CN104968704B - The manufacture method of polyarylate - Google Patents
The manufacture method of polyarylate Download PDFInfo
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- CN104968704B CN104968704B CN201480005463.5A CN201480005463A CN104968704B CN 104968704 B CN104968704 B CN 104968704B CN 201480005463 A CN201480005463 A CN 201480005463A CN 104968704 B CN104968704 B CN 104968704B
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/79—Interfacial processes, i.e. processes involving a reaction at the interface of two non-miscible liquids
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/785—Preparation processes characterised by the apparatus used
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Optimal way according to the present invention, the manufacture method of a kind of polyarylate utilizing dihydric phenol composition and aromatic dicarboxylic acid composition to be formed can be provided, this manufacture method is characterised by: in interface polymerization reaction operation, in the presence of the polymerization catalyst shown in following formula (1), progressive rotation type blender is used to carry out interface polymerization reaction.(n in formula represents any one in 2,3,4, and Y represents ethyl, propyl group, butyl or benzyl, and X represents Cl, Br, OH or HSO4。)
Description
Technical field
The present invention relates to the manufacture method of polyarylate, particularly polystyrene conversion weight average molecular weight be more than 20,000, low
The manufacture method of effect is played in the manufacture of the polyarylate of 150,000.
Background technology
The excellences such as the mechanical property of polyarylate, electrical characteristic, as engineering plastics at electric and electronic field, automobile
It is widely used in the various fields such as field, OA field of machines.Particularly polystyrene conversion weight average molecular weight 20,000 with
Polyarylates upper, less than 150,000 have high intensity when using as covering material, and industrial value is high.
Polyarylate, with dihydric phenol and aromatic dicarboxylic acid or their derivant as raw material, uses known polyester side
Method manufactures.As polymerization, can enumerate interfacial polymerization, polymerisation in solution, dissolve polymerization etc., preferred interfaces is polymerized.
Interfacial polymerization by the presence of a catalyst, mixing dihydric phenol is dissolved in the aqueous phase obtained in aqueous alkali
It is not dissolved in the organic facies obtained in the organic solvent of water carries out with dicarboxylic acids carboxylic acid halides is dissolved in.(non-patent literature
1, patent documentation 1)
Interfacial polymerization is compared with polymerisation in solution, and reaction is fast, the hydrolysis of acyl halide is suppressed in Min., as result,
The polyarylate of high molecular can be obtained.
Particularly, when manufacturing the polyarylate of high molecular, need to make the hydrolysis minimization of acyl halide.As the method,
Such as, as shown in patent documentation 2, there is following method: in interface polymerization reaction operation, use MAXBLEND type blade
(Sumitomo Heavy Industries, Ltd's registered trade mark), at the polymerization catalyst (three normal-butyl benzyl ammonium chlorides) that polymerization speed is fast
In the presence of, adjust the rotating speed of blender so that stirring power is 0.4～1.2kW/m3, carry out interfacial polymerization, thus make
Make the polyarylate of high molecular.But, in said method, there is also room for improvement at polymerization time etc..
Patent documentation 3 is recorded following method: in the manufacture method of aromatic carbonate, use as agitating device
Progressive rotation type blender.But, patent documentation 3 not relates to the manufacture method of resin, not to mention relates to the system of polyarylate
Make method.
In patent documentation 4, as the agitating device used, list the various stirrings including progressive rotation type blender
Machine, but it is silent on preferred blender.Further, patent documentation 4 not relates to the manufacture method of aliphatic polyester, does not has completely
The manufacture method of polyarylate on the books.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Patent Publication 40-1959 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2007-217502 publication
Patent documentation 3: Japanese Unexamined Patent Publication 7-224008 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2009-256643 publication
Non-patent literature
Non-patent literature 1:W.M.EARECKSON, J.Poly.Sci.XL399 (1959)
Summary of the invention
Invent problem to be solved
The problem of the present invention is to provide a kind of industrially stable and during with shorter than existing manufacture method polymerization
Between manufacture the method for polyarylate efficiently.
