CN1281655C - Polycarbonate resin and method for producing same - Google Patents

Polycarbonate resin and method for producing same Download PDF

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Publication number
CN1281655C
CN1281655C CN 02818104 CN02818104A CN1281655C CN 1281655 C CN1281655 C CN 1281655C CN 02818104 CN02818104 CN 02818104 CN 02818104 A CN02818104 A CN 02818104A CN 1281655 C CN1281655 C CN 1281655C
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polycarbonate resin
long
phenol
straight chain
polycarbonate
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CN1630675A (en
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石川康弘
井上哲也
安田俊之
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority claimed from JP2001295483A external-priority patent/JP2003096180A/en
Priority claimed from JP2002026667A external-priority patent/JP3995945B2/en
Priority claimed from JP2002026669A external-priority patent/JP4025083B2/en
Priority claimed from JP2002026668A external-priority patent/JP2003226750A/en
Priority claimed from JP2002029175A external-priority patent/JP4104873B2/en
Application filed by Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04Aromatic polycarbonates
    • C08G64/06Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/14Aromatic polycarbonates not containing aliphatic unsaturation containing a chain-terminating or -crosslinking agent

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The present invention is a linear polycarbonate resin which uses a long-chain monoalkylphenol having an alkyl group with an average carbon number of 12 to 35 as an end-capping agent and has a viscosity average molecular weight of 13500 to 30000, in which the amount of unreacted long-chain monoalkylphenol is 300ppm or less. Therefore, the polycarbonate resin of the present invention has improved flowability, and the appearance of the molded article is good because there is no adhesive on the mold during injection molding.

Description

Polycarbonate resin and manufacture method thereof
Technical field
The present invention relates to straight chain shape polycarbonate resin and manufacture method thereof, more particularly, do not have bur, also good straight chain shape polycarbonate resin and the manufacture method thereof of moulding product outward appearance on the mould when relating to improvement flowability and injection molding.
Technical background
Polycarbonate resin because mechanical properties (especially, shock-resistant characteristic), electrical property, the transparency etc. are good, therefore is widely used in office equipment or electrical equipment, electronic device field, various fields such as building field as engineering plastics.
Especially, at optical applications, for example, and the substrate of optical information recording media, daylighting is in the field of generic request transparency, tone of window glasss such as the shielding, automobile of purpose etc., generally uses the polycarbonate resin plate about thick 0.6~6mm.
When the tone band of the polycarbonate resin plate that this purposes is used was yellow, not only bad in appearance but also dyestuff etc. caused matching colors irregular or blackout, can not obtain good goods.
Therefore, general, for example the thick polycarbonate resin plate of 3.2mm requires YI (yellowness index value) below 1.5, and is preferred below 1.3.
In addition, in recent years, expectation moulding product thin-walled property, maximization or raising shaping cycle more require to improve mobile.
In order to improve flowability, the well-known long chain alkylphenol that is to use is as end-capping reagent.
For example, alkylphenol, carboxylic acid or the acyl halide of the carbon number 8~20 that uses alkyl have been put down in writing in claims of special public clear 52-50078 communique as end-capping reagent.
Yet, do not put down in writing the chloride of acid of the carbon number 9~17 of alkyl among the embodiment, in addition, put down in writing carbon number and surpassed at 20 o'clock, system emulsification was difficult to washing when polymer fluid was washed, and the heat-drawn wire of gained polycarbonate resin obviously reduces in addition.
In addition, put down in writing the alkylphenol of the carbon number 8~30 that uses alkyl in claims of special fair 7-25871 communique as end-capping reagent.
But, only put down in writing the alkylphenol of the carbon number 18 of alkyl among the embodiment.
In addition, for example, using phenol with carbon number chain alkyl below 17 is technique known (spy open clear 51-34992 communique, spy are opened clear 60-203632 communique, the spy opens clear No. 6116962 communiques, spies and opens flat 11-269260 communique) as end-capping reagent.
Yet this long chain alkylphenol is the polycarbonate resin of end group, generally uses p-tert-butylphenol (PTBP) to compare as the polycarbonate resin of end group with the past, has that thermotolerance is low, a painted problem easily during moulding.
Therefore,, explored to use to limit and replaced alkylphenol, improved thermotolerance (spy opens flat 11-269290 communique, the spy opens the 2001-89559 communique) as end-capping reagent as the contraposition of the contained ortho position scale of construction of impurity in order to solve this class problem.
Moreover, use to 4-dodecylphenol with to the embodiment of octyl phenol though put down in writing in the above-mentioned communique as end-capping reagent, to the amount of unreacted alkylphenol in the polycarbonate resin without any record.
In addition, for example, Te Kaiping 11-269260 communique and the special 2001-89559 communique of opening disclose the affixture that uses the trimer that makes propylene or iso-butylene in the presence of acid catalyst or tetramer and the phenol addition long-chain monoalkyl phenol as end-capping reagent, also have, the tetramer of industrial general use propylene and phenol addition make to 4-dodecylphenol.
Yet this long-chain monoalkyl phenol is the polycarbonate resin of end group, exists tone than PTBP or to the shortcoming for the common polycarbonate resin difference of end group such as cumylphenol (PCP).
As this reason, can enumerate proton on the direct-connected tertiary carbon of aromatic nucleus in (1) and the alkyl and at high temperature exist in poor heat stability, (2) the long-chain monoalkyl phenol and have dioxane matrix (spy opens clear 49-55613 communique) etc. in ortho isomer (spy opens clear 49-55613 communique), (3) the long-chain monoalkyl phenol.
Among these, (1) owing to be structural essence problem, so seek to solve by the use or the condition of molding of selected various additives, (3) are because the boiling-point difference of dioxane matrix and monoalkyl body is big, so be by distilling refining soluble problem.
Therefore, when manufacturing long-chain monoalkyl phenol is the polycarbonate resin of end group, so far, for the existence that prevents ortho isomer causes painted, by ortho isomer is refined to below the particular value, carry out improve (spy opens flat 11-269260 communique, the spy opens the 2001-89559 communique) of tone.
Yet, even this situation, the reduction of ortho position body rests on about 1 weight %, the improvement of tone is insufficient, with PTBP be the polycarbonate resin of end group when comparing, tone is still poor, further improves tone to being used for transparent purposes expectation.
On the other hand, when the polycarbonate resin that uses long chain alkylphenol to make as end-capping reagent is carried out injection molding, bur is arranged on the mould, the moulding product also exist the surface to be easy to generate the tendency of speckle.
Under this situation, present inventors have at first proposed to use the long-chain monoalkyl phenol with average carbon number 19~35 alkyl to make as end-capping reagent and the amount of unreacted long-chain monoalkyl phenol is the straight chain shape polycarbonate resin (the special 2000-344862 of hope communique) of the viscosity-average molecular weight below the 300ppm 14000~30000
This motion has when improving mobile and injection molding and do not have bur on the mould, can obtain having the feature of the formed body etc. of good appearance.
