzene sulphonic acid ester, octyl benzene sulfonic acid ester and phenyl benzene sulphonic acid ester, methyl are to toluene Sulphonic acid ester, ethyl p-methyl benzenesulfonic acid ester, normal-butyl p-methyl benzenesulfonic acid ester, octyl group p-methyl benzenesulfonic acid ester and phenyl p-methyl benzenesulfonic acid Ester.Sulphonic acid ester can include alkyl benzenesulfonates (alkyl p-methyl benzenesulfonic acid ester, alkyl tosylate), such as normal-butyl toluene Sulphonic acid ester (normal-butyl p-methyl benzenesulfonic acid ester, n-butyl tosylate).Sulphonic acid ester can be with based on the total of quencher compositions The amount presence of 0.1 to 10 percentage by volume (vol%) of volume, especially 0.1 to 5vol%, more particularly 0.5 to 2vol% In quencher compositions.

Quencher can include borate (such as B (OCH₃)₃、B(OCH₂CH₃)₃With B (OC₆H₆)₃), Firebrake ZB, boron phosphate, Aluminum stearate, alumina silicate, zirconium carbonate, C₁-C₁₂Alkoxide zirconium, hydroxycarboxylic acid zirconium, gallium phosphide, gallium antimonide, germanium oxide, C₁-C₃₂Have Machine germanium compound, C₄-C₃₂Four organic group tin tin compounds, C₆-C₃₂Six organic group tin compound (such as [(C₆H₆O)Sn (CH₂CH₂CH₂CH₃)₂]₂O)、Sb₂O₃, antimony 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, sulphur 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 is (for example, sulfuric acid two Methyl esters and dibutyl sulfate), formula (R^aSO₃ ^-)(PR^b ₄)⁺Sulfonic acid phosphonium salt, wherein, R^aIt is hydrogen, C₁-C₁₂Alkyl, C₆-C₁₈Aryl, Or C₇-C₁₉Alkaryl and each R^bIt is independently hydrogen, C₁-C₁₂Alkyl, C₆-C₁₈Aryl, formula A¹-(Y¹-SO₃X¹)_mSulfnic acid derivatives Biology, wherein, A¹It is the C with m valencys₁-C₄₀Hydrocarbyl group, Y¹It is singly-bound or oxygen atom, X¹It is formula-CR¹⁵R¹⁶R¹⁷Secondary or uncle Alkyl group, the metal cation of monovalent, ammonium cation (such as NR^b ₃ ⁺, wherein, each R^bIt is independently hydrogen, C₁-C₁₂Alkyl Or C₆-C₁₈Aryl), Huo Phosphonium (such as PR^b ₄ ⁺, wherein, each R^bIt is independently hydrogen, C₁-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 with 1 to 5 carbon atom Alkyl group, and R¹⁷With R¹⁵It is identical or different, and have and R¹⁵Identical is defined, and condition is R¹⁵、R¹⁶And R¹⁷In Two are hydrogen atoms, and m is 1 to 4 integer, and condition is to work as Y¹When being singly-bound, the X of all m amount¹It can not be monovalent Metal cation, formula⁺X²-A²-Y¹-SO₃ ^-Compound, wherein, A²It is divalent hydrocarbyl mission,⁺X²It is secondary, tertiary or quaternary ammonium cation Or secondary (for example, tertiary Huo quaternary phosphines cation, and Y¹It is singly-bound or oxygen atom, formula A³-(⁺X³)_n·(R-Y¹-SO₃ ^-)_nCompound, Wherein, A³It is the C with n valencys₁-C₄₀Alkyl,⁺X³It is secondary, tertiary or quaternary ammonium cation (for example, NR^b ₃ ⁺, wherein, each R^bIndependently It is hydrogen, C₁-C₁₂Alkyl or C₆-C₈Aryl) or secondary, tertiary Huo quaternary phosphines cation (for example, PR^b ₄ ⁺, wherein, each R^bIt is independently Hydrogen, C₁-C₁₂Alkyl or C₆-C₈Aryl), R is the C of unit price₁-C₄₀Alkyl, n are 2 to 4 integers, and Y¹It is that singly-bound or oxygen are former Son, formulaCompound, wherein, A⁵It is unit price or the C of divalence₁-C₄₀Alkyl, A⁴It is the C of divalence₁- C₄₀Alkyl, Ad¹And Ad²It is to be selected from-SO independently of one another₂-O-SO₂-、-SO₂- O-CO- and-CO-O-SO₂- anhydride group, and AndIt is 0 or 1, condition is to work asWhen being 0,It is hydrogen atom or A⁴And A⁵Between key, wherein, A⁵It is bivalent hydrocarbon radical Group or singly-bound, with 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_bEither individually or in combination with N formation aromatic series or non-aromatic heterocyclic compound (such as pyrrole radicals, pyridine radicals, pyrimidine radicals, pyrazinyl, carbazyl, quinolyl, imidazole radicals, piperazinyl, oxazolyls, thiazolyl, pyrrole Oxazolyl, pyrrolinyl, indyl, purine radicals, pyrrolidinyl etc.), R_cIt is hydrogen, and A is C₁-C₁₂Alkyl, C₆-C₂₂Aryl or C₇-C₁₉Alkaryl (for example, compound, such as N- (2- hydroxyethyls) piperazine-N'-3- propane sulfonic acid, Isosorbide-5-Nitrae-piperazine double (ethyl sulfonic acids), With 5- dimethylamino -1- naphthyl sulphonic acids), formula R_aR_bR_cN⁺-A-SO₃ ^-Ammonium sulphonic acid ester, wherein, R_a、R_bBe independently of one another hydrogen, C₁-C₁₂Alkyl, C₁-C₁₂Aryl, C₇-C₁₉Alkaryl or R_aAnd R_bEither individually or in combination with N formation aromatic series or non-aromatic Heterocyclic compound is (for example, pyrrole radicals, pyridine radicals, pyrimidine radicals, pyrazinyl, carbazyl, quinolyl, imidazole radicals, piperazinyl, oxazoles 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, methyl acrylate-sulfonated phenylethylene copolymer and comprising foregoing At least one combination.

Quencher compositions can be added with solid or liquid form.When in liquid form, quencher compositions can For example to be added by add-on system.Add-on system can include the first rotary drum (roller, drum)；Buffering drum (dsah-pot, buffer drum)；Measuring pump；Filter；Syringe or including foregoing one or more combination, wherein, the first rotary drum eases up One or two of punching drum can include agitator and/or heating system.For example, quencher and liquid-carrier can be added to the One rotary drum and then addition buffering drum.Can by liquid quencher compositions from buffering drum by positioned at polymerized unit, anti- Answer it is one or more in device, transmission line, blender and extruder in injector be injected to paradigmatic system.Quencher compositions Pump to measuring pump can be controlled by main dispensing loop (main distribution loop), wherein can be continued with flowmeter Ground or the addition for intermittently monitoring quencher compositions.The pump, which may further include, to be monitored and adjusts for automating flowmeter The controller of the amount of the whole quencher compositions to polymerized unit.Can be more than or equal to 2 bars, specifically greater than or equal to 3 Liquid quencher compositions are added to makrolon under bar, the more particularly pressure of 3 to 100 bars.It again may be by liquid Body injection (spraying, spray) adds liquid quencher compositions in solid polycarbonate substrate.Can be in its addition polymerization Filtered fluid quencher compositions before system.

When in solid form, quencher compositions can include quencher and optional solid carrier, for example, gather Polycarbonate powder, wherein, polycarbonate powder can be included, for example, the melting in powder type gathers as described in this article Carbonic ester and/or interfacial polycarbonate.When in solid form, solid quencher compositions only can be with, such as with masterbatch or Extruder and/or downstream is directly added into by spraying to solid polycarbonate substrate.Similarly, solid quencher compositions It can be added by feeder, such as feed screw (feed screw, screw feeder).Especially, it is solid for adding The method of body quencher compositions can include melt polycarbonate granulation forming makrolon；By makrolon feed to Extruder；Solid quencher compositions are added to makrolon；And by quencher compositions and makrolon to poly- carbon Acid esters adds period of the mixing more than or equal to 5 seconds before any reactive additive, wherein, reactive additive has anti- The OH groups of answering property or the ester group of reactivity.Can add solid quencher compositions before melt polycarbonate.