For the method solving problem
The present inventor is studied intensively to solve above-mentioned problem, it was found that at interface polymerization reaction
In operation, use progressive rotation type blender to carry out interface polymerization reaction, it is possible to solve above-mentioned problem, thus complete this
Invention.That is, the present invention includes following mode.
<1>manufacture method of a kind of polyarylate, this polyarylate utilizes dihydric phenol composition and aromatic dicarboxylic acid composition to be formed,
This manufacture method is characterised by: in interface polymerization reaction operation, uses progressive rotation type blender to carry out interfacial polymerization anti-
Should.
The manufacture method of the polyarylate described in<2>above-mentioned<1>, wherein, depositing of the polymerization catalyst shown in following formula (1)
Under, carry out interface polymerization reaction.
(n in formula represents any one in 2,3,4, and Y represents ethyl, propyl group, butyl or benzyl, X represent Cl, Br, OH or
HSO4。)
<3>above-mentioned<1>or<2>described in the manufacture method of polyarylate, wherein, in interface polymerization reaction operation, by past
Stirring dynamic Control when answering the use of rotary agitator is 1～10kW/m3。
<4>above-mentioned<1>～<3>according to any one of the manufacture method of polyarylate, wherein, in interface polymerization reaction operation
In, the blade shape of the progressive rotation type blender used is delta-blade.
<5>above-mentioned<1>～<4>according to any one of the manufacture method of polyarylate, wherein, be obtained by gel infiltration color
The polystyrene conversion weight average molecular weight (Mw) that records of spectrum is more than 20,000, polyarylate less than 150,000.
The effect of invention
Optimal way according to the present invention, it is possible to stablizing and manufacturing polystyrene conversion weight average molecular weight efficiently is 20,000
Above, the polyarylate less than 150,000.The intensity of the polyarylate obtained with the optimal way of the present invention significantly improves, accordingly, as
During covering material, it is possible to being widely used in electric and electronic field etc., industrial value is high.
Detailed description of the invention
Hereinafter, the present invention is described in detail.
Polyarylate in the present invention is the polyester utilizing dihydric phenol composition and aromatic dicarboxylic acid composition to constitute.
In the present invention, as dihydric phenol composition, for instance, it is possible to use 1,1 '-xenyl-4,4 '-glycol, double (4-hydroxyl
Phenyl) methane, double (4-hydroxy phenyl) sulfone, double (4-hydroxy phenyl) sulfide, double (4-hydroxy phenyl) ketone, double (the 4-hydroxyl of 1,1-
Base phenyl) ethane, double (4-hydroxy phenyl) propane (bisphenol-A of 2,2-；BPA), double (4-hydroxy phenyl) butane of 2,2-, 1,1-are double
(4-hydroxy phenyl) hexamethylene (bisphenol Z；BPZ), double (4-hydroxy phenyl) cyclododecane of 1,1-, double (the 4-hydroxy phenyl) six of 2,2-
Fluoro-propane, 4,4 '-[1,3-phenylene double (1-methyl ethylidene)] bis-phenols, double (4-hydroxyl-3-tert-butyl-phenyl) propane of 2,2-,
Double (4-hydroxyl-3,5-dibromo phenyl) propane of 2,2-, double (4-hydroxyl-3,5-Dichlorobenzene base) propane of 2,2-, double (the 4-hydroxyl of 2,2-
