CN101541854B - Branched polycarbonate resins and processes to prepare the same - Google Patents
Branched polycarbonate resins and processes to prepare the same Download PDFInfo
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- CN101541854B CN101541854B CN2007800395038A CN200780039503A CN101541854B CN 101541854 B CN101541854 B CN 101541854B CN 2007800395038 A CN2007800395038 A CN 2007800395038A CN 200780039503 A CN200780039503 A CN 200780039503A CN 101541854 B CN101541854 B CN 101541854B
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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Abstract
A method of increasing the branching and polydispersity of a polycarbonate includes the steps of: (a) including in the polycarbonate at least one species of an alkyl substituted monomer, and (b) treating the polycarbonate at an elevated temperature and for a sufficient time to increase the branching and polydispersity relative to an otherwise equivalent polycarbonate without alkyl substituents.
Description
The cross reference of related application
The application is the non-provisional application of the U.S. Patent application 60/862555 of submission on October 23rd, 2006; The U.S. Patent application of submitting in the application and on July 12nd, 2,006 11/456991 and the U.S. Patent application of submitting on June 30th, 2,006 60/806304 are relevant and require its interests, and all these applications all are unsettled, incorporate this paper into through reference here.
Background of invention
Having the branching polycarbonate that strengthens melt strength can be used for coming production polymer profiles, solid sheet, multi-layer sheet or corrugation sheet material like application such as blowing and extrusion blow expressing techniques.In addition, the branching of polycarbonate has generally also improved its flame retardant resistance and chemical-resistant.The method that is used for preparing branching polycarbonate in the past usually requires technology long transit time (transition time), extra starting material such as branching agent, perhaps requires to add high-caliber catalyzer.Need make the short-cut method of the defective in the polycarbonate branching and the past method of overcoming.
Summary of the invention
The present invention provides a kind of transit time long in smelting process that need not; Extra starting material such as branching agent; Perhaps add the catalyzer of the high-caliber Fries of inducing and make the method for polycarbonate branching, the catalyzer of the said high-caliber Fries of inducing causes excessive colouring and product unstable.Method of the present invention makes the substituted monomer of alkyl incorporate polycarbonate into, and at high temperature handles this polycarbonate time enough and improve branching and polymolecularity with the polycarbonate that is equal to respect to there not being alkyl substituent but in others.And; Branched polymer through method preparation of the present invention can be generated by following polycarbonate: the polycarbonate that has used phosgene to aggregate into as carbonate source through interfacial polymerization method, the polycarbonate that has perhaps used diphenyl carbonate (DPC) or carbonic acid two (wintergreen oil base) ester (BMSC) to aggregate into through melt polymerization process.
In one embodiment of the present invention, a kind of branching of polycarbonate and method of polymolecularity of improving is provided, this method comprises the following steps:
(a) make and comprise the substituted monomer of at least a alkyl in the said polycarbonate; And
(b) at high temperature handle said polycarbonate time enough,, improve branching and polymolecularity with the polycarbonate that is equal to respect to there not being alkyl substituent but in others.
A kind of polycarbonate of branching is provided in another embodiment of the invention.The polycarbonate of said branching has alkyl-branched unit between polymer chain.Found the NMR Equipment Inspection capable of using of this branching unit.Therefore, in another kind of embodiment, the present invention provides a kind of polycarbonate that in using the proton N MR spectrum of the described NMR analytical procedure of the application, has the wide NMR band between the about 3.95～4.05ppm of the chemical shift of being centered close to.
Description of drawings
Fig. 1 is a polymerization reaction system.
Fig. 2 illustrates two kinds of different polycarbonate proton N MR spectrums.
Embodiment
The polycarbonate of branching has the enhanced melt strength, therefore is useful on such as blowing and extrusion blow technology etc. and should be used for preparing section bar, solid sheet, multi-layer sheet or corrugation sheet material.In addition, the polycarbonate of comparing branching with branching polycarbonate not generally also will improve flame retardant resistance and chemical-resistant.
The present invention provides a kind of transit time long in smelting process that need not; Extra starting material such as branching agent; Perhaps add the catalyzer of the high-caliber Fries of inducing and make the method for polycarbonate branching, the catalyzer of the said high-caliber Fries of inducing also causes excessive colouring and product unstable usually.Method of the present invention makes the substituted monomer of alkyl incorporate said polycarbonate into, and at high temperature handles this polycarbonate time enough and improve branching and polymolecularity with the polycarbonate that is equal to respect to there not being alkyl substituent but in others.And can generate by following polycarbonate: the polycarbonate that has used phosgene to aggregate into through interfacial polymerization method, the polycarbonate that has perhaps aggregated into through melt polymerization process use diphenyl carbonate (DPC) or carbonic acid two (wintergreen oil base) ester (BMSC) as carbonate source through the branched polymer of method of the present invention preparation.
Cast aside the constraint of concrete mechanism; It is believed that in the polymer chain that aromatic ring or another alkyl substituent of the substituted monomer of alkyl (the substituted monomer of another alkyl in the perhaps same chain) react through free radical addition mechanism on the substituted monomeric alkyl substituent of alkyl (the for example alkyl substituent of those on aromatic ring) and another polymer chain.It is believed that this free radical addition reaction generates covalently bound through the alkyl of bridging at interchain.
The branching of raising polycarbonate provided by the invention and the method for polymolecularity comprise the following steps:
(a) make and comprise the substituted monomer of at least a alkyl in the said polycarbonate, and
(b) at high temperature handle said polycarbonate time enough, improve branching and polymolecularity with the polycarbonate that is equal to respect to there not being alkyl substituent but in others.
Definition
This paper is with reference to many terms, and it should be defined as has following implication:
Singulative " one ", " a kind of " comprise plural indicator with " being somebody's turn to do ", only if context is clearly pointed out in addition.
" comprise " with the term of step (a) (promptly (a) makes and comprise the substituted monomer of at least a alkyl in the said polycarbonate) coupling of this paper disclosed method, be interpreted as in this article being meant that the polycarbonate of having handled is by comprising the monomeric monomer source preparation of one or more alkylations as herein described.
" polycarbonate " is meant the polycarbonate that comprises the repeating unit that is derived from least a dihydroxy aromatic compounds and comprises copolyestercarbonates, for example comprise the polycarbonate of the repeating unit that is derived from toluhydroquinone, dihydroxyphenyl propane and dodecanedioic acid.As the polycarbonate of the object of the inventive method for having (promptly comprising) at least a those polycarbonate that are derived from the monomeric repeating unit of alkylation.In the application's specification sheets and claim, polycarbonate is not restricted to only a kind of dihydric residues, only if clearly done qualification in the context.Therefore, the application contain and contain 2,3, the Copolycarbonate of the residue of 4 kind or more kinds of dihydroxy compound.(carbonic ether-ester) altogether oligopolymer and polymkeric substance contained and gathered to term " polycarbonate ".