Solid quencher compositions can include 0.1 to 100wt% of the gross weight based on solid quencher compositions, spy Not 10 to 99wt% quencher.

When in liquid form, quencher compositions can include liquid-carrier.Liquid-carrier can include low boiling Solvent, to cause the boiling point of low boiling point solvent to be less than the boiling point for the quencher being present in quencher compositions.If for example, sudden Agent of going out includes butyl tosylate, then low boiling point solvent can have the boiling point less than 140 DEG C.Low boiling point solvent can squeezed Go out under the conditions of the temperature and pressure of machine, such as do not reacted under high-temperature vacuum with makrolon substantially.Low boiling point solvent can So that quencher can be dissolved.Low boiling point solvent can include dimethylbenzene, toluene, benzene, ethylbenzene, methyl phenyl ethers anisole, chlorobenzene, and comprising Foregoing one or more combination.Low boiling point solvent can include water, organic solvent (such as acetone), or include foregoing one kind or two The combination planted.

Liquid-carrier can include high boiling solvent so that the boiling point of high boiling solvent is more than or equal to and is present in quencher The boiling point of quencher in composition.For example, if quencher includes butyl p-toluenesulfonate, low boiling point solvent can have Boiling point more than or equal to 140 DEG C.High boiling solvent can include the compound being present in melt polymerization.For example, in bisphenol-A In the melt polymerization of type makrolon, high boiling solvent can include diphenyl carbonate, phenol, bisphenol-A, oligomeric polycarbonate Thing, bisphenol-a derivative, propylene carbonate (propylene glycol carbonate, propylene carbonate) or comprising foregoing a kind of or A variety of combinations.

If both low boiling point solvent and high boiling solvent are present, they can dissolve each other each other.In quencher combination The ratio of low boiling point solvent and high boiling solvent can be 4 in thing:1 to 1:4, especially 2:1 to 1:2, more particularly 1.5:1 to 1:1.5.Similarly, quencher compositions can be free of liquid-carrier.

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

Similarly, quencher compositions can be free of carrier.For example, quencher compositions can include quencher, addition Agent, and without carrier；For example, can be made up of quencher and optional additive.Quencher can (melting as melting Change) quencher addition.When quencher compositions are free of carrier, quencher compositions can be included based on carrier-free sudden Go out agent composition gross weight 0.1 to 100wt% quencher.

Quencher can be more than or equal to 5 parts by weight (ppm) in parts per million with the total amount based on makrolon, especially The amount that ground is more than or equal to 10ppm is added.Quencher can be less than or equal to 5ppm with the total amount based on makrolon, especially The amount that ground is less than or equal to 10ppm is added.Quencher compositions can be added polymerized unit so that quencher is with based on poly- carbon The 0.5 of the gross weight of acid esters is to 15ppm, and especially 1 to 10ppm, more particularly 1.5 to 5ppm, specifically 1.5 to 3ppm Amount add.Likewise it is possible to which quencher compositions are added into polymerized unit so that with the gross weight based on makrolon 5 to 10ppm, especially 6 to 8ppm amount add quencher.Likewise it is possible to add quencher so that quencher or its derivative Thing is with 0.1 to 50 times, and especially the amount of 0.5 to 30 times of catalyst used per neutralization equivalent is present.

Quencher compositions can be added in one or more of the melting preparation of makrolon position.For example, quenching Agent composition can add polymerized unit upstream, be directly added into polymerized unit (such as in porch, in the charging aperture of side, in row In outlet or including foregoing one or more combination), the downstream of polymerized unit, add and do not polymerize the reaction of makrolon Device, the upstream of extruder, extruder is directly added into (for example, at the feed throat of extruder, in the charging aperture of side, in outlet In or including foregoing one or more combination), the downstream of extruder or including foregoing one or more combination.Work as addition During the upstream of extruder, quencher compositions can be added to the upstream of final polymerized unit and/or final polymerization is added Among unit and/or after final polymerized unit.Quencher compositions can be added among final polymerized unit.Can be with By the outlet of quencher compositions the first polymerized unit of addition, the outlet of the second polymerized unit, positioned at final polymerization list Reactor, extruder or including foregoing one or more combination between member and extruder.Likewise it is possible to will be a certain amount of Quencher compositions add and/or after one or more stage feeding polymerization units and/or among final extruder.For example, Quencher compositions can be added after initial polymerization unit, then can add fresh catalyst, and further gathering Other quencher can be added after conjunction.

Polymerization can include the part (area of parallel polymerization (parallel polymerization, parallel polymerization) Section, section), wherein, parallel polymerization refers to polycarbonate flow being divided into 2 or more streams, and hereafter it may or may not It is subjected to identical polymerizing condition (i.e. they can reach different molecular weight, with different additives being added thereto etc.). For example, makrolon can be prepared in the Part I of polymerization process；Can by the flow point comprising makrolon be two or It is multiple to flow and guide to 2 or more parallel operation lines.For example, method can be included in a series of oligomeric polymerized unit Middle polymerization makrolon；The flow point that the oligomeric stage can be discharged is two kinds of streams：A and B, wherein, by A streams guiding to polymerized unit A simultaneously guides B streams to polymerized unit B.Similarly, method can be included in a series of oligomeric unit and polymerize makrolon, Then it polymerize in a series of polymerized unit；The flow point that polymerization stage can be discharged is two kinds of streams：A and B, wherein, A is flowed Guiding is guided to extruder B to extruder A, and by B streams.Similarly, method can be included in a series of oligomeric unit and gather Makrolon is closed, is then polymerize in a series of polymerized unit；The flow point that the first polymerized unit can be discharged is two plumes： A and B, wherein, A streams are guided to the second polymerized unit A and guide B streams to the second polymerized unit B.In any aforementioned circumstances In, can by quencher compositions added to stream A and B one or two, wherein, quencher compositions can be identical or Different.Those skilled in the art, which can easily be contemplated to other, includes the embodiment of more than two concurrent flow, Yi Jiqi In the embodiment that is separately flowed in different positions.

When quencher compositions are added into polymerized unit and/or extruder, quencher compositions can be with, for example by Henschel mixer (Henschel mixer) is alternatively mixed, and is introduced to feeder, such as gravity-feeder, and is then led to Feeder is crossed, such as side feeder feeds to polymerized unit and/or extruder and/or is directly fed into the feed throat of extruder.

When by quencher compositions added to connection first module and the connection flow of second unit, then comprising the sudden of addition The connection flow of agent composition of going out can be by, for example, setting up turbulent flow (line mixer (online mixer, in-line Mixer static mixer and/or the mixer unit of receiving rotation oar)), for example in the pipeline containing connection flow, example Such as continue the static mixer mixing in tank diameter.Mixing can occur 0.3 to 5 minute, such as 0.5 to 3 minute, such as 1 to 2 Minute.Likewise it is possible to which quencher compositions are not mixed added to connection flow.

Quencher compositions can be added after polycarbonate compositions formation after extrusion and/or melt filteration. For example, after polycarbonate compositions are prepared, polycarbonate compositions and quencher compositions can be existed, such as pipeline is mixed Mix, and then granulate in clutch, bitubular agitator etc..Likewise it is possible to first by polycarbonate compositions granulate and Then quencher compositions can be introduced.It by, for example, flowing or can spray, be combined quencher with solid or liquid form Thing is added on polycarbonate pellet and alternatively can mixed in such as melt kneading machine with pellet.In this case, Additive can be introduced after quencher compositions are introduced.For example, granular (pelletized) makrolon, such as without adding Plus the granular makrolon of agent, it can be combined with quencher compositions and can then add antioxidant and/or releasing agent.

Polycarbonate compositions devolatilization can be removed to low molecule amount and (be less than or equal to 1,000 dalton as having Molecular weight those).Devolatilization can occur in polymerized unit in (for example, in polymerized unit), reactor, extruder In, in blender or in including foregoing one or more combination.Makrolon can be quenched before devolatilization.For example, Quencher can be added to extruder upstream and/or extruder is directly added into, can be by extruder devolatilization, it is possible to which addition adds Plus agent.

