CN103476561B - The manufacture method of polycarbonate resin, the manufacture method of polycarbonate resin, polycarbonate resin film and polycarbonate resin pellets - Google Patents

The manufacture method of polycarbonate resin, the manufacture method of polycarbonate resin, polycarbonate resin film and polycarbonate resin pellets Download PDF

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CN103476561B
CN103476561B CN201280016791.6A CN201280016791A CN103476561B CN 103476561 B CN103476561 B CN 103476561B CN 201280016791 A CN201280016791 A CN 201280016791A CN 103476561 B CN103476561 B CN 103476561B
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polycarbonate resin
filter
manufacture method
temperature
polycarbonate
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CN103476561A (en
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横木正志
金政智亮
白石义隆
并木慎悟
永尾刚
永尾刚一
山本正规
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Mitsubishi Chemical Corp
Mitsubishi Rayon Co Ltd
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Mitsubishi Kasei Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/305—General preparatory processes using carbonates and alcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/10—Conditioning or physical treatment of the material to be shaped by grinding, e.g. by triturating; by sieving; by filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The present invention relates to a kind of manufacture method of polycarbonate resin, it can effectively and stably manufacture the polycarbonate resin of heat stability, form and aspect and mechanical strength and few foreign.

Description

The manufacture method of polycarbonate resin, polycarbonate resin, polycarbonate resin film And the manufacture method of polycarbonate resin pellets
Technical field
The present invention relates to one kind effectively and stably manufactures heat stability, form and aspect and mechanical strength and few foreign Polycarbonate resin method.
Background technology
Polycarbonate resin generally using bisphenols as monomer component, effectively utilizes its in the transparency, thermostability or machinery The superiority of the aspects such as intensity, in optical fields such as electrical and electronic parts, automotive part, optical record medium or lens etc. It is widely applied as so-called engineering plastics.
But, in the optical compensation films purposes of the flat faced display just rapidly popularized recently etc. it is desirable to low-birefringence or The optical characteristics of the more height such as low photoelastic coefficient, for the conventional aromatic copolycarbonate with bisphenols as monomer component It is impossible to adapt to this requirement for resin.
In addition, conventional polycarbonate resin is manufactured using raw material derived from petroleum resources, but in recent years, face Face the exhausted danger of petroleum resources it is desirable to provide using the poly- carbonic acid obtained from raw material being obtained by biomass resources such as plants Ester resin.
Further, since the increase of CO2 emissions or accumulation and the global warming that leads to can lead to climate change etc. Danger, though also require that exploitation carry out after a procedure waste treatment also can keep neutral carbon, with the monomer from plant be The polycarbonate resin of raw material.
In such a case it is proposed that a kind of using special dihydroxy compounds as monomer component, by with carbonic acid Diester carries out ester exchange, one side is distilled off the monohydroxy compound of by-product under reduced pressure while obtaining the side of polycarbonate resin Method (referring for example to patent documentation 1～6).
But, the polycarbonate resin being achieved in that can be mixed into foreign body in its manufacture process etc., therefore there is foreign body and mix Enter to using the problem leading to its commodity value to be remarkably decreased in molded body obtained from this resin forming.Wherein, in optics In purposes etc., be mixed into foreign body or coloring be especially severe problem.
As reducing the method that foreign body is mixed into, it is proposed that making in the polycarbonate resin with bisphenols as monomer component The method (referring for example to patent documentation 7,8) resin obtained from polycondensation being filtered with filter.
Prior art literature
Patent documentation
Patent documentation 1：International Publication No. 04/111106
Patent documentation 2：Japanese Unexamined Patent Publication 2006-232897 publication
Patent documentation 3：Japanese Unexamined Patent Publication 2006-28441 publication
Patent documentation 4：Japanese Unexamined Patent Publication 2008-24919 publication
Patent documentation 5：Japanese Unexamined Patent Publication 2009-91404 publication
Patent documentation 6：Japanese Unexamined Patent Publication 2009-91417 publication
Patent documentation 7：Japanese Unexamined Patent Publication 5-239334 publication
Patent documentation 8：Japanese Unexamined Patent Publication 2000-219737 publication
Content of the invention
Problems to be solved by the invention
But, compared with the polycarbonate resin with bisphenols as monomer component, with the special dihydroxy beyond bisphenols Compound is that the polycarbonate resin of monomer component starts to decompose at low temperature.
Therefore, if it is desired to the temperature in the decomposition not producing polycarbonate resin is filtered, then there are following problems： The pressure loss in the filter under common filter area because viscosity is too high becomes big, thus lead to filter breakage or Person leads to resin to deteriorate because of shear heat evolution when filtering.On the contrary, if breakage to be avoided, have to use the pressure loss The filter of little, filtering accuracy low (mesh size is big).
In addition, if the breakage of filter to be used or the deterioration leading to because of the shear heat evolution of resin are inhibited and mistake If it has to make filter area excessive, there is time required for filtration treatment in result to the filter of filter high precision elongated and lead The problems such as deterioration of cause polycarbonate resin.
Additionally, in order to suppress the pressure loss in the filter, shortening the time required for filtration treatment, if will reduce The melt viscosity of polycarbonate resin, then need to reduce the molecular weight of polycarbonate resin itself or improve filtration temperature.
But, if reducing the molecular weight of polycarbonate resin itself, existing and leading to mechanical strength or thermostability to decline Such problem.In addition, when improving temperature when filtering, resin is decomposed, deteriorated, do not simply fail to be met machinery by force The resin of the physical property such as degree, but also encouraged coloring or led to because of decomposition gas the gas of strand to cut off, thus exist cannot Stably carry out granular problem.
The problems referred to above are reducing the mesh size of filter with when removing less foreign body or the resin high to molecular weight Particularly significant when being filtered.Reduce the mesh size of filter, pressure reduction in the filter becomes big, not only to mistake Filter supply polycarbonate resin becomes unstable, and also results in the breakage of filter as described above or because cutting off heat release And the deterioration of the polycarbonate resin causing.Therefore it is difficult to obtain form and aspect are good, few foreign and mechanical strength sufficiently poly- carbon Acid ester resin.
It is an object of the invention to, eliminate above-mentioned conventional problem, provide one kind can effectively and stably manufacture heat steady The method of the polycarbonate resin of qualitative, form and aspect and mechanical strength and few foreign.The method of solve problem
The present inventor, in order to solve the above problems, has been repeated further investigation, it is found that a kind of poly- carbonic acid of manufacture The method of ester resin, the method includes：Catalyst and specific dihydroxy compounds as starting monomer and carbonic acid two are used Ester, makes their polycondensations by ester exchange reaction, thus obtaining polycarbonate resin, in the method, by under given conditions Polycarbonate resin is filtered, can stably manufacture mechanical strength and form and aspect are excellent and the polycarbonate resin of few foreign Granule.
That is, the present invention is characterized by following [1]～[23].
[1] a kind of manufacture method of polycarbonate resin, the method includes：Using filter by dihydroxy compounds and carbon After polycarbonate resin obtained from acid diesters polycondensation filters, cooled and solidified, wherein, described dihydroxy compounds at least wrap Containing having the dihydroxy compounds as a part for its structure for the position that following formulas (1) represent, the mesh of described filter For less than 50 μm, polycarbonate resin is filtered so that polycarbonate resin after being filtered with described filter Temperature is 200 DEG C less than 280 DEG C.
[chemical formula 1]
[position that wherein, described formula (1) represents is-CH2Except the situation of a part of-O-H.]
The manufacture method of the polycarbonate resin described in [2] above-mentioned [1], wherein, described poly- carbon obtained from described polycondensation Acid ester resin does not make it be supplied to described filter with solidifying to be kept molten by, and is filtered.
The manufacture method of the polycarbonate resin described in [3] above-mentioned [1] or [2], wherein, be fed into described filter it The terminal double bond of front described polycarbonate resin is set to X μ eq/g, by polycarbonate resin obtained from described cooling and solidifying In the case that terminal double bond is set to Y μ eq/g, meet following formula (2).
Y-X≤10 (2)
The manufacture method of the polycarbonate resin any one of [4] above-mentioned [1]～[3], wherein, is fed into described The reduced viscosity (η sp/c) of the described polycarbonate resin before filter be set to A, by described cooling and solidifying obtained from poly- carbon In the case that the reduced viscosity (η sp/c) of acid ester resin is set to B, meet following formula (3).
0.8 ＜ B/A ＜ 1.1 ... (3)
The manufacture method of the polycarbonate resin any one of [5] above-mentioned [1]～[4], wherein, using described cooling Polycarbonate resin obtained from solidification, 240 DEG C of mensure shear rates 91.2sec-1Under melt viscosity be 500Pa s Above and below 3000Pa s.
The manufacture method of the polycarbonate resin any one of [6] above-mentioned [1]～[5], wherein, using described cooling Polycarbonate resin obtained from solidification, glass transition temperature when being measured with differential scanning calorimeter are more than 50 DEG C And it is less than 160 DEG C.
The manufacture method of the polycarbonate resin any one of [7] above-mentioned [1]～[6], wherein, using described cooling Polycarbonate resin obtained from solidification, measure at concentration 0.6g/dL, 20.0 DEG C ± 0.1 DEG C of temperature in dichloromethane Reduced viscosity (η sp/c) is more than 0.3dL/g and below 1.2dL/g.
The manufacture method of the polycarbonate resin any one of [8] above-mentioned [1]～[7], wherein, described filter is received Receive in a reservoir, the internal capacity (m of this accommodating container3) divided by above-mentioned polycarbonate resin to be filtered flow (m3/ point) and The value obtaining is 2 minutes～10 minutes.
The manufacture method of the polycarbonate resin any one of [9] above-mentioned [1]～[8], wherein, described cooling and solidifying Obtained from contained aromatic monohydroxy compound content in polycarbonate resin be 0.0001 mass % less than 0.1 Quality %.
The manufacture method of the polycarbonate resin any one of [10] above-mentioned [1]～[9], wherein, is carrying out polycondensation With the filtered filter of raw material, described starting monomer is filtered before reaction.
The manufacture method of the polycarbonate resin any one of [11] above-mentioned [1]～[10], wherein, described filter Containing in advance more than 350 DEG C and less than 500 DEG C of temperature implements the metal of calcination process.
The manufacture method of the polycarbonate resin any one of [12] above-mentioned [1]～[11], wherein, before described filtration The accommodating container from described filter for the polycarbonate resin bottom supply, the polycarbonate resin after filtration holds from this storage The top of device is discharged.
The manufacture method of the polycarbonate resin any one of [13] above-mentioned [1]～[12], wherein, described polycondensation is Carried out using catalyst, described catalyst is at least one in the metal and lithium of long period type periodic chart the 2nd race Metallic compound.
The manufacture method of the polycarbonate resin any one of [14] above-mentioned [1]～[13], wherein, described have on Stating the position that formula (1) represents is isosorbide as the dihydroxy compounds of a part for its structure.
The manufacture method of the polycarbonate resin any one of [15] above-mentioned [1]～[14], wherein, logical with having QI KOU and there is the extruder of twin screw polycarbonate resin obtained from described polycondensation is carried out, after the operation of devolatilization, being supplied to Described filter.
The manufacture method of the polycarbonate resin described in [16] above-mentioned [15], wherein, the screw rod of described extruder is by multiple Element is constituted, and at least one of this element is kneading disk, the total length of this kneading disk be described screw rod overall length 20% with Under.
The manufacture method of the polycarbonate resin described in [17] above-mentioned [15] or [16], wherein, is supplied to described extruder Polycarbonate resin temperature be 200 DEG C less than 250 DEG C.
The manufacture method of the polycarbonate resin any one of [18] above-mentioned [15]～[17], wherein, is supplied to institute The temperature stating the polycarbonate resin of filter is 220 DEG C less than 280 DEG C.
The manufacture method of the polycarbonate resin any one of [19] above-mentioned [15]～[18], wherein, will supply To the polycarbonate resin of described extruder reduced viscosity (η sp/c) be set to a, by described cooling and solidifying obtained from poly- carbonic acid In the case that the reduced viscosity (η sp/c) of ester resin is set to B, meet following formula (4).
0.8 ＜ B/a ＜ 1.1 ... (4)
The manufacture method of the polycarbonate resin any one of [20] above-mentioned [15]～[19], wherein, squeezes described Go out configuration gear pump between machine and described filter.
[21] a kind of polycarbonate resin, it is to be obtained by the manufacture method any one of above-mentioned [1]～[20] , and its yellow colour index value is less than 30.
[22] a kind of polycarbonate resin film, it is by by the manufacturer any one of above-mentioned [1]～[20] Thickness obtained from polycarbonate resin extrusion molding described in polycarbonate resin that method obtains or above-mentioned [21] is 20 μm～ 200 μm of film, wherein, in this film contained greatest length be more than 25 μm foreign body be 1000/m2Below.
[23] a kind of manufacture method of polycarbonate resin pellets, the method includes：Catalyst will be used and as former The dihydroxy compounds of material list body and carbonic diester are by polycarbonate resin filter obtained from ester exchange reaction polycondensation Filtered, extruded with the form of strand from die head, after cooling, manufacture polycarbonate resin pellets using cutting knife, wherein,
Described dihydroxy compounds include at least the part having the position that following formulas (1) represent as its structure Dihydroxy compounds, the mesh of described filter is less than 50 μm, from the temperature of the resin of described die head extrusion for 200 DEG C with Above and less than 280 DEG C,
[chemical formula 2]
[position that wherein, described formula (1) represents is-CH2Except the situation of a part of-O-H.]
The effect of invention
According to the present invention, effectively and stably can manufacture polycarbonate resin pellets, it has mechanical strength and form and aspect Excellent, few foreign and have and can be applied to the injection mo(u)lding such as electrical and electronic parts or automotive part field, film or piece neck The lens application such as domain, bottle or field of containers and camera lens, finder lens, CCD or CMOS lens, be used for liquid The films such as the phase retardation film of brilliant or plasma scope etc., diffusion sheet, polarizing coating, piece, CD, optical material, opticses or Person is used for such for immobilized to pigment or charge transfer agent etc. adhesive applications extensive field.
Brief description
[Fig. 1] Fig. 1 is the process chart of the example of the manufacturing process illustrating the present invention.
Symbol description
1a raw material (carbonic diester) supply mouth
1b, 1c raw material (dihydroxy compounds) supply mouth
1d catalyst supply mouth
2a raw material mixing channel
3a anchor formula stirring paddle
4a raw material mixed liquor shifting pump
4b, 4c, 4d gear pump
The filtered filter of 5a raw material
6a the first vertical mixing reactive tank
6b the second vertical mixing reactive tank
6c the 3rd vertical mixing reactive tank
6d the 4th Horizontal stirring reactive tank
7a, 7b, 7c Max Blend blade
7d twin shaft spectacle stirring paddle
8a, 8b inner heat exchanger
9a, 9b reflux condenser
10a, 10b return duct
11a, 11b, 11c, 11d distillate pipe
12a, 12b, 12c, 12d condenser
13a, 13b, 13c, 13d decompressor
14a distillate recycling can
15a extruder
15b (polymer) filter
15c die head
16a strand cooling bath
16b strand cutting knife
16c air conveys aerator
16d product hopper
16e quantifier
16f product bag (paper bag, container bag etc.)