Yet when using this long-chain monoalkyl phenol as end-capping reagent, the interpolation of end-capping reagent is very important period.
For example, with phosgene coexistence under when adding because behind the long-chain monoalkyl phenol and phosgene reaction of 2 molecules, generate the diphenyl carbonate thing mostly, volatile component increases and not preferred when moulding.
Therefore, the oligopolymer stage of estimation after consuming phosgene adds just favourable.
Yet, this situation, long-chain monoalkyl phenol is because reactive generally likening to into the PTBP of end-capping reagent use, to tert-octyl phenol, PCP equal difference, therefore at the unreacted reactant of polymerization ending phase residual minim, perhaps because the washing operation of employing alkali aqueous solution etc. can not be removed unreacted reactant, therefore in order to remove unreacted reactant, there is the problem that needs to increase other operations.
In addition, the spy opens and has put down in writing the Production Example that adopts the interfacial polycondensation manufactured polycarbonate resin that the 4-dodecylphenol of the alkylphenol of alkyl carbon number 12 is used as end-capping reagent in the 2001-89559 communique, but when adopting washing operation to remove triethylamine, a spot of alkali composition and chlorion, reaction solution after will finishing polymerization is diluted to the concentration of about 8 weight %, and washing times is many.
So, in order to improve the flowability of polycarbonate resin, in adopting interfacial polycondensation manufactured polycarbonate resin, when using long-chain monoalkyl phenol as end-capping reagent, in washing procedure since emulsification etc. cause washing difficulty etc., often bring bad result.
In this case, significantly dilution polymer fluid or increase washing times unavoidably produce washing procedure and enrichment process are after this strengthened the problem of loading.
The present invention is under this situation and the research of finishing.
The present invention 1, and its purpose is to provide when improving mobile and injection molding does not have bur, the yet good straight chain shape polycarbonate resin of moulding product outward appearance on the mould.
The present invention 2, its purpose be to provide improve mobile, have a good thermotolerance simultaneously, and during long-time continuous injection molding, suppress on the mould the bur amount, can obtain the polycarbonate resin of good appearance formed body.
The present invention 3, and its purpose is to provide uses long-chain monoalkyl phenol as end-capping reagent, improve mobile, the good tone that is equal to mutually when having with use PTBP simultaneously, the straight chain shape polycarbonate resin that is suitable for optical applications as end-capping reagent.
The present invention 4, its purpose is to provide uses long-chain monoalkyl phenol as end-capping reagent, improve mobile, suppress simultaneously to generate the residual few of deutero-diphenyl carbonate thing and unreacted long-chain monoalkyl phenol, make the method that produces the straight chain shape polycarbonate resin of volatile matter when suppressing moulding effectively by long-chain monoalkyl phenol.
The present invention 5, and its purpose is to provide when adopting the interfacial polycondensation manufactured to use long-chain monoalkyl phenol to improve mobile straight chain shape polycarbonate resin as end-capping reagent, improve the manufacture method of the polycarbonate resin of detergency in the washing procedure.
Summary of the invention
Present inventors etc. have finished the present invention in order to reach the result that aforementioned purpose is concentrated on studies repeatedly according to following experience.
That is, the long-chain monoalkyl phenol that present inventors find to have specific carbon number by use is as end-capping reagent, and the amount of regulating unreacted long-chain monoalkyl phenol in the polycarbonate resin that makes, and can reach this purpose.
Based on this experience, the present invention 1 provides
1. that make and amount unreacted long-chain monoalkyl phenol is the straight chain shape polycarbonate of the viscosity-average molecular weight below the 300ppm 13500~30000 as end-capping reagent to use long-chain monoalkyl phenol with average carbon number 19~35 alkyl.
2. above-mentioned 1 described straight chain shape polycarbonate, wherein, the average carbon number of the alkyl of long chain alkylphenol is 21~25.
In addition, the containing ratio that find to use the ortho position body certain value following to 4-dodecylphenol as end-capping reagent, and can reach this purpose by the amount that limits unreacted neighbour 4-dodecylphenol residual in the gained polycarbonate resin.
Based on this experience, the present invention 2 provides
1. polycarbonate resin, the containing ratio that it is characterized in that using dihydric phenol, carbonic ether raw material and ortho position body at 3 moles of end-capping reagents that 4-dodecylphenol is formed below the % that make and residual quantity unreacted adjacent 4-dodecylphenol as the polycarbonate resin below the 300ppm,
2. above-mentioned 1 described polycarbonate resin, wherein, dihydric phenol is 2, two (4-hydroxy phenyl) propane of 2-,
3. above-mentioned 1 or 2 described polycarbonate resins, its viscosity-average molecular weight is 14000~30000.
In addition, the long-chain monoalkyl phenol of finding to have the alkyl that specific average carbon number and skeleton are arranged by use is as end-capping reagent, and it doesn't matter with the existence of ortho position body, can reach this purpose.
Provide based on this experience, the present invention 3
1. straight chain shape polycarbonate, it is characterized in that make and YIs value formula (IV) expression of end-capping reagent that the long-chain monoalkyl phenol of the alkyl that uses dihydric phenol, carbonic ether raw material and have average carbon number 12~35 forms be below 1.0 polycarbonate,
YIs=(YIa-YIb)×0.76+0.11 (IV)
(in the formula, YIa is dissolved in POLYCARBONATE SHEET 3g among the methylene dichloride 34.5g, the YI value that in the silica glass rounding cartridge type pond of optical length 50mm, internal diameter 25mm, adds this measured in solution, YIb adds the YI value that methylene dichloride is measured in above-mentioned silica glass rounding cartridge type pond)
2. straight chain shape polycarbonate is characterized in that (80 * 40 * 3.2mm) YI value is below 1.5 to that make and the thickness 3.2mm matrix band that become 340 ℃ of injection moldings of end-capping reagent that the long-chain monoalkyl phenol of the alkyl that uses dihydric phenol, carbonic ether raw material and have average carbon number 12~35 forms.
3. above-mentioned 1 or 2 described straight chain shape polycarbonate, wherein, as long-chain monoalkyl phenol, the long-chain dialkyl phenol below the amount 1 weight % of use dioxane matrix,
4. any 1 described straight chain shape polycarbonate of above-mentioned 1~3, wherein, as long-chain monoalkyl phenol, the APHA under using 50 ℃ be below 30 long-chain monoalkyl phenol,
5. any 1 described straight chain shape polycarbonate of above-mentioned 1~4, wherein, adopt the interfacial polycondensation manufactured and polymerization in the 380nm absorbancy of water be more than 0.005 polycarbonate,
6. any 1 described straight chain shape polycarbonate of above-mentioned 1~5, wherein, dihydric phenol is 2, two (4-hydroxy phenyl) propane of 2-,
Any 1 described straight chain shape polycarbonate of 7. above-mentioned 1~6, its viscosity-average molecular weight be 14000~30000,
8. any 1 described straight chain shape polycarbonate of above-mentioned 1~7, wherein, the amount of unreacted long-chain monoalkyl phenol is below the 300ppm.