Base-3-bromophenyl) propane, double (4-hydroxyl-3-chlorphenyl) propane of 2,2-, double (the 4-hydroxy-3-methyl phenyl) propane of 2,2-is (double
Phenol C；BPC), double (4-hydroxyl-3,5-3,5-dimethylphenyl) propane of 2,2-, double (4-the hydroxy phenyl)-1-diphenylphosphino ethane of 1,1-, double
Double (4-hydroxy phenyl) fluorenes of (4-hydroxy phenyl) diphenyl methane, 9,9-, 9,9-double (4-hydroxy-3-methyl phenyl) fluorenes, 2,2-
Double (4-hydroxyl-3-poly dimethyl propyl group phenyl) propane, double (4-hydroxy phenyl) ether, double (4-hydroxy-3-methyl phenyl) ether, double
(4-hydroxyl-3-ethylphenyl) ether, double (4-hydroxyl-3-tert-butyl-phenyl) ether, double (4-hydroxyl-3-allyl phenyl) ether, double
(2-hydroxy phenyl) ether, double (4-hydroxyl-3,5-3,5-dimethylphenyl) ether, double (4-hydroxyl-3-fluorophenyl) ether, double (4-hydroxyl-3-
Phenyl) ether, α, ω-bis-[2-(p-hydroxybenzene) ethyl] polydimethylsiloxane, α, ω-bis-[3-(o-hydroxy-phenyl)
Propyl group] polydimethylsiloxane, α, ω-bis-[3-(4-hydroxy 3-methoxybenzene base) propyl group] polydimethylsiloxane, α, ω-
Double [3-(p-hydroxybenzene) propyl group] polydimethylsiloxane, α, ω-bis-[2-methyl-2-(p-hydroxybenzene) ethyl] poly-diformazan
Radical siloxane etc..Among these, preferably enumerate 2, double (4-hydroxy phenyl) propane (bisphenol-A of 2-；BPA), double (the 4-hydroxy benzenes of 1,1-
Base) hexamethylene (bisphenol Z；BPZ), double (4-hydroxy-3-methyl phenyl) propane (bisphenol-c of 2,2-；BPC).
It addition, as aromatic dicarboxylic acid composition, adipic acid, suberic acid, decanedioic acid, diphenic acid, adjacent benzene can be enumerated
Dioctyl phthalate, M-phthalic acid, p-phthalic acid, 4,4 '-dicarboxylic acids, 3-tert-butyl isophthalic acid, Toluene-2,4-diisocyanate, 5-dicarboxylic acids,
Xylol-2,5-dicarboxylic acids, pyridine-2,3-dicarboxylic acids, pyridine-2,4-dicarboxylic acids, pyridine-2,5-dicarboxylic acids, pyridine-2,6-
Dicarboxylic acids, pyridine-3,4-dicarboxylic acids, pyridine-3,5-dicarboxylic acids, naphthalene-1,4-dicarboxylic acids, naphthalene-2,3-dicarboxylic acids, naphthalene-2,6-two
Carboxylic acid, xenyl-2,2 '-dicarboxylic acids, xenyl-4,4 '-dicarboxylic acids, diphenyl ether-2,2 '-dicarboxylic acids, diphenyl ether-2,
3 '-dicarboxylic acids, diphenyl ether-2,4 '-dicarboxylic acids, diphenyl ether-3,3 '-dicarboxylic acids, diphenyl ether-3,4 '-dicarboxylic acids, hexichol
Base ether-4,4 '-dicarboxylic acids, double (4-carboxyl-3-aminomethyl phenyl) ether, double (4-carboxyl-2-aminomethyl phenyl) ether, double (4-carboxyl-3-
Ethylphenyl) ether, double (4-carboxyl-2-ethylphenyl) ether, double (2-carboxyl-3-aminomethyl phenyl) ether, double (2-carboxyl-4-methyl
Phenyl) ether, double (2-carboxyl-5-aminomethyl phenyl) ether, double (2-carboxyl-6-aminomethyl phenyl) ether, double (2-carboxyl-3-ethylphenyls)
Ether, double (2-carboxyl-4-ethylphenyl) ether, double (2-carboxyl-5-ethylphenyl) ether, double (2-carboxyl-6-ethylphenyl) ether, double
(3-carboxyl-2-aminomethyl phenyl) ether, double (3-carboxyl-4-aminomethyl phenyl) ether, double (3-carboxyl-5-aminomethyl phenyl) ether, double (3-carboxylic
Base-6-aminomethyl phenyl) ether, double (3-carboxyl-2-ethylphenyl) ether, double (3-carboxyl-4-ethylphenyl) ether, double (3-carboxyl-5-