Specific embodiment
Hereinafter, embodiments of the present invention are described in detail, but the following explanation to constitutive requirements recorded is this One (typical example) of the embodiment of invention, the present invention, without departing from its purport, is not just limited by herein below.
The manufacture method of the polycarbonate resin pellets of the present invention is to dihydroxy compounds and carbonic acid two using filter After polycarbonate resin obtained from ester polycondensation filters, then the manufacture method of the polycarbonate resin being cooled and solidified, it is special Levy and be, above-mentioned dihydroxy compounds include at least has the position that following formulas (1) represent as a part for its structure Dihydroxy compounds, the mesh of above-mentioned filter is less than 50 μm, after carrying out filtering so that being filtered with described filter The temperature of resin is 200 DEG C less than 280 DEG C.
[chemical formula 3]
Wherein, the position that described formula (1) represents is-CH2Except the situation of a part of-O-H.
＜ starting monomer and polymerization catalyst ＞
(dihydroxy compounds)
In the manufacture method of the polycarbonate resin of the present invention, carbonic diester and dihydroxy compounds are used as raw material Monomer, but it is characterized in that, at least one of dihydroxy compounds is that have the position that following formulas (1) represent as its structure A part specific dihydroxy compounds (below, sometimes referred to as " dihydroxy compounds of the present invention ").That is, the two of the present invention Hydroxy compounds refer at least contain the material of the construction unit of 2 hydroxyls and above-mentioned formula (1).
As the dihydroxy compounds of the invention described above, as long as there is the position that above-mentioned formula (1) represents as its structure A part, be not particularly limited.Specifically can enumerate for example：Diethylene glycol, triethylene glycol, TEG, poly- second two The oxidative olefinic diols class such as alcohol, polypropylene glycol, polytetramethylene glycol；9,9- double [4- (2- hydroxyl-oxethyl) phenyl] fluorenes, 9,9- Double [4- (2- the hydroxyl-oxethyl) -3- isopropyl phenyl] fluorenes of double [4- (2- hydroxyl-oxethyl) -3- aminomethyl phenyl] fluorenes, 9,9-, 9, Double [4- (2- the hydroxyl-oxethyl) -3- isobutyl phenenyl] fluorenes of 9-, 9,9- are double [4- (2- hydroxyl-oxethyl) -3- tert-butyl-phenyl] Double [4- (2- the hydroxyl-oxethyl) -3- cyclohexyl phenyl] fluorenes of fluorenes, 9,9-, double [4- (2- the hydroxyl-oxethyl) -3- phenyl benzene of 9,9- Base] fluorenes, double [4- (2- the hydroxyl-oxethyl) -3,5- 3,5-dimethylphenyl] fluorenes of 9,9-, double [4- (2- the hydroxyl-oxethyl) -3- uncle of 9,9- Butyl -6- aminomethyl phenyl] side chain such as double [4- (3- hydroxyl -2,2- dimethyl propylene epoxide) phenyl] fluorenes of fluorenes and 9,9- has aromatic series Group and main chain have the compound of the ether being bonded on aromatic group；The dihydroxy compounds that following formulas (5) represent There is the compound of ring-type ether structure for the sugar alcohol acid anhydride that represents and the spiroglycol of representing of following formula (6) etc..
Wherein, the color of the reactivity when easiness obtaining, operability, polymerization and obtained polycarbonate resin From the viewpoint of phase, preferably diethylene glycol, triethylene glycol or Polyethylene Glycol.
In addition, from the viewpoint of thermostability, the dihydroxy compounds that preferably represented with following formulas (5) sugar as representative The spiroglycol that alcohol acid anhydride or following formula (6) represent etc. has the ring-type ether structure [position that preferably above-mentioned formula (1) represents A part for ring-type ether structure] compound.
According to the requirement performance of obtained polycarbonate resin, above-mentioned dihydroxy compounds can be used alone, and also may be used To combine two or more use.
[chemical formula 4]
[chemical formula 5]
It should be noted that the dihydroxy compounds representing as above-mentioned formula (5), such as presence can be enumerated three-dimensional different The isosorbide of structure body relation, different mannide or different iditol.They can be used alone one kind it is also possible to combine 2 Plant used above.
In these dihydroxy compounds, from the viewpoint of the form and aspect of polycarbonate resin, preferably use and there is no fragrance The dihydroxy compounds of ring structure.Wherein, from the easy degree obtaining and manufacturing, light resistance, optical characteristics, mouldability, heat-resisting Property and neutral carbon from the aspect of, most preferably by as from plant aboundresources exist and can easily obtain various The Sorbitol that starch manufactures is through isosorbide obtained from dehydrating condensation.
In the manufacture method of the polycarbonate resin of the present invention, as starting monomer, can contain and come from above-mentioned The structure list of the dihydroxy compounds (below, sometimes referred to as " other dihydroxy compounds ") beyond the dihydroxy compounds of invention Unit.
As other dihydroxy compounds, can enumerate for example：Ethylene glycol, 1,3- propylene glycol, 1,2- propylene glycol, 1,4- fourth The aliphatic dihydroxy compounds such as glycol, 1,3 butylene glycol, 1,2- butanediol, 1,5- heptandiol and 1,6-HD, 1,2- ring Hexane dimethanol, 1,3- cyclohexanedimethanol, 1,4 cyclohexane dimethanol, Tricyclodecane Dimethanol, pentacyclopentadecane dimethanol, 2,6- naphthalane dimethanol, 1,5- naphthalane dimethanol, 2,3- naphthalane dimethanol, 2,3- norbornane dimethanol, 2,5- norbornane Double (4- hydroxy phenyl) propane of the ester ring type dihydroxy compounds such as dimethanol and 1,3- diamantane (obsolete) dimethanol and 2,2- [=bis- Phenol A], double (4- hydroxyl -3,5- 3,5-dimethylphenyl) propane of 2,2-, 2,2- double (4- hydroxyl -3,5- diethyl phenyl) propane, 2,2- Double (4- hydroxyl -3,5- dibromo phenyl) propane of double [4- hydroxyl-(3,5- diphenyl) phenyl] propane, 2,2-, double (the 4- hydroxyl of 2,2- Phenyl) pentane, 2,4 '-dihydroxydiphenyl methane, double (4- hydroxy phenyl) methane, double (4- hydroxyl -5- nitrobenzophenone) methane, Double (4- hydroxy phenyl) ethane of 1,1-, 3,3- double (4- hydroxy phenyl) pentane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, double (4- Hydroxy phenyl) sulfone, 2,4 '-dihydroxy-diphenyl sulfone, double (4- hydroxy phenyl) thioether, 4,4 '-dihydroxydiphenyl ether, 4,4 '- Dihydroxy -3,3 '-Dichlorodiphenyl ether, double [4- (2- hydroxyl-oxethyl -2- methyl) phenyl] fluorenes of 9,9-, double (the 4- hydroxyl of 9,9- Phenyl) the aromatic bisphenols class such as fluorenes and double (the 4- hydroxy-2-methyl phenyl) fluorenes of 9,9-.
In above-mentioned such other dihydroxy compounds, from the viewpoint of the form and aspect of polycarbonate resin, preferably make There are no in molecular structure the dihydroxy compounds of aromatic ring structure, be selected from aliphatic dihydroxy compounds and ester ring type At least one compound in dihydroxy compounds.
As aliphatic dihydroxy compounds, particularly preferred 1,3-PD, BDO or 1,6- hexanediol.Separately Outward, as ester ring type dihydroxy compounds, particularly preferred 1,4-CHDM or Tricyclodecane Dimethanol.Wherein, from poly- From the viewpoint of closing reactivity and toughness improvement, preferably 1,4-CHDM.
By using these other dihydroxy compounds, it is possible to obtain the flexibility, the raising that improve polycarbonate resin are resistance to Hot or improve mouldability and other effects, but if the content ratio coming from the construction unit of other dihydroxy compounds is excessive, Then sometimes result in the reduction of mechanical properties or the reduction of thermostability.
Therefore, the construction unit of dihydroxy compounds coming from the present invention is with respect to coming from whole dihydroxy compounds The ratio of construction unit be preferably 20 moles of more than %, more preferably 30 moles more than %, particularly preferably 50 moles % with On.
That is, preferably with respect to coming from the construction unit of whole dihydroxy compounds, come from other dihydroxy compounds Construction unit ratio be less than 80 moles of %, more preferably 70 moles below %, particularly preferably 50 moles below %.
The dihydroxy compounds of the present invention can be steady containing reducing agent, antioxidant, deoxidizer, light stabilizer, antacid, pH Determine the stabilizers such as agent or heat stabilizer.Particularly in acid condition, the dihydroxy compounds of the present invention are apt to deteriorate, therefore, When preferably being preserved before use so as in contain alkaline stabiliser.
As alkaline stabiliser, can enumerate for example：Long period type periodic chart (Nomenclature of Inorganic Chemistry IUPAC Recommendations2005) in the hydroxide of 1 race or 2 race's metals, carbonate, phosphate, Asia Phosphate, hypophosphite, borate and soap, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl hydroxide Ammonium, TBAH, trimethylethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, trimethylphenyl ammonium hydroxide, three Ethyl-methyl ammonium hydroxide, triethylbenzyl ammonium hydroxide, triethyl group phenyl ammonium hydroxide, tributyl benzyl ammonium hydroxide, three Butyl phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyltriphenyl phosphonium ammonium hydroxide, methyl triphenyl ammonium hydroxide and butyl three The alkaline ammonium compounds such as phenyl ammonium hydroxide and 4-aminopyridine, PA, N, N- dimethyl -4-aminopyridine, 4- Diethyl amino yl pyridines, 2 hydroxy pyrimidine, 2- methoxypyridine, 4-methoxypyridine, 2- dimethylamino imidazoles, 2- methoxyl group The aminated compoundss such as imidazoles, imidazoles, 2- mercaptoimidazole, 2-methylimidazole and quinolin-2-ylamine.Wherein, from its effect and steaming described later From the point of view of evaporating the easy degree of removing, the preferably phosphate of Na or K or phosphite, particularly preferred disodium hydrogen phosphate or hydrogen phosphite Disodium.
Content in the dihydroxy compounds of the present invention for these stabilizers is not particularly limited, but if it contained Less it is likely that the effect that the dihydroxy compounds of the present invention go bad cannot be obtained preventing, if its content excessive it is likely that Lead to the modification of the dihydroxy compounds of the present invention.Accordingly, with respect to the dihydroxy compounds of the present invention, stabiliser content leads to Often it is preferably 0.0001 weight %～1 weight %, more preferably 0.001 weight %～0.1 weight %.
In addition, in the case that the dihydroxy compounds of the present invention have ring-type ether structure for isosorbide etc., due to easy Slowly oxidized under the effect of the oxygen, therefore, when taking care of or when manufacturing, in order to prevent the decomposition being caused by oxygen, preferably do not make Moisture is mixed into and using deoxidizer etc., or is operated under nitrogen atmosphere.
Particularly, if isosorbide is oxidized, the analytes such as formic acid are produced sometimes.If using comprising these points Solution thing isosorbide as polycarbonate resin manufacture raw material it is likely that leading to the coloring of gained polycarbonate resin, Additionally, physical property not only may be made significantly to deteriorate, and sometimes impact is brought on polyreaction, thus macromolecule cannot be obtained The polymer of amount, it is not preferable.
(carbonic diester)
In the present invention, can be to comprise the dihydroxy compounds of dihydroxy compounds and the carbonic acid of the invention described above Diester, as raw material, makes their polycondensations obtain polycarbonate resin by ester exchange reaction.
As the carbonic diester using in the present invention, the carbonic diester that following structural formula (7) represents can be enumerated.These carbon Acid diesters can be used alone one kind it is also possible to mix two or more use.
[chemical formula 6]
In structural formula (7), A1、A2It is aliphatic group or the replacement of substituted or unsubstituted carbon number 1～18 Or unsubstituted aromatic group, A1With A2Can be the same or different.
A1And A2Preferably substituted or unsubstituted aromatic hydrocarbyl, more preferably unsubstituted aromatic hydrocarbyl.Need explanation It is, as the substituent group of aliphatic alkyl, can to enumerate for example：Ester group, ether, carboxylic acid, amide groups and halogen.As aromatic series The substituent group of alkyl, can enumerate for example：The alkyl such as methyl and ethyl..
The carbonic diester representing as above-mentioned formula (7), for example, can include：Diphenyl carbonate and carboxylol ester Deng replacement diphenyl carbonate, dimethyl carbonate, diethyl carbonate and dimethyl dicarbonate butyl ester etc..Wherein, preferably diphenyl carbonate Or replacement diphenyl carbonate, particularly preferably diphenyl carbonate.
It should be noted that carbonic diester is sometimes with impurity such as chloride ions, thus exist obstruction polyreaction or Person makes the situation that the form and aspect of obtained polycarbonate resin deteriorate, and therefore, as needed, preferably uses by purification such as distillations Carbonic diester afterwards.
In the method for the invention, the dihydroxy of the dihydroxy compounds making by ester exchange reaction to comprise the present invention Compound and carbonic diester carry out polycondensation, thus obtain polycarbonate resin.Dihydroxy compounds as raw material and carbonic acid two Ester can independently be put in reactive tank and carry out ester exchange reaction it is also possible to equably mix before transesterification.
The temperature of above-mentioned mixing is preferably more than 80 DEG C, more preferably more than 90 DEG C, preferably less than 250 DEG C of its upper limit, More preferably less than 200 DEG C, more preferably less than 150 DEG C.Wherein, preferably more than 100 DEG C and less than 130 DEG C.
If the temperature of above-mentioned mixing is too low it is likely that dissolution velocity is slack-off or dissolubility is not enough, frequently result in solidification A problem that.If the temperature of above-mentioned mixing is too high, there is the situation leading to dihydroxy compounds heat deterioration, its result It is that the form and aspect of obtained polycarbonate resin are possible to deteriorate, thus bringing harmful effect to light resistance or thermostability.
In the method for the invention, using the dihydroxy chemical combination of the dihydroxy compounds comprising the present invention as raw material The oxygen concentration of the operating environment that thing is mixed with carbonic diester is preferably below 10 volumes %, from the viewpoint of preventing form and aspect from deteriorating, More preferably in 0.0001 volume %～10 volume %, further preferably in 0.0001 volume %～5 volume %, particularly preferably 0.0001 Carry out under the atmosphere of volume %～1 volume %.
In the present invention, with respect to whole dihydroxies of the dihydroxy compounds comprising the present invention used in reaction Based compound, carbonic diester is preferably used with 0.90～1.20 molar ratio, and more preferably 0.95～1.10, further preferably For 0.97～1.03, particularly preferably 0.99～1.02.
If above-mentioned molar ratio diminishes, the terminal hydroxyl of manufactured polycarbonate resin increases, the heat of polymer Stability deteriorates, and leads in molding colour or so that the speed of ester exchange reaction is reduced, consequently, it is possible to cannot obtain desired High molecular body.
On the other hand, if above-mentioned molar ratio becomes big, there are following situations：The speed of ester exchange reaction reduces, hardly possible So that the Merlon of molecular weight desired by manufacture or the remaining carbonic diester amount in polycarbonate resin increase in extrusion Or during molding, lead to the generation of gas.The reduction of ester exchange reaction speed makes thermal history during polyreaction lengthen, its result It is it is possible to make the form and aspect of obtained polycarbonate resin deteriorate.