At the application's specification sheets and the numerical value in the claim, when especially they related to polymer compsn, reflection can comprise the MV of the compsn of each polymkeric substance of different nature.And this numerical value should be understood and comprises: it is the numerical value that is equal to when reverting to the significant figure of same number, and with the difference of said value numerical value less than the experimental error of measuring the used measuring technology of this value among the application.
" alkylation monomer ", " alkyl monomer " and " the substituted monomer of alkyl " commutative in this article use.
Used among this paper " handling polycarbonate " should be understood and be meant polycarbonate is incorporated into the time fully long in the hot environment, with based on the branching and the polymolecularity that improve this polycarbonate before being incorporated in the said hot environment.The step of handling polycarbonate can be in the process that is formed polycarbonate by monomer or oligopolymer fusion, in the compounding process and/or in moulding process, carry out.The raising amount of the branching of said polycarbonate and polymolecularity is greater than there not being alkyl substituent but handle the branching that obtains and the raising amount of polymolecularity under the same conditions at the polycarbonate that others are equal to.
" do not have alkyl substituent but be equal in others polycarbonate " is meant: this polycarbonate is not to be derived from the alkylation monomer source; But others comprise the similar non-alkylation monomer of same amount, and are by the reaction (for example fusion or interface) of same type preparation.For example, the polycarbonate that contains the repeating unit that is derived from quinhydrones (HQ) is for being derived from " do not have alkyl substituent but be equal in others polycarbonate " of the monomeric polycarbonate of toluhydroquinone (MeHQ), and methyl is the alkyl substituent in this example.
(a) alkylation monomer
Polycarbonate of the present invention has at least a alkylation monomer.Said monomeric " alkylation " or " alkyl replacement " part preferably is positioned at ring with the alkyl substituent form and goes up (for example with scheme a, in question " R " group that c is relevant with e).In one embodiment, at least a alkylation monomer is selected from:
Wherein substituting group Y is hydroxyl, alcohol, ester or carboxylic acid functional independently of one another, and substituent R is C independently of one another
1～C
6Side chain, straight chain or cyclic aliphatic group, x respectively does for oneself and comprises 1 and 4 1～4 integer, and all x be less than or equal to 4,
Wherein substituting group Y is hydroxyl, alcohol, ester or carboxylic acid functional independently of one another, and substituent R is C independently of one another
1～C
6Side chain, straight chain or cyclic aliphatic group, x respectively does for oneself 0 or comprise 1 and 3 1～3 integer, and all x be at least 1 and be less than or equal to 6, and
Wherein substituting group Y is hydroxyl, alcohol, ester or carboxylic acid functional independently of one another, and substituent R is C independently of one another
1～C
6Side chain, straight chain or cyclic aliphatic group, x respectively does for oneself 0 or comprise 1 and 4 1～4 integer, all x be at least 1 and be less than or equal to 8, and Z represents one of following formula group:
R wherein
1, R
2And R
3Be C independently
1～C
18Side chain, straight chain or cyclic aliphatic group, and R
4Be C
3～C
12Cyclic substituents.In concrete embodiment preferred, the R substituting group is C independently of one another
1～C
4Side chain or linear aliphatic group, for example wherein the R substituting group is C independently of one another
1Or C
2Aliphatic group, for example wherein each R substituting group is methyl.
The non-limiting tabulation that preferably is applicable to alkylation monomeric substance of the present invention is a toluhydroquinone, tertiary butylated hydroquinone, and DMBPC i.e. two (3-methyl-4-hydroxy phenyl) hexanaphthene, and 2; 2 '-thiobis (4-tert-octyl phenol), TMBPA (tetramethyl-dihydroxyphenyl propane, tetra-methyl bisphenol acetone); DMBPA (dimethyl-dihydroxyphenyl propane), DEBPA (diethylammonium dihydroxyphenyl propane), two-o-isopropyl-BPA; Two-o-sec-butyl-BPA, two-o-tert-butyl-BPA, two-ortho-cresol fluorenes; Methylresorcinol, two-tert-butyl resorcin, and two-tertiary butylated hydroquinone.
In a concrete embodiment preferred, be used at least a tertiary butylated hydroquinone of alkylation monomer of polycarbonate for having formula:
Therefore, in another embodiment, the present invention provides a kind of polycarbonate that comprises the polycarbonate repeat unit that is derived from the tertiary butylated hydroquinone monomer source.
Polycarbonate of the present invention also can comprise non-alkylation monomer.As known in the art is that the desirable properties of final polymer materials is depended in so monomeric selection, and can use any monomer as known in the art.As limiting examples, when the R group not when the alkyl (a) above (for example when the R group is hydrogen or halogen), (c) and (e) described in monomer can be used as non-alkylation monomer.
It is believed that the monomeric content of alkylation is relevant with the crosslinked of polycarbonate interchain or branching chance in said polycarbonate.In one embodiment, the amount that the alkylation monomer exists in the said polycarbonate is greater than 10 moles of %, by monomeric total mole number in the polycarbonate.In other embodiments, the amount that the alkylation monomer exists in the said polycarbonate is greater than 20 moles of %, for example greater than 30 moles of %; Greater than 40 moles of %; Greater than 50 moles of %, greater than 60 moles of %, greater than 70 moles of %; Greater than 80 moles of % or greater than 90 moles of %, by monomeric total mole number in the polycarbonate (for example wherein the monomer of 100 moles of % is the alkylation monomer).
(b) handle polycarbonate:
The said polycarbonate time enough of at high temperature handling is with respect to there not being alkyl substituent but can occur in perhaps all three phases of arbitrary stage in three different stepss in the step that polycarbonate that others are equal to improves branching and polymolecularity.First; If this polycarbonate is to prepare through melt transesterification reaction (for example utilizing the melt transesterification reaction of diaryl carbonate (for example DPC) or the substituted diaryl carbonate of ester (for example BMSC)), then said treatment step can carry out in certain in the melt transesterification reaction process.Second; No matter how polycarbonate prepares; Said treatment step can carry out in melting mixing/compounding step process, wherein can other compound of choosing wantonly added in the said polycarbonate or wherein just handle said polycarbonate according to the present invention to produce branching.The 3rd, no matter how polycarbonate prepares, said treatment step can carry out in the process that molded polycarbonate is become goods once more.
The description of the instance from this paper can find out that required concrete time and the temperature of polymolecularity that obtains specified level depends on the operation stage of handling and depend on monomeric person's character of the alkylation that is comprised and relative content.Yet, utilizing the application's instruction, those of skill in the art can confirm suitable treatment condition easily for given polymkeric substance.