Ethylphenyl) ether, double (3-carboxyl-6-ethylphenyl) ether etc..Among these, preferably adipic acid, decanedioic acid, phthalic acid,
M-phthalic acid, p-phthalic acid, naphthalene-1,4-dicarboxylic acids, naphthalene-2,6-dicarboxylic acids, xenyl-2,2 '-dicarboxylic acids, xenyl-
4,4 '-dicarboxylic acids, diphenyl ether-2,2 '-dicarboxylic acids, diphenyl ether-3,3 '-dicarboxylic acids, diphenyl ether-4,4 '-dicarboxylic acids, double
(4-carboxyl-3-aminomethyl phenyl) ether, double (4-carboxyl-2-aminomethyl phenyl) ether, double (2-carboxyl-3-aminomethyl phenyl) ether, double (2-carboxylic
Base-4-aminomethyl phenyl) ether, double (2-carboxyl-5-aminomethyl phenyl) ether, double (2-carboxyl-6-aminomethyl phenyl) ether, double (3-carboxyl-2-
Aminomethyl phenyl) ether, double (3-carboxyl-4-aminomethyl phenyl) ether, double (3-carboxyl-5-aminomethyl phenyl) ether, double (3-carboxyl-6-methyl
Phenyl) ether, it is possible to the equal amount of mixture that aromatic dicarboxylic acid is p-phthalic acid and M-phthalic acid used suitably especially.
Dihydric phenol is substantially dissolved in aqueous alkali and obtains by mixing in the presence of a catalyst by the present invention
Aqueous phase and being dissolved in by dicarboxylic acids carboxylic acid halides is not dissolved in the organic facies obtained in the organic solvent of water to carry out interfacial polymerization,
Manufacture polyarylate, as the alkali used in aqueous phase, sodium hydroxide, potassium hydroxide can be enumerated.
It addition, as the solvent used in organic facies, it is possible to use incompatible with water and dissolve the polyarylate of generation
Solvent, specifically, can enumerate dichloromethane, 1,2-dichloroethanes, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetra-chloroethene
The virtue of the chlorine series solvent of alkane, 1,1,1-trichloroethane, o-dichlorohenzene, m-dichlorobenzene, paracide etc., toluene, benzene, dimethylbenzene etc.
Fragrant family hydrocarbon, oxolane etc..
As specific polymerization catalyst used in the present invention, preferably enumerate the chemistry knot having shown in following formula (1)
The quaternary ammonium salt of structure.Alternatively, it is also possible to preferably enumerate the quaternary ammonium salt with the chemical constitution shown in following formula (1) '.
(n in formula represents any one in 2,3,4, and Y represents ethyl, propyl group, butyl or benzyl, X represent Cl, Br, OH or
HSO4。)
(Y in formula represents butyl or benzyl, and X represents Cl, Br, OH or HSO4。)
Specifically, triethyl benzyl ammonia chloride, triethylbenzyl ammonium bromide, triethylbenzyl hydroxide can be enumerated
Ammonium, triethylbenzyl ammonium hydrogen sulfate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethyl ammonium hydroxide, tetraethyl hydrogen sulfate
Ammonium, tripropyl benzyl ammonium chloride, tripropyl Benzylphosphonium Bromide ammonium, tripropyl benzyl ammonium hydroxide, tripropyl benzyl ammonium hydrogen sulfate, four
Propyl ammonium chloride, 4-propyl bromide, TPAOH, tetrapropyl ammonium hydrogen sulfate, three normal-butyl benzyl ammonium chlorides, three just
Butyl benzyl ammonium bromide, three normal-butyl benzyl ammonium hydroxide, three normal-butyl benzyl ammonium hydrogen sulfates, tetrabutylammonium chloride, four just
Butylammonium bromide, 4-n-butyl ammonium hydroxide, 4-n-butyl ammonium hydrogen sulfate.