If additionally, increasing carbonic acid with respect to whole dihydroxy compounds of the dihydroxy compounds comprising the present invention , then there are following situations in the molar ratio of diester：Remaining carbonic diester amount in obtained polycarbonate resin increases, its It is changed into gas during molding and lead to molding bad or ooze out from product, thus not preferred.
In the polycarbonate resin pellets that profit is obtained by the present invention, the concentration of the carbonic diester of remaining is preferably 200 Below weight ppm, below more preferably 100 weight ppm, below particularly preferably 60 weight ppm, especially preferably 30 weight Below ppm.
(catalyst)
In the method for the invention, the dihydroxy compounds containing the present invention are made in interior dihydroxy as described above When compound and carbonic diester carry out polycondensation to manufacture polycarbonate resin by ester exchange reaction, there may be ester exchange catalyst (below, also referred to as " catalyst " or " polymerization catalyst ").
In the method for the invention, ester exchange catalyst (catalyst) particularly can be thermally-stabilised to polycarbonate resin Property or represent form and aspect yellow colour index (YI) value produce impact.As the ester exchange catalyst being used, as long as meeting poly- carbon The heat stability of acid ester resin and the catalyst of form and aspect, then do not limit.
The metallization of 1 race in long period type periodic chart or 2 races (hereinafter referred to as " 1 race ", " 2 race ") for example can be enumerated The alkali compoundss such as compound, alkaline boron compound, alkaline phosphating compound, alkaline ammonium compound and aminated compoundss.
Preferably use 1 race's metallic compound and/or 2 race's metallic compounds.It is more preferably selected from long period type periodic chart the 2nd race Metal and lithium in metal metallic compound.
As the form of above-mentioned 1 race's metallic compound and/or 2 race's metallic compounds, generally with hydroxide, carbonate, The form of carboxylate or the such salt of phenates uses, and considers from the easy degree of the easy degree obtaining, operation, preferably hydroxide Thing, carbonate or acetate, from the viewpoint of form and aspect and polymerization activity, preferably acetate.
As specifically above-mentioned 1 race's metallic compound, can enumerate for example：Sodium hydroxide, potassium hydroxide, Lithium hydrate, Cesium hydrate., sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, caesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, acetic acid Sodium, potassium acetate, Quilonorm (SKB), cesium acetate, sodium stearate, potassium stearate, lithium stearate, stearic acid caesium, sodium borohydride, hydroboration Potassium, lithium borohydride, hydroboration caesium, phenylating boron sodium, phenylating boron potassium, phenylating boron lithium, phenylating boron caesium, sodium benzoate, benzene Potassium formate, lithium benzoate, benzoic acid caesium, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphoric acid hydrogen two lithium, phosphoric acid hydrogen two caesium, phosphenylic acid Disodium, phosphenylic acid dipotassium, phosphenylic acid two lithium, phosphenylic acid two caesium, sodium, potassium, lithium, the alkoxide of caesium, phenates, the two of bisphenol-A Sodium salt, di-potassium, dilithium salt and two cesium salts etc..Wherein preferred lithium compound.
In addition, as specifically above-mentioned 2 race's metallic compounds, can enumerate for example：Calcium hydroxide, barium hydroxide, hydrogen-oxygen Change magnesium, Strontium hydrate., calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, Calcium Carbonate, brium carbonate, magnesium carbonate, carbonic acid Strontium, calcium acetate, Barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate and Strontium bis(stearate) etc..
Wherein preferred magnesium compound, calcium compounds or barium compound, from polymerization activity and obtained polycarbonate resin Form and aspect from the viewpoint of, be more preferably selected from least one metallic compound in magnesium compound and calcium compounds, most preferably calcium Compound.
It should be noted that can also be auxiliary while using above-mentioned 1 race's metallic compound and/or 2 race's metallic compound Helping property it is applied in combination the alkali compoundss such as alkaline boron compound, alkaline phosphating compound, alkaline ammonium compound or aminated compoundss, But become due to fault due to being possible to volatilize in the polymerization, therefore particularly preferably only using 1 race's metallic compound And/or 2 race's metallic compounds.
As the above-mentioned alkaline boron compound that can be applied in combination, for example, can enumerate：Tetramethyl boron, tetraethyl boron, four Propyl group boron, tetrabutyl boron, trimethylethyl boron, trimethyl benzyl boron, trimethylphenyl boron, triethyl methyl boron, triethyl group benzyl Base boron, triethyl group phenyl boron, tributyl benzyl boron, tributyl phenyl boron, tetraphenyl boron, benzyltriphenyl phosphonium boron, methyl triphenyl The sodium salt of boron and butyl triphenyl boron etc., potassium salt, lithium salts, calcium salt, barium salt, magnesium salt and strontium salt etc..
As the above-mentioned alkaline phosphating compound that can be applied in combination, for example, can enumerate：Triethyl phosphine, three n-pro-pyl phosphines, Tri isopropyl phosphine, tri-n-butyl phosphine, triphenylphosphine, tributylphosphine and seasonSalt etc..
As the above-mentioned alkaline ammonium compound that can be applied in combination, for example, can enumerate：Tetramethylammonium hydroxide, tetraethyl Ammonium hydroxide, TPAOH, TBAH, trimethylethyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, Trimethylphenyl ammonium hydroxide, triethyl methyl ammonium hydroxide, triethylbenzyl ammonium hydroxide, triethyl group phenyl ammonium hydroxide, Tributyl benzyl ammonium hydroxide, tributyl phenyl ammonium hydroxide, tetraphenyl ammonium hydroxide, benzyltriphenyl phosphonium ammonium hydroxide, methyl Triphenyl ammonium hydroxide and butyl triphenyl ammonium hydroxide etc..
As the above-mentioned aminated compoundss that can be applied in combination, for example, can enumerate：4-aminopyridine, PA, N, N- dimethyl -4-aminopyridine, 4- lignocaine pyridine, 2 hydroxy pyrimidine, 2- methoxypyridine, 4-methoxypyridine, 2- Dimethylamino imidazoles, 2- methoxyl group imidazoles, imidazoles, 2- mercaptoimidazole, 2-methylimidazole and quinolin-2-ylamine etc..
The usage amount of above-mentioned catalyst with respect to the every 1mol of whole dihydroxy compounds being used be preferably 0.1 μm of ol～ 300 μm of ol, more preferably 0.5 μm ol～100 μm ol, more preferably 0.5 μm ol～50 μm ol, much further preferably from 0.5 μm of ol～20 μm ol, particularly preferably 1 μm ol～5 μm ol.
Wherein, in the metallic compound using at least one in selected from the metal and lithium of long period type periodic chart the 2nd race In the case of, in the every 1mol of whole dihydroxy compounds being used, with metal gauge it is often preferred that 0.1 μm of more than ol, more It is preferably 0.5 μm of more than ol, particularly preferably 0.7 μm more than ol.In addition, as its upper limit it is often preferred that 20 μm of ol, more excellent Elect 10 μm of ol, more preferably 3 μm ol, particularly preferably 1.5 μm ol, especially preferably 1.0 μm ol as.
On the other hand, if the usage amount of described catalyst is excessively it is likely that make gained because of undesirable side reaction The form and aspect of the polycarbonate resin arriving or heat stability etc. deteriorate.
In addition, 1 race's metal, especially sodium, potassium and caesium, if particularly sodium contains in polycarbonate resin in a large number, It is possible to form and aspect are had undesirable effect, this metal comes not only from used catalyst, and sometimes from raw material or reaction It is mixed in device.Therefore, the total amount of these compounds in polycarbonate resin is preferably generally 1 weight with metal gauge Below ppm, below more preferably 0.8 weight ppm, below more preferably 0.7 weight ppm.
It should be noted that amount of metal in polycarbonate resin can reclaim poly- carbonic acid the method such as being ashed using wet type After metal in ester resin, lighted using atom, atom extinction or inductively coupled plasma (Inductively Coupled Plasma, ICP) etc. method measure.
In addition, above-mentioned catalyst can be directly appended in reactor be added to dihydroxy compounds it is also possible to take In the raw material preparation vessel being pre-mixed with carbonic diester and then be allowed to the method being present in reactor, can also be to reaction Add in the pipe arrangement of device base feed.
If the usage amount of above-mentioned catalyst is very few, sufficient polymerization activity can not be obtained, the carrying out of polyreaction becomes Slowly, accordingly, it is difficult to the polycarbonate resin of molecular weight desired by obtaining, in addition, being subject to long thermal history, form and aspect are possible to Deteriorate.
＜ manufacture method ＞
(polycondensation method)
In the method for the invention, above-mentioned dihydroxy compounds and above-mentioned carbonic diester polycondensation is made to obtain polycarbonate resin The method of fat can in the presence of above-mentioned catalyst, using multiple reactor multistages implement.
The form of reaction can be any one method combining of batch (-type), continuous way or batch (-type) and continuous way.Its In, from the viewpoint of the stabilisation of quality, preferably continuous way.Preferably in polymerization initial stage, obtain under relative low temperature, coarse vacuum Prepolymer, after polymerisation the phase under relatively-high temperature, fine vacuum, molecular weight is increased to specified value, from form and aspect or heat stability Viewpoint considers, preferably rightly selects the pressure in the jacket temperature and interior temperature, reaction system in each molecular weight stage.
For example, if some too fast change in temperature and pressure before polyreaction reaches specified value, Unreacted monomer can be distilled out, make dihydroxy compounds disorderly with the molar ratio of carbonic diester, lead to the fall of polymerization speed Low or the polymer with given molecular weight or end group cannot be obtained, as a result, being possible to realize the present invention Purpose.
Additionally, in order to suppress the amount of monomer distilling out, the use of reflux condenser is effective in polymer reactor, special It is not that its effect is larger in the reactor of the polymerization initial stage more than unreacted monomer composition.Import to the cause in reflux condenser The temperature of cryogen suitably can select according to the monomer being used.
As a rule, the temperature importing to the cryogen in reflux condenser is preferably 45 in the entrance of this reflux condenser ～180 DEG C, more preferably 80～150 DEG C, particularly preferably 100～140 DEG C.
If the temperature of cryogen is too high, capacity of returns reduces, and its effect reduces, on the contrary, if the temperature mistake of cryogen Low, then the efficiency that is distilled off of the monohydroxy compound originally should being distilled off has the trend of reduction.As cryogen, permissible Enumerate such as warm water, steam and heat kerosene etc., preferably steam or heat kerosene.
In order to be properly maintained speed, while the distillating of monomer of suppression of above-mentioned polymerization, suppress final poly- carbonic acid The foreign body of ester resin produces, and does not damage form and aspect or heat stability, and the species of described catalyst is selected particularly significant with amount.
In the present invention, it is preferred to use above-mentioned catalyst, and manufactured using the ground polymerization of multiple reactor multistages.Use The reasons why multiple reactors implement polymerization is：In order to make contained monomer in reactant liquor many at the polyreaction initial stage, important Be intended to keep necessary polymerization speed while, suppression monomer volatilization, in order to the phase makes balance to polymerization after polymerization , it is important to the monohydroxy compound of by-product is fully distilled off, polymerization desired with the later stage is anti-in the early stage for side shifting Answer condition different.So, in order to set different polymeric reaction conditions, from the viewpoint of production efficiency, preferably use series connection Multiple polymer reactors of configuration.
The reactor using in described polymerization in the present invention is preferably at least more than 2 as mentioned above, from production efficiency Consider etc. viewpoint, more preferably more than 3, more preferably 3～5, particularly preferably 4.
In the present invention, if reactor is more than 2, can impose a condition in each reactor different reactions Condition, continuously can be changed to temperature, pressure in each reactor.
In the present invention, described polymerization catalyst both can be added to raw material preparation vessel, in storage groove it is also possible to straight Connect and be added in polymerization tank, but from the viewpoint of the control of the stability from supply and polymerization, preferably supplying it to polymerization tank The midway setting catalyst supplying tubing of front raw material pipe arrangement, is more preferably supplied with aqueous solution.
If the temperature of above-mentioned polyreaction is too low, productivity can be led to reduce or make product heat to be experienced and to go through Cheng Yanchang, and if the temperature of described polyreaction is too high, then not only result in the volatilization of monomer, and be possible to encourage poly- carbon The decomposition of acid ester resin or coloring.
Specific said temperature is as follows.For the reaction of first paragraph, as polymer reactor interior temperature High-temperature, preferably 140～270 DEG C, more preferably 170～240 DEG C, more preferably 180～210 DEG C, and preferably exist 110～1kPa, more preferably in 70～5kPa, further preferably under the pressure of 30～10kPa (absolute pressure), by by-product Monohydroxy compound be distilled off to outside reaction system while be preferable to carry out 0.1～10 hour, more preferably implement 0.5～3 little When reaction.
The reaction of the so-called first paragraph in the present invention, refers to the 5 of the monohydroxy compound distillating through whole polyreaction Reaction in the reactor of the most upstream being in technique in the middle of the reactor more than weight % distillating.
The later reaction of second segment is as follows：The pressure of reaction system is slowly reduced by the pressure of first paragraph, will connect The monohydroxy compound of generation of getting off is rejected to outside reaction system, finally makes the pressure (absolute pressure) of reaction system preferably For below 2kPa, it is more preferably below 1kPa, and preferably more than 210 DEG C, more preferably more than 220 DEG C and preferably 270 Below DEG C, more preferably below 250 DEG C, further preferably preferably carry out below 240 DEG C 0.1～10 hour, more preferably carry out 1 ～6 hours, particularly preferably carry out 0.5～3 hour.
Particularly, in order to suppress coloring or the heat deterioration of polycarbonate resin, obtain the poly- of form and aspect or good thermal stability Carbonate resin, preferably smaller than 260 DEG C of the maximum temperature of the interior temperature in preferably all stages of reaction, more preferably less than 250 DEG C, spy You Xuan little Yu 245 DEG C.
What interior temperature mentioned here represented is the temperature of process liquid, generally can be using making of possessing in reactor Measured with the thermometer of thermocouple etc..In addition, the reduction of the polymerization speed in order to suppress polyreaction back segment, will be gone through by heat The degradation inhibiting of Cheng Zaocheng uses plug flow characteristic and interface renewal property excellent in Min., the preferably terminal stage in polymerization Horizontal reactor.
But, in order to obtain the polycarbonate resin of given molecular weight, if made, polymerization temperature is too high, make polymerization time mistake Length, then it represents that yellow colour index (YI) value of form and aspect has the trend becoming big, needs to pay attention to for this point.
The monohydroxy compound that by-product in described reaction is distilled off, from the viewpoint of utilization of resources, Raw material preferably as fuel or chemicals uses.Particularly preferably carry out after purification as needed, as diphenyl carbonate or double The raw material of phenol A etc. recycles.
(the later operation of polycondensation reaction)
The polycarbonate resin of the present invention, after carrying out above-mentioned polycondensation reaction, is filtered using filter.Wherein, Interpolation in order to implement removing or the heat stabilizer of contained low molecular weight compositions in polycarbonate resin etc. kneads, and preferably will The polycarbonate resin obtaining in polycondensation imports extruder, the polycarbonate resin that then will discharge from extruder using filter Filtered.
Method as utilizing as discussed above the polycarbonate resin filtration that polycondensation obtains using filter is for example permissible Enumerate method below.