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

Fig. 1 shows the method that quencher compositions are added to paradigmatic system.Especially, Fig. 1 is shown, quencher group Compound can be added by one or more quencher stream 40-50, wherein quencher stream 40-50 can be liquid quencher stream simultaneously And quencher stream 46-50 can be solid quencher stream.For example, quencher stream 40 can be added to stream 20, and can be right Stream 20 is alternatively mixed in blender 10 afterwards；Quencher stream 42 can be added to reactor unit 2, wherein, reactor Unit 2 can be the first aggregation container, middle aggregation container, final aggregation container and after final aggregation container it is anti- Answer the one or more of device；Can by quencher stream 44 be added to aggregated flow 22, and can then by aggregated flow 22 alternatively Mixed in blender 10；Can by quencher stream 46 by extruder feed throat 8 be added to extruder 4；Can be by quencher Stream 48 is by surveying charging aperture 12 added to extruder 4；And quencher stream 50 can be added to extrudate flow 24 and can be alternatively Mixed in blender 10.Extrudate flow 24 can be fed to fondant filter 6 to form polycarbonate compositions stream 26.Mixing Device 10 can be, such as line mixer, turbulent flow or continue agitating unit.It should be noted that fondant filter 6 can be equally located on The upstream of extruder 4 and quencher compositions can be added before or after the fondant filter.It is further 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 in any appropriate position Container.

Fig. 1 shows the method that quencher compositions are added to the polycarbonate compositions further granulated in addition.It is special Not, Fig. 1, which is shown, to add quencher compositions by one or more quencher stream 52-58, wherein, quencher stream 52-58 can be solid quencher stream or liquid quencher stream.For example, quencher stream 52 can be added into optional blender 14, wherein, optional blender 14 can be that (such as the bitubular is extruded for such as line mixer, turbulent flow or lasting agitating unit Machine)；Quencher stream 56 can be added comminutor 16 for example at the feed throat of comminutor；Can be by quencher stream 58, such as By the way that quencher compositions are sprayed to the pellet of formation, added to granulation stream 30.Although it should be noted that quencher stream 56 and 58 It is illustrated into the corresponding side of container, it is readily appreciated that these streams can enter container in any appropriate position.Such as accompanying drawing acceptance of the bid Bright, stream 40,44 and 26 includes being used for other potential processes, the polymerized unit being such as likely to occur, transmitting step and purification step The mark of rapid position.

The one or more positions that can be prepared in addition in the melting of the makrolon of the present invention add additive.For example, Additive can be added polymerized unit upstream, be directly added into polymerized unit (for example porch, in the charging aperture of side, In outlet or including foregoing one or more combination), polymerized unit downstream, not polymerization makrolon reactor in, Extruder upstream, be directly added into extruder (for example, at the feed throat of extruder, in the charging aperture of side, in outlet, Or including foregoing one or more combination), extruder downstream or including foregoing one or more combination.It will can add Agent is added and/or can be individually added into as the part of quencher compositions.For example, can be by the quencher comprising heat stabilizer Composition is added to makrolon, and the compositions of additives comprising releasing agent and UV reagents can be added to the group of quenching Compound.Additive can be added with molten condition or can after melting be added in the makrolon of extrusion.Can be in addition Additive is filtered before to polymerized unit.

Additive can be included, and for example impact modifier, flow ability modifying agent, filler are (for example, particle polytetrafluoroethylene (PTFE) (PTFE), glass, carbon, mineral or metal), reinforcing agent (for example, glass fibre), antioxidant, heat stabilizer, light stabilizer, (e.g., releasing agent is (such as list for ultraviolet (UV) reagent (e.g., UV light stabilizers and UV absorbing additives), plasticizer, lubricant, release agent Tristerin, stearic acid pentaerythritol ester, glyceryl tristearate, stearyl stearate etc.)), it is antistatic additive, antifog Agent, antifreezing agent (antifrost agent), antimicrobial, colouring agent (for example, dyestuff or pigment), skin effect additive, Stable radiation agent, fire retardant, the anti-dripping agent SAN (TSAN) of encapsulation (for example, PTFE) or comprising preceding State the combination of one or more.It is, for example, possible to use the combination of heat stabilizer, releasing agent and UV light stabilizing agent.Generally, may be used Use the commonly known additive effectively measured.For example, compositions of additives total amount (except any impact modifier, filler, Or reinforcing agent) can be 0.001 to 10.0 percetage by weight for being each based on the gross weight of polymer in polymeric compositions , or 0.01 to 5wt% (wt%).

Heat stabilizer additive includes organic phosphite (for example, triphenyl phosphite, three-(2,6- 3,5-dimethylphenyl) Phosphite ester, three-(the single- and di- nonyl phenyl of mixing) phosphite esters etc.), phosphonate ester is (for example, dimethylbenene phosphonate Deng), phosphate (for example, trimethyl phosphate etc.) or the combination for including at least one of foregoing heat stabilizer.Heat stabilizer can be with Comprising IRGAPHOS can be used as^TM168 three (2,4- di-tert-butyl-phenyls) phosphates obtained.Heat stabilizer can be included IRGAPHOS^TM205.Heat stabilizer is generally used with the amount of 0.01 based on the gross weight of polymer in composition to 5wt%.

Term " antistatic additive " refers to that polymer can be processed as and/or is injected on material or product conductive special to improve Monomer, the oligomeric or polymeric material of property and overall physical properties.The example of monomeric antistatic agents include ethoxylated amine, primary, Secondary and tertiary amine, ethoxylated alcohol, alkyl sulfate, alkaryl sulfate, alkyl microcosmic salt, alkyl amino sulfate, alkyl sulfonic acid Salt, such as stearoyl acyl sodium sulfonate, neopelex, quaternary ammonium salt, quaternary ammonium polymer, imidazolidine derivatives, dehydration mountain Pears sugar alcohol ester, glycollic amide, glycine betaine etc., or include the combination of at least one of aforementioned monomer antistatic additive.

Polymer antistatic agent includes specific polyesteramide, polyphenylene ether-polyamide (polyetheramides) block copolymer, polyether ester Amide block copolymers, polyether ester, or polyurethane, each contain polyalkylene glycol moiety polyalkylene oxide units, such as poly- second two Alcohol, polypropylene glycol, polytetramethylene glycol etc..This polymer antistatic agent is commercially available, such as PELESTAT^TM 6321 Or PEBAX (Sanyo)^TM MH1657(Atofina)、IRGASTAT^TMP18 and P22 (Ciba-Geigy).It may be used as anti-quiet Other polymeric materials of electric agent are intrinsic conduction polymer, and such as polyaniline (can be used as PANIPOL^TMEB commercially available from Panipol), polypyrrole and polythiophene (available commercially from Bayer), it keeps some it after melt-processed at elevated temperatures Intrinsic conductivity.In embodiments, carbon fiber, carbon nano-fiber, CNT, carbon black, or include foregoing at least one The combination planted can be used for polymer composition, and it contains chemical antistatic additive so that said composition is electrostatic dissipation.

There can also be stable radiation agent, especially, γ-stable radiation agent.γ-stable radiation agent includes alkylene polyol Alcohol, such as ethylene glycol, propane diols, 1,3-PD, 1,2- butanediols, BDO, meso -2,3-butanediol, 1,2- penta Glycol, 2,3- pentanediols, 1,4- pentanediols, 1,4- hexylene glycols etc.；Cycloalkylidene polyalcohol, such as 1,2- rings pentanediol, 1,2- rings Hexylene glycol etc.；Branched alkylen polylol, such as Pinacol (pinacol), and alkoxy substitution Ring-type or acyclic alkanes.Unsaturated enol can also be used, the example includes 4- methyl -4- amylene -2- alcohol, 3- methyl-penta Alkene -3- alcohol, 2- methyl -4- amylene -2- alcohol, 2,4- dimethyl -4- amylenes (pene) -2- alcohol and 9- decen-1-ols and have The tertiary alcohol of the tertiary carbon of at least one hydroxyl substitution, such as 2- methyl -2,4- pentanediol (hexylene glycol), 2- phenyl -2- butanol, 3- hydroxyls Base -3- methyl -2- butanone, 2- phenyl -2- butanol etc., and the ring tertiary alcohol, such as 1- hydroxyls -1- methyl-cyclohexyl alkane.It can also use Specific methylol aromatic compounds with hydroxyl substitution in the saturated carbon of unsaturated carbon is being connected in aromatic ring.Hydroxyl replaces Saturated carbon can be methylol groups (- CH₂OH) or it can be more complicated alkyl, such as-CR⁴HOH or-CR₂ ⁴In OH Member, wherein, R⁴It is complicated or simple hydrocarbons.Specific hydroxymethyl aromatic compound includes benzhydrol, 1,3- benzene two Methanol, benzylalcohol, 4- benzyloxybenzyl alcohols and benzyl benzylalcohol.2- methyl -2,4-PD, polyethylene glycol and polypropylene glycol is frequently used for γ-stable radiation.