Present inventors etc. find using long chain alkylphenol as end-capping reagent, making dihydric phenol and phosgene or phosgene derivative carry out interfacial polycondensation makes in the method for straight chain shape polycarbonate resin, under the existence that is implemented in organic solvent, alkaline aqueous solution and catalyzer, be W/O and disperse to implement under state, certain temperature to comprise the dihydric phenol polycarbonate oligomer that contains the chloroformic acid ester group and the operation of long-chain monoalkyl phenol reaction process, can reach this purpose.
Provide based on this experience, the present invention 4
1. the manufacture method of straight chain shape polycarbonate, it is characterized in that using long-chain monoalkyl phenol as end-capping reagent, making dihydric phenol and phosgene or phosgene derivative carry out interfacial polycondensation makes in the method for straight chain shape polycarbonate, implementing (A) makes dihydric phenol and phosgene or phosgene derivative carry out the operation that the interfacial polycondensation preparation contains the dihydric phenol polycarbonate oligomer of chloroformic acid ester group, (B1) make 50% long-chain monoalkyl phenol of oligopolymer that above-mentioned (A) operation makes and total at least usage quantity, at organic solvent, under the existence of alkali aqueous solution and catalyzer, be W/O and disperse state, the operation of reacting under the temperature below 25 ℃, and (B2) in the reaction solution that above-mentioned (B1) operation makes, add dihydric phenol, carry out the operation of interfacial polycondensation again;
2. the manufacture method of above-mentioned 1 described straight chain shape polycarbonate, wherein in (B) operation, the addition of catalyzer is [A] mole, the amount of the chloroformic acid ester group that oligopolymer had is during for [B] mole, [A]/[B] 0.0001~0.02 scope,
3. the manufacture method of above-mentioned 1 or 2 described straight chain shape polycarbonate, wherein, dihydric phenol is 2, two (4-hydroxy phenyl) propane of 2-,
4. the manufacture method of any 1 described straight chain shape polycarbonate of above-mentioned 1-3, wherein, in the straight chain shape polycarbonate amount of unreacted long-chain monoalkyl phenol be 300ppm following,
5. the manufacture method of any 1 described straight chain shape polycarbonate of above-mentioned 1~4, wherein, the viscosity-average molecular weight of straight chain shape polycarbonate is 14000~30000.
In addition, the long-chain monoalkyl phenol of also finding to have specified property by use can reach this purpose as long-chain monoalkyl phenol.
Provide based on this experience, the present invention 5
1. the manufacture method of straight chain shape polycarbonate, it is characterized in that to use the long-chain monoalkyl phenol of alkyl as end-capping reagent with average carbon number 12~35, when making dihydric phenol and phosgene or phosgene derivative carry out interfacial polycondensation manufacturing straight chain shape polycarbonate, as aforementioned long-chain monoalkyl phenol, the tone under using 50 ℃ be with APHA be below 30 long-chain monoalkyl phenol,
2. the manufacture method of above-mentioned 1 described straight chain shape polycarbonate, wherein, dihydric phenol is 2, two (4-hydroxy phenyl) propane of 2-,
3. the manufacture method of above-mentioned 1 or 2 described straight chain shape polycarbonate, wherein, the viscosity-average molecular weight of straight chain shape polycarbonate is 14000~30000.
In sum, the invention provides
1. straight chain shape polycarbonate resin, wherein, the long-chain monoalkyl phenol of alkyl that uses dihydric phenol, carbonic ether raw material and have an average carbon number 12~35 as end-capping reagent that make and amount unreacted long-chain monoalkyl phenol as the viscosity-average molecular weight below the 300ppm 13500~30000,
2. above-mentioned 1 described straight chain shape polycarbonate resin, wherein, the average carbon number of the alkyl of long-chain monoalkyl phenol is 19~35,
3. above-mentioned 2 described straight chain shape polycarbonate resins, wherein, the average carbon number of the alkyl of long-chain monoalkyl phenol is 21~25,
4. above-mentioned 1 described straight chain shape polycarbonate resin, wherein, the amount of the dioxane matrix in the long-chain monoalkyl phenol be 1 weight following,
5. above-mentioned 1 described straight chain shape polycarbonate resin, wherein, the APHA of long-chain monoalkyl phenol under 50 ℃ be below 30,
6. above-mentioned 1 described straight chain shape polycarbonate resin, wherein, long-chain monoalkyl phenol is to 4-dodecylphenol, the containing ratio of the ortho position body of this phenol be the following and unreacted 4-dodecylphenol of 3 moles of % be the ortho position body,
7. above-mentioned 1 described straight chain shape polycarbonate resin, wherein, dihydric phenol is 2, two (4-hydroxy phenyl) propane of 2-,
8. above-mentioned 1 described straight chain shape polycarbonate resin, its viscosity-average molecular weight be 14000~30000,
9. the described straight chain shape of claim 1 polycarbonate resin, wherein, the YIs value of formula (IV) expression is below 1.0,
YIs=(YIa-YIb)×0.76+0.11 (IV)
(in the formula, YIa is dissolved in POLYCARBONATE SHEET 3g among the methylene dichloride 34.5g, the YI value that in the silica glass rounding cartridge type pond of optical length 50mm, internal diameter 25mm, adds this measured in solution, YIb adds the YI value that methylene dichloride is measured in above-mentioned silica glass rounding cartridge type pond)
10. above-mentioned 1 described straight chain shape polycarbonate resin, wherein, the matrix band of 340 ℃ of injection molding thickness 3.2mm (80 * 40 * 3.2mm) YI value is below 1.5,
11. above-mentioned 9 or 10 described straight chain shape polycarbonate resins, wherein adopt the interfacial polycondensation manufactured and polymerization in the absorbancy of 380nm of water be more than 0.005,
12. the manufacture method of above-mentioned 1 described straight chain shape polycarbonate resin, working as use long-chain monoalkyl phenol as end-capping reagent, when making dihydric phenol and phosgene or phosgene derivative carry out interfacial polycondensation manufacturing straight chain shape polycarbonate resin, implementing (A) makes dihydric phenol and phosgene or phosgene derivative carry out the operation that the interfacial polycondensation preparation contains the dihydric phenol polycarbonate oligomer of chloroformic acid ester group, (B1) make 50% long-chain monoalkyl phenol of oligopolymer that above-mentioned (A) operation makes and total at least usage quantity, at organic solvent, under the existence of alkali aqueous solution and catalyzer, be W/O and disperse state, the operation that temperature below 25 ℃ is reacted, and (B2) in the reaction solution that above-mentioned (B1) operation makes, add dihydric phenol, carry out the operation of interfacial polycondensation again;
13. the manufacture method of above-mentioned 12 described straight chain shape polycarbonate resins, wherein, in (B1) operation, the addition of catalyzer is for the amount of [A] mole, the chloroformic acid ester group that contains of oligopolymer during for [B] mole, [A]/[B] 0.0001~0.02 scope,
14. the manufacture method of above-mentioned 1,9 or 10 described straight chain shape polycarbonate resins, wherein, use has the long-chain monoalkyl phenol of alkyl of average carbon number 12~35 as end-capping reagent, when making dihydric phenol and phosgene or phosgene derivative carry out interfacial polycondensation manufacturing straight chain shape polycarbonate resin, as long-chain monoalkyl phenol, the tone under using 50 ℃ is to be long-chain monoalkyl phenol below 30 with APHA.