1. the processing in melt polymerization or transesterify process:
At the free hydroxyl end of dihydroxy compound and the melt polymerization/transesterification reaction between the carbonate source is well-known.The free hydroxyl end through dihydroxy compound and the melt transesterification of carbonate source (for example DPC) increase the molecular weight of polycarbonate.Same well-known is to improve transesterification reaction speed through diaryl carbonate such as the BMSC that uses transesterify.The raising of this speed of reaction makes the generation of polycarbonate to betide on the reactive extruder.
The invention provides the branching of raising polycarbonate in the melt polymerization process and the method for polymolecularity; In said melt polymerization process, at high temperature handle the polycarbonate time enough so that the polymolecularity of said polycarbonate greater than 2.3; For example polymolecularity is greater than 2.4; Greater than 2.5, and greater than 2.6.The residing temperature of raising that in melt polymerization process, such branching and polymolecularity takes place is usually greater than 330 ℃, for example greater than 340 ℃ or greater than 350 ℃.
The embodiment and the presentation of results that provide in the table 1 of following embodiment part: the reactive extruder working temperature of rising under the melt polymerization state improved the branching that is derived from the monomeric polycarbonate of alkylation and the polymolecularity of gained.
Those of ordinary skills can understand after reading the disclosure: polycarbonate required residence time in equipment will change according to the working temperature of this equipment.For example, if use higher temperature to need the short residence time so, vice versa.The residence time in the melt devolatilization forcing machine can pass through to change the flow velocity of polymkeric substance in this forcing machine, waits through change screw conditions such as speed, diameter and element to change.
2. in melting mixing/compounding step, handle:
No matter polycarbonate is (promptly no matter it prepares through interfacial polymerization, solid-state polymerization or melt polymerization etc.) how to prepare, treatment step can occur in the compounding step, and wherein this polymkeric substance is exposed to heat (for example melting mixing step).Usually the compounding step allows other compound to incorporate in this polycarbonate.Said other compound can comprise for example thermo-stabilizer, dripping inhibitor and/or anti-oxidation and antisepsis agent etc.Yet said in the present invention compounding step can occur in not to be had to add under the situation of optional additive, wherein just handles said polycarbonate and produces branching as herein described.
In the compounding step, at high temperature handle the polycarbonate time enough, so that the polymolecularity of said polycarbonate improves more than 10%.In preferred embodiments, in the raising amount of polymolecularity described in the compounding step greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%; Greater than 70%, greater than 80%, greater than 90%, greater than 100%, greater than 110%, greater than 120%; Greater than 130%, greater than 140%, greater than 150%, greater than 160%, greater than 170%, greater than 180%; Greater than 190%, greater than 200%, greater than 210%, greater than 220%, greater than 230%, and greater than 240%.
Usually, said compounding step occurs in temperature greater than 330 ℃, for example in temperature greater than 350 ℃ or 370 ℃.Those skilled in the art can understand, polycarbonate in equipment required residence time will according to temperature, polycarbonate type and in said polycarbonate the monomeric amount of alkylation and type and change.For example, in one embodiment, with said polycarbonate in the compounding step in greater than 330 ℃ Temperature Treatment more than or equal to 20 minutes, more than or equal to 40 minutes, more than or equal to 60 minutes, perhaps longer time.The data that are included among the following embodiment table 2A-2C partly further specify the notion of the said polycarbonate of processing in the compounding step and the relation between these factors.
3. in moulding process, handle:
No matter polycarbonate be how to prepare also no matter its before whether carried out compounding, said treatment step can occur in molded polycarbonate is become in the process of goods.In said moulding process, at high temperature handle the polycarbonate time enough, so that the polymolecularity of said polycarbonate improves more than 10%.In preferred embodiments, polycarbonate polymolecularity in moulding process has increased more than 12%, for example more than 14%, more than 16%, more than 18%, more than 20%; More than 22%, more than 24%, more than 26%, more than 28%, more than 30%, more than 32%; More than 34%, more than 36%, more than 38%, more than 40%, more than 42%; More than 44%, more than 46%, more than 48%, more than 50%, and more than 52%.
Usually, it is following more than 10 minutes that said molding step occurs in hot conditions (for example greater than 320 ℃, greater than 330 ℃, and/or greater than 340 ℃), for example more than 15 minutes, and more than 20 minutes, more than 25 minutes, and more than 30 minutes.Those of ordinary skills can understand after reading the disclosure: polycarbonate required residence time in mold apparatus will change according to the temperature of this equipment etc.The data that are included in the following embodiment table 4 partly further specify the notion of in molding step, handling said polycarbonate.
Those of skill in the art will appreciate that the step of said processing polycarbonate can occur in the arbitrary stage or arbitrary combination in the above stage of enumerating.
Polycarbonate of the present invention
Method of the present invention provides that branching, melt stability and polymolecularity improve contains alkylation monomeric polycarbonate.In certain embodiments, prepared polycarbonate comprises following branching unit:
Wherein R as above with figure a, c, description that e is relevant with f, y is 0～3 integer, and R
2Be C
1～C
12The straight or branched alkyl.In other embodiment, prepared polycarbonate comprises following branching unit:
Wherein R as above with figure g relevant description, y is 0～3 integer, and R
2Be C
1～C
12The straight or branched alkyl.In another embodiment, prepared polycarbonate comprises following branching unit:
Wherein R as above with figure g relevant description, z is 0～2 integer, and R
2Be C
1～C
12The straight or branched alkyl.In one embodiment, R
2Be selected from: methyl, ethyl, the tertiary butyl and octyl group.
According to the temperature used in the aforesaid method and the residence time and the monomeric amount of alkylation that is used to prepare said polycarbonate, said polycarbonate can have the detectable wide NMR band between the about 3.95～4.05ppm of the chemical shift of being centered close in the proton N MR spectrum according to following detectability.
Embodiment:
Specifically described the present invention, the elaboration of the following example is used for providing to those of ordinary skill in the art the detailed description of the method that to how par this paper requires to protect, and is not intended to restriction its invention protection domain that the contriver thought.Only if point out in addition, umber is by weight, and temperature unit is ℃.
Molecular-weight determination
Through the molecular weight character of gel permeation chromatography (GPC) assay determination polymkeric substance, wherein use PS molecular weight standard thing to make up the wide standard calibration curve that is used to measure polymericular weight.The temperature of gel permeation chromatographic column is about 25 ℃, and moving phase is chloroform.Solvent for use is CHCl
34: 1 mixtures (for terpolymer, 60% HQ multipolymer and 90% MeHQ multipolymer, CHCl is used in combination
3With 1,1,1,3,3,3-hexafluoroisopropanol (HFIP)).At first said terpolymer was handled in ultra sonic bath 15 minutes, vibrated again 2 hours.Polydispersity index (PDI) calculates divided by number-average molecular weight (Mw/Mn) through weight-average molecular weight.
NMR analyzes
All NMR spectrums obtain on Bruker Avance 400MHz nmr spectrometer for 55 ℃ in temperature.Prepared in 5% solution (wt/v) of sym.-tetrachloroethane-d2 (CAS#33685-54-0) and be used for analyzing.All spectrums obtain by spin rate 20Hz.