In order to regulate the molecular weight of polyarylate, end terminator can be used when polymerization.Example as end terminator
Son, can enumerate phenol, paracresol, orthoresol, 2,4-xylenols, p-t-butyl phenol, o-allyl phenol, to pi-allyl
Phenol, 4-Vinyl phenol, to hydroxy-alpha-methyl styrene, n-propyl phenol, p-cumylphenol, 4-hydroxydiphenyl, adjacent phenyl
Phenol, p-trifluoromethyl-phenol, nonylphenol, to 1 phenols of valency such as dodecyl phenol, eugenol, Benzenecarbonyl chloride., first
The acyl halide etc. of 1 valency of alkanesulphonyl chlorides, phenyl chloroformate etc..
In interfacial polymerization, the solution of the solution of organic facies with above-mentioned aqueous phase is mixed, generally with less than 40 DEG C, enter
Temperature that one step is preferably less than 25 DEG C stirs 0.1～5 hour, while carrying out interfacial polycondensation reaction, it is possible to obtain high score
The polyarylate of son amount.
The polystyrene conversion weight recorded by gel permeation chromatography (hreinafter referred to as GPC) of the polyarylate of the present invention
Average molecular weight (Mw) be preferably more than 20,000, less than 150,000, more preferably more than 30,000, less than 130,000.It addition, polystyrene conversion
Number-average molecular weight (Mn) is preferably more than 0.4 ten thousand, less than 80,000.When polystyrene conversion weight average molecular weight (Mw) is less than 20,000, make
Mechanical strength for covering material reduces, and on the other hand, when polystyrene conversion weight average molecular weight (Mw) is more than 150,000, makes and covers
Processability during film reduces.
Reactor as polyarylate used in the present invention, it is possible to use the grooved possessing progressive rotation type blender anti-
Answer device.Feature of this invention is that, in interface polymerization reaction operation, use progressive rotation type blender to carry out interface and gather
Close reaction.In the present invention, progressive rotation type blender refers to that shaft is not that a direction rotates, but every 1/4 rotates the most instead
The blender turned.About the stirring in reaction, it is preferably 1～10kW/m by stirring dynamic Control3Scope, more preferably 1～
8kW/m3, particularly preferably 1～5kW/m3.Stirring power is less than 1kW/m3Time, it is impossible to obtain aqueous phase and the abundant of organic facies mixes
Closing, the contact area of aqueous phase and organic facies reduces, and response speed is slack-off, therefore, it is impossible to stablize and manufacture polyarylate tree efficiently
Fat.
It addition, stirring power is more than 10kW/m3Time, the decomposition rate of polymer chain and acyl halide rises, molecular weight control
Become difficulty.It addition, resin solution emulsifying produces nebulousurine, thus, the resin solution purification efficiency after polymerization process terminates reduces.
Due to above-mentioned two reason, it is impossible to stablize and manufacture polyarylate resin efficiently.
It addition, as the stirring vane for utilizing above-mentioned stirring power to be stirred, from until the time of mixing and
Conduct heat in making tank from the viewpoint of homogenizing, delta-blade is preferably used.Here, delta-blade refers to that cross sectional shape is stirring of triangle
Mix blade.
Embodiment
Then, the present invention is described in further detail by embodiment, but the present invention is not by any limit of these embodiments
Fixed.
<GPC condition>
With Waters company Alliance HPLC system,
2, Showa Denko K. K's Shodex805L post,
0.25w/v% chloroformic solution sample, 1ml/ minute chloroform eluent,
The condition of the UV detection of 254nm is measured.