Can also there are colouring agent, such as pigment and/or dye additive.Useful pigment can include, such as inorganic face Material, such as metal oxide and the metal oxide of mixing, such as zinc oxide, titanium dioxide, iron oxide；Sulfide, such as zinc sulphide Deng；Aluminate；Sulfo group-silicic acid sodium sulphate, sodium chromate etc.；Carbon black；Zinc ferrite；Ultramarine；Organic pigment, such as azo, two azos, quinoline Acridone, perylenes, 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 29th, pigment blue 15, pigment blue 60, pigment Green 7, pigment yellow 119, pigment yellow 147, pigment yellow 150 and pigment brown 24；Or comprising The combination of foregoing at least one pigment.

Dyestuff is typically organic material and including coumarine dye, such as cumarin 460 (blueness), coumarin 6 (green), Nile red etc.；Lanthanide series compound；Hydrocarbon and the hydrocarbon dyestuff of substitution；Ppolynuclear aromatic hydrocarbon dyestuff；Scintillation dyes , such as oxazole Huo Evil Two thiiazole dyes；Aryl or the poly- (C of heteroaryl substitution_2-8) alkene dyestuff；Carbonyl cyanine dye；Indanthrone dyes；Phthalocyanine dye；Evil Piperazine dyestuff；Hydroxyquinoline dye；Naphthalene tetracarboxylic acid dyestuff；Porphyrin dye；Double (styryl) biphenyl dyestuffs；Acridine dye；Anthraquinone Dyestuff；Cyanine dye；Methine dyes；Arylmethane dyes；Azo dyes；Bipseudoindoxyl dye；Thioindigo color；Diazo colours；Nitre Radical dye；Quinoneimine dye；Aminoketone dye；Tetrazolium dye；Thiazole dye；Perylene dyes；Cyclic ketones dyestuff；Double benzos are disliked Azoles thiophene (BBOT)；Triarylmethane dye；Thioxanthene dye；Naphthalimide dye；Lactone colouring matters；Fluorogen, such as absorbs Near-infrared wavelength simultaneously launches anti-stoke shift (anti-stokes shift) dyestuff of visible wavelength etc.；Luminescent dye, such as 7- Amino -4- methylcoumarins；3- (2'- benzothiazolyls) -7- diethyl amino coumarins；2- (4- xenyls) -5- (tertiary fourths of 4- Base phenyl) -1,3,4- oxadiazoles；2,5- pairs-(4- xenyls)-oxazoles；2,2'- dimethyl-to quaterphenyl；2,2- dimethyl- Para-terpheny；3,5,3 " ", 5 " "-tetra-tert-to quinquephenyl；2,5- diphenyl furans；2,5- diphenyl-oxazoles；4,4'- bis- Phenyl stilbene；4- dicyano methylene -2- methyl -6- (to dimethylaminostyryl) -4H- pyrans；1,1'- diethyl -2, 2'- carbocyanine iodide；3,3 '-diethyl -4,4 ', the carbocyanine iodide of 5,5 '-bisbenzothiazole three (dibenzothiatricarbocyanineiodide)；7- dimethylamino -1- methyl -4- methoxyl group -8- azepines quinolone - 2；7- dimethyl amido -4- methyl quinolone -2；2- (4- (4- dimethylaminophenyls) -1,3- butadienyls) -3- ethylo benzenes And thiazole perchlorate；3- diethylamino -7- diethyl imino group phenoxazine perchlorate (3-diethyla mino- 7-diethyli minophenoxazonium perchlorate)；2- (1- naphthyls) -5- Ben Ji oxazoles；2,2'- is to sub- benzene Base-bis- (5- Ben Ji oxazoles)；Rhodamine 700；Rhodamine 800；Pyrene,Rubrene, coronene etc.；Or comprising in abovementioned dyes extremely A kind of few combination.

Possible filler or reinforcing agent include, for example mica, clay, feldspar, quartz, quartzite, perlite, tripoli (tripoli), diatomite (diatomaceous earth), alumina silicate (mullite), synthetic calcium silicate, fused silica, Aerosil, sand (sand), boron-nitride powder, boron-silicate powder, calcium sulfate, calcium carbonate (such as chalk, lime Stone, marble and synthesis winnofil), talcum (including fiber, module, needle-like and lamella talc), wollastonite, in Empty or solid glass ball, silicate ball, cenosphere, aluminosilicate or (armouring ball (armosphere)), kaolin；Carbonization Silicon, aluminum oxide, boron carbide, iron, the whisker of nickel or copper；Continuous and chopped carbon fiber or glass fibre, molybdenum sulfide, vulcanization Zinc, barium titanate, barium ferrite, barium sulfate, barite, TiO₂, aluminum oxide, magnesia, particle or fiber aluminium, bronze, zinc, copper, Or nickel, sheet glass, thin slice carborundum, sheet aluminium diboride, flaky aluminum, steel disc, natural stuffing, such as wood chip, fibrous cellulose, Cotton, sisal hemp, jute, starch, lignin, the shuck (peanut shell, ground nut shell) of grinding or grain of rice shell, Strengthen organic fibrous fillers, such as poly- (ether ketone), polyimides, polybenzoxazole, poly- (diphenyl sulfide), polyester, polyethylene, aromatic series Polyamide, aromatic polyimide, PEI, polytetrafluoroethylene (PTFE) and poly- (vinyl alcohol) and include aforementioned filler or increasing The combination of at least one of strong agent.Filler and reinforcing agent can be applied coated with promotion electric conductivity with metal material layer, or use silane table Face handles to improve its adhesiveness and dispersiveness with polymeric matrix.With 1 parts by weight of the total composition based on 100 parts by weight Amount to 200 parts by weight uses filler.

Antioxidant includes organic phosphite, such as three (nonyl phenyl) phosphite esters, three (2,4- di-tert-butyl-phenyls) Phosphite ester, double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, Distearyl pentaerythritol；Alkane The monohydric phenol or polyphenol of base；The hydrocarbyl reaction product of polyphenol and diene, such as four [methylene (3,5- di-t-butyl -4- hydroxyls Hydrogenated cinnamate)] methane；The butylation product of paracresol or bicyclopentadiene；Alkvlated hvdroquinones；It is hydroxylated thio Diphenyl ether；Alkylidenebisphenols；Benzyl compounds；β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid and unitary or polyalcohol Ester；β-(5- tertiary butyl-4-hydroxy -3- aminomethyl phenyls)-propionic acid and unitary or the ester of polyalcohol；Alkylthio or thioaryl The ester of compound, such as propane thioic acid distearyl base ester, propane thioic acid dilauroyl ester, thio-2 acid double tridecyl Ester, octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester, the [3- (3,5- di-t-butyls -4- of pentaerythrityl-four Hydroxy phenyl) propionic ester；The acid amides of β-(3,5- di-tert-butyl-hydroxy phenyl)-propionic acid, or comprising in foregoing antioxidant extremely A kind of few combination.Can be with the amount of 0.01 to 0.1 parts by weight of the total composition in addition to any filler based on 100 parts by weight Use antioxidant.