1H NMR measurement is to utilize 5mm diameter QNP probe to carry out at 400MHz, wherein adopts the sweep length (13～-3ppm chemical shift interval) of 6410Hz, 30 ° flip angle, 10 seconds relaxation time, the data point of 64k and 256 scanning.All data processing are to utilize the pack processing of GRC exploitation (by T.A.Early exploitation, inner publication 94CRD204) to carry out.For
1H NMR, data processing comprises the apodization (apodization) with 0.3Hz.Used relevant description that can detected NMR peak is meant this methodological detectivity of employing among the application.The lower method of sensitivity should be understood and the peak can not be detected.
Melt volume speed
Melt strength is the measuring of complicated rheological property of polymkeric substance, and it can be represented through melt index ratio (MIR).This is the ratio of melt volume speed of under 2.16kg bears a heavy burden, measuring (MVR) and the MVR that under the 21.6kg heavy burden, measures.Branching in the polycarbonate terpolymer causes complicated rheology.Known branching polycarbonate has the melt strength higher than linear polycarbonate.Used test temperature is 280 ℃.
The parallel plate rheology
Except MIR, the shearing thinning behavior of polymkeric substance (shear thinning behavior) also can be used for characterizing melt strength.As previously mentioned, branching polycarbonate has the melt strength higher than linear polycarbonate.It is also known that branching causes stronger shearing thinning behavior.Therefore, the terpolymer that adopts various melt temperatures on the S-extrusion system, to prepare is carried out the test of parallel plate rheology.For each sample, when two kinds of melt temperatures (promptly 240 and 260 ℃), carry out the frequency sweeping of 0.1～500 radian per second.Utilize the data of gained, will the complex viscosity when 100 radian per seconds equal 2000 handkerchiefs during second residing temperature be used as melt temperature (PPT).The melt temperature of guaranteeing gained falls between the actual tests temperature to allow interpolation.When the melt temperature of gained, also measured the plural melt viscosity when shearing rate 1 radian per second.R
*Be calculated as the ratio of plural melt viscosity and plural melt viscosity when 100 radian per seconds when 1 radian per second, wherein the latter is fixed in 2000 handkerchief seconds of interpolation at present.Higher R
*Thereby the shearing thinning behavior that value explanation is strong and because branching and higher melt strength.
1. in melt polymerization process, handle polycarbonate
Use the melt polymerization process of activatory diaryl carbonate (BMSC) to be used to prepare several kinds of terpolymers that BPA, HQ and MeHQ by mol ratio 33/33/34 form.Prepared material through in polymerization process, in reactive extruder, using multiple melt temperature with higher polymolecularity.As can from appended form, observe, use R
*The melt strength of these materials that characterize with MIR has improved.The controlled rising that therefore the forcing machine melt temperature is described can be used to prepare the terpolymer that melt strength improves.
Sample 1,2 and 3 is the polycarbonate terpolymer through the preparation of BMSC/ frit reaction expressing technique.These samples are synthetic as follows.The BPA, the HQ of 5891g, the MeHQ of 6455.2g, the BMSC of 53069g and the PCP of 561.4g that add 11855g in the stainless steel cauldron in stirring are so that BMSC/BPA+HQ+MeHQ mol ratio 1.021.Also in reactor drum, add the TMAH (TMAH) of 2694 μ l and the aqueous catalyst solution of sodium hydroxide (NaOH), the amount of TMAH and NaOH is equivalent to the total mole number 2.5 * 10 of per 1 mole BPA/HQ/MeHQ
-5The TMAH and 2.0 * 10 of mole
-6The NaOH of mole.Then this reactor drum is vacuumized and with purging with nitrogen gas three times removing residual oxygen, and remain on 800 millibars of constant vacuum pressures.For the fusion and the reaction of mixture, then this reactor drum is warming up to 170 ℃.After the heating of reaction kettle begins about 4 hours 11 minutes, with nitrogen this reactor drum is forced into the constant overvoltage of 0.9 crust, and with speed 13.5kg/h molten reaction mixture is conducted in the forcing machine through the supply line of 170 ℃ of heating.Measured corresponding to 6.0 * 10 by it in the past in 15 minutes
-6Total BPA/HQ/MeHQ that moles of NaOH is every mole begins to add to forcing machine sodium hydroxide (NaOH) aqueous catalyst solution of 2694 μ l.Said forcing machine is the W&P ZSK25WLE 25mm 13-machine barrel twin screw extruder of L/D=59.The forcing machine of accepting feed comprises flash valve (flash-valve) to stop the boiling of molten mixture.This reaction mixture carries out reactivity with screw speed 300rpm and extrudes.This forcing machine is equipped with 5 forward vaccum exhaust outlets and a reverse venting port.The wintergreen oil by product is removed through these venting ports through devolatilization.The vacuum pressure of reverse venting port is 11 millibars.The vacuum pressure of the first forward venting port is 21 millibars.The vacuum pressure of last 4 forward venting ports is less than 1 millibar.
Sample 1 is in temperature and prepares for 310 ℃ through making all extruder barrels be in 300 ℃ of temperature and forcing machine die head.Sample 2 is in 300 ℃ through making machine barrel 1 to machine barrel 4, and machine barrel 5 is in 305 ℃, and machine barrel 6 is in 309 ℃, and machine barrel 7 is in 312 ℃, and machine barrel 8 is in 312 ℃, and machine barrel 9 is in 318 ℃, and machine barrel 10 to machine barrel 13 is in 320 ℃ and die head and is in 330 ℃ and prepares.Sample 3 is in 300 ℃ through making machine barrel 1 to machine barrel 4, and machine barrel 5 is in 310 ℃, and machine barrel 6 is in 318 ℃, and machine barrel 7 is in 324 ℃, and machine barrel 8 is in 330 ℃, and machine barrel 9 is in 336 ℃, and machine barrel 10 to machine barrel 13 is in 340 ℃ and die head and is in 350 ℃ and prepares.
Table 1 is handled the result of polycarbonate in melt polymerization process
The melt temperature of the data declaration rising forcing machine in the table 1 can be used for improving the branching that contains in the monomeric polycarbonate of alkylation.Preparation sample 2 and 3 under the higher gradually melt temperature of relative sample 1.Along with the rising of melt temperature, can find out R
*All systematically increase with the MIR value.Therefore, the melt strength of said terpolymer systematically increases with the rising of melt temperature.Simultaneously, also correspondingly system's increase of the peak of branching unit in proton N MR.