Obtain weight average molecular weight (Mw) and the number-average molecular weight (Mn) of polystyrene conversion.
<embodiment 1>
In grooved reaction vessel, as blender, in progressive rotation type blender AJITER (the rugged making in Co., Ltd. island
Institute's registered trade mark) assembling delta-blade.Wherein using as the 2 of dihydric phenol, double (4-hydroxy phenyl) propane of 2-(below, is abbreviated
For BPA.) 49g (0.21 mole), as end terminator p-t-butyl phenol (following, be abbreviated as PTBP.)0.63g
(0.0042 mole), be the three normal-butyl benzyl chlorides as polymerization catalyst of 1 mole of % (0.67g) relative to whole dihydric phenols
Change ammonium and (below, be abbreviated as TBBAC.) it is dissolved in (aqueous phase) in the sodium hydrate aqueous solution 730ml of 3w/w%.With this additionally,
In dichloromethane 530ml, dissolve paraphthaloyl chloride/m-phthaloyl chloride=1/1 mixture (below, be abbreviated as MPC.)44g
(0.22 mole) (organic facies).
The stirring power of blender is being adjusted to 7kW/m3Aqueous phase in, add organic facies under strong agitation, with 15 DEG C
Carry out interfacial polycondensation reaction in 1 hour.After stopping polymerization, polymer fluid being separated into aqueous phase and organic facies, utilizing phosphoric acid to neutralize has
Machine phase, repeats washing until the pH of washing liquid is neutral and aqueous phase conductivity is 10 below μ S/cm, afterwards, by obtained
Polymer solution be added drop-wise to remain in the warm water of 50 DEG C, utilize homogenizer to pulverize evaporation of solvent, obtain
White powdery precipitate.Obtained precipitate is filtered, is dried 24 hours with 120 DEG C, obtains dried powder.
<embodiment 2>
In embodiment 1, as dihydric phenol, replace BPA, use 2,2-double (4-hydroxy-3-methyl phenyl) propane (letter below
It is designated as BPC) 55g (0.21 mole), in addition, carry out operation similarly to Example 1, obtain polyarylate resin.
<embodiment 3>
In embodiment 1, as dihydric phenol, replacing BPA, use 1,1-bis(4-hydroxyphenyl)cyclohexane is (hereinafter referred to as
BPZ) 57.5g (0.21 mole), is changed to 0.51g (0.0034 mole) using the PTBP as end terminator, in addition, enters
Row operation similarly to Example 1, obtains polyarylate resin.
<embodiment 4>
In embodiment 1, stirring power is changed to 3kW/m3, in addition, carry out operation similarly to Example 1,
To polyarylate resin.
<embodiment 5>
In embodiment 1, stirring power is changed to 1kW/m3, in addition, carry out operation similarly to Example 1,
To polyarylate resin.
<embodiment 6>
In embodiment 1, polymerization catalyst is changed to triethyl benzyl ammonia chloride and (below, is abbreviated as TEBAC.), by it
It is 10 moles of % (4.9g) that usage amount is changed to relative to whole dihydric phenols, in addition, carries out behaviour similarly to Example 1
Make, obtain polyarylate resin.
<embodiment 7>
In embodiment 1, stirring power is changed to 12kW/m3, in addition, carry out operation similarly to Example 1, knot
Really, it is possible to obtain polyarylate resin, but, resin solution emulsifying and there is nebulousurine, the resin after thus polymerization process terminates is molten
Liquid purification efficiency reduces.
<embodiment 8>
In embodiment 1, stirring power is changed to 0.8kW/m3, in addition, carry out operation similarly to Example 1,
Obtain polyarylate resin.
<comparative example 1>
In embodiment 1, a rotary-type blender in direction assembles MAXBLEND type blade, by stirring dynamic Control is
1kW/m3, carry out interfacial polycondensation reaction, in addition, carry out operation similarly to Example 1, obtain polyarylate resin.