The optimum implementation of invention
Below, the present invention is at length described.
Though it is multiple that straight chain shape polycarbonate resin of the present invention can be enumerated, preferably has the polymkeric substance of the represented structural repeat unit of general expression (I).
General expression (I)
Figure C0281810400121
In the above-mentioned general expression (I), X 1And X 2Represent C respectively 1~C 6Straight chain shape, chain or cyclic alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopentyl, cyclohexyl etc. particularly.
This X 1And X 2Can be mutually the same also can be different.
A and b represent X respectively 1And X 2The displacement number, be 0~4 integer.
X 1A plurality of X is arranged when a plurality of 1Can be mutually the same also can be different, X 2Have when a plurality of, a plurality of X 2Can be mutually the same also can be different.
Y represents singly-bound, C 1-C 8Alkylidene group (for example, methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene etc.), C 2~C 8Alkylidene (for example, ethidine, isopropylidene etc.), C 5~C 15Cycloalkylidene (for example, cyclopentylidene, cyclohexylidene etc.), C 5~C 15Ring alkylidene (for example, cyclopentylidene base, cyclohexylidene base etc.) ,-S-,-SO-,-SO 2-,-O-,-key of CO-key or formula (II-1) or formula (II-2) expression.
Above-mentioned polymkeric substance can be by making common general expression (III) expression the carbonic ether presoma reaction manufacturing of dihydric phenol and phosgene or carbonate products etc.
General expression (III)
Figure C0281810400131
(in the formula, X 1, X 2, a, b and Y as hereinbefore).
Dihydric phenol as general expression (III) expression can be enumerated various dihydric phenols.
Most preferably 2, two (4-hydroxy phenyl) propane (claiming dihydroxyphenyl propane usually) of 2-.
As the dihydric phenol beyond the dihydroxyphenyl propane, for example, can enumerate two (4-hydroxy phenyl) methane; 1, two (4-hydroxy phenyl) ethane of 1-; 1, two (4-hydroxy phenyl) alkanes, 1 of two (4-hydroxy phenyl) ethane of 2-etc., 1-bis(4-hydroxyphenyl) cyclohexane; 1, two (4-hydroxy phenyl) loop chain alkane, 4 of two (4-hydroxy phenyl) cyclodecane of 1-etc., 4 '-dihydroxybiphenyl, two (4-hydroxy phenyl) sulphur, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) ether, two (4-hydroxy phenyl) ketone etc.
In addition, as dihydric phenol, can enumerate Resorcinol etc.
These dihydric phenol can be used alone, can also be 2 or more kinds in combination respectively.
Here, the present invention 1 straight chain shape polycarbonate resin is meant the polycarbonate resin that does not use branching agent to make.
Among the present invention 2, can use suitable branching agent with dihydric phenol.
As this branching agent, can enumerate the above polyphenol of trivalent, can enumerate 1 particularly, 1,1-three (4-hydroxy phenyl) ethane, α, α ', α "-three (4-hydroxy phenyls)-1; 3,5-triisopropylbenzene, 1-[Alpha-Methyl-α-(4 '-hydroxy phenyl) ethyl] 4-[α ', α '-two (4 "-hydroxy phenyl) ethyl] benzene, Phloroglucinol monomethyl ether, isatin two (neighbour-cresols) etc.
The usage quantity of these branching agents is according to the desired degree of branching and difference is about 0.05~2 mole of % with respect to dihydric phenol usually.
On the other hand, so-called carbonic ether raw material is the compound that can generate carbonic acid ester bond by the reaction of generation polymkeric substance such as polycondensation or permutoid reaction in the polycarbonate resin main chain.
As such compound, when adopting interfacial polycondensation to make polycarbonate resin, can at first enumerate phosgene and triphosgene, bromophosgene, two (2,4, the 6-trichlorophenyl) carbonic ether, two (2,4 dichloro benzene base) carbonic ether, two (2-cyano-phenyl) carbonic ether, superpalite etc.
In addition, adopt transesterification reaction to make polycarbonate resin, can enumerate diaryl carbonate compound, dialkyl carbonate ester cpds, alkyl aryl carbonate ester cpds.
Here, concrete example as the diaryl carbonate compound, can enumerate diphenyl carbonate, the carboxylol ester, carbonic acid two (chloro-phenyl-) ester, the carbonic acid m-tolyl ester, carbonic acid dinaphthyl ester, carbonic acid two (phenylbenzene) ester, dihydroxyphenyl propane diphenyl carbonate etc., concrete example as the dialkyl carbonate ester cpds, can enumerate diethyl carbonate, methylcarbonate, dibutyl carbonate, carbonic acid two cyclohexyls, dihydroxyphenyl propane methylcarbonate etc., as the concrete example of alkyl aryl carbonate ester cpds, can enumerate carbonic acid methyl phenyl ester, carbonic acid ethyl phenyl ester, carbonic acid butyl phenyl ester, plutonium carbonate hexyl phenyl ester, dihydroxyphenyl propane carbonic acid methyl phenyl ester etc.
Among the present invention 1, when making the reaction of dihydric phenol and carbonic ether presoma make polycarbonate resin,, must use the long-chain monoalkyl phenol of alkyl with average carbon number 12~35 as end-capping reagent (also claiming molecular weight regulator).
During average carbon number less than 12, mobile improvement is insufficient, surpasses at 35 o'clock, and is reactive poor, so the loss of long-chain monoalkyl phenol increases.
Being more preferably long-chain monoalkyl phenol with 19~35 average carbon numbers, preferably having the long-chain monoalkyl phenol of 21~35 average carbon numbers again, most preferably is the long-chain monoalkyl phenol with 21~25 average carbon numbers.
Moreover, the average carbon number of so-called abovementioned alkyl be meant [(carbon number of alkyl) with (mole fraction of this alkyl) long-pending] and.
Long-chain monoalkyl phenol can use separately, also can be used in combination more than two kinds.
Situation about being used in combination more than two kinds, the carbon number of alkyl adopt average carbon number to represent.
In addition, long-chain monoalkyl phenol has ortho position body, a position body and contraposition body as isomer, can be any.