2. in melting mixing (for example compounding) process, handle polycarbonate
Embodiment 1 (to the research of the processing in 370 ℃ compounding process)
In order to study the influence of temperature, in 25 gram graded response apparatuses, various polymkeric substance are carried out melting mixing to the polymkeric substance that contains the alkylation monomer residue.For from removing any sodium, this reactor leaching in the HCl of 1M 24 hours, is cleaned 5 times with 18.2Mohm at least more at least from glass.Keep the temperature of reactor drum with the heating jacket of equipment PID unit.Control in the vacuum pump in the downstream of the pressure of reactor drum through nitrogen discharge being collected bottle to distillation, and use gauge measurement.Assembling and sealed reactor are with nitrogen exchange of air 3 times.Make this reactor drum near normal atmosphere, be set to its first moment of being provided with a little at well heater and start the reaction times.
This reactor drum is set to 370 ℃, 800 millibars pressure, and top arrangement (overhead) is heated to 100 ℃.Turn on agitator (40rpm) after 12 minutes.When fusion time of reaching 60 minutes, stop to mix.After completion, make reactor drum get back to normal atmosphere with the demulcent nitrogen gas stream.When reaching normal atmosphere, stop to stir, and, come to discharge product from reactor tube through opening reactor drum in the bottom and product being extruded with slight nitrogen overpressure.Product with results is used for analyzing then.
Table 2A: the result who in 370 ℃ compounding process, handles polycarbonate
Can find out from table 2A that branching and polymolecularity improve the polymkeric substance that only betides by substituted phenol of at least a alkyl or bis-phenol preparation.For example, for based on homopolymer and the multipolymer of the substituted bis-phenol DMBPC of terpolymer, alkyl of toluhydroquinone, contain the multipolymer of substituted aromatic dihydroxy compound MeHQ of alkyl and t-ButHQ, polymolecularity significantly improves.Can find out as a comparison: for the homopolymer of BPA (it is not the substituted bis-phenol of alkyl by the application's definition) and the multipolymer that contains quinhydrones (it is not the substituted aromatic dihydroxy compound of alkyl by the application's definition), polymolecularity does not improve.In addition, also can find out, can make polycarbonate that adopts the phosgene interfacial polymerization and the polycarbonate that adopts DPC or BMSC melt polymerization form branching.
Embodiment 2 (to the research of the processing in being lower than 350 ℃ compounding process)
Adopt with laboratory, front compounding example (being embodiment 1) in identical reactor drum assembling study 300～350 ℃ of temperature with step (except the place difference of pointing out); 20～40 minutes fusion residence time, and under the condition of 25～100 moles of % of alkylation monomer concentration (with respect to the concentration of the diol residue of incorporating in this polymkeric substance) compounding to the influence of branching reaction.
After with the nitrogen exchange of air, reactor drum is under the nitrogen atmosphere (1000 millibars), and reaches required temperature at well heater and start the reaction times constantly.Turn on agitator (40rpm) after 5 minutes.When reaching required fusion during the residence time, stop to stir, discharge product from reactor tube again.Product with results is used for gel permeation chromatography (GPC) analysis then.The used solvent of polymers soln that preparation is used for gpc analysis is CHCl
3, and all molecular weight are reported with respect to polystyrene standards here.
Following polycarbonate sample is used for present embodiment:
1. the DMBPC homopolymer through the interfacial polymerization prepared.
2. the DMBPC/BPA multipolymer of 50/50 (moles/mole) through the interfacial polymerization prepared.
3. the DMBPC/BPA blend polymer of DMBPC/BPA multipolymer through aforesaid 50/50 (moles/mole) of blend and an amount of BPA homopolymer preparation 25/75 (moles/mole) of passing through the interfacial polymerization prepared.
4. comprise that the DMBPC homopolymer for preparing through fusion (DPC) polymerization is to be used for comparison.
5. the BPA homopolymer through the interfacial polymerization prepared.
The molecular weight character of these raw materials 2B that is listed in the table below, the molecular weight character of the polymkeric substance of compounding (melting mixing) 2C that is listed in the table below.
Table 2B comprises the raw material of the alkylation monomer (DMBPC) of different levels
| Mole %DMBPC | Polymerization method | Mw(PS) | Mn(PS) | Pd |
| 0 | The interface | 42894±412 | 17731±135 | 2.42±0.01 |
| 25 | The interface | 43547±210 | 16561±31 | 2.63±0.01 |
| 50 | The interface | 44044±302 | 15528±92 | 2.83±0.01 |
| 100 | The interface | 49376±269 | 15923±55 | 3.10±0.01 |
| 100 | Fusion | 47888±155 | 18656±67 | 2.57±0.01 |
The polymkeric substance of table 2C compounding under relatively lower temp (melting mixing)
The result of the compounding of in 300～350 ℃ TR, carrying out (melting mixing) embodiment (table 2C) explains: the branching reaction that carries out through the reaction of the DMBPC alkylation monomer residue incorporated into depends on the amount of the alkylation monomer of in this TR interpolymer, incorporating into (being DMBPC).For example compare with the less DMBPC polymer of monomers of handling under the same conditions that contains, 100% DMBPC homopolymer (interface and melt polymerization, its compounding (melting mixing) 40 minutes in the time of 350 ℃) shows that polymolecularity improves.And although two kinds of initial polymer (being 100%DMBPC fusion and interfacial polymerization) have similar molecular weight character in these embodiment, the raising of the polymolecularity of the DMBPC homopolymer through fusion (DPC) polymerization preparation is much bigger.The raising of polymolecularity that it is believed that fusion (DPC) homopolymer is more owing to the contribution of Fries branching to polymolecularity.Fries branching is known owing to adopt alkali metal hydroxide as catalyzer and the reaction that when high temperature, in melt polycarbonate, takes place.
3. in moulding process, handle polycarbonate
Embodiment 1
In moulding process, handle the various polymkeric substance that use activatory carbonic ether (BMSC) to prepare through melt polymerization.Before moulding, under the high temperature that is suitable for most relevant polymkeric substance with dry 2-3 hour of pellet.These dryings are: for the BPA-homopolymer 120 ℃ of dryings 2 hours; For terpolymer (BPA/HQ/MeHQ) 105 ℃ of dryings 3 hours; For multipolymer (BPA/HQ) 120 ℃ of dryings 2 hours; For the DMBPC-homopolymer 120 ℃ of dryings 2 hours; For terpolymer (DMBPC/HQ/MeHQ) 105 ℃ of dryings 3 hours.The value that provides for initial pellet is the MV that is used to prepare the different production batch pellets of pellet original mixture
Used mould machine is Engel 45T, and its equipment produces the built-in mould of 60 * 60 * 2.5mm test plate (panel).Condition I in the employing table 3 begins moulding.Open and minimum 5 injections of stable mode molding machine after, based on melts fixed residence time in the mould machine machine barrel be about 180 seconds preparation test plate (panel)s.Behind the test plate (panel) of having collected desired number, will rise to 344 seconds from 20 seconds cooling time (table 3 condition II).After 5 transition test plate (panel)s, realize stable operation and preparation about 33 minutes test plate (panel) of the residence time once more.Also collect the transition test plate (panel) and be used for estimating, because they have the middle residence time, the said residence time progressively was increased to 33 minutes from 3 minutes.Thereby prepared test plate (panel): 180 seconds (condition I), 540 seconds, 900 seconds, 1360 seconds, 1620 seconds (all transition conditions) and 1980 seconds (condition II) with following residence time.