<comparative example 2>
In comparative example 1, stirring power is changed to 3kW/m3, in addition, carry out the operation as comparative example 1, knot
Really, due to stirring stream, solution extrudes wall the most consumingly, disperses from reactive tank, it is impossible to synthesis.
<comparative example 3>
In comparative example 1, stirring power is changed to 7kW/m3, in addition, carry out the operation as comparative example 1, knot
Really, with comparative example 2 similarly, since stirring stream, solution extrudes wall the most consumingly, disperses from reactive tank, it is impossible to synthesis.
Sum up in Table 1 and represent embodiment 1～8, the result of comparative example 1～3.
[table 1]
Industrial utilizability
In accordance with the invention it is possible to industrially stablize and make efficiently with the polymerization time shorter than existing manufacture method
Make polyarylate.Because obtained polyarylate is high molecular, intensity significantly improves, time therefore as covering material, and energy
Enough being widely used in electric and electronic field etc., industrial value is high.
Claims (5)
1. a manufacture method for polyarylate, this polyarylate utilizes dihydric phenol composition and aromatic dicarboxylic acid composition to be formed, described
Manufacture method is characterised by:
In interface polymerization reaction operation, progressive rotation type blender is used to carry out interface polymerization reaction.
2. the manufacture method of polyarylate as claimed in claim 1, it is characterised in that:
In the presence of the polymerization catalyst shown in following formula (1), carry out interface polymerization reaction,
N in formula represents any one in 2,3,4, and Y represents ethyl, propyl group, butyl or benzyl, and X represents Cl, Br, OH or HSO4。
3. the manufacture method of polyarylate as claimed in claim 1 or 2, it is characterised in that:
In interface polymerization reaction operation, it is 1～10kW/m by the stirring dynamic Control during use of progressive rotation type blender3。
4. the manufacture method of polyarylate as claimed in claim 1 or 2, it is characterised in that:
In interface polymerization reaction operation, the blade shape of the progressive rotation type blender used is delta-blade.
5. the manufacture method of polyarylate as claimed in claim 1 or 2, it is characterised in that:
Be obtained by polystyrene conversion weight average molecular weight Mw that gel permeation chromatography records be more than 20,000, poly-less than 150,000
Aromatic ester.
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| JP2013-011113 | 2013-01-24 | ||
| PCT/JP2014/051204 WO2014115746A1 (en) | 2013-01-24 | 2014-01-22 | Method of manufacturing polyacrylate |
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| CN101977963A (en) * | 2008-03-28 | 2011-02-16 | 三菱化学株式会社 | Production method of aliphatic polyester |
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| US3216970A (en) * | 1956-12-14 | 1965-11-09 | Gevaert Photo Prod Nv | Production of linear aromatic polyesters containing isophthalic acid |
| JPS5541249B2 (en) * | 1972-12-01 | 1980-10-23 | ||
| JPS5545566B2 (en) * | 1972-12-12 | 1980-11-18 | ||
| AT386217B (en) * | 1986-10-21 | 1988-07-25 | Isovolta | METHOD FOR PRODUCING AROMATIC POLYESTER |
| JPH07224008A (en) * | 1994-02-10 | 1995-08-22 | Mitsubishi Gas Chem Co Inc | Production of aromatic carbonic acid estr |
| JP3498768B2 (en) * | 1995-08-23 | 2004-02-16 | 三菱瓦斯化学株式会社 | Method for producing polycarbonate resin |
| JP4895632B2 (en) * | 2006-02-15 | 2012-03-14 | ユニチカ株式会社 | Method for producing polyarylate |
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|---|---|
| WO2014115746A1 (en) | 2014-07-31 |
| JPWO2014115746A1 (en) | 2017-01-26 |
| CN104968704A (en) | 2015-10-07 |
| JP6187479B2 (en) | 2017-08-30 |
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