In addition, chain alkyl can be that straight chain shape, a catenate are any.
Among the present invention 2, the manufacture method of using as end-capping reagent (yet claiming molecular weight regulator) to 4-dodecylphenol does not have particular restriction, can preferably use the propylene tetramer and phenol addition to make and the amount of ortho position body be below 3 moles of % to 4-dodecylphenol.
When the containing ratio of ortho position body surpassed 3 moles of % 4-dodecylphenol is used as end-capping reagent, prepared polycarbonate resin thermotolerance was low, painted easily during moulding.
In addition, to the amount of the dioxane matrix in the 4-dodecylphenol preferably below 1 weight %.
When the amount of this dioxane matrix surpasses 1 weight %, become the reason that obtained polycarbonate resin thermotolerance reduces.
This depends on the molecular weight that polycarbonate resin is desired to 4-dodecylphenol, but uses 1.8~7.0 moles of % usually, preferably uses in the scope of 2.0~5.5 moles of % with respect to dihydric phenol.
Among the present invention 3,, be amphyl with alkyl of average carbon number 12~35 as the long-chain monoalkyl phenol that end-capping reagent (also claiming molecular weight regulator) uses.
As the alkyl of average carbon number 12~35, can preferably use by linear alpha-olefin deutero-alkyl.
As linear alpha-olefin, the linear alpha-olefin that can use known method to make.
For example, can be the alpha-olefin that constitutes by the oligopolymer that vinyl polymerization makes, perhaps, also can be to derive behind straight chained alkyl-1-halogenide by straight chained alkyl-1-alcohol, the alpha-olefin that makes through dehydrohalogenation.
As such linear alpha-olefin, for example, can enumerate 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene, 1-two dodecylenes, 1-tetracosene etc.
The alpha-olefin of average carbon number 12~35 for example, has the situation of the alpha-olefin of this branching of propylene oligomer, and the long-chain monoalkyl phenol that is made by this alpha-olefin is difficult to obtain the good resin of tone as the polycarbonate resin of end-capping reagent.
In addition, during the average carbon number less than 12 of alkyl, mobile improved effect is insufficient, surpasses at 35 o'clock, and is reactive poor.
The preferred average carbon number of alkyl is 12~25 scope.
Long-chain monoalkyl phenol can use separately, also can be used in combination more than two kinds.
Situation about being used in combination more than two kinds, the carbon number of alkyl is represented with average carbon number.
In addition, long-chain monoalkyl phenol as isomer, has ortho position body, a position body and contraposition body, can be any.
Among the present invention 3, long-chain monoalkyl phenol can be made with the phenol addition in the presence of catalyzer by making the linear alpha-olefin of average carbon number 12~35.
The long-chain monoalkyl phenol that so makes, the amount of the mixture of position body, dioxane matrix was preferably below 1 weight % between normally ortho position, contraposition reached.
When the amount of this dioxane matrix surpasses 1 weight %, be difficult to make the good polycarbonate resin of tone.
In addition, containing of each isomer in the monomer is proportional, and usually, the ortho position body is about 2~60 moles of %, a position body is about 1~3 mole of %, all the other are contraposition bodies.
In addition, the tone of long-chain monoalkyl phenol, the APHA under 50 ℃ is preferred below 30, most preferably below 20.
This tone surpasses at 30 o'clock with APHA, is difficult to obtain the good polycarbonate resin of tone.
This long-chain monoalkyl phenol depends on the molecular weight that polycarbonate resin is desired, but uses 1.8~7.0 moles of % usually, preferably uses in the scope of 2.0~5.5 moles of % with respect to dihydric phenol.
The present invention 3 straight chain polycarbonate resin, the YIs value of representing with formula (IV) is below 1.0.
YIs=(YIa-YIb)×0.76+0.11 (IV)
(in the formula, YIa is dissolved in polycarbonate resin plate 3g among the methylene dichloride 34.5g, the YI value that in the silica glass rounding cartridge type pond of optical length 50mm, internal diameter 25mm, adds this measured in solution, YIb adds the YI value that methylene dichloride is measured in above-mentioned silica glass rounding cartridge type pond)
This YIs value surpasses at 1.0 o'clock, and the tone of polycarbonate resin is bad, can not reach the present invention 3 purpose.
Preferred YIs value is below 0.8.
In addition, the present invention 3 straight chain shape polycarbonate resin, (80 * 40 * 3.2mm) YI value (to call the YIp value in the following text) is below 1.5 at 340 ℃ of injection molding thickness 3.2mm matrix bands.
This YIp value surpasses 1.5 polycarbonate resin, and the tone of polycarbonate resin plate is bad, be not suitable for optical applications, can not reach the present invention 3 purpose.
Preferred YIp value is below 1.3.
The present invention 4 long-chain monoalkyl phenol is the alkylphenol that uses as end-capping reagent (also claiming molecular weight regulator), preferred amphyl of using the alkyl with average carbon number 19~35.
During the average carbon number less than 19 of alkyl, mobile improved effect may be insufficient, surpasses 35 o'clock reactive differences and not preferred.
The preferred average carbon number of alkyl is 21~35, most preferably 21~25 scope.
Long-chain monoalkyl phenol can use separately, also can be used in combination more than two kinds.
Situation about being used in combination more than two kinds, the carbon number of alkyl is represented with average carbon number.
In addition, long-chain monoalkyl phenol has ortho position body, a position body and contraposition body as isomer, can be any.
Chain alkyl can be any a kind of straight chain shape, a catenate.
This long-chain monoalkyl phenol uses 1.8~7.0 moles of % usually with respect to dihydric phenol, preferably uses in the scope of 2.0~5.5 moles of %.
The present invention 5 long-chain monoalkyl phenol is the alkylphenol that uses as end-capping reagent (also claiming molecular weight regulator), the amphyl of using the alkyl with average carbon number 12~35.
During the average carbon number less than 12 of alkyl, mobile improved effect is insufficient, surpass 35 o'clock reactive poor.
The preferred average carbon number of alkyl is 12~25 scope.
Above-mentioned long-chain monoalkyl phenol can use separately, also can being used in combination more than two kinds.
When being used in combination more than two kinds, the carbon number of alkyl is represented with average carbon number.
In addition, long-chain monoalkyl phenol has ortho position body, a position body and contraposition body as isomer, can be any a kind.
In addition, chain alkyl can be any a kind of straight chain shape, a catenate.
Among the present invention 5, as long-chain monoalkyl phenol, must use the tone under 50 ℃ is long-chain monoalkyl phenol below 30 with APHA.
Have this APHA and surpass the long-chain monoalkyl phenol of 30 tone, the detergency of polymer fluid is bad, can not reach the present invention 5 purpose.
This long-chain monoalkyl phenol depends on the molecular weight that polycarbonate resin is desired, but with respect to dihydric phenol, uses 1.8~7.0 moles of % usually, preferably uses in the scope of 2.0~5.5 moles of %.