UV absorbing additives include dihydroxy benaophenonel；Hydroxybenzotriazole；Hydroxy benzo triazine；Cyanoacrylate； Oxanilide；Benzoxazinone；Bigcatkin willow acid aryl ester；The monoesters of diphenol, such as resorcinol monobenzoate；2- (2H- benzos three Azoles -2- bases) -4- (1,1,3,3- tetramethyl butyls)-phenol (CYASORB^TM5411)；2-hydroxy-4-n-octoxybenzophenone (CYASORB^TM531)；2- [double (2,4- the 3,5-dimethylphenyls) -1,3,5- triazine -2- bases of 4,6-] -5- (octyloxy)-phenol (CYASORB^TM1164)；Double (4H-3,1- benzoxazine -4- the ketone) (CYASORB of 2,2'- (1,4- phenylenes)^TMUV-3638)； Poly- [(6- morpholinyl-s- triazine -2,4- diyls) [2,2,6,6- tetramethyl -4- piperidyls) imino group]-hexa-methylene [(2,2, 6,6- tetramethyl -4- piperidyls) imino group], 2- hydroxyl -4- octyloxybenzophenones (UVINUL^TM3008), the 6- tert-butyl groups -2- (the chloro- 2H- BTAs -2- bases of 5-) -4- aminomethyl phenyls (UVINUL^TM3026), 2,4- di-t-butyls -6- (the chloro- 2H- benzos of 5- Triazole -2- bases)-phenol (UVINUL^TM3027), 2- (2H- BTA -2- bases) tertiary phenylphenol (UVINUL of -4,6- two^TM 3028), 2- (2H- BTA -2- bases) -4- (1,1,3,3- tetramethyl butyls)-phenol (UVINUL^TM3029), 1,3- is double [(2' cyano group -3', 3'- diphenylacryloyl) oxygen] -2,2- pairs-[2'- cyano group -3', 3'- diphenylacryloyl) oxygen] first Base }-propane (UVINUL^TM3030), 2- (2H- BTA -2- bases) -4- methylphenols (UVINUL^TM 3033)、2-(2H- BTA -2- bases) double (1- methyl isophthalic acids-phenylethyl) phenol (UVINUL of -4,6-^TM3034), ethyl -2- cyano group -3,3- two Phenyl acrylate (UVINUL^TM3035), (2- ethylhexyls) -2- cyano group -3,3- diphenylacrylate esters (UVINUL^TM 3039) double (2,2,6,6- tetramethyl -4- piperidyls) hexamethylene diamine (UVINUL of the double formyl-N, N'- of, N, N'-^TM 4050H), double-(2,2,6,6- tetramethyl -4- piperidyls) sebacate (UVINUL^TM4077H), double-(first of 1,2,2,6,6- five Base -4- piperidyls)-sebacate+methyl-(1,2,2,6,6- pentamethyl -4- piperidyls)-sebacate (UVINUL^TM 4092H), the double [[(2- cyano group -3,3- diphenyl acryloyls of double [(2- cyano group -3,3- diphenylacryloyls) the oxygen] -2,2- of 1,3- Base) oxygen] methyl] propane (UVINUL^TM3030)；2,2'- (1,4- phenylenes) double (4H-3,1- benzoxazine -4- ketone)；1,3- Double [(2- cyano group -3,3- diphenylacryloyls) oxygen] 2,2- are double [[(2- cyano group -3,3- diphenylacryloyls) oxygen] methyl] Propane；TINUVIN^TM234；Nano-sized inorganic material, such as titanium dioxide, cerium oxide and zinc oxide, are respectively provided with and are less than or wait In 100 nanometers of particle diameter；Etc., or include the combination of at least one of foregoing UV absorbents.Can be with based on 100 parts by weight The amount of 0.01 to 1 parts by weight of makrolon and impact modifier uses UV absorbents.Can especially with it is disclosed herein The UV absorbents that polycarbonate compositions are used together include 2- (2H- BTA -2- bases) -4- (1,1,3,3- tetramethyl fourths Base)-phenol is (for example, CYASORB^TM5411, available commercially from Cytec Industries, Inc., Woodland Park, New ) and double (4H-3,1- benzoxazine -4- ketone) (such as CYASORB of 2,2'- (1,4- phenylenes) Jersey^TMUV-3638, can business Purchased from Cytec Industries, Inc., Woodland Park, New Jersey), and include foregoing at least one combination. UV stabilizer can arrive 1wt% with 0.01 of the gross weight based on polycarbonate compositions, especially 0.1 arrive 0.5wt%, and More particularly 0.15 to 0.4wt% amount is present.

Plasticizer, lubricant and/or releasing agent can also be used.Exist among the material of these types considerable heavy Folded, it includes, phthalic acid ester, such as dioctyl -4,5- epoxy radicals-hexahydrophthalic acid ester；Three-(carbonyl octyloxy second Base) cyanurate；Glyceryl tristearate；Two or multi-functional aromatic phosphoric esters, such as resorcinol tetraphenyl diphosphonic acid Double (diphenyl) phosphates of ester (RDP), double (diphenyl) phosphates of quinhydrones and bisphenol-A；Polyalphaolefin；Epoxidised soybean Oil；Silicone, including silicone oil；Ester, such as fatty acid ester, such as alkyl stearates, such as methyl stearate, stearyl stearate, Pentaerythritol tetrastearate etc.；The combination of methyl stearate and hydrophily and Hydrophobic nonionic surfactant, including it is poly- Ethylene glycol polymer, polypropylene glycol polymers, poly- (ethylene glycol -co- propane diols) copolymer, or include foregoing ethylene glycol polymer At least one of combination, such as methyl stearate and polyethylene glycol propylene glycol copolymers in suitable solvent；Wax, such as Beeswax, lignite wax, paraffin etc..

Plasticizer, lubricant and/or releasing agent can include the compound of formula (I)

Wherein, R₁、R₂And R₃It can be same or different, the degree of unsaturation with 8 to 20 carbon atoms and 0 to 6 Hydrocarbon chain, wherein R₁、R₂And R₃It is each independently selected from C₈-C₂₀Alkyl, C₈-C₂₀Haloalkyl, C₈-C₂₀Multi-haloalkyl, C₈- C₂₀Alkene and C₈-C₂₀Alkoxy.R₁、R₂And R₃C can be come from independently of one another₁₇H₃₅, or all R₁、R₂And R₃Can be with It is C₁₇H₃₅.Plasticizer, lubricant, and/or releasing agent can include glycerin monostearate, monopalmitin, three tristearin Acid glyceride, glyceryl tristearate, stearyl stearate include foregoing one or more combination.Foregoing one kind or A variety of acid numbers that can have by 2 to 20 milligrams of (mg) KOH identified below：The isopropanol of 100 milliliters (ml) is added 2.5 The partial ester of gram (g) is so as to dissolving the partial ester；Phenolphthalein is regard as indicator added to the solution obtained；Use 0.1 mol/L (mol/L) mixture that standard potassium hydroxide solution titration is obtained is so as to obtain acid number (mg KOH).In the measurement of acid number, When expected partial ester has 1 or lower acid number, the quantitative change that will be subjected to the partial ester of measurement is 20g；When expected partial ester has 1 to 4 Acid number when, will be subjected to measurement partial ester quantitative change be 10g；And, will be through when expected partial ester has 15 or higher acid number The quantitative change of the partial ester measured is 0.5g.

Plasticizer, lubricant, and/or releasing agent can be with the makrolon based on 100 parts by weight and impact modifiers The amount presence of 0.01 to 5 parts by weight, especially 0.01 to 0.1 parts by weight.

Useful fire retardant includes the organic compound for including phosphorus, bromine, and/or chlorine.Non-brominated and non-chlorinated phosphor-containing flame-proof Agent can be preferred in specific applications for the reason for regulation, for example, organophosphorus ester and contain the organic of phosphorus-to-nitrogen bonds Compound.