In order to produce pressure necessary to filtration, using gear pump or screw rod etc. with molten from final polymer reactor State extracts polycarbonate resin, the method being filtered with described filter out；
From final polymer reactor, polycarbonate resin is supplied to single screw rod or double screw extruder with molten condition, melt After melting extrusion, filtered with described filter, with the form cooling and solidifying of strand, carry out granular side with rotary cutter etc. Method；
From final polymer reactor so that it is solidified to be kept molten by supply to single screw rod or double screw extruder To polycarbonate resin, after melt extruding, granulated with the form cooling and solidifying of strand, this granule is imported extruder again And filtered using described filter, then cooled and solidified with the form of strand, then carry out granular method；
Or, from final polymer reactor, polycarbonate resin is extracted out with molten condition, not by extruder with stock The form of bar cools and solidifies and so that it is granulated, and then supplies granule to single screw rod or double screw extruder, after melt extruding, uses Described filter filters, and with the form cooling and solidifying of strand, then makes its granular method；Etc..
Wherein, in order to by thermal history boil down to Min., suppress the heat deterioration such as the deterioration of form and aspect or the reduction of molecular weight, It is preferably as follows method：Do not make state that it solidifies from final polymer reactor to be kept molten by single screw rod or double spiral shell Bar extruder supplies resin, after melt extruding, is supplied to described filter using gear pump and is filtered, after die head extrusion With the form cooling and solidifying of strand, rotary cutter etc. is recycled to be granulated.
One ＞ of ＜ manufacture device
The process chart of Fig. 1 is illustrated that for implementing assembly of the invention, to obtain by the raw material recorded above Polycarbonate resin obtained from monomer cooling and solidifying is (below, sometimes by " polycarbonate resin after cooling and solidifying " referred to as " polycarbonate resin ") granule.
As the dihydroxy compounds of the present invention of starting monomer, use isosorbide (ISB), as other dihydroxies Based compound, uses 1,4-CHDM (CHDM), as carbonic diester, uses diphenyl carbonate (DPC), As polymerization catalyst, use calcium acetate.
First, in raw material preparation section, in a nitrogen atmosphere, by the fused solution of the DPC preparing at a given temperature from Raw material supply mouth 1a continuously feeds to raw material mixing channel 2a.In addition, the fused solution of the ISB measuring in a nitrogen atmosphere, CHDM Fused solution continuously feed to raw material mixing channel 2a from raw material supply mouth 1b, 1c respectively.Then, profit in raw material mixing channel 2a With stirring paddle 3a, they are mixed, obtain raw material mixed melting liquid.
Then, obtained raw material mixed melting liquid is stood to first through raw material supply pump 4a, raw material filtered filter 5a Formula stirred tank 6a continuously feeds.In addition, catalyst material is in form of an aqueous solutions from the transfer of raw material mixed melting liquid Catalyst supply mouth 1d of pipe arrangement midway continuously feeds.
In the polycondensation step of the manufacture device of Fig. 1, by the first vertical mixing reactive tank 6a, the second vertical mixing reactive tank 6b, the 3rd vertical mixing reactive tank 6c, the 4th Horizontal stirring reactive tank 6d are arranged in series.In each reactor, liquid level is kept For constant, carry out polycondensation reaction, the polymerization liquid discharged from the bottom land of the first vertical mixing reactive tank 6a is vertical to second successively Formula stirred tank 6b, continuously supply followed by the 3rd vertical mixing reactive tank 6c, the 4th Horizontal stirring reactive tank 6d, carry out Polycondensation reaction.Reaction condition in each reactor is preferably respectively set as reaching a high temperature with the propulsion of polycondensation reaction, Gao Zhen Empty, low mixing speed.
In the first vertical mixing reactive tank 6a, the second vertical mixing reactive tank 6b and the 3rd vertical mixing reactive tank 6c, It is respectively equipped with Max Blend blade 7a, 7b, 7c.In addition, in the 4th Horizontal stirring reactive tank 6d, being provided with twin shaft spectacle and stir Mix oar 7d.Reactant liquor due to transfer after the 3rd vertical mixing reactive tank 6c is changed into high viscosity, is therefore provided with gear pump 4b.
It is especially big that first vertical mixing reactive tank 6a and the second vertical mixing reactive tank 6b supplies heat sometimes, therefore in order to Do not make heat medium temperature too high, be respectively equipped with inner heat exchanger 8a, 8b.
And, in above-mentioned 4 reactors, it is separately installed with for discharging the by-product generating because of polycondensation reaction etc. Distillate pipe 11a, 11b, 11c, 11d.For the first vertical mixing reactive tank 6a and the second vertical mixing reactive tank 6b, in order to evaporate The part going out liquid sends reaction system back to, is respectively equipped with reflux condenser 9a, 9b and return duct 10a, 10b.Reflux ratio can be led to Cross and suitably adjust the pressure of reactor and the heat medium temperature of reflux condenser to control.
Above-mentioned pipe 11a, 11b, 11c, 11d of distillating is connected with condenser 12a, 12b, 12c, 12d respectively, in addition, each react Device is maintained at given decompression state by decompressor 13a, 13b, 13c, 13d.
In addition, by condenser 12a, 12b, 12c, the 12d being respectively arranged in each reactor, continuously Pyrogentisinic Acid is (monohydroxylated Compound) etc. by-product carry out liquefaction reclaim.In addition, being respectively arranged in the 3rd vertical mixing reactive tank 6c and the 4th Horizontal stirring The downstream of condenser 12c, 12d of reactor 6d is provided with cold-trap (not shown), and by-product is reclaimed in continuously solidification.
The reactant liquor being increased to given molecular weight is drawn out of from the 4th Horizontal stirring reactive tank 6d, is transferred to by gear pump Extruder 15a.Possess vacuum venting mouth in extruder 15a, remove the remaining low molecular composition in Merlon.In addition, according to Need to add antioxidant, light stabilizer, coloring agent or releasing agent etc..
Supply resin from extruder 15a to filter 15b using gear pump 4d, and filter foreign body.Have passed through filter 15b Resin be drawn out of with strand shape by die head 15c, after resin being cooled down using water in strand cooling bath 16a, use strand cutting knife 16b makes granule.The polycarbonate resin pellets so obtaining carry out pneumatic conveying by air conveying aerator 16c, deliver to product In product hopper 16d.With quantifier 16e the product packaging of specified rate is product bag 16f.
The details ＞ of the granule manufacture operation after ＜ polyreaction
(extruder)
The form of heretofore described extruder does not limit, it is possible to use single screw rod or double screw extruder.In order to carry High devolatilization performance described later or the uniform mixing realizing additive, preferably double screw extruder.In the case of being somebody's turn to do, the rotation side of axle To both can be different directions can also be equidirectional, but from the viewpoint of mixing behavior, preferably equidirectional.Pass through Using extruder, polycarbonate resin not only can be made stable to the supply of described filter, and devolatilization can be carried out simultaneously Or the mixing of additive.
In addition, in polycarbonate resin obtained from polycondensation as described above, often remaining is possible to because of form and aspect or heat surely Qualitative and ooze out etc. and product is had undesirable effect starting monomer, in ester exchange reaction by-product monohydroxy chemical combination The low molecular weight compound such as thing or polycarbonate oligomer.
Vacuum pump etc. can also be preferably used by using there is the extruder of blow vent as above-mentioned extruder from ventilation Mouth is reduced pressure, and thus removes above-mentioned low molecular weight compound devolatilization.Furthermore it is also possible to import water etc. into above-mentioned extruder Volatile liquid, promotes devolatilization.It can also be multiple that blow vent can be 1, but preferably more than 2.
Further, it is also possible to be entered to additives such as heat stabilizer described later, releasing agent or coloring agent using above-mentioned extruder Row mixing.
In addition, for the heat deterioration suppressing the polycarbonate resin in extruder, the axle possessing in extruder (is had below When be referred to as screw rod) rotating speed be preferably set to below 300rpm, be more preferably set to below 250rpm, be further preferably set to 200rpm Below.By make described screw rod rotating speed be below 300rpm, the shear heat evolution of polycarbonate resin can be suppressed, such that it is able to Prevent the deterioration of form and aspect or the reduction of molecular weight.
On the other hand, if the rotating speed of described screw rod is too small, not only it is likely to result in the deterioration of devolatilization performance or adds The deterioration of the mixing behavior of agent, and the treating capacity of time per unit reduces, and leads to productive deterioration, it is therefore preferable that being More than 50rpm, more preferably more than 70rpm.
Additionally, the peripheral speed of described screw rod suitably can be determined using the screw diameter of described extruder and rotating speed, but In order to suppress coloring caused by the heat release being caused by shearing of polycarbonate resin or the heat deterioration such as molecular weight reduces, generally excellent Elect the 1.0m/ second below as, more preferably below the 0.6m/ second, particularly preferably below the 0.4m/ second.
On the other hand, if peripheral speed is too small, steam vent buildup during vacuum volatilization can be led to excessive (vent up), The dispersive property of devolatilization performance or additive has the trend of reduction, therefore it is usually preferred to for 0.05m/ more than the second, more preferably 0.1m/ is more than the second.
As a rule, in order to have various functions, the screw rod of extruder is made to be made up of multiple element (screw element), one As for, mainly by for the purpose of the conveyance of resin only comprise the full thread of screw thread (flight), with the mixing of resin as mesh Kneading disk, sealing ring for the purpose of the sealing of resin etc. constituted, can also be used in the conveyance with resin according to purpose Direction in opposite direction configures threaded left-hand thread.
In addition, two line styles or three line styles are had according to the cutting process of screw thread, but in the present invention, it is preferred to squeeze with respect to described The screw diameter going out machine can obtain big treating capacity two line styles of the shear heat evolution that can suppress to produce because of screw rod rotation Shallow/deep groove type.
In the present invention, being constructed without of these screw elements limits, but preferably has the screw element of kneading disk, wherein excellent Select this kneading disk total length be whole screw rod length less than 20%, more preferably less than 15%, most preferably 10% with Under.
If the total length of this kneading disk is long, cause localized heat release to increase by the shearing of resin, easily produce poly- The form and aspect of carbonate resin deteriorate or molecular weight reduces such problem.
On the other hand, if the total length of described kneading disk is too short, during the mixing of above-mentioned devolatilization or additive Performance is likely to decrease, therefore more than the 3% of the total length of this kneading disk preferably length of whole screw rod, and more preferably 5% More than.
As described kneading disk, have along sending type, orthogonal type, inverse send type, Ke Yigen for the conveyance direction of resin Viscosity or required performance according to the resin being used suitably select.
As the material of described screw element, preferably improve the content of the nickel on surface etc. and iron content is suppressed relatively low, Or the material of the process improving case hardness is implemented with TiN or CrN.
In the present invention, excellent with resin temperature when being kept molten by supplying polycarbonate resin in described extruder Elect more than 200 DEG C as, wherein preferably more than 210 DEG C, particularly preferably more than 220 DEG C.In addition, its upper limit is preferably smaller than 250 DEG C, wherein preferably smaller than 245 DEG C, particularly preferably less than 240 DEG C.
If the temperature to the polycarbonate resin of described extruder supply is too low, it is not only the possibility to because of polycarbonate resin The melt viscosity of fat becomes too high and makes supply become unstable, and the shear heat evolution in extruder becomes greatly it is possible to lead Cause the deterioration of polycarbonate resin, and if this temperature is too high, then easily cause the deterioration of polycarbonate resin, exist and lead to color The mutually trend of deterioration, molecular weight reduction or mechanical strength reduction together therewith.
The temperature of the polycarbonate resin supplying to described extruder is except passing through to control final polymer reactor Beyond interior temperature is to be controlled, can also by control be used for extruder supply polycarbonate resin pipe arrangement temperature or Arrange the methods such as heat exchanger to be controlled.
Additionally, in the present invention, the temperature of the polycarbonate resin discharged from described extruder is preferably set to less than 280 DEG C, more preferably less than 270 DEG C, particularly preferably it is less than 260 DEG C.From described extruder, the polycarbonate resin of discharge is When more than 280 DEG C, easily cause the deterioration of polycarbonate resin, exist lead to form and aspect deteriorate or molecular weight reduce or therewith The trend that mechanical strength together reduces.
If in addition, on the contrary, from extruder discharge polycarbonate resin temperature too low, polycarbonate resin Melt viscosity uprise, the load for extruder becomes big, the over loading that screw rod rotation becomes unstable or leads to motor, Therefore it is preferably more than 220 DEG C, more preferably more than 230 DEG C, particularly preferably more than 240 DEG C.
As a rule, there is the caused heat release of the shearing of the resin that the rotation along with screw rod produces in extruder, one As for, compared with the temperature of the polycarbonate resin being supplied, the temperature of the polycarbonate resin discharged has uprise to become Gesture, particularly in the case of the molecular weight height and melt viscosity height of polycarbonate resin, this trend becomes obvious.
If improving the temperature of polycarbonate resin, melt viscosity reduces, and exists and suppresses becoming of this Partial Shear heat release Gesture, if however, the temperature of polycarbonate resin itself is higher, easily causing deterioration, existing and leading to form and aspect to deteriorate or molecule The trend that amount reduces or mechanical strength together reduces therewith, it is therefore prevented that the high viscosity polycarbonate resin of heat stability difference The deterioration of fat is not easy to carrying out extrusion.
The temperature of the polycarbonate resin discharged from described extruder generally can pass through supplied polycarbonate resin Temperature or the incidental heater of machine barrel temperature being controlled, but due to sometimes with polycarbonate resin to described The screw speed of the quantity delivered of extruder or extruder and change, therefore preferably also add these conditions being controlled.
The extra high polycarbonate resin for viscosity, becomes big by the screw rod shear heat evolution that causes of rotation, with respect to being supplied The temperature of the resin given, the temperature of the resin discharged has the trend of rising, therefore, in order to keep the dispersion of additive, take off Wave deterioration, the rotating speed of screw rod or the circle of the polycarbonate resin that suppression is caused while performance or productivity etc. by this shear heat evolution The selection of circular velocity and element composition is particularly significant.
(filter)
In the present invention, in order to remove the foreign bodies such as the focal spot in polycarbonate resin obtained from polycondensation or gel and used Filter is filtered.Wherein, in order to phenol of residual monomers or by-product etc. is removed using decompression devolatilization and by heat stabilizer or The additives such as releasing agent mix, and preferably after extrude polycarbonate resin with extruder, are filtered with filter.
As the form of described filter, the such as known filter such as candle formula, convolution and vane type can be enumerated.Its In, preferably with respect to the vane type that can obtain big filter area for the accommodating container of filter, in addition, big in order to obtain Filter area, preferred compositions use multiple.
Described leaf filter is to combine filter element (hereinafter sometimes referred to as in holding member (also referred to as keeper) Medium) and constitute, these filters (according to circumstances for multi-disc, multiple) are with the assembly that is accommodated in accommodating container (sometimes Be referred to as filter assemblies) form use.
In the present invention, in order that the pressure reduction (pressure loss) of described filter diminishes, preferably by the medium of multiple meshes Overlapping and the type that width of mesh diminishes successively from the approach axis of resin, in order to crush gel, it is possible to use in mistake Filter surface has sintered the type of metal powder.