Polycarbonate resin of the present invention can adopt any method manufacturing of interface polycondensation and ester-interchange method, but generally is interface polycondensation.
Manufacturing process as interface polycondensation does not have particular restriction, can adopt the habitual operation of existing interfacial polycondensation manufactured polycarbonate resin.
For example, by the above-mentioned oligopolymer polymerization process of preparation section, (B), (C) washing procedure and (D) polycarbonate resin separation, the recovery process of implementing (A) dihydric phenol polycarbonate oligomer, can make desired straight chain shape polyacid ester resin effectively.
Below, each operation of interface polycondensation is described.
(A) operation:
Should (A) operation be to make dihydric phenol and phosgene or phosgene derivative carry out the operation of interfacial polycondensation prepared in reaction (containing the chloroformic acid ester group) dihydric phenol polycarbonate oligomer.
The preparation method of this dihydric phenol polycarbonate oligomer does not have particular restriction, for example, can preferably adopt method shown below.
At first, preparation contains the alkali aqueous solution of raw material dihydric phenol, this solution is mixed with inert organic solvents, under the coexistence of alkali aqueous solution that contains dihydric phenol and inert organic solvents, make it while stirring and phosgene or phosgene derivatives reaction, make the dihydric phenol polycarbonate oligomer.
At this moment, as alkali aqueous solution, the alkali aqueous solution of usually preferred working concentration 1~15 weight %.
In addition, the amount of dihydric phenol in the alkali aqueous solution is selected in the scope of 0.2~20 weight % usually.
In addition, the usage quantity of inert organic solvents, the volume ratio of preferably selected organic phase and water is 5/1~1/7, is preferably 2/1~1/4.
Temperature of reaction is selected 0~50 ℃ usually, preferably 5~40 ℃ scope.
In this reaction, make phosgene or phosgene derivatives reaction after, add the alkali aqueous solution contain dihydric phenol again, add a part of end-capping reagent (long-chain monoalkyl phenol, to 4-dodecylphenol) as required and add catalyzer as requested, react.
In addition, among the present invention 4, as the usage quantity of the long-chain monoalkyl phenol of end-capping reagent not Football Association's usage quantity 50%.
Contain the alkali that the alkali aqueous solution of dihydric phenol uses as preparation, for example, can enumerate sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide etc., but wherein preferred sodium hydroxide and potassium hydroxide, most preferably sodium hydroxide.
On the other hand, as inert organic solvents, all kinds of SOLVENTS is arranged.
For example, can enumerate methylene dichloride; Trichloromethane; Tetracol phenixin; 1, the 1-ethylene dichloride; 1, the 2-ethylene dichloride; 1; Vinyl trichloride; Unsym.-tetraehloroethane; Sym.-tetrachloroethane; Pentaline; The chlorinated hydrocarbon of chlorobenzene etc. or toluene, methyl phenyl ketone etc.
These organic solvent can be distinguished use separately, also can be used in combination more than two kinds.
Wherein, most preferably use methylene dichloride.
In addition,, can preferably use alternate moving catalyst as catalyzer, for example, tertiary amine or its salt, quaternary ammonium salt, season  salt etc.
As tertiary amine, for example, can enumerate triethylamine, Tributylamine, N, N-dimethylcyclohexylamine, pyridine, xylidine etc. in addition, as tertiary ammonium salt, for example, can be enumerated the hydrochloride of these tertiary amines, bromate etc.
As quaternary ammonium salt, for example, can enumerate Variquat B 200,3-ethyl benzyl ammonium chloride, chlorination tributyl hexadecyldimethyl benzyl ammonium, tricaprylylmethylammchloride chloride, tetrabutylammonium chloride, Tetrabutylammonium bromide etc., as season  salt, for example, can enumerate chlorination tetrabutyl , bromination tetrabutyl  etc.
These catalyzer can be distinguished use separately, also can be used in combination more than two kinds.
Among these catalyzer, preferred tertiary amine, most preferably triethylamine.
After the reaction,, be separated into water and contain the organic phase of polycarbonate oligomer by leaving standstill or the operation of centrifugation etc.
Organic phase can not separated polycarbonate oligomer and is used for following operation.
(B) operation:
It should (B) operation be the polymerization process of the polycarbonate oligomer that makes of aforementioned (A) operation, be remaining end-capping reagent (long-chain monoalkyl phenol, to 4-dodecylphenol), as requested employed catalyzer, alkali aqueous solution and inert organic solvents in the presence of, make polycarbonate oligomer and dihydric phenol carry out the operation of interfacial polycondensation.
Specifically be polycarbonate oligomer solution that aforementioned (A) operation is made with remaining end-capping reagent (long-chain monoalkyl phenol, to 4-dodecylphenol) and employed as requested catalyzer, inert organic solvents, alkali aqueous solution, and the alkali aqueous solution of dihydric phenol mix, usually 0~50 ℃, preferably carry out interfacial polycondensation 5~40 ℃ temperature range.
At this moment, employed alkali, inert organic solvents and catalyzer, can enumerate with (A) operation in the identical material of explanation.
In addition, the organic phase in this interfacial polycondensation and the volume ratio of water are identical with the situation of (A) operation.
Pre-polymerization) and this polymerization (B2 operation: post polymerization) carry out polymerization moreover this polymerization process can be divided into prepolymerization (B1 operation:.
Promptly, at first, the polycarbonate oligomer solution that aforementioned (A) operation is made and remaining end-capping reagent (long-chain monoalkyl phenol, 4-dodecylphenol) and employed as required catalyzer, and inert organic solvents and alkali aqueous solution mix, in lower temperature, for example, carry out prepolymerization (B1 operation: pre-polymerization) under the temperature of 20 ℃ of less thaies.
Then, in prepolymerization liquid, add the alkali aqueous solution of dihydric phenol,, for example, carry out this polymerization (B2 operation: post polymerization) under the temperature about 20~40 ℃ in higher temperature.
After reaction back uses inert organic solvents suitably to dilute,, be separated into water and contain the organic phase of polycarbonate resin by leaving standstill or the operation of centrifugation etc.
The present invention 4 is 50% the long-chain monoalkyl phenol that makes the dihydric phenol carbonate oligomer that contains the carbonochloridic acid ester group that aforementioned (A) operation makes and total at least usage quantity, in the presence of organic solvent, alkali aqueous solution and catalyzer, disperse the B1 operation (prepolymerization operation) of reacting under state, the temperature below 25 ℃ with W/O.
As the catalyzer in this reaction, can enumerate with (A) operation in as the identical compound of the cited compound of catalyzer, but preferred tertiary amine, most preferably triethylamine.
In addition, the addition of catalyzer is for the amount of [A] mole, carbonochloridic acid ester group that oligopolymer contained during for [B] mole, and the amount of preferred control catalyst makes [A]/[B] in 0.0001~0.02 scope.