The condition of moulding of the branching moulding that table 3 is controlled
Table 4: the result who in moulding process, handles polycarbonate
From table 4 data can draw with preceding table 2 in similar conclusion.For branching reaction takes place, said polycarbonate must comprise at least a monomer alkyl substituted (for example alkylation) phenol or bis-phenol.For example, for the terpolymer that contains MeHQ, DMBPC homopolymer and the multipolymer that contains MeHQ, polymolecularity enlarges markedly; Yet for the BPA homopolymer or contain the multipolymer of HQ, polymolecularity does not obviously increase.
Another group data are used to contain two kinds of other conditions of moulding (III and IV) of the MeHQ terpolymer of different stabilizers.Table 5 has shown the condition of moulding of the Engel 45T mould machine that is used for said test.
Table 5: the condition of moulding of mould machine (Engel 45T)
| Condition | Unit | III | IV |
| Hopper temperature | ℃ | 40 | 40 |
| Distinguish 1 temperature | ℃ | 280 | 320 |
| Distinguish 2 temperature | ℃ | 290 | 330 |
| Distinguish 3 temperature | ℃ | 300 | 340 |
| Nozzle temperature | ℃ | 295 | 335 |
| Die temperature | ℃ | 90 | 100 |
| Hold-time | Second | 10 | 10 |
| Cooling time | Second | 20 | 1238 |
| Cycling time | Second | 36 | 144 |
| The residence time | Second | 180 | 720 |
Use BMSC through used polycarbonate in these samples of melt polymerization preparation according to description.This polyreaction is carried out in the illustrated reactor assembly in Fig. 1.In this system, in the oligomerization container A, adding the solid diol monomer under envrionment temperature and the pressure.Monomer molar % in the terpolymer is 33%BPA, 34% quinhydrones (HQ) and 33% toluhydroquinone (MeHQ).The add-on of PCP chain terminator makes on target molecular weight the PCP end group that generates about 50mol%.Add catalyzer TMAH and sodium hydroxide with aqueous solution form then.Concentration with 25mEq/ mole glycol is used TMAH; Use sodium hydroxide for homopolymer with the concentration of 4mEq/ mole BPA; Use sodium hydroxide for terpolymer with the concentration of 2mEq/ mole BPA.After this, with this oligomerizing device sealing.Through the oligomerizing device is simply vacuumized the oxygen that inflated with nitrogen removes system again.This process repeats 3 times.After process was at least about 4 hours, add the sodium hydroxide of other quantity to fusion terpolymer oligopolymer with the concentration of 6mEq/ mole glycol.
Then this fusion oligopolymer is added among the ZSK-25 forcing machine C through pump and supply line 1.This ZSK-25 forcing machine is diameter 25mm, twin screw, the forcing machine of engagement in the same way, and its length-to-diameter ratio (L/D) is about 59.About 12～14kg/h is conducted to forcing machine with oligopolymer with speed, and screw speed is about 300rpm.The machine barrel of forcing machine is set to 300 ℃, and die head is set to 310 ℃.Z-SK 25 forcing machines are equipped with high and rough vacuum system to remove in polycondensation the wintergreen oil as by product formation.The rough vacuum system is by line 2, condensing surface D, vacuum pump F and MS storage receptacle H.High vacuum system is by line 3, condensing surface E, vacuum pump G and MS storage receptacle I.This two rough vacuum relief outlet is worked under about 14～20 millibars condition of vacuum level, and 4 high vacuum relief outlets are worked under about 0.5～4 millibar condition of vacuum level subsequently.Forcing machine promotes to work under the conditions such as polymeric temperature, vacuum, the residence time and mixture strength being enough to.
Then with the various stablizer compoundings described in the terpolymer of above-prepared and the U.S. Provisional Application 60/806304 submitted on June 30th, 2006, this U.S. Provisional Application is through with reference to incorporating this paper into.The compounding on W&P ZSK25 twin screw extruder of this polycarbonate material.With the artificial premix of said additive and polycarbonate resin powder and use and shake the further homogenize of equipment.Then this polycarbonate Preblend is added in the forcing machine with 1: 19 ratio with the S-polycarbonate material.The barrel zone temperature of forcing machine is set to 300 ℃, is applied to the vacuum in 150～350 millibars of scopes simultaneously.The polymer strands of extruding is cooled off through water-bath, and last granulation is used for further processing.Table 6 provided with each sample in the amount of stablizer of terpolymer compounding.Table 7 shows behind the moulding when each step and the polydispersity value when condition III and IV.
Table 6: additive capacity
| Sample number | Additive | Amount (ppm) |
| 4 | Do not have | 0 |
| 5 | H 3PO 3 | 2 |
| 6 | H 3PO 3 | 9 |
| 7 | H 3PO 3 | 15 |
| 8 | (NH
4)
2 |
3 |
| 9 | (NH 4) 2HPO 4 | 14 |
| 10 | (NH 4) 2HPO 4 | 25 |
Table 7: polymolecularity result
| Sample number | Initial pellet | Pellet after the compounding | Condition III | Condition IV |
| 4 | 2.61 | 2.63 | 2.73 | 2.83 |
| 5 | 2.61 | 2.57 | 2.58 | 2.76 |
| 6 | 2.61 | 2.60 | 2.68 | 2.77 |
| 7 | 2.61 | 2.59 | 2.63 | 2.69 |
| 8 | 2.61 | 2.58 | 2.62 | 2.76 |
| 9 | 2.61 | 2.59 | 2.63 | 2.68 |
| 10 | 2.61 | 2.58 | 2.63 | 2.71 |
Can find out that from table 7 polymolecularity of sample increases along with the increase that comes from the monomeric polycarbonate of alkylation.In addition, this increase is not only depended on the temperature of molding step but also is depended on the residence time that in moulding technology, is in the pyritous polycarbonate.When the polymolecularity under comparison condition III (lesser temps and the residence time 180 seconds) and the condition IV (comparatively high temps and the residence time 720 seconds), can be observed this conclusion.