In the present invention, as the mesh of described filter, it is calculated as less than 50 μm with 99% filtering accuracy, preferably 30 μ Below m, is preferably less than 15 μm in the case of particularly desirable minimizing foreign body by more preferably less than 20 μm, but when mesh diminishes When, the pressure loss in described filter will increase it is possible to leading to the breakage of described filter or making because of shear heat evolution Polycarbonate resin deteriorates, therefore, for 99% filtering accuracy, preferably more than 1 μm.
It should be noted that the mesh with 99% filtering accuracy definition mentioned here, refer to according to ISO16889 The value for χ when 100 for the β χ value that the following formula (8) that (2008) determine represents.
β χ=(population of 1 side more than χ μm)/(populations of 2 sides more than χ μm) ... (8)
(before 1 side expression mentioned here is filtered with filter, after 2 times described sides represent filtration)
As the material of the medium of described filter, as long as having for intensity necessary to the filtration of resin and heat-resisting Property, just do not limit, but the stainless steel-like such as few SUS316 or SUS316L of iron content preferably wherein.In addition, as woven Species, in addition to the trapping part of the foreign bodies such as plain weave, twill, plain weave superposition or twill superposition is the textile-like of rule, also Non-woven fabric type can be used.In the present invention, it is preferred to the high non-woven fabric type of the trapping ability of gel, nonwoven particularly preferably will be constituted Sinter and fixing type between the steel wire of cloth.
In addition, if containing ferrous components in described filter, then, when filtering under the high temperature more than 200 DEG C, exist and make The trend of resin deterioration, therefore as described above, in the case of stainless steel, the content of preferably ferrous components is few, furthermore it is preferred that making It is passivated in advance processing with front.
As Passivation Treatment, for example, can enumerate and impregnated in described filter in the acid such as nitric acid or make acid by described Filter and make surface formed the method for passive state and carry out in the presence of vapor or oxygen method that roasting (heating) processes, with And the method that they are applied in combination etc., wherein, it is preferable to carry out nitric acid treatment and roasting.
Described filter is carried out with temperature during calcination process and is preferably 350 DEG C～500 DEG C, more preferably 350 DEG C～450 DEG C, roasting time preferably generally 3 hours～200 hours, more preferably 5 hours～100 hours.
If the temperature of roasting is too low or the time is too short, the formation of passive state is insufficient, and existing when filtering makes poly- carbonic acid The trend of ester resin deterioration.On the other hand, if the temperature of roasting is too high or overlong time, the damage of filter media adds Play is it is possible to necessary filtering accuracy cannot be formed.
In addition, being preferably generally 5 weight %～50 weight % with concentration of nitric acid during filter described in nitric acid treatment, more preferably For 10 weight %～30 weight %, temperature during process is preferably generally 5 DEG C～100 DEG C, more preferably 50 DEG C～90 DEG C, during process Between be preferably generally 5 minutes～120 minutes, more preferably 10 minutes～60 minutes.
If the concentration of nitric acid is too low or treatment temperature is too low or process time is too short, the formation of passive state is insufficient, If the excessive concentration of nitric acid or treatment temperature is too high or process time is long, the damage aggravation of filter media, having can Can cannot form necessary filtering accuracy.
If described filter is accommodated in accommodating container, easily applies pressure and filtered, therefore preferably.For For the material of this accommodating container, as long as there is the intensity being resistant to resin filter and thermostability does not just limit, but preferably For stainless steel-likes such as few SUS316 or SUS316L of iron content.If the content of ferrum is many, same as described above, polycarbonate resin Fat is possible to deteriorate.
The accommodating container of described filter is either by the supply mouth of polycarbonate resin with outlet essentially horizontally Configuration, still essentially vertically configuration, still obliquely configuration can, but in order to suppress gas and polycarbonate resin Delay in described accommodating container, prevents the deterioration of polycarbonate resin, preferably configures the supply mouth of polycarbonate resin In the bottom of filter accommodating container, outlet is configured at the top of filter accommodating container.
In addition, if internal capacity (the m of filter accommodating container3) divided by polycarbonate resin flow (m3/ point) and obtain Value too small, then the pressure reduction of filter becomes big and is likely to result in the breakage of filter, if excessive, can lead to when filtering The deterioration of polycarbonate resin, therefore preferably 1 minute～20 minutes, more preferably 2 minutes～10 minutes, more preferably 2 minutes～5 minutes.
In the method for the invention, the temperature being supplied to the polycarbonate resin before the filtration in described filter is generally excellent Choosing is less than 280 DEG C, more preferably less than 270 DEG C, particularly preferably less than 265 DEG C, particularly preferably less than 260 DEG C.
It is less than 280 DEG C by making the temperature before being filtered using described filter, can suppress in filter assemblies Heat deterioration, and the reduction of the deterioration of form and aspect or the reduction of molecular weight or mechanical strength together therewith can be prevented.
If in addition, on the contrary, the temperature before being filtered using described filter becomes too low, Merlon Melt viscosity is high, and the load that described filter is caused becomes greatly it is possible to lead to the breakage of described filter, it is therefore preferable that being More than 220 DEG C, more preferably more than 230 DEG C, particularly preferably more than 240 DEG C.
In addition, in the present invention, the temperature of the polycarbonate resin after filtration is more than 200 DEG C, preferably 220 DEG C with On, more preferably more than 230 DEG C.If the temperature of the polycarbonate resin after being filtered using above-mentioned filter is too low, Then there is melt viscosity to uprise, the strand extruded and formed is unstable, being carried out with rotary cutter etc. granulating becomes difficulty Trend.
On the other hand, the temperature of the polycarbonate resin after filtration is less than 280 DEG C, preferably smaller than 270 DEG C, more preferably less than 265 DEG C, it is further preferably no larger than 260 DEG C.If the temperature of the polycarbonate resin after being filtered using above-mentioned filter Too high, then easily cause the heat deterioration of polycarbonate resin, there is the machine that form and aspect deteriorate or molecular weight reduces or accompanies therewith The trend of tool intensity decreases.
As the resin temperature after above-mentioned filtration, for example, can enumerate the resin taking out from filter discharge and directly be surveyed Fixed method and inside the pipe arrangement of filter outlet stream setting sensor come the method to be measured etc..
In the case that inside the pipe arrangement of described filter outlet stream, setting sensor is to be measured, due to setting The impact of the heater outside in the pipe arrangement of sensor perimeter, is difficult to measure accurate resin temperature sometimes.In filter outlet Nearby being provided with die head etc. makes resin extruded device and will be considered as the tree with filter outlet side by the resin temperature that it is extruded In the case that fat temperature is equal, can be using the temperature of the resin by extrusions such as die heads as the resin temperature after the filtration of the present invention Degree.
It should be noted that for the precision improving the resin temperature after filtration, filter outlet stream can also be implemented in Inside the pipe arrangement on road, setting sensor is squeezed by die head being arranged near filter outlet etc. come the method to be measured and mensure Both methods of the resin temperature going out.
In the method for the invention, described filter assemblies are generally provided with the heater being made up of multiple element outside it To carry out temperature control, but if its design temperature is too high, then to have the situation leading to polycarbonate resin deterioration, therefore logical Often it is preferably set to less than 280 DEG C, is more preferably set as less than 260 DEG C, be particularly preferably set as less than 250 DEG C.
On the other hand, if design temperature is too low, melt viscosity uprises it is difficult to be filtered with filter, therefore logical Often it is preferably set to more than 150 DEG C, is more preferably set to more than 180 DEG C, be particularly preferably set to more than 200 DEG C.
In addition, also generally existing for the polycarbonate resin discharged from described filter assemblies being guided the pipe arrangement of die head Its outside setting heater, but if its design temperature is too high, then has the situation leading to polycarbonate resin deterioration, therefore logical Often it is preferably set to less than 280 DEG C, is more preferably set as less than 260 DEG C, be particularly preferably set as less than 250 DEG C.
On the other hand, if design temperature is too low, melt viscosity raises, and the pressure loss in pipe arrangement becomes big, therefore logical Often it is preferably set to more than 150 DEG C, is more preferably set to more than 180 DEG C, be particularly preferably set to more than 200 DEG C.
If additionally, the holdup time exporting to the polycarbonate resin of die head from filter assemblies is long, having and lead to The situation of polycarbonate resin deterioration, is therefore generally preferably set to 1～30 minute, is more preferably set to 3～20 minutes.
In the method for the invention, the polycarbonate resin extruded from described die head through the filtration of described filter Temperature be preferably more than 200 DEG C, more preferably more than 220 DEG C, more preferably more than 230 DEG C, its upper limit is preferably little In 280 DEG C, more preferably less than 270 DEG C, it is further preferably no larger than 265 DEG C, particularly preferably less than 260 DEG C.
If through filtration from described die head extrusion polycarbonate resin temperature too low, melt viscosity raise and Make the strand being extruded into unstable it is possible to be difficult to be granulated with rotary cutter etc..On the other hand, if temperature mistake High then easily cause polycarbonate resin heat deterioration it is possible to lead to form and aspect deteriorate or molecular weight reduce or accompany therewith Mechanical strength reduce.
In described die head, generally heater is set, but if its design temperature is too high, then has and lead to polycarbonate resin The situation of fat deterioration, is therefore generally preferably set as less than 280 DEG C, is more preferably set as less than 260 DEG C, is particularly preferably set as Less than 250 DEG C.
On the other hand, if design temperature is too low, melt viscosity raises, and the pressure loss in pipe arrangement becomes big, therefore logical Often it is preferably set to more than 150 DEG C, is more preferably set to more than 180 DEG C, be particularly preferably set to more than 200 DEG C.
Generally, when the described filter little with mesh filters polycarbonate resin, temperature liter can be made because of shear heat evolution Height, in the case of using extruder, also therefore, can pass through to control plus the shear heat evolution being caused by screw rod rotation The temperature of the polycarbonate resin from described die head extrusion for the filter, the mesh size of filter, filter area, temperature described in Comprehensive Control Degree setting, the temperature setting of the molecular weight of polycarbonate resin, filter assemblies or the temperature from filter outlet to die head set Fixed etc. particularly significant.
In addition, to described filter supply when using described extruder in the case of, also as described above, described extrusion The selection of the composition of the treating capacity of the polycarbonate resin in machine, the rotating speed of screw rod or peripheral speed or element etc. is particularly significant.
In addition, in the method for the present invention, using temperature and the filtration of the polycarbonate resin before the filtration of described filter Within the temperature difference of polycarbonate resin afterwards is preferably 50 DEG C, within more preferably 30 DEG C, within most preferably 10 DEG C.
If the temperature of polycarbonate resin before being filtered using described filter and the polycarbonate resin after filtration Temperature difference excessive, then particularly in the case of being constituted filter assemblies with multiple leaf filters, will be in resin Supply side and discharge side breakdown pressure balance and be likely to result in the breakage of described filter.
In the method for the invention, be fed into before described filter described is obtained by ester exchange reaction polycondensation Polycarbonate resin terminal double bond be set to X μ eq/g, will constitute polycarbonate resin pellets polycarbonate resin end In the case that double bond is set to Y μ eq/g, preferably meet following formula (2), described polycarbonate resin pellets obtain as follows, i.e. use Described filter is filtered and is extruded with the form of strand by described die head, after cooling, is obtained using cutting knife.
Y-X≤10 (2)
More preferably Y-X≤8, particularly preferred Y-X≤5.By making Y-X be less than 10, can suppress to be considered by this double bond The generation of the coloring components deriving from, can suppress in described filter simultaneously or its periphery produces gas, and the extrusion of strand is stable, Easily granulated with cutting knife, therefore preferably.
In addition, Y is preferably below 50 μ eq/g, below more preferably 30 μ eq/g, particularly preferably below 20 μ eq/g.As Fruit Y is excessive, then may lead to the coloring of polycarbonate resin pellets.
In addition, in the method for the invention, in the ratio of the described polycarbonate resin being fed into before above-mentioned filter Dense viscosity (ηsp/ c) it is set to A, by filtering using described filter, after die head is extruded and cooled down with the form of strand, using cutting Reduced viscosity (the η of the polycarbonate resin pellets that knife obtainssp/ c) be set to B in the case of, preferably meet following formula (3).
0.8 ＜ B/A ＜ 1.1 ... (3)
More preferably B/A ＞ 0.85, more preferably B/A ＞ 0.9, particularly preferably B/A ＞ 0.95.By making B/A More than 0.8, can suppress is considered as the generation of the coloring components generating because of side reaction or the composition of precursor becoming coloring, Therefore preferred.On the other hand, if reduced viscosity raises in polymer filter, the generation of the foreign body such as gel or focal spot is just Can come back, therefore more preferably B/A≤1.0.Algoscopy for reduced viscosity will be described later.
It should be noted that in the case that described extruder is set between described polycondensation reactor and described filter, In the case that the reduced viscosity (η sp/c) by the polycarbonate resin supplying to described extruder is set to a, for described B, Preferably meet following formula (4).
0.8 ＜ B/a ＜ 1.1 ... (4)
More preferably B/a ＞ 0.85, particularly preferably B/a ＞ 0.9.By making B/a more than 0.8, can suppress to be considered It is the generation of the coloring components generating because of side reaction or the composition of precursor becoming coloring, therefore preferably.On the other hand, if Reduced viscosity raises, then the generation of the foreign body such as gel or focal spot will come back, therefore more preferably B/a≤1.0.
In order that the change of the reduced viscosity in polymer filter or extruder is in above range, final reactor In the temperature of polycarbonate resin, enter polymer filter the temperature of polycarbonate resin, from polymer filter Extrusion the selection of the temperature of polycarbonate resin, the treating capacity of polymer filter time per unit or mesh, from polymer Filter to the temperature control of die head or holdup time, in the case of using extruder also oriented extruder supply poly- carbonic acid The temperature of ester resin, from extruder the temperature of polycarbonate resin of extrusion, devolatilization pressure, the presence or absence of water filling or water injection rate, The selection that the rotating speed of screw rod or peripheral speed or element are constituted is particularly significant.
Additionally, in the case of using described extruder, in order that polycarbonate resin is to the quantity delivered of described filter Stabilisation, configures gear pump preferably between described extruder and described filter.Species for gear pump does not limit, but From the viewpoint of reducing foreign body, preferably in sealing, wherein do not use the self-circulation type of gland packing.
In the present invention, in the strand that polycarbonate resin is directly contacted with ambient atmos, granulating, in order to prevent Foreign body from ambient atmos is mixed into, preferably higher than the rank 7 defined in JISB9920 (2002), more preferably in cleanliness factor Implement in the dust free room higher than rank 6.
The solidification in addition, polycarbonate resin after being filtered with described filter is cooled, is carried out with rotary cutter etc. Granulation, and when it granulates, preferably use the cooling means such as air cooling or water-cooled.
The air using during air cooling is preferably used the sky eliminating the foreign body of in the air in advance with HEPA filter etc. Gas, prevents the adhering to again of foreign body of in the air.When using water-cooled, preferably use spent ion exchange resin etc. and eliminate in water Metal ingredient, reuse the water after the foreign body that described filter eliminates in water.The mesh size of the filter being used with 99.9% removes preferably 10～0.45 μm for filtering accuracy.
Additionally, commonly known heat stabilizer in described extruder, nertralizer, ultraviolet can also be added in the present invention Light absorbers, releasing agent, coloring agent, antistatic agent, slipping agent, lubricant, plasticizer, compatilizer or fire retardant etc. are simultaneously mixed Refining.