The value of more preferably [A]/[B] is 0.001~0.01 scope, most preferably 0.002~0.007 scope.
In addition, 50% o'clock of the total usage quantity of quantity not sufficient of the long-chain monoalkyl phenol that uses in this operation, insufficient purpose that reaches the present invention 4.
In addition, make reacting under the oil droplet dispersion state in the water, or temperature of reaction is when surpassing 25 ℃, the residual quantity of unreacted long-chain monoalkyl phenol increases in the polycarbonate resin, and the bur during moulding on the mould increases.
(B1) preferred 0~25 ℃ scope of the temperature of reaction in the operation, most preferably 10~20 ℃ scope.
(B2) operation of the present invention 4 is to add dihydric phenol in the reaction solution that (B1) operation makes, and carries out the operation (this polymerization process) of interfacial polycondensation again.
Dihydric phenol can be used as alkali aqueous solution and adds, and temperature of reaction is selected 10~50 ℃, preferred 20~40 ℃ scope usually.
The straight chain shape polycarbonate resin of Sheng Chenging like this, can according to known following (C) operation and (D) operation separate from reaction solution and make.
Among the present invention 5 and since use tone with APHA be alkylphenol 30 below as the long-chain monoalkyl phenol of end-capping reagent, so water is good with the separation property of the organic phase that contains polycarbonate resin, an almost event mutually when using normally used PTBP as end-capping reagent.
When using APHA to surpass the long-chain monoalkyl phenol of 30 tone, separation property is poor, separate need long-time.
(C) operation:
Should (C) operation being above-mentioned (B) or (B2) washing procedure of the polycarbonate resin solution that makes of operation, be the operation by the order washing polycarbonate resin solution of alkali aqueous solution, aqueous acid and water.
Specifically be at first with respect to polycarbonate resin solution, use aqueous sodium hydroxide solution 10~20 volume % of 0.01~0.1 mol concentration usually, make both contacts carry out alkali cleaning and handle.
Then, leave standstill, be separated into water and organic phase after, with respect to organic phase, use usually about hydrochloric acid 10~20 volume % of 0.05~0.5 mol concentration, make both contacts carry out cleanup acid treatment.
Thereafter, leave standstill, be separated into water and organic phase, organic phase is implemented washing and is handled.
This washes processing, makes about water 10~20 volume % with respect to organic phase, contact handles by making both.
After washing is handled, leave standstill, be separated into water and organic phase after, this organic phase is implemented and above-mentioned same washing processing again.
Wash repeatedly processing up to the specific conductivity of water usually below 0.01 μ S/m.
Among the present invention 5, long-chain monoalkyl phenol as end-capping reagent, because using tone is alkylphenol below 30 with APHA, therefore the separation property during alkali cleaning processing, cleanup acid treatment, washing are handled is good, almost be equal to mutually when using normally used PTBP as end-capping reagent, and the washing number of processes is also few.
Use has APHA when surpassing the long-chain monoalkyl phenol of 30 tone, and the separation property in the aforementioned reason is poor, and the washing number of processes is also many.
Contain last washing and handle separation, recovery process back, that organic phase that leave standstill, separate the polycarbonate resin that makes is supplied with the polycarbonate resin of following operation.
(D) operation:
This operation is separation, the recovery process of polycarbonate resin.
Specifically be after polycarbonate resin solution after the carrying out washing treatment that above-mentioned (C) operation is made concentrates, to carry out pulverization process,, make the goods polycarbonate resin by the resin sheet of gained being implemented the drying treatment of vacuum-drying etc.
The present invention 1 straight chain shape polycarbonate resin considers that from the viewpoint of physical strength and formability etc. viscosity-average molecular weight must be in 13500~30000 scope.
Preferred 14000~25000 scope is more preferably 14500~21000 scope.
The present invention 2 polycarbonate resin and the present invention's 3 straight chain shape polycarbonate resin is considered from the viewpoint of physical strength and formability etc., and preferred viscosity-average molecular weight (Mv) is in 14000~30000 scope.
More preferably Mv is 15000~25000, most preferably 15000~21000 scope.
The straight chain shape polycarbonate resin that adopts the present invention 4 and 5 manufacture method to make, from the viewpoint consideration of physical strength and formability etc., viscosity-average molecular weight (Mv) is preferably in 14000~30000 scope.
More preferably Mv is 15000~25000, most preferably 15000~21000 scope.
Moreover this viscosity-average molecular weight (Mv) is to use Ubbelohde type viscometer, measures the viscosity of 20 ℃ of following dichloromethane solutions, asks limiting viscosity [η] by this viscosity, adopts [η]=1.23 * 10 -5Mv 0.83The value of calculating.
The residual quantity of unreacted long-chain monoalkyl phenol is necessary for below the 300ppm in the present invention 1 the straight chain shape polycarbonate resin.
Do not have particular determination as the method that becomes below the 300ppm, for example, solution method can filtering separation be used the precipitation of the polycarbonate resin that lean solvent generates.
When surpassing 300ppm, on the injection molding mould bur is arranged, or the outward appearance of moulding product is bad and not preferred.
Below the preferred 200ppm, more preferably not enough 100ppm.
The residual quantity of unreacted adjacent 4-dodecylphenol is necessary for below the 300ppm in the present invention 2 the polycarbonate resin.
When injection molding, the bur amount on the mould increased, and can not obtain to have the formed body of good appearance when this residual quantity surpassed 300ppm.
In addition, the present invention 2 polycarbonate resin, owing to use 4-dodecylphenol as end-capping reagent, so have good flowability, and it is 3 moles below the % to the containing ratio of ortho position body in the 4-dodecylphenol, and because the residual quantity of unreacted ortho position body is below the 300ppm, thus good heat resistance, painted in the time of can suppressing moulding.
The residual quantity of unreacted long-chain monoalkyl phenol is preferably below the 300ppm in the present invention 3 the straight chain shape polycarbonate resin.
If below the residual quantity 300ppm, the amount of the bur in the time of then can suppressing injection molding on the mould can obtain to have the formed body of good appearance.
In addition, the present invention 3 straight chain shape polycarbonate resin is owing to use long-chain monoalkyl phenol as end-capping reagent, so have good flowability and because tone is good, so applicable to optical applications.
Adopt the present invention 4 manufacture method, the residual quantity of unreacted long-chain monoalkyl phenol can be below 300ppm in the straight chain shape polycarbonate resin.
Therefore, the amount of bur on mould in the time of can suppressing injection molding can obtain to have the formed body of good appearance.
The straight chain shape polycarbonate resin that employing the present invention's 4 manufacture method makes has aforesaid feature, simultaneously owing to use long-chain monoalkyl phenol as end-capping reagent, so have good flowability.