Fire retardant aromatic phosphoric ester includes triphenyl phosphate, tricresyl phosphate, isopropylation triphenyl phosphate, phenyl Double (neopentyl) esters of double (dodecyl) phosphates, phosphoric acid phenyl, phosphoric acid phenyl double (3,5,5'- trimethyls) ester, phosphoric acid Ethyl diphenyl ester, phosphoric acid 2- ethylhexyls two (p-methylphenyl) ester, phosphoric acid double (2- ethylhexyls) p-methylphenyl ester, tripotassium phosphates Double (2- ethylhexyls) phenyl esters of phenyl ester, phosphoric acid, tricresyl phosphate (nonyl phenyl) ester, double (dodecyl) the p-methylphenyl esters of phosphoric acid, phosphorus Double (2,5,5'- trimethyls) esters of sour dibutylphenyl ester, phosphoric acid 2- chloroethyls diphenyl, phosphoric acid p-methylphenyl and phosphorus Sour 2- ethylhexyl diphenyl phosphates.Two or polyfunctional aromatic series phosphorus-containing compounds are also useful, for example, be isophthalic two respectively Double (diphenyl) phosphates of phenol tetraphenyldiphosphate (RDP), double (diphenyl) phosphates of quinhydrones and bisphenol-A, and it Oligomer and polymer homologue.Flame retardant compound containing phosphorus-to-nitrogen bonds includes phosphonium chloride nitrile, phosphide acid amides, phosphoric acid acyl Amine, phosphonic acid amide, phosphinic acid amide and three (sub- third piperidinyl) phosphine oxides.When deployed, phosphonium flame retardant with based on 100 weights The 0.1-30 parts by weight of the total composition in addition to any filler of part are measured, the more particularly amount of 1-20 parts by weight is present.

Halogenated material is also used as fire retardant, such as following bis-phenol is representational：2,2- pairs-(3,5- dichloro-benzenes Base)-propane；Double-(2- chlorphenyls)-methane；Double (2,6- dibromo phenyls)-methane；1,1- pairs-(3- iodophenyls)-ethane；1,2- Double-(2,6- dichlorophenyls)-ethane；Double (the 2- chlorine-4-iodines phenyl) ethane of 1,1-；1,1- pairs-(the chloro- 4- aminomethyl phenyls of 2-)-second Alkane；1,1- pairs-(3,5- dichlorophenyls)-ethane；2,2- pairs-(3- phenyl -4- bromophenyls)-ethane；2,6- pairs-(4,6- dichloros Naphthyl)-propane；With 2,2- pairs-(the chloro- 4- hydroxy phenyls of 3,5- bis-)-propane；2,2- pairs-(3- bromo -4- hydroxy phenyls)-the third Alkane.Other halogenated materials include 1,3- dichloro-benzenes, Isosorbide-5-Nitrae-dibromobenzene, the chloro- 4- hydroxy benzenes of 1,3- bis- and biphenyl, such as 2,2'- dichloros Biphenyl, the phenoxy group benzene of many bromination Isosorbide-5-Nitraes-two, 2,4'- '-dibromobiphenyls, 2,4'- dichlorobenzenes and decabrominated dipheny base oxide, with And oligomeric and polymerization halogenated aromatic compounds, such as bisphenol-A and tetrabromobisphenol A and carbonate precursor, for example, phosgene Copolycarbonate.Metal synergist, such as antimony oxide, can also be used together with fire retardant.When it is present, containing halogen flame retardant Agent with based on 100 parts by weight the total composition in addition to any filler 1 to 25 parts by weight, more particularly 2 to 20 parts by weight Amount exist.

Inorganic combustion inhibitor, such as C can also be used_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、 CaCO₃And 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 of the total composition in addition to any filler based on 100 parts by weight The amount of parts by weight, more particularly 0.02 to 1 parts by weight is present.

Anti-dripping agent can be used for the fluoropolymer of composition, such as fibrillation formation or non-protofibre formation, such as poly- Tetrafluoroethene (PTFE).Anti-dripping agent can be encapsulated by rigid copolymer, such as SAN (SAN).Encapsulation PTFE in SAN is referred to as TSAN.The gross weight of fluoropolymer based on encapsulation, TSAN includes 50wt%PTFE and 50wt% SAN.Gross weight based on copolymer, SAN can be included, such as 75wt% styrene and 25wt% acrylonitrile.Based on 100 The total composition in addition to any filler of parts by weight, can use anti-drip agents with the amount of 0.1 parts by weight to 10 parts by weight.

The composition of quenching can be substantially free of chlorine and bromine." substantially free of chlorine and bromine " is defined as being based on filling out except any The total weight parts of composition outside material, with less than or equal to every 1,000,000 parts by weight (ppm), less than or equal to 75ppm or Bromine and/or chlorinity less than or equal to 50ppm.

The composition of quenching can have as using sample thick 3.2mm, using ASTMD1003-00, program B, used CIE standard illuminant C, what is determined with one way vision is more than 90% translucency.Therefore, as having when the composition of quenching During translucency, it is herein referred to as " optical-grade " composition.

Embodiment 1：A kind of melt polymerization process, including：In the presence of carbon monoxide-olefin polymeric melt polymerization thing with Makrolon is formed, wherein, carbon monoxide-olefin polymeric includes catalyst；Quencher compositions are added to makrolon, wherein, it is sudden The agent composition that goes out includes quencher；And guide makrolon to extruder.

Embodiment 2：A kind of melt polymerization process, including：In at least two polymerized units, exist in carbon monoxide-olefin polymeric Lower melt polymerization thing to form makrolon, wherein, carbon monoxide-olefin polymeric include α catalyst；By liquid-carrier and quenching Agent is combined to form quencher compositions in quenching agent container；By quencher compositions under the pressure more than or equal to 2 bars Added to makrolon；To makrolon add any additive with reactivity OH groups or reactive ester group it Before, quencher compositions are mixed into the period more than or equal to 5 seconds with makrolon；And guide makrolon to extrusion Machine.

Embodiment 3：According to any one of embodiment 1-2 method, wherein, quencher compositions include dipheryl carbonate Ester.

Embodiment 4：According to the method for embodiment 3, wherein, liquid-carrier includes low boiling point solvent and/or higher boiling Solvent.

Embodiment 5：According to the method for embodiment 4, wherein, liquid-carrier is molten comprising low boiling point solvent and higher boiling Agent, and the ratio of low boiling point solvent and high boiling solvent is 4:1 to 1:4.

Embodiment 6：According to any one of embodiment 3-5 method, wherein, liquid-carrier is poly- comprising melting is present in Compound in conjunction.

Embodiment 7：According to any one of embodiment 3-6 method, wherein, liquid-carrier includes diaryl carbonates Ester, phenol, bisphenol-A, polycarbonate oligomer, bisphenol-a derivative, propylene carbonate include foregoing one or more group Close.

Embodiment 8：According to any one of embodiment 3-7 method, wherein, liquid-carrier comprising dimethylbenzene, toluene, Benzene, ethylbenzene, methyl phenyl ethers anisole, chlorobenzene include foregoing one or more combination.

Embodiment 9：According to any one of embodiment 3-8 method, wherein, liquid-carrier includes toluene.

Embodiment 10：According to any one of embodiment 3-9 method, wherein, liquid-carrier comprising water, acetone or Include foregoing one or more combination.

Embodiment 11：A kind of melt polymerization process, including：In at least two polymerized units in melt polymerization thing, Makrolon is formed in the presence of carbon monoxide-olefin polymeric, wherein, carbon monoxide-olefin polymeric includes α catalyst；Quencher is melted with shape Into quencher compositions, wherein, quencher compositions are free of carrier；Quencher compositions are added into makrolon；Makrolon； And guide makrolon to extruder.

Embodiment 12：According to any one of embodiment 1-11 method, wherein, occur by makrolon guide to After extruder.

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

Embodiment 14：According to any one of embodiment 1-13 method, wherein, quencher compositions include poly- carbonic acid Ester and/or additive.

Embodiment 15：According to any one of embodiment 1-14 method, wherein, add quencher compositions and occur Makrolon is guided to before or after extruder.

Embodiment 16：According to any one of embodiment 1-15 method, wherein, melt polymerization is included in a series of It polymerize makrolon in polymerized unit, and wherein, this method further comprises adding after one or more polymerized units Quencher compositions.

Embodiment 17：According to any one of embodiment 1-16 method, wherein, quencher compositions include sulfonic acid Ester.

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

Embodiment 19：According to the method for embodiment 18, wherein, quencher compositions are added to the charging of extruder Larynx.

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

Embodiment 21：According to any one of embodiment 1-20 method, wherein, carbon monoxide-olefin polymeric is catalyzed comprising β Agent.

Embodiment 22：According to the method for embodiment 21, wherein, beta catalyst includes acetic acid tetraphenylphosphoniphenolate.

Embodiment 23：According to any one of embodiment 21-22 method, wherein, melt polymerization is urged including the use of than α The a greater amount of beta catalyst of agent.