Can detected NMR peak
Be illustrated in fig. 2 shown below, the characteristic peak (the about 0.05ppm of width) of a non-constant width at the about 3.99ppm of chemical shift place in the proton N MR of the sample that polymolecularity improves spectrum, occurs being centered close to.In polymolecularity or the proton N MR spectrum of melt strength (MIR), there is not this NMR spectrum signature less than the untreated polymkeric substance that improves.This characteristic peak (the proton N MR peak of for example in said polymkeric substance, incorporating into that methyl substituted monomeric methyl substituents belonged to) is with respect to interior target relative intensity, and is quantitatively relevant with the increase of observing Pd and MIR value.Do not observe the J coupling for this new NMR peak, as the methyl that two aromatic rings are linked together is expected.This broad peak can not belong to only a kind of concrete branched structure characteristic, and this is because in branching reaction, can form various such branched substances.According to estimates, this method is limited to respect to monomeric total CH for the detection of these branching units
3Content (the unitary CH of BPA that for example incorporates into and MeHQ
3The mole number sum) about 0.05 mole of %.
Embodiment sums up:
Find:, branching takes place when when comprising polycarbonate such as substituted glycol of alkyl such as toluhydroquinone, tertiary butylated hydroquinone or DMBPC and carry out specific high-temperature heating treatment.Interfacial polymerization capable of using of suitable polycarbonate or melt polymerization (DPC or BMSC) method prepares.As the MIR of the polymkeric substance of handling and polymolecularity improve confirmation, this branching reaction causes the increase of melt strength.Follow the raising of this MIR and Pd, in proton N MR, observe the new broadband that is centered close to the about 3.99ppm of chemical shift place and show gradually.The increase of this NMR characteristic peak and branching (Pd) and melt strength (MIR or R
*) raising quantitatively relevant.
When processing only comprises the polycarbonate of the substituted glycol of non-alkyl such as BPA or quinhydrones similarly, do not observe significantly improving of polymolecularity (Pd) or MIR or branching taken place.
The tB-HQ polycarbonate
According to top embodiment and disclosure, tB-HQ is for preferably being used to incorporate into the alkylation monomer of polycarbonate.Tertiary butylated hydroquinone (CAS#1948-33-0) is by Acros supply, catalog number (Cat.No.) 15082.Other supplier comprises: Dalian (China), Hunan (China), Jan Dekker (Holland), Camlin (India).The tB-HQ polycarbonate can use DPC or BMSC to prepare through melt polymerization as carbonate source.
Use DPC to come and the tB-HQ melt polymerization
20% tBHQ and the multipolymer of BPA are through carrying out melt transesterification reaction (LX) preparation in 25 gram grade batch reactor.For from removing any sodium from glass, in the HCl of 1M at least 24 hours, the water with 18.2M Ω cleaned 5 times at least again with this reactor leaching.Keep the temperature of reactor drum with the heating jacket of equipment PID unit.Control in the vacuum pump in the downstream of the pressure of reactor drum through nitrogen discharge being collected bottle to distillation, and use gauge measurement.Through (Acros 0.5mol/l) is diluted to suitable concentration and prepares catalyst solution with TMAH (Sachem, 25% in water) and NaOH with the water of 18.2M Ω.2.5 * 10
-4React under the existence of mole TMAH/ mole glycol, it is with 100 microlitres and 2.5 * 10
-6Moles of NaOH/mole glycol adds together.The total amount of the catalyst solution that adds remains on 100 microlitres.In this glass reaction tube, add solid BPA (0.08645mol), solid tBHQ (0.02161mol) and solid DPC (0.1167mol), the target mol ratio is 1.08 (carbonic ethers/dihydroxy compound sum).Assembling and sealed reactor are with nitrogen exchange of air 3 times.Catalyzer is added in the monomer.Make this reactor drum near normal atmosphere.In polymerization process, make the top arrangement of reactor assembly remain on 100 ℃.Adopted following temperature/pressure curve.
Fusion: 180 ℃, 1000 millibars, (open after 6 minutes and stir), 10 minutes
Step 1:230 ℃, 170 millibars, 60 minutes
Step 2:270 ℃, 20 millibars, 30 minutes
Step 3:300 ℃, perfect vacuum (～0.5 millibar), 30 minutes
After polymerization is accomplished, make reactor drum get back to normal atmosphere with the demulcent nitrogen gas stream.When reaching normal atmosphere, stop to stir, and, come to discharge product from reactor tube through opening reactor drum in the bottom and product being extruded with slight nitrogen overpressure.Product with results is used for analyzing then.This reaction produces little Huang, transparent polymer, and molecular weight is 35kg/mol (with respect to a PS), and Pd is 2.50.
Use BMSC to come and the tB-HQ melt polymerization:
Tertiary butylated hydroquinone and BPA are that the Copolycarbonate of 80/20 (mol/mol) prepares through BMSC/ molten reactive expressing technique.The BPA that adds 6100g in the synthetic following stainless steel cauldron in stirring of sample, the tertiary butyl HQ (TBHQ) of 17767g, and the BMSC of 44971g, thus make [carbonic ether]/[glycol] mol ratio equal about 1.017.The aqueous catalyst solution that also in reactor drum, adds TMAH (TMAH) and sodium hydroxide (NaOH), the total mole number 5.0 * 10 of the BPA/TBHQ that the amount of TMAH and NaOH is quite per 1 mole
-5The TMAH and 4.0 * 10 of mole
-6The NaOH of mole.Then this reactor drum is vacuumized and with purging with nitrogen gas three times removing residual oxygen, and remain on 800 millibars of constant vacuum pressures.For the fusion and the reaction of mixture, then this reactor drum is heated to 170 ℃.After the heating of reaction kettle begins about 4 hours 15 minutes, with nitrogen this reactor drum is forced into the constant overvoltage of 0.9 crust, and with speed 10kg/h molten reaction mixture is conducted in the forcing machine through the supply line of 170 ℃ of heating.Measured corresponding to 17.0 * 10 by it in the past in 15 minutes
-6Total BPA/TBHQ that moles of NaOH is every mole begins to add sodium hydroxide (NaOH) aqueous catalyst solution to forcing machine.Said forcing machine is the W&P ZSK25WLE 25mm 13-machine barrel twin screw extruder of L/D=59.The forcing machine of accepting feed comprises flash valve to stop the boiling of molten mixture.This reaction mixture carries out reactivity with screw speed 300rpm and extrudes.This forcing machine is equipped with 5 forward vaccum exhaust outlets and a reverse venting port.The wintergreen oil by product is removed through these venting ports through devolatilization.The vacuum pressure of reverse venting port is 11 millibars.The vacuum pressure of the first forward venting port is 3 millibars.The vacuum pressure of last 4 forward venting ports is less than 1 millibar.This TBHQ/BPA (80/20) multipolymer is in temperature and prepares for 280 ℃ through making all extruder barrels be in 270 ℃ of temperature and forcing machine die head.