(filtration before polymerization)
On the other hand, in the method for the invention, in order to reduce further in the polycarbonate resin pellets finally giving Contained foreign body, maximally effective way is, before making starting monomer polycondensation, with the filtered filter of raw material, it is carried out in advance Filter.
As the shape of the filtered filter of described raw material, can be basket, disc type, vane type, duct type, plane cylinder The arbitrary pattern such as formula or close pleat type drum type brake, close pleat type that is wherein preferably compact and can obtaining big filter area filters Device.
In addition, as constitute the filtered filter of this raw material filter material, can be metal wound wire, lamination metal net, metal no Spin any one in cloth or expanded metal etc., but from the viewpoint of filtering accuracy, preferably lamination metal net or metal be no Spin cloth, particularly preferably metal non-woven fabrics are sintered and fixing type.
Material for the filtered filter of this raw material is not particularly limited, it is possible to use metal system, resin-made, ceramic Deng, but from the viewpoint of thermostability and minimizing coloring, preferably iron content is less than 80% metal filter, wherein preferably The stainless steel such as SUS304, SUS316, SUS316L or SUS310S.
In addition, in the filtration of starting monomer, in order to extend described raw material Filtration Filtration while guaranteeing strainability In the life-span of device, preferably use multiple filter assemblies, the mesh of the filter especially in the assembly that will be in upstream side Size is set to C μm, the mesh size of the filter in the assembly being in downstream side is set to D μm in the case of, preferably exist In the combination of at least one, C is more than D (C ＞ D).In the case of meeting this condition, the filtered filter of described raw material is less susceptible to block up Plug, it is possible to achieve the reduction of the replacement frequency of the filtered filter of described raw material.
The mesh size of the filtered filter of described raw material is not particularly limited, but preferably filters in raw material described at least one With for 99.9% filtering accuracy for less than 10 μm in filter, it is being configured with multiple composition filtered filters of described raw material In the case of filter assemblies, it is preferably more than 8 μm in most upstream side, more preferably more than 10 μm, preferred in its most downstream side For less than 2 μm, more preferably less than 1 μm.It should be noted that the mesh size of the filtered filter of described raw material mentioned here It is also to determine according to above-mentioned ISO16889 (2008) benchmark.
In the present invention, for making raw material not limit by the temperature of material flow during the filtered filter of described raw material System, but if too low, then raw material solidification, if too high, exist thermal decomposition a problem that, therefore preferably generally 100 DEG C ～200 DEG C, more preferably 100 DEG C～150 DEG C.
In addition in the present invention it is possible to filter any one raw material in the middle of the plurality of raw materials being used it is also possible to complete All filter, its method does not limit, the raw mixture of dihydroxy compounds and carbonic diester can be filtered it is also possible to distinguish Remix after filtration.In addition, it is also possible to by the reactant liquor of the midway of polycondensation reaction with former with described in the manufacture method of the present invention Expect that filtered filter identical filter is filtered.
(obtained polycarbonate resin)
The yellow colour index value of the polycarbonate resin pellets that profit is obtained by the present invention is preferably less than 70, more preferably For less than 30, particularly preferably less than 15, most preferably less than 10.In order to reduce yellow colour index value, as previously mentioned it is necessary to fit When the selection carrying out monomer preparation condition, polymeric reaction condition, filtercondition, in the case of using extruder, also squeezed Go out the selection of condition or screw element etc..
In addition, using the present invention polycarbonate resin pellets, in dichloromethane, using Ubbelodhe viscosity pipet dense The reduced viscosity measuring at degree 0.6g/dL, 20.0 DEG C ± 0.1 DEG C of temperature is preferably more than 0.3dL/g, more preferably 0.35dL/g Above, it is more preferably more than 0.4dL/g.The upper limit of reduced viscosity is preferably below 1.2dL/g, more preferably 0.8dL/g Hereinafter, particularly preferably below 0.7dL/g.
If reduced viscosity is too low, the mechanical strength of products formed may be less, if reduced viscosity is excessive, molding When mobility reduce, do not only exist the trend that productivity or mouldability reduce, and deterioration when filtering or extruding be possible to Aggravation.
Using the polycarbonate resin pellets being obtained by the method for the present invention, the shear rate measuring at 240 DEG C 91.2sec-1Under melt viscosity be preferably more than 500Pa s, more preferably more than 800Pa s, particularly preferably More than 1000Pa s, its upper limit is preferably below 3000Pa s, more preferably below 2000Pa s.
If melt viscosity is too low, the mechanical strength of products formed has the trend of variation, if too high, as it was previously stated, Shear heat evolution in filter or extruder becomes big, and deterioration during filtration or when extruding may aggravate.It should be noted that due to Melt viscosity, in addition to changing with molecular weight, changes also as molecular structure, therefore with required Performance Match Ground selects them and to be controlled to above range particularly significant.
Surveyed using the polycarbonate resin pellets being obtained by the method for the present invention, with differential scanning calorimeter (DSC) The glass transition temperature of timing is preferably more than 50 DEG C, more preferably more than 80 DEG C, more preferably more than 90 DEG C.If Glass transition temperature is too low, then poor heat resistance, is therefore restricted when making products formed use.
On the other hand, if glass transition temperature is high, melt viscosity when being filtered with filter is too high and may lead Cause the deterioration of polycarbonate resin, therefore preferably smaller than 160 DEG C, more preferably less than 145 DEG C, be further preferably no larger than 140 DEG C, special You Xuan little Yu 130 DEG C.
It should be noted that the glass transition temperature of the present invention refers to, under nitrogen flowing, with 20 DEG C/minute of intensification speed From room temperature to the temperature exceeding well over glass transition temperature, keeping temperature, after 3 minutes, is cooled down degree with 20 DEG C/minute of speed To 30 DEG C, keep 3 minutes at 30 DEG C, again the temperature exceeding well over glass transition temperature is warming up to 20 DEG C/minute of programming rate Degree, the extrapolation glass transition started temperature obtained by obtained (obtained from heating up for the 2nd time) DSC data.
In addition, the following structural formula (9) of the polycarbonate resin of polycarbonate resin pellets obtained by the composition present invention Represent end group concentration be preferably more than 20 μ eq/g, more than more preferably 40 μ eq/g, particularly preferably 50 μ eq/g with On.
If the concentration of this end group is too low, there is the big trend of complexion changed when filtering.In addition, this end group Excessive concentration, there is the trend easily producing gas when filtering, a problem that the gas of strand may be led to cut off, because This is preferably below 200 μ eq/g, below more preferably 150 μ eq/g, below particularly preferably 100 μ eq/g.
[chemical formula 7]
As the method for the concentration of the end group controlling structure above (9) to represent, can enumerate for example：Control conduct The dihydroxy compounds of the dihydroxy compounds comprising the present invention of raw material and the method for molar ratio of carbonic diester or Person controls polymerization pressure or polymerization temperature or reflux condensation mode during ester exchange reaction according to the easy degree of the volatilization of monomer The method of the temperature of device etc..Wherein, dense for above-mentioned end group using the reactor with reflux condenser in polymerization initial stage The stabilisation of degree is effective.
For the ester exchange reaction carrying out in the present invention, replace carbon using diphenyl carbonate or carboxylol ester etc. In the case that the carbonic diester that diphenyl phthalate represents as above-mentioned formula (7) to manufacture the polycarbonate resin of the present invention, can not By-product can go out the aromatic monohydroxy compounds such as phenol or fortified phenol and remain in polycarbonate resin with avoiding.
The reason aromatic monohydroxy compound is likely to become foul smell during generation or the molding of gas during filtration, therefore Using the extruder with vacuum venting mouth, preferably make this compounds content in polycarbonate resin obtained from cooling and solidifying little In 0.1 mass %, more preferably less than 0.05 mass %, particularly preferably less than 0.03 mass %.But, industrially it is difficult to these Compound completely removes, and the lower limit of the content of aromatic monohydroxy compound is usually 0.0001 mass %.
It should be noted that according to the difference of the raw material being used, these aromatic monohydroxy compounds can certainly There is substituent group, for example, it is possible to have alkyl that carbon number is less than 5 etc..Diphenyl carbonate is being used as carbonic diester In the case of, aromatic monohydroxy compound is phenol.
The polycarbonate resin pellets that profit is obtained by the present invention can using injection molding method, extrusion moulding or The commonly known method such as compression forming methods makes article shaped.In addition, before carrying out various molding, as needed, acceptable With rotary drum mixer, super mixer, float (floater), V-mixer, Nauta mixer, banbury mixers or extrusion Machine etc. mixes heat stabilizer, nertralizer, UV absorbent, releasing agent, coloring agent, antistatic agent, slipping agent, profit in resin The additives such as lubrication prescription, plasticizer, compatilizer or fire retardant.
Using the method for the present invention, can obtain colouring less, the polycarbonate resin pellets of few foreign, therefore, by this tree In the film that 30 μm ± 5 μm of the thickness that fat molding obtains, contained more than 25 μm of foreign body is preferably 1000/m2Hereinafter, more preferably For 500/m2Hereinafter, most preferably 200/m2Below.
The polycarbonate resin pellets that profit is obtained by the present invention for example can also be with aromatic copolycarbonate, fragrance Adoption ester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic resin, amorphous polyolefin, ABS or AS etc. close One kind or two or more mixed in the Biodegradable resins such as resin, polylactic acid or poly butylene succinate or rubber etc. Refining, makes polymer alloy and uses.
According to the present invention it is possible to provide the poly- carbonic acid of heat stability, form and aspect and mechanical strength and few foreign Ester resin particle.
Embodiment
Hereinafter, by embodiment, the present invention will be described in more detail, but the present invention is without departing from its purport, just not Limited by following examples.Hereinafter, the physical property of Merlon or the evaluation of characteristic have been carried out using method below.
(1) mensure of oxygen concentration
Using oxygen analyzer, (AMI company manufactures：1000RS) oxygen concentration in polymerizing reactor is determined.
(2) mensure of reduced viscosity
It is used dichloromethane to dissolve polycarbonate resin pellets as solvent, be prepared for the poly- carbonic acid of concentration 0.6g/dL Ester solution.The Ubbelodhe viscosity pipet being manufactured using Sen You physics and chemistry Industrial Co., Ltd, is carried out at 20.0 DEG C ± 0.1 DEG C of temperature Measure, relative viscosity η rel obtained by time t using following formula by time t0 and solution according to solvent,
η rel=t/t0
Intrinsic viscosity η sp is obtained using following formula according to relative viscosity.
η sp=(η rel- η 0)/η 0=η rel-1
By intrinsic viscosity divided by concentration c (g/dL), obtain reduced viscosity η sp/c.The more high then molecular weight of this value is bigger.
(3) terminal phenyl concentration, the mensure of terminal double bond concentration
Weigh polycarbonate resin pellets about 30mg so as to be dissolved in weight chloroform about 0.7mL, make solution, with 1,1, 2,2- tetrabromoethanes add known quantity as internal standard substance, add it in the NMR pipe of internal diameter 5mm, using NEC strain The JNM-AL400 (resonant frequency 400MHz) that formula commercial firm manufactures measures at normal temperatures1H NMR spectra, based on the end with internal standard substance End phenyl, the signal intensity ratio of terminal double bond are obtained.
Weigh Merlon 30mg so as to be dissolved in weight chloroform about 0.7mL, the NMR adding it to internal diameter 5mm uses Guan Zhong, determines1H NMR spectra.By the letter based on each end group and the construction unit from each dihydroxy compounds Number strength ratio has carried out quantitation to the amount of terminal phenyl, terminal hydroxyl and terminal double bond.The device being used or condition are as follows Described.
Device：The JNM-AL400 (resonant frequency 400MHz) of Jeol Ltd.'s manufacture
Temperature of the measurement：Room temperature
Relaxation time：6 seconds
Cumulative frequency：512 times
In the case of the copolymerization polycarbonate that the ISB that the present invention illustrates and CHDM is formed1The parsing of H NMR is entered as follows OK.Calculate the integrated value at following peak.
(a)：5.6-4.8ppm：All from ISB construction unit (proton number：3rd, molecular weight：172.14)
(b)：2.2-0.5ppm：All from CHDM construction unit (proton number：10th, molecular weight：170.21)
(c)：4.4ppm：Terminal hydroxyl (proton number from ISB：1st, molecular weight：173.14)
(d)：3.6-3.5ppm：Terminal hydroxyl (proton number from ISB：1st, molecular weight：173.14) and derive from Terminal hydroxyl (the proton number of CHDM：2nd, molecular weight：171.21)
(e)：3.5-3.4ppm：Terminal hydroxyl (proton number from CHDM：2nd, molecular weight：171.21) and derive from Terminal double bond (the proton number of ISB：1st, molecular weight：155.13)
(f)：2.6ppm：Terminal hydroxyl (proton number from ISB：1st, molecular weight：173.14)
(g)：6.7-6.5ppm：Terminal double bond (proton number from ISB：1st, molecular weight：155.13)
(h)：2.3ppm：Terminal double bond (proton number from CHDM：2nd, molecular weight：153.20)
(i)：7.5-7.3ppm：From terminal phenyl (proton number：2nd, molecular weight：93.10)
＜ is equivalent to value ＞ of the molal quantity of each structure
All ISB construction units：(a) integrated value/3=(a ')
All CHDM construction units：(b) integrated value/10=(b ')
The terminal hydroxyl of ISB：(c) integrated value+(f) integrated value=(c ')
The terminal hydroxyl of CHDM：{ (d) integrated value-(f) integrated value }/2+ (e) integrated value-(g) integrated value) }/2= (d′)
The terminal double bond of ISB：(g) integrated value=(e ')
The terminal double bond of CHDM：(h) integrated value/2=(f ')
Terminal phenyl：(i) integrated value/2=(g ')
Amount (the unit of each end group of ＜：μ eq/g) ＞
The terminal hydroxyl amount of ISB：(c′)/(i′)×1000000
The terminal hydroxyl amount of CHDM：(δ′)/(i′)×1000000
The terminal double bond amount of ISB：(e′)/(i′)×1000000
The terminal double bond amount of CHDM：(f′)/(i′)×1000000
Terminal phenyl amount：(g′)/(i′)×1000000
Wherein, (i ')=(a ') × 172.14+ (b ') × 170.21.
(4) mensure of glass transition temperature
Using differential scanning calorimeter (SII Nanotechnology company manufacture DSC6220), by polycarbonate resin Fat granule be cut into appropriately sized, by the sample being cut into about 10mg put into SIINanotechnology company manufacture aluminium dish in After sealed, under the stream of nitrogen gas that 50mL/ divides, with 20 DEG C/minute of programming rate from room temperature to 250 DEG C.By temperature After keeping 3 minutes, it is cooled to 30 DEG C with 20 DEG C/minute of speed.Keep 3 minutes at 30 DEG C, then heated up with 20 DEG C/minute of speed To 200 DEG C.By the 2nd DSC data obtaining that heats up, obtain extrapolation glass transition initial temperature.
(5) phenol content in polycarbonate resin pellets, the mensure of DPC content
Accurate weighing polycarbonate resin pellets sample 1.25g is dissolved in dichloromethane 7ml, after making solution, adds Acetone simultaneously makes total amount reach 25ml, has carried out reprecipitation process.Then, this treatment fluid was carried out with 0.2 μm of disc filter Filter, has carried out quantitation using liquid chromatograph.