Embodiment 24：According to any one of embodiment 1-20 method, wherein, α catalyst is used only in melt polymerization.

Embodiment 25：A kind of melt polymerization process, including：In the presence of carbon monoxide-olefin polymeric melt polymerization thing with Makrolon is formed, wherein, carbon monoxide-olefin polymeric only includes beta catalyst；Quencher compositions are added to makrolon, its In, quencher compositions include quencher；And guide makrolon to extruder.

Embodiment 26：According to any one of embodiment 1-25 method, wherein, quencher compositions are included and are based on The 1 of 100 parts of makrolon to 10ppm alkyl tosylate.

Embodiment 27：According to any one of embodiment 1-25 method, wherein, quencher compositions are included and are based on The 1 of 100 parts of makrolon to 10ppm phosphorous acid.

Embodiment 28：According to any one of embodiment 1-27 method, wherein, quencher compositions are included and are based on The 2 of 100 parts of makrolon to 5ppm alkyl tosylate and 2 to 5ppm phosphorous acid.

Embodiment 29：According to any one of embodiment 1-28 method, wherein, quencher compositions are included to toluene Sulfonic acid N-butyl.

Embodiment 30：According to any one of embodiment 1-27 method, wherein, quencher compositions are included and are based on The 1 of 100 parts of makrolon to 7ppm quencher.

Embodiment 31：According to any one of embodiment 1-27 method, wherein, quencher compositions are included and are based on The 1.5 of 100 parts of makrolon to 3ppm quencher.

Embodiment 32：According to any one of embodiment 1-31 method, wherein, quencher is included with acid or acid esters Part and the difunctional compound of amine moiety.

Embodiment 33：According to any one of embodiment 1-32 method, wherein, quencher compositions include formula R_a R_b R_c N⁺-A-SO₃ ^-Compound, wherein, R_aAnd R_bIt is hydrogen, C independently of one another₁-C₁₂Alkyl, C₁-C₁₂Aryl or C₁-C₁₈Alkane virtue Base；R_cIt is hydrogen；R_a、R_bIndividually or combination formed with N heterocycle structure；And A is C₁-C₁₂Alkyl, C₁-C₁₂Aryl or C₁-C₁₈Alkaryl.

Embodiment 34：According to any one of embodiment 1-33 method, wherein, a certain amount of quencher is added to incite somebody to action Side chain (branched, branching) is reduced to less than or equal to 100ppm.

Embodiment 35：According to any one of embodiment 1-34 method, wherein, quencher, which has, is less than or equal to 5 PKa.

Embodiment 36：According to any one of embodiment 1-35 method, wherein, quencher, which has, is less than or equal to 3 PKa.

Embodiment 37：According to any one of embodiment 1-36 method, wherein, melt polymerization includes making reactant exist Line it is wet fall type polymerizer in react.

Embodiment 38：According to any one of embodiment 1-37 method, wherein, melt polymerization includes making reactant exist Reacted in the presence of carbon monoxide-olefin polymeric, add other catalyst and further melt polymerization thing.

Embodiment 39：According to the method for embodiment 38, further comprise adding before other catalyst is added Quencher.

Embodiment 40：According to any one of embodiment 38-39 method, further comprise in further melt polymerization Quencher is added after reactant.

Embodiment 41：According to any one of embodiment 1-40 method, further comprise introducing an additive into poly- Carbonic ester.

Embodiment 42：According to any one of embodiment 1-41 method, wherein, quencher compositions are comprising thermally-stabilised Agent, and additive generation is introduced after quencher compositions are added, and wherein, additive is tried comprising releasing agent and UV Agent.

Embodiment 43：According to any one of embodiment 41-42 method, wherein, introduce an additive into reaction and hold At least one of device, extruder and blender.

Embodiment 44：According to any one of embodiment 41-43 method, further comprise introduce an additive into Filtration additives before makrolon.

Embodiment 45：According to any one of embodiment 1-44 method, further comprise adding quencher combination Quencher compositions are filtered before thing.

Embodiment 46：According to any one of embodiment 1-45 method, further comprise adding quencher combination Before thing, by quencher compositions pump to the measuring pump controlled by main dispensing loop.

Embodiment 47：According to the method for embodiment 46, wherein, measuring pump has 300 to 1550rpm speed.

Embodiment 48：According to any one of embodiment 46-47 method, further comprise with flowmeter continue or Quencher compositions are monitored to having a rest property to the addition of makrolon.

Embodiment 49：According to the method for embodiment 48, further comprise controller, for monitoring flowmeter simultaneously automatically Quencher compositions are adjusted to the amount of makrolon.

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

Embodiment 51：According to any one of embodiment 1-26 and 28-48 method, wherein, quencher compositions bag 1 to the 10ppm phosphorous acid containing the makrolon based on 100 parts, and wherein, quencher compositions are 1 to 5kg/hr Added under flow velocity.

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

Embodiment 53：According to any one of embodiment 1-52 method, wherein, melt polymerization is included in 100 DEG C extremely It is oligomeric under 280 DEG C of oligomerization temperature, and polymerize under 250 DEG C to 310 DEG C of polymerization temperature, and wherein, oligomerization temperature is low In polymerization temperature.

Embodiment 54：According to the method for embodiment 53, wherein, it is oligomeric under the oligomeric pressure more than 100mbara.

Embodiment 55：According to any one of embodiment 53-54 method, wherein, it is oligomeric to be included in 150 DEG C to 260 DEG C the first oligomerization temperature, first under the first oligomeric pressure more than or equal to 100mbara be oligomeric；And at 230 DEG C extremely It is subsequent oligomeric under 280 DEG C of the second oligomerization temperature and the second of 15 to 90mbara the oligomeric pressure.

Embodiment 56：According to any one of embodiment 53-55 method, wherein, polymerization is included in 260 DEG C to 310 DEG C the first polymerization temperature, the first polymerization under 1 to 10mbara polymerization pressure；And 260 DEG C to 300 DEG C second gather Close the subsequent polymerization at temperature, and the second polymerization pressure less than or equal to 5mbara.

Embodiment 57：According to the method for embodiment 56, wherein, the first polymerization temperature is 260 DEG C to 285 DEG C；And Second polymerization temperature is 260 DEG C to 285 DEG C.

Embodiment 58：According to any one of embodiment 56-57 method, wherein, the first polymerization temperature be 270 DEG C extremely 280℃；And the second polymerization temperature is 270 DEG C to 280 DEG C.

Embodiment 59：According to any one of embodiment 56-58 method, wherein, adding quencher compositions includes Quencher compositions are added before second polymerize.

Embodiment 60：According to any one of embodiment 56-59 method, wherein, adding quencher compositions includes Quencher compositions are added after polymerizeing second.

Embodiment 61：According to any one of embodiment 53-54 method, wherein, polymerization is in one or more lines It is wet fall type polymerizer in, and polymerization temperature is 200 DEG C to 300 DEG C, and polymerization pressure is less than or equal to 4mbara.

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

Embodiment 63：According to any one of embodiment 53-62 method, wherein, polymerization includes the first polymerized unit And second unit, wherein, the makrolon produced in the first polymerized unit has the number of 20,000 to 50,000 dalton equal Molecular weight.

Embodiment 64：According to the method for embodiment 63, wherein, makrolon increases its molecular weight in second unit Less than or equal to 10wt%, and wherein, method further comprises the devolatilization in second unit.

Embodiment 65：According to any one of embodiment 1-64 method, wherein, extruder is counter rotating double screw Extruder.

Embodiment 66：According to any one of embodiment 20-65 method, wherein, beta catalyst includes tetraphenylphosphoniacetate acetate Phosphonium.

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

Embodiment 68：According to any one of embodiment 1-67 method, wherein, before melt polymerization, further Including the first reactant is introduced into blender；Melt the first reactant；Then the second reactant and carbon monoxide-olefin polymeric are added Add to blender.

Embodiment 69：According to the method for embodiment 68, wherein, the first reactant is selected from diaryl carbonate and dihydroxy Based compound.

Embodiment 70, according to any one of embodiment 68-69 method, wherein, the second reactant is selected from carbonic acid two Aryl ester and dihydroxy compounds.