Claims (20)
1. one kind is improved the branching of polycarbonate and the method for polymolecularity, may further comprise the steps:
(a) make and comprise the substituted monomer of at least a alkyl in the said polycarbonate, the amount that the substituted monomer of wherein said alkyl exists in said polycarbonate is greater than 10 moles of %, by monomeric total mole number in the polycarbonate, and
(b) at high temperature handle said polycarbonate time enough,, improve branching and polymolecularity with the polycarbonate that is equal to respect to there not being alkyl substituent but in others,
The wherein said polycarbonate time enough of at high temperature handling is with respect to there not being alkyl substituent but carry out in the compounding step in the step that polycarbonate that others are equal to improves branching and polymolecularity.
2. the process of claim 1 wherein that the substituted monomer of said at least a alkyl is selected from:
Wherein substituting group Y is hydroxyl, alcohol, ester or carboxylic acid functional independently of one another, and substituent R is C independently of one another
1～C
6Side chain, straight chain or cyclic aliphatic group, x respectively does for oneself and comprises 1 and 4 1～4 integer, and all x be less than or equal to 4,
Wherein substituting group Y is hydroxyl, alcohol, ester or carboxylic acid functional independently of one another, and substituent R is C independently of one another
1～C
6Side chain, straight chain or cyclic aliphatic group, x respectively does for oneself 0 or comprise 1 and 3 1～3 integer, and all x be at least 1 and be less than or equal to 6, and
Wherein substituting group Y is hydroxyl, alcohol, ester or carboxylic acid functional independently of one another, and substituent R is C independently of one another
1～C
6Side chain, straight chain or cyclic aliphatic group, x respectively does for oneself 0 or comprise 1 and 4 1～4 integer, all x be at least 1 and be less than or equal to 8, and Z represents one of following formula group:
R wherein
1, R
2And R
3Be C independently
1～C
18Side chain, straight chain or cyclic aliphatic group, and R
4Be C
3～C
12Cyclic substituents.
3. the method for claim 2, wherein the R substituting group is C independently of one another
1～C
4Side chain or linear aliphatic group.
4. the method for claim 3, wherein the R substituting group is C independently of one another
1Or C
2Aliphatic group.
5. the process of claim 1 wherein that the substituted monomer of said at least a alkyl is selected from: toluhydroquinone, tertiary butylated hydroquinone, DMBPC two (3-methyl-4-hydroxy phenyl) hexanaphthene; 2,2 '-thiobis (4-tert-octyl phenol), TMBPA (tetramethyl-dihydroxyphenyl propane); DMBPA (dimethyl-dihydroxyphenyl propane), DEBPA (diethylammonium dihydroxyphenyl propane), two-o-isopropyl-BPA; Two-o-sec-butyl-BPA, two-o-tert-butyl-BPA, two-ortho-cresol fluorenes; Methylresorcinol, two-tert-butyl resorcin, and two-tertiary butylated hydroquinone.
6. the method for claim 5, the substituted monomer of wherein said at least a alkyl is a tertiary butylated hydroquinone.
7. the process of claim 1 wherein that amount that the substituted monomer of said alkyl exists is greater than 20 moles of %, by monomeric total mole number in the polycarbonate in said polycarbonate.
8. one kind is improved the branching of polycarbonate and the method for polymolecularity, may further comprise the steps:
(a) make and comprise the substituted monomer of at least a alkyl in the said polycarbonate, the amount that the substituted monomer of wherein said alkyl exists in said polycarbonate is greater than 10 moles of %, by monomeric total mole number in the polycarbonate, and
(b) at high temperature handle said polycarbonate time enough,, improve branching and polymolecularity with the polycarbonate that is equal to respect to there not being alkyl substituent but in others,
The wherein said polycarbonate time enough of at high temperature handling is being to carry out in the melt transesterification reaction process at the molecular weight of the said polycarbonate of increase with respect to there not being alkyl substituent but in the step that polycarbonate that others are equal to improves branching and polymolecularity.
9. the method for claim 8 is wherein at high temperature handled time enough at polycarbonate described in the melt polymerization process, so that the polymolecularity of polycarbonate is greater than 2.3.
10. the method for claim 9 is wherein at high temperature handled time enough at polycarbonate described in the melt polymerization process, so that the polymolecularity of polycarbonate is greater than 2.5.
11. the method for claim 8 is wherein handled under greater than 330 ℃ temperature at polycarbonate described in the melt polymerization process.
12. the method for claim 8 is wherein handled under greater than 340 ℃ temperature at polycarbonate described in the melt polymerization process.
13. the process of claim 1 wherein and at high temperature handle time enough at polycarbonate described in the compounding step, so that the polymolecularity of said polycarbonate improves more than 10%.
14. the method for claim 13 is wherein at high temperature handled time enough at polycarbonate described in the compounding step, so that the polymolecularity of said polycarbonate improves more than 50%.
15. the process of claim 1 wherein that said compounding step carries out in the temperature greater than 330 ℃.
16. the method for claim 15, wherein said compounding step is carried out in the temperature greater than 340 ℃.
17. the method for claim 15, wherein said compounding step was carried out more than or equal to 20 minutes.
18. the method for claim 17, wherein said compounding step was carried out more than or equal to 40 minutes.
19. the method for claim 18, wherein said compounding step was carried out more than or equal to 60 minutes.
20. the process of claim 1 wherein that said polycarbonate at high temperature handles time enough, to be created in the polycarbonate that has the wide NMR band between the chemical shift of being centered close to 3.95～4.05ppm in the proton N MR spectrum.
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| US11/623,847 US7759456B2 (en) | 2006-06-30 | 2007-01-17 | Branched polycarbonate resins and processes to prepare the same |
| US11/623,847 | 2007-01-17 | ||
| PCT/US2007/075888 WO2008051652A1 (en) | 2006-10-23 | 2007-08-14 | Branched polycarbonate resins and processes to prepare the same |
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| CN1340083A (en) * | 1999-02-12 | 2002-03-13 | 通用电气公司 | PC/ABS blends possessing high melt flow having controlled levels of Fried branching species |
| US6365710B1 (en) * | 2001-08-29 | 2002-04-02 | General Electric Company | Method for removing volatile components from solid polymeric materials |
| CN1620473A (en) * | 2001-12-21 | 2005-05-25 | 通用电气公司 | Process for the production of branched melt polycarbonate by late addition of fries-inducing catalyst |
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| JPH03269017A (en) * | 1990-03-19 | 1991-11-29 | Chisso Corp | Heat-resistant polycarbonate resin |
| WO2002022708A1 (en) * | 2000-09-12 | 2002-03-21 | Teijin Limited | Aromatic polycarbonates and process for their production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340083A (en) * | 1999-02-12 | 2002-03-13 | 通用电气公司 | PC/ABS blends possessing high melt flow having controlled levels of Fried branching species |
| US6365710B1 (en) * | 2001-08-29 | 2002-04-02 | General Electric Company | Method for removing volatile components from solid polymeric materials |
| CN1620473A (en) * | 2001-12-21 | 2005-05-25 | 通用电气公司 | Process for the production of branched melt polycarbonate by late addition of fries-inducing catalyst |
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