(6) form and aspect of polycarbonate resin pellets
The granule of gained is filled up 1cm cell, using the colour photometer (CM- that Konica Minolta company manufactures 3700d), yellow colour index (YI) value under reflected light is carried out with 3 mensure, calculates its meansigma methods.YI value is less, more without Yellow, shows that quality is more excellent.
(7) quantitation of foreign body
The barrels set temperature that will be provided with the single screw extrusion machine of diameter 20mm of T-shaped mould head sets from the supply side of granule It is set to 210 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 220 DEG C, polycarbonate resin pellets are melt extruded, is shaped to using chill roll The film that 35 μm ± 5 μm of thickness, using the manufacture of Optical ControlSystem company, Film Quality Testing System (model FSA100) determines and is equivalent to every 1m2More than 25 μm of foreign body number.
(8) mensure of melt viscosity (Pa s)
The sample being dried 6 hours at 120 DEG C is used the capillary pipe flow of the die head possessing diameter 1mm φ × 10mmL Become instrument (manufacture of Toyo Seiki Co., Ltd.) and be heated to uniform temperature, in shear rate γ=9.12～1824 (sec-1) between carry out Measure, have read in 91.2sec-1Under melt viscosity.
The abbreviation of the compound used in the record of below example is as follows.
·ISB：Isosorbide (manufacture of Roquette Freres company, trade name POLYSORB)
·TCDDM：Tricyclodecane Dimethanol (manufacture of OXEA (オ Network セ ア) company)
·CHDM：1,4-CHDM [New Japan Chem Co., Ltd manufactures, trade name SKYCHDM]
·DPC：Diphenyl carbonate [Mitsubishi chemical Co., Ltd's manufacture]
[embodiment 1]
(reaction in the 1st stage)
Distillate the poly- of pipe and condenser what the heating agent chuck possessing using oil as heating agent and stirring paddle and vacuum pump linked Close in reactor with the mol ratio of ISB/TCDDM/DPC for 70/30/100 charging, add the cesium carbonate making aqueous solution, make Obtain 1mol every with respect to whole dihydroxy compounds and reach 2.5 × 10-6Mol (is converted into caesium metallic atom), is then filled Nitrogen displacement (oxygen concentration 0.0005 volume %～0.001 volume %) dividing.Now, DPC uses and carries out distillation purifying and make chlorination Thing ion concentration is the DPC of below 10ppb.Then, make the heating agent after circulation is heated in the heating agent chuck of this reactor, in reaction The moment that liquid (i.e. interior temperature) reaches 100 DEG C starts to stir, and makes to keep internal temperature at 100 DEG C, so that content is melted and reaches uniformly.
Then start to warm up, made interior temperature be 220 DEG C with 40 minutes, the moment reaching 220 DEG C in interior temperature starts to reduce pressure, and goes forward side by side Row controls so that reached 13.3kPa (absolute pressure, similarly hereinafter) at 90 minutes.After decompression starts, the phenol vapor of generation in reaction Start rapidly to distillate, the oil temperature (heating agent JI temperature) importing in heating agent chuck is suitably adjusted so that interior temperature Control constant in 220 DEG C of holdings.The temperature of the time-bands heat kerosene distillating more than quantitative change of phenol is 242 DEG C, in addition when Between band be less than 242 DEG C.
After reaching 13.3kPa, kept further 60 minutes with the state keeping this pressure, obtained oligomeric polycarbonate Thing.The phenol distillating in this stage is the 94% of theoretical quantity of distillate.
(reaction in the 2nd stage)
Under nitrogen atmosphere, distillate pipe to what the heating agent chuck possessing using oil as heating agent and stirring paddle and vacuum pump linked Polymer reactor in transfer the polycarbonate oligomer obtaining in the 1st stage.It is provided with distillating pipe using warm water (entrance Temperature 45 C) as the condenser of cryogen, in the further downstream cold-trap being provided with dry ice as cryogen.
After oligomer transfer, start to reduce pressure, make interior temperature be 220 DEG C with 60 minutes, pressure is 200Pa.Then, with 20 minutes Interior temperature is made to be 230 DEG C, pressure is below 133Pa, recovers pressure in the moment reaching given stirring power, by content with strand Form extract out, make granule with rotary cutter.
The reduced viscosity of the granule obtaining is 0.362, terminal phenyl concentration is 66 μ eq/g, terminal double bond is 7.5 μ eq/g, YI is 25.4, phenol content be 965ppm, DPC content be 19ppm, more than 25 μm foreign body amount be 3035/m2.
Double screw extruder (the LABOTEX30HSS- manufacturing in the Corporation Japan Steel Works with 2 blow vents 32：The discharge side of resin L/D=32) configures the gear pump (EPG-28/20) that Dynisco Japan company manufactures, and then at it It is configured with inside the accommodating container of internal capacity 0.91 (L) in downstream and 4 pieces of external diameter 112mm, internal diameter 38mm, 99% filtration are installed Precision is 10 μm of leaf filter [Japan Jingxian Co., Ltd's manufacture] [material is rustless steel (SUS304, SUS316)] Filter assemblies.This filter before use under steam atmosphere, carried out the calcination process of 40 hours in 310 DEG C, then In air atmosphere, carried out the calcination process of 52 hours in 420 DEG C, after being cooled to room temperature, in the aqueous solution of nitric acid of 30 weight % Middle dipping 30 minutes, forms oxide film thereon, then is washed and be dried.
The entrance side of filter assemblies and discharge side are arranged according to the mode of level, install in the discharge side of filter assemblies For carrying out the die head of strand.The shared ratio in constituting the leement duration of the whole screw rod of extruder of the length of kneading disk Example (kneading member ratio) is 13.9%.In the outlet flow passage of extruder and the inlet fluid path of filter assemblies and filter group The outlet flow passage setting of part is used for measuring the sensor of resin temperature, and the setting of the barrel zone temperature of extruder is as follows：From granule Supply side rises, and is set as 220 DEG C, 230 DEG C, 230 DEG C, 235 DEG C, 240 DEG C, 240 DEG C, 240 DEG C, 240 DEG C, 240 DEG C.
Polycarbonate resin pellets obtained above are supplied thereto with 10kg/h, the screw speed simultaneously making extruder is 100rpm, has carried out devolatilization using vacuum pump from blow vent.Now ventilation oral area pressure with absolute pressure be calculated as 300Pa with Under.
Using thermometer, the temperature of the polycarbonate resin discharged by die head by filter assemblies is determined, knot Fruit is 257 DEG C, and the polycarbonate resin discharged carries out water-cooled, solidification with the form of strand, is then carried out with rotary cutter Granulating.
The reduced viscosity of this granule is 0.332, YI is 59.6, phenol content is 25ppm for 427ppm, DPC content.Enter one Step, using purifying baking oven at 110 DEG C by this particle drying 12 hours, shaping membrane in aforementioned manners, and determines foreign body amount.Above-mentioned Result is shown in Table 1.
It should be noted that above-mentioned kneading member ratio refers to the value being calculated by following formula.
Kneading member ratio (%)=(the total length of the kneading disk/overall length of screw rod) × 100
[embodiment 2]
In addition to being set to 15kg/h, screw speed is set to 130rpm to the resin quantity delivered of extruder, with enforcement Example 1 is similarly operated.The temperature of the polycarbonate resin discharged by die head is 264 DEG C, reduced viscosity is 0.334, granule YI be 63.2, phenol content be 476ppm, DPC content be 27ppm.
[embodiment 3]
In addition to being set to 20kg/h, screw speed is set to 150rpm to the resin quantity delivered of extruder, with enforcement Example 1 is similarly operated.The temperature of the polycarbonate resin discharged by die head is 269 DEG C, reduced viscosity is 0.328, granule YI be 65.6, phenol content be 482ppm, DPC content be 29ppm.
[embodiment 4]
In addition to the leaf filter the use of 99% filtering accuracy being 40 μm, operated similarly to Example 1. The YI of granule is 55.3, better than embodiment 1, but foreign body amount is 1710/m2, it is slightly increased than embodiment 1.
[comparative example 1]
The setting of the barrel zone temperature of extruder is as follows：From the supply side of granule, be set as 260 DEG C, 270 DEG C, 270 DEG C, 275 DEG C, 280 DEG C, 280 DEG C, 280 DEG C, 280 DEG C, 280 DEG C, and the screw speed of extruder is 250rpm, in addition, with reality Apply example 1 similarly to be operated.The temperature of the polycarbonate resin discharged from die head is 282 DEG C, reduced viscosity is reduced to 0.275.In addition, the YI of granule is deteriorated, it is 81.1.
[embodiment 5]
In the raw material preparation vessel fully having carried out nitrogen displacement (oxygen concentration 0.0005 volume %～0.001 volume %), will be former Material continuously supplies a certain amount of in the first polymer reactor, is supplied by the catalyst that links with raw material supplying tubing simultaneously and joins Pipe continuously feeds the calcium acetate monohydrate being made for aqueous solution so that its 1mol every with respect to whole dihydroxy compounds reaches To 1.25 × 10-6Mol (is converted into calcium metallic atom), and described raw material is with the mol ratio of ISB/CHDM/DPC for 50/50/100 Mode prepare, described first polymer reactor possesses：Heating agent chuck with oil as heating agent, heating agent Inside coil, stirring paddle, Manage and condenser with distillating of vacuum pump link.
After raw material is mixed in pipe arrangement with aqueous catalyst solution, arrange 2 in entering the stream before first reactor The filtered filter of raw material of platform close pleat type drum type brake, the mesh size of filtered for the raw material of upstream side filter is set to 10 μm, will The mesh size in downstream is set to 1 μm.Distillating in pipe in the first polymer reactor, has been configured with oily (inlet temperature 130 DEG C) as cryogen reflux condenser, in order that the phenol etc. not being refluxed condenser condensation condenses, further in returned cold It has been configured with warm water (45 DEG C of inlet temperature) as the condenser of cryogen between condenser and vacuum pump.
Make the invariablenes turning speed of the stirring paddle of the first polymer reactor, simultaneously in 185 DEG C of interior temperature, pressure 25kPa, holdup time 1.5 little be controlled to constant at present, reactant liquor is continuously extracted out from reactive tank bottom land, supplies to the second polymer reactor.
Second polymer reactor is identical with the first polymer reactor, possess heating agent chuck, heating agent Inside coil, stirring paddle, Distillate pipe and distillate reflux condenser in pipe, condenser with vacuum pump links, in 213 DEG C of interior temperature, pressure 14kPa, stagnant Stay the time 1 little be controlled to constant at present, reactant liquor is continuously extracted out from reactive tank bottom land, to the supply of third polymerization reactor.
Third polymerization reactor 229 DEG C of interior temperature, pressure 6kPa, holdup time 1 little be controlled to constant at present, next exist Carry out polycondensation reaction while the phenol that by-product is distilled off, reactant liquor is continuously extracted out from reactive tank bottom land, to having 2 The Horizontal stirring reactor (of feathering axis and the mutually discontinuous stirring paddle installed at a substantially right angle with this trunnion axis Four polymer reactors) supply.
4th polymer reactor so that the interior temperature of entrance be 228 DEG C, the interior temperature of near exit be 240 DEG C, pressure be 0.07kPa, holdup time are that the mode of 2 hours controls, and carry out polycondensation reaction further.
By the polycarbonate resin obtaining continuously to there is additive supply mouth and 3 blow vents and L/D=42, pinch The length of conjunction disk shared ratio in constituting the leement duration of whole screw rod of extruder is 6% double screw extruder supply.
Supply the water being 0.1% with respect to pending polycarbonate resin into extruder, blow vent is with vacuum pump even Knot, eliminates contained volatile ingredient in polycarbonate resin.The setting of the barrel zone temperature of extruder is by 4 parts of upstream It is set to 245 DEG C, 6 parts in downstream are set to 225 DEG C, screw speed is set to 250rpm.
Now, the polycarbonate resin supplying to extruder is extracted out temporarily, carried out the mensure of temperature and various analysis. The results are shown in table 2.
Configured for the polycarbonate resin being processed with the extruder gear pump exporting at it is located to the entrance of resin Bottom, outlet superposed filter assemblies supply.In the temperature of the resin just above sampling of filter assemblies and various Measured value is shown in table 2.In the inside of filter assemblies, leaf filter (the Nihon Pall company of 7 μm of mesh size is installed Manufacture), eliminate the foreign body in polycarbonate resin.
Above-mentioned filter uses following filter：Before use under steam atmosphere, carry out 40 in 310 DEG C The calcination process of hour, has carried out the calcination process of 52 hours then in air atmosphere, in 420 DEG C, after being cooled to room temperature, Impregnate 30 minutes in the aqueous solution of nitric acid of 30 weight %, form oxide film thereon, then washed and be dried.
Filter assemblies possess the heater being made up of multiple parts, and respective temperature is set as 230～240 DEG C.? The outlet side of filter assemblies, arranges die head, polymer by the polymer pipe arrangement possessing the heater being made up of multiple parts The design temperature of the heater of pipe arrangement is set to 220～230 DEG C, and the heater of die head is set to 220 DEG C.
Determine the outlet resin temperature of filter and the outlet resin temperature of die head similarly to Example 1.Keeping In room for the cleanliness factor of rank 10000, from this die head, polycarbonate resin is extracted out with the form of strand, in the sink So that it is solidified, granulated with rotary cutter.Assay value is shown in Table 2.
[embodiment 6]
By the interior temperature of the 1st polymer reactor be set to 194 DEG C, pressure be set to 27kPa, the interior temperature of the 2nd polymer reactor is set For 190 DEG C, pressure be set to 19kPa, by the interior temperature of the 3rd polymer reactor be set to 213 DEG C, pressure be set to 7.5kPa, by the 4th be polymerized The interior temperature of the entrance of reactor be set to 214 DEG C, the interior temperature of near exit be set to 228 DEG C, pressure be set to 0.7kPa, by die head Heater be set as 230 DEG C, in addition, operated similarly to Example 1.
[embodiment 7]
By the interior temperature of the 1st polymer reactor be set to 190 DEG C, pressure be set to 25kPa, the interior temperature of the 2nd polymer reactor is set For 196 DEG C, pressure be set to 17.7kPa, by the interior temperature of the 3rd polymer reactor be set to 215 DEG C, pressure be set to 6.9kPa, the 4th is gathered Close reactor entrance interior temperature be set to 218 DEG C, the interior temperature of near exit be set to 232 DEG C, pressure be set to 0.9kPa, make to squeeze 4 parts being set as upstream going out the barrel zone temperature of machine are 240 DEG C, 6 parts in downstream are 185 DEG C, in addition, with reality Apply example 1 similarly to be operated.
[embodiment 8]
In raw material preparation vessel, the mol ratio by ISB/CHDM/DPC is preparing raw material in the way of in the of 70/30/100, by the 1st The interior temperature of polymer reactor be set to 188 DEG C, pressure be set to 24.2kPa, the interior temperature of the 2nd polymer reactor is set to 194 DEG C, pressure Be set to 19.9kPa, by the interior temperature of the 3rd polymer reactor be set to 214 DEG C, pressure be set to 9.9kPa, by entering of the 4th polymer reactor Mouthful near interior temperature be set to 218 DEG C, the interior temperature of near exit be set to 232 DEG C, pressure be set to 0.1kPa, make the machine barrel temperature of extruder 4 parts being set as upstream of degree are 240 DEG C, 6 parts in downstream are 195 DEG C, in addition, similarly to Example 1 Operated.