Embodiment 71：According to any one of embodiment 1-70 method, further comprise devolatilization makrolon group Compound.

Embodiment 72：According to the method for embodiment 71, wherein, devolatilization occurs in an extruder and/or polymerization is single In member.

Embodiment 73：According to embodiment 71-72 method, wherein, devolatilization occurs after quenching.

Embodiment 74：According to any one of embodiment 1-73 method, wherein, method includes the portion of parallel polymerization Point.

Embodiment 75：According to the method for embodiment 74, wherein, the part of parallel polymerization includes：A series of low It polymerize makrolon in poly- unit；It is A streams and B streams by the flow point for discharging oligomeric unit, by A stream guiding to polymerized unit A and by B Stream is guided to polymerized unit B.

Embodiment 76：According to the method for embodiment 74, wherein, the part of parallel polymerization oligomeric unit, then one It polymerize in the polymerized unit of series, is that A streams and B flow by the flow point for discharging final polymerized unit, by A streams guiding to extruder A And guide B streams to extruder B.

Embodiment 77：According to the method for embodiment 74, wherein, the part of parallel polymerization includes：A series of low It polymerize makrolon in poly- unit；Then it polymerize in a series of two polymerized units；The stream of the first polymerized unit will be discharged It is divided into A streams and B streams, A streams is guided to the second polymerized unit A and guide B streams to the second polymerized unit B.

Embodiment 78：According to any one of embodiment 1-77 method, wherein, addition quencher compositions include will Quencher compositions are injected on granular makrolon.

Embodiment 79：A kind of melt polymerization process, including：Melt polymerization makrolon, wherein, melt polymerization includes making Reactant reacts in the presence of carbon monoxide-olefin polymeric；Makrolon is guided to extruder；Based on color stability, UV reagents Reservation and the Balancing selection quencher compositions of hydrolytic stability；And add quencher compositions in extruder upstream, or Extruder is directly added into, wherein, quencher compositions include quencher.

Embodiment 80：A kind of melt polycarbonate, by being prepared according to any one of embodiment 1-79 method.

Embodiment 81：According to any one of embodiment 1-80 method, wherein, makrolon is polymer with bis phenol A carbonic acid Ester.

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

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

Embodiment 84：According to the method for embodiment 11, wherein, quencher compositions are added to makrolon Under the pressure more than or equal to 2 bars, and/or wherein, to makrolon addition it is any have reactivity OH groups or Before the additive of reactive ester group, quencher compositions mix the period occurred more than or equal to 5 seconds with makrolon.

Embodiment 85：A kind of method for adding quencher compositions, including：Makrolon is fed to extruder, will Quencher compositions are added to makrolon, wherein, quencher compositions are solid quencher compositions；And to poly- carbonic acid Ester is added before any reactive additive, and quencher compositions are mixed into the period more than or equal to 5 seconds with makrolon, Wherein, reactive additive has reactivity OH groups or reactive ester group；Wherein, makrolon is melt polycarbonate.

Embodiment 86：According to the method for embodiment 85, further comprise the makrolon of polymerization before charging Granulation.

Embodiment 87：According to any one of embodiment 85-86 method, further comprise adding solid quencher The makrolon of melt polymerization before composition.

Embodiment 88：According to any one of embodiment 85-87 method, wherein, solid quencher compositions are included Polycarbonate powder.

Embodiment 89：According to any one of embodiment 85-88 method, wherein, quencher compositions are free of carrier.

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

Embodiment 91：According to any one of embodiment 1-90 method, wherein, quencher reduces the work of catalyst Property.

As it is used in the present context, when being related to " reactivity " or " reactive group ", such as with reactive OH-group group Or reactive ester group, the reactivity is relative to makrolon.

Generally, the present invention can alternatively include any suitable part disclosed herein, be made from it or substantially by It is constituted.The present invention can with addition, or alternatively, prepared so as not to containing or there is no prior art compositions Middle using or other function and/or target any component not necessarily to realizing the present invention, material, composition, adjuvant Or species.

All scopes disclosed herein include end points, and these end points can be independently combined with each other (for example, " many Up to 25wt%, or more particularly, 5wt% to 20wt% scope ", including end points and " in the range of 5wt% to 25wt% " All medians etc.)." combination " includes blend, mixture, alloy, reaction product etc..In addition, term " first ", " second " Deng, any order, amount or importance are not offered as herein, and be intended to indicate that an element and be different from another element.This Term " one " and " one kind " and "the" in text do not indicate that the limitation to amount, and should be interpreted that including both odd number and plural number, It is unless otherwise indicated herein or otherwise clearly contradicted.Suffix " (s) " as used in this article is intended to include the term Both the odd number and plural number of modification, thus one or more (for example, film (s) includes one or more films) including the term. " a kind of embodiment ", " another embodiment ", " embodiment " referred to through specification etc. refers to together with the embodiment The element-specific (for example, characteristic, structure, and/or feature) of description is included herein at least one embodiment of description, And there may be or can be not present in other embodiment."or" means "and/or".Further, it is understood that institute The element of description can be incorporated into various embodiments in any suitable manner.The disclosed narrower model outside wider range Enclose or group particularly is not to give up broader scope or bigger group.This application claims the Europe submitted on October 23rd, 2013 The patent application 13382423.5 in continent and EP13382419.3 priority, by being cited being integrally joined to them herein In.

Although it have been described that embodiment, but applicant or others skilled in the art can be it is contemplated that do not have at present The replacement that has or possibly can not predict, modification, change, improvement and substantial equivalents.Therefore, the institute that proposes and may be changed Attached claim is intended to all such replacements, modification, change, improvement and substantial equivalents.

Claims (14)

1. a kind of melt polymerization process, including：

Melt polymerization thing to be to form makrolon in the presence of carbon monoxide-olefin polymeric, wherein, the carbon monoxide-olefin polymeric is only Comprising beta catalyst, wherein, the beta catalyst is comprising quaternary ammonium compound, quaternary phosphonium compounds or includes foregoing at least one group Close；

Quencher compositions are added to the makrolon, wherein, the quencher compositions include quencher；And

The makrolon is guided to extruder.

2. according to the method described in claim 1, wherein, the beta catalyst include acetic acid tetraphenylphosphoniphenolate.

3. according to the method described in claim 1, wherein, the quencher compositions include based on 100 parts of the poly- carbonic acid The 1 of ester to 10ppm alkyl tosylate.

4. according to the method described in claim 1, wherein, the quencher compositions include based on 100 parts of the poly- carbonic acid The 1 of ester to 10ppm phosphorous acid.

5. according to the method described in claim 1, wherein, the quencher compositions include toluenesulfonic acid N-butyl.

6. the method according to any one of claim 1-5, wherein, melt polymerization include making reactant it is online it is wet fall type gather Reacted in clutch.

7. the method according to any one of claim 1-5, further comprises before the quencher compositions are added Filter the quencher compositions.

8. the method according to any one of claim 1-5, wherein, the melt polymerization is included in 100 DEG C to 280 DEG C It is oligomeric under oligomerization temperature, and wherein, the polymerization include generation 260 DEG C to 310 DEG C the first polymerization temperature and 1 to The first polymerization under 10mbara the first polymerization pressure；And occur 260 DEG C to 300 DEG C the second polymerization temperature and be less than Or the second polymerization under the second polymerization pressure equal to 5mbara.

9. the method according to any one of claim 1-5, wherein, the ratio of quencher and catalyst is 3:1 to 2:1.

10. the method according to any one of claim 1-5, further comprises after the quencher compositions are added The makrolon devolatilization of polymerization is set to be more than or equal to 5 seconds.

11. the method according to any one of claim 1-5, wherein, adding the quencher compositions is included by described in Quencher compositions are injected on granular makrolon.

12. the method according to any one of claim 1-5, wherein, the carbon monoxide-olefin polymeric includes tetraphenylphosphoniacetate acetate Phosphonium.

13. the method according to any one of claim 1-5, wherein, the α catalyst is used only in the melt polymerization.

14. the method according to any one of claim 1-5, wherein, the melt polymerization is included in the catalyst group Make the reactant reaction in the presence of compound, add reactant described in other catalyst and further melt polymerization；And Further comprise adding the first liquid quencher before the other catalyst is added.