[embodiment 9]
In addition to the mesh size making filter is 22 μm, operated similarly to Example 6.In polymer filtration The pressure loss in device diminishes, and molecular weight reduces and the increase of double bond end also has repressed trend, and granule tone is changed Kind, but foreign body amount increased.
[embodiment 10]
Except make the total length of kneading disk of extruder be screw rod overall length 12% in addition to, similarly to Example 9 Operated.
[comparative example 2]
By the interior temperature of the 3rd polymer reactor be set to 240 DEG C, pressure be set to 4kPa, by the entrance of the 4th polymer reactor Interior temperature be set to 240 DEG C, the interior temperature of near exit be set to 252 DEG C, pressure be set to 0.02kPa, make the barrel zone temperature of extruder 4 parts being set as upstream are 250 DEG C, 6 parts in downstream are 260 DEG C, screw speed is 280rpm, by filter assemblies Heater setpoint temperatures be set as 270～280 DEG C, the design temperature of the heater of polymer pipe arrangement is set as 270～280 DEG C, and the heater of die head is set as 280 DEG C, in addition, operated similarly to Example 1.
Although the pressure loss in polymer filter has repressed trend, from the polycarbonate resin of die head extrusion The temperature of fat is 285 DEG C, and coloring is substantially.In addition, producing gas from die head and making strand in disorder it is impossible to obtain granule.
It should be noted that being hereby incorporated the description of Japanese patent application 2011-77377, claims, attached Partial content or all interior disclosed in all the elements of figure and summary and the patent documentation quoted in this manual etc. Hold, be introduced into as the disclosure of description of the invention.

Claims (28)

1. a kind of manufacture method of polycarbonate resin, the method includes：Using filter by dihydroxy compounds and carbonic acid two After polycarbonate resin obtained from ester polycondensation filters, cooled and solidified, wherein,
The dihydroxy compounds that described dihydroxy compounds represent including at least following formulas (5),
The mesh of described filter is less than 50 μm,
Described filter is received in a reservoir, the internal capacity (m of this accommodating container3) divided by described polycarbonate resin to be filtered Flow (the m of fat3/ point) obtained from be worth for 2 minutes～10 minutes,
The temperature difference of the Merlon after the temperature of the Merlon before being filtered using described filter and filtration is 50 DEG C Within,
Polycarbonate resin is filtered so that the temperature of polycarbonate resin after being filtered with described filter is 200 DEG C less than 270 DEG C,
2. the manufacture method of polycarbonate resin according to claim 1, wherein, described poly- carbon obtained from described polycondensation Acid ester resin does not make it be supplied to described filter with solidifying to be kept molten by, and is filtered.
3. the manufacture method of polycarbonate resin according to claim 1, wherein,
The terminal double bond being fed into the described polycarbonate resin before described filter is set to X μ eq/g, will described cool down admittedly In the case that the terminal double bond of polycarbonate resin obtained from change is set to Y μ eq/g,
Meet following formula (2),
Y-X≤10 (2).
4. the manufacture method of polycarbonate resin according to claim 2, wherein,
The terminal double bond being fed into the described polycarbonate resin before described filter is set to X μ eq/g, will described cool down admittedly In the case that the terminal double bond of polycarbonate resin obtained from change is set to Y μ eq/g,
Meet following formula (2),
Y-X≤10 (2).
5. the manufacture method of polycarbonate resin according to claim 1, wherein,
The reduced viscosity (η sp/c) being fed into the described polycarbonate resin before described filter is set to A, by described cooling In the case that the reduced viscosity (η sp/c) of polycarbonate resin obtained from solidification is set to B,
Meet following formula (3),
0.8 ＜ B/A ＜ 1.1 ... (3).
6. the manufacture method of polycarbonate resin according to claim 2, wherein,
The reduced viscosity (η sp/c) being fed into the described polycarbonate resin before described filter is set to A, by described cooling In the case that the reduced viscosity (η sp/c) of polycarbonate resin obtained from solidification is set to B,
Meet following formula (3),
0.8 ＜ B/A ＜ 1.1 ... (3).
7. the manufacture method of polycarbonate resin according to claim 3, wherein,
The reduced viscosity (η sp/c) being fed into the described polycarbonate resin before described filter is set to A, by described cooling In the case that the reduced viscosity (η sp/c) of polycarbonate resin obtained from solidification is set to B,
Meet following formula (3),
0.8 ＜ B/A ＜ 1.1 ... (3).
8. the manufacture method of polycarbonate resin according to claim 4, wherein,
The reduced viscosity (η sp/c) being fed into the described polycarbonate resin before described filter is set to A, by described cooling In the case that the reduced viscosity (η sp/c) of polycarbonate resin obtained from solidification is set to B,
Meet following formula (3),
0.8 ＜ B/A ＜ 1.1 ... (3).
9. the manufacture method of the polycarbonate resin according to any one of claim 1～8, wherein, using described cooling Polycarbonate resin obtained from solidification, in shear rate 91.2sec of 240 DEG C of mensure-1Under melt viscosity be 500Pa s Above and below 3000Pa s.
10. the manufacture method of the polycarbonate resin according to any one of claim 1～8, wherein, using described cooling Polycarbonate resin obtained from solidification, glass transition temperature when being measured with differential scanning calorimeter are more than 50 DEG C And it is less than 160 DEG C.
The manufacture method of 11. polycarbonate resins according to any one of claim 1～8, wherein, using described cooling Polycarbonate resin obtained from solidification, measure in dichloromethane, at concentration 0.6g/dL, 20.0 DEG C ± 0.1 DEG C of temperature Reduced viscosity (η sp/c) is more than 0.3dL/g and below 1.2dL/g.
The manufacture method of 12. polycarbonate resins according to any one of claim 1～8, wherein, described cooling and solidifying Obtained from contained aromatic monohydroxy compound content in polycarbonate resin be 0.0001 mass % less than 0.1 Quality %.
The manufacture method of 13. polycarbonate resins according to any one of claim 1～8, wherein, carrying out, polycondensation is anti- With the filtered filter of raw material, described starting monomer should be filtered before.
The manufacture method of 14. polycarbonate resins according to any one of claim 1～8, wherein, described filter bag Containing metal, and described filter is in advance more than 350 DEG C and less than 500 DEG C of temperature implements calcination process.
The manufacture method of 15. polycarbonate resins according to any one of claim 1～8, wherein, before described filtration The bottom supply of the accommodating container from described filter for the polycarbonate resin, the polycarbonate resin after filtration is from this accommodating container Top discharge.
The manufacture method of 16. polycarbonate resins according to any one of claim 1～8, wherein,
Described polycondensation is carried out using catalyst,
Described catalyst is at least one metallic compound in the metal and lithium of long period type periodic chart the 2nd race.
The manufacture method of 17. polycarbonate resins according to any one of claim 1～8, wherein, described formula (5) The dihydroxy compounds representing are isosorbide.
The manufacture method of 18. polycarbonate resins according to any one of claim 1～8, wherein, with having ventilation Mouthful and there is the extruder of twin screw polycarbonate resin obtained from described polycondensation carried out, after the operation of devolatilization, being supplied to institute State filter.
The manufacture method of 19. polycarbonate resins according to claim 18, wherein, the screw rod of described extruder is by multiple Element is constituted, and at least one of this element is kneading disk, the total length of this kneading disk be described screw rod overall length 20% with Under.
The manufacture method of 20. polycarbonate resins according to claim 18, wherein, is supplied to the poly- carbon of described extruder The temperature of acid ester resin is 200 DEG C less than 250 DEG C.
The manufacture method of 21. polycarbonate resins according to claim 18, wherein, is supplied to the poly- carbon of described filter The temperature of acid ester resin is 220 DEG C less than 280 DEG C.
The manufacture method of 22. polycarbonate resins according to claim 18, wherein,
The reduced viscosity (η sp/c) of the polycarbonate resin being fed into described extruder be set to a, by described cooling and solidifying and In the case that the reduced viscosity (η sp/c) of the polycarbonate resin obtaining is set to B,
Meet following formula (4),
0.8 ＜ B/a ＜ 1.1 ... (4).
The manufacture method of 23. polycarbonate resins according to claim 18, wherein, in described extruder and described filtration Gear pump is configured between device.
The manufacture method of 24. polycarbonate resins according to any one of claim 1～8, wherein, with respect to whole two Hydroxy compounds, the ratio of the dihydroxy compounds that described formula (5) represents is 20 moles of more than %.
A kind of 25. polycarbonate resins, it is to be obtained by the manufacture method any one of claim 1～24, and Its yellow colour index value is less than 30.
A kind of 26. polycarbonate resin films, it is will to be obtained by the manufacture method any one of claim 1～24 Polycarbonate resin or claim 25 described in thickness obtained from polycarbonate resin extrusion molding be 20 μm～200 μ The film of m, wherein,
In this film contained greatest length be more than 25 μm foreign body be 1000/m2Below.
A kind of 27. manufacture methods of polycarbonate resin pellets, the method includes：Catalyst will be used and as raw material list The dihydroxy compounds of body and carbonic diester are carried out with filter by polycarbonate resin obtained from ester exchange reaction polycondensation Filter, extruded with the form of strand from die head, after cooling, manufacture polycarbonate resin pellets using cutting knife, wherein,
The dihydroxy compounds that described dihydroxy compounds represent including at least following formulas (5),
The mesh of described filter is less than 50 μm,
Described filter is received in a reservoir, the internal capacity (m of this accommodating container3) divided by described polycarbonate resin to be filtered Flow (the m of fat3/ point) obtained from be worth for 2 minutes～10 minutes,
The temperature difference of the Merlon after the temperature of the Merlon before being filtered using described filter and filtration is 50 DEG C Within,
From described die head extrusion resin temperature be 200 DEG C less than 280 DEG C,
The manufacture method of 28. polycarbonate resin pellets according to claim 27, wherein, with respect to whole dihydroxies Compound, the ratio of the dihydroxy compounds that described formula (5) represents is 20 moles of more than %.
CN201280016791.6A 2011-03-31 2012-03-23 The manufacture method of polycarbonate resin, the manufacture method of polycarbonate resin, polycarbonate resin film and polycarbonate resin pellets Active CN103476561B (en)

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JP2011-077377 2011-03-31
PCT/JP2012/057619 WO2012133236A1 (en) 2011-03-31 2012-03-23 Method for manufacturing polycarbonate resin, polycarbonate resin, and methods for manufacturing polycarbonate-resin film and polycarbonate-resin pellets

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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI574991B (en) * 2012-04-18 2017-03-21 Teijin Ltd Copolycarbonate
JP6006653B2 (en) * 2013-02-04 2016-10-12 出光興産株式会社 Polycarbonate resin extrusion granulator and polycarbonate resin extrusion granulation method
JP2015187204A (en) * 2014-03-26 2015-10-29 三菱化学株式会社 Extrusion molded product formed of polycarbonate resin
CN104893271B (en) * 2015-05-27 2016-08-17 金发科技股份有限公司 A kind of polycarbonate compositions and preparation method thereof
JP2017165892A (en) * 2016-03-17 2017-09-21 三菱ケミカル株式会社 Transparent resin film
JP6915609B2 (en) * 2016-03-30 2021-08-04 三菱瓦斯化学株式会社 Aromatic Polycarbonate Resin Composition and Method for Producing Aromatic Polycarbonate Resin
JP6759871B2 (en) * 2016-08-31 2020-09-23 三菱ケミカル株式会社 A method for producing a film having a negative thickness retardation (Rth).
CN111993616A (en) * 2020-08-10 2020-11-27 广西长科新材料有限公司 Efficient BR and SBR rubber dissolving equipment

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3103652B2 (en) 1992-02-27 2000-10-30 日本ジーイープラスチックス株式会社 Method for producing optical polycarbonate composition
JP2000219737A (en) 1999-01-29 2000-08-08 Teijin Ltd Preparation of polycarbonate resin, and molded article
JP2000178355A (en) * 1998-12-18 2000-06-27 Ge Plastics Japan Ltd Production of polycarbonate
WO2001083584A1 (en) * 2000-04-13 2001-11-08 Teijin Limited Method for production of polycarbonate and filtering device
JP5092182B2 (en) * 2000-09-22 2012-12-05 三菱瓦斯化学株式会社 Production method of polycarbonate
JP2002265583A (en) * 2001-03-09 2002-09-18 Mitsubishi Gas Chem Co Inc Process for producing aromatic/aliphatic copolycarbonate
JP2002293913A (en) * 2001-03-29 2002-10-09 Mitsubishi Gas Chem Co Inc Method for manufacturing aromatic-aliphatic copolymerized polycarbonate
JP4088762B2 (en) * 2002-05-17 2008-05-21 三菱瓦斯化学株式会社 Process for producing aromatic-aliphatic copolymer polycarbonate resin composition
JP4196326B2 (en) * 2002-06-12 2008-12-17 三菱瓦斯化学株式会社 Polycarbonate copolymer
ATE455812T1 (en) 2003-06-16 2010-02-15 Teijin Ltd POLYCARBONATE AND PRODUCTION PROCESS THEREOF
JP2006028441A (en) 2004-07-21 2006-02-02 Teijin Ltd Optical film comprising aliphatic polycarbonate
JP4626847B2 (en) 2005-02-22 2011-02-09 三菱瓦斯化学株式会社 Copolycarbonate resin
JP2007070392A (en) * 2005-09-05 2007-03-22 Mitsubishi Gas Chem Co Inc Araliphatic polycarbonate resin copolymer
JP5532531B2 (en) 2006-06-19 2014-06-25 三菱化学株式会社 Polycarbonate copolymer and method for producing the same
JP5245272B2 (en) * 2007-03-29 2013-07-24 三菱化学株式会社 Method for producing aromatic polycarbonate
BRPI0806334B1 (en) * 2007-08-20 2019-02-19 Mitsubishi Chemical Corporation PROCESS FOR PRODUCTION OF AROMATIC POLYCARBONATE RESIN
JP5233203B2 (en) * 2007-08-20 2013-07-10 三菱化学株式会社 Process for producing purified aromatic polycarbonate resin
JP5415685B2 (en) 2007-10-04 2014-02-12 帝人株式会社 Polycarbonate having plant-derived components and process for producing the same
JP2009091417A (en) 2007-10-05 2009-04-30 Teijin Ltd Manufacturing method for polycarbonate having component originated from plant
JP4697295B2 (en) * 2007-12-13 2011-06-08 三菱化学株式会社 Method for producing polycarbonate
JP2010058410A (en) * 2008-09-04 2010-03-18 Fujifilm Corp Thermoplastic resin composition, method of manufacturing the same, thermoplastic resin film, method of manufacturing the same, polarizing plate, and liquid crystal display
JP5875747B2 (en) * 2008-11-28 2016-03-02 三菱化学株式会社 Preservation method of dihydroxy compound for polycarbonate raw material
JP5402067B2 (en) * 2009-02-19 2014-01-29 三菱化学株式会社 Method for producing polycarbonate

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