The residual quantity of unreacted long-chain monoalkyl phenol is preferably below the 300ppm in the straight chain shape polycarbonate resin that employing the present invention's 5 manufacture method makes.
If below the residual quantity 300ppm, the amount of bur on mould in the time of then can suppressing injection molding can obtain to have the formed body of good appearance.
In addition, the straight chain shape polycarbonate resin that employing the present invention's 5 method makes owing to use long-chain monoalkyl phenol as end-capping reagent, therefore has good flowability.
Polycarbonate resin of the present invention in not destroying the object of the invention scope, also can make it suitably to contain various additives as requested, for example, and oxidation inhibitor, brightening agent, releasing agent, fire retardant, dripping inhibitor, other inorganic fillers etc.
By in polycarbonate resin of the present invention, cooperating various additives, carry out mixingly can preparing constituent.
As cooperating and compounding process, the method that can directly use common resin combination to use is preferably used ribbon blender, is enjoyed the above multiple screw extruder of She Er mixing machine, Banbury, drum-type rotary drum, single screw rod or 2 screw rods, kneader etc. at a high speed.
Moreover melting temperature does not have particular determination, usually preferred 240~340 ℃ scope.
The polycarbonate resin composition that makes is like this adopted common forming method, and for example, injection moulding or compressed moulding method are carried out moulding, can make formed body.
Below, illustrate in greater detail the present invention by embodiment, but the present invention is not subjected to any qualification of these embodiment.
The physical property measurement method of<polycarbonate resin 〉
(1) viscosity number [VN], viscosity-average molecular weight [Mv]
Measure the specific viscosity η of the dichloromethane solution under 20 ℃ of the temperature Sp, calculate viscosity-average molecular weight [Mv] by following formula.
η sp/C=[η]×(1+0.28×η sp)
[η]=1.23×10 -5×Mv 0.83
Moreover C is polycarbonate resin lipid concentration [g/ liter], η Sp/ C is that reducing viscosity (viscosity number [VN]), [η] are limiting viscosities.
(2) Q value (yield point value)
Be under the melt viscosity that adopts overhead system flow velocity tester to measure, be illustrated under 280 ℃, the pressure of 15.7MPa from the effusive molten resin amount of the nozzle of 1mm φ * 10mmL that yield point value [Q value] increases with the reduction of melt viscosity with milliliters/second.
(3) mensuration of initial stage YI, Δ YI
1. initial stage YI
Make polycarbonate resin plate 3.0g be dissolved in methylene dichloride 34.5g, use the quartz cell of optical length 57mm to adopt color measuring meter-SM-3 (ス ガ trier corporate system) to measure the YI (yellowness index) of this solution.
This measured value is YIa, asks YI with following formula.
YI=0.76(YIa-YI o)+0.11
(in the formula, YI oBe the YI value of methylene dichloride)
②ΔYI
Weighing polycarbonate resin plate 3.0g puts into aluminum dish, under nitrogen environment, 340 ℃ the heating 30 minutes.
After the cooling, make it to be dissolved among the methylene dichloride 34.5g.
Remove by filter insoluble part, measuring this YI is YIb, calculates Δ YI by following formula.
ΔYI=0.76(YIb-YIa)
(4) mensuration of YIa, YIb
①YIa
Be that polycarbonate resin plate 3g is dissolved among the methylene dichloride 34.5g, this solution added the value of measuring in the silica glass system torch type pond of optical length 50mm, internal diameter 25mm.
②YIb
Be that methylene dichloride is added to the YI value of measuring in the above-mentioned silica glass rounding cartridge type pond.
Calculate YIs by following formula.
YIs=(YIa-YIb)×0.76+0.11 (IV)
(5) Tg (second-order transition temperature)
Use パ one キ Application エ Le マ one corporate system DSC 7, measure by following order.
By 320 ℃/minute the 10mg sample is warmed up to 260 ℃ from 50 ℃, kept 5 minutes, cool to 50 ℃ by 320 ℃/minute then, kept 5 minutes, be warmed up to 260 ℃ by 40 ℃/minute more at last, measure second-order transition temperature.
The preparation of Production Example 1[long-chain monoalkyl phenol (a)]
In reactor, press the mixture [ratio of components (mole %) of phenol 300 mass parts and 1-eicosylene, 1-two dodecylenes and 1-tetracosene with plate washer and agitating vane; 53.3: 40.2: 6.5] 105 mass parts [phenol/alkene=9/1 (mol ratio)] and as the strongly-acid polystyrene sulfonic acid cation resin of catalyzer (Amberlyst 15; Rohm and Haas Company's system) charge ratio of 10.5 mass parts, add reaction raw materials and catalyzer, 120 ℃, stir and carry out reaction in 3 hours.
After reaction finishes, adopt underpressure distillation to make with extra care, obtain long-chain monoalkyl phenol (a).The average carbon number of the alkyl of this long-chain monoalkyl phenol (a) that makes is 21
The preparation of Production Example 2[long-chain monoalkyl phenol (b)]
In the preparation of aforesaid long-chain monoalkyl phenol (a), except using 1-two dodecylenes 110 mass parts (phenol/alkene=9/1 (mol ratio)) as alkene, and catalytic amount is outside 11 mass parts, and other similarly make long-chain monoalkyl phenol (b).
The average carbon number of the alkyl of this long-chain monoalkyl phenol (b) that makes is 22.
Among the following embodiment 1~6 and comparative example 1~12, the long-chain monoalkyl phenol (a) that uses above-mentioned Production Example 1~2 to make reaches (b).
Embodiment 1
(1) preparation of polycarbonate oligomer
Dihydroxyphenyl propane is dissolved in the aqueous sodium hydroxide solution of 5.6 quality %, and making bisphenol A concentration is 13.5 quality %, the aqueous sodium hydroxide solution of preparation dihydroxyphenyl propane.
Adopt 41 liters/hour of the aqueous sodium hydroxide solutions of this dihydroxyphenyl propane, the flow of the flow that methylene dichloride is 15 liters/hour, phosgene 4.0kg/ hour is supplied with the tube-type reactor of internal diameter 6mm, pipe range 30m continuously.
Tube-type reactor has the chuck part, feeds cold water in chuck, and the temperature of reaction solution is remained on below 40 ℃.
The effusive reaction solution of tube-type reactor is imported the tank reactor of the internal volume 40 liter band plate washers with swept-back wing continuously, in this reactor, add 2.8 liters/hour of aqueous sodium hydroxide solutions, 0.07 liter/hour of the aqueous sodium hydroxide solution of 25 quality %, 17 liters/hour in the water of dihydroxyphenyl propane again, the triethylamine aqueous solution of 1 quality % reacts for 0.32 liter/hour.
Extract the reaction solution that overflows from tank reactor continuously out, remove water, get the methylene dichloride phase by standing separation.
The concentration of the polycarbonate oligomer that makes like this is the 355g/ liter, and chloroformic acid ester group concentration is 0.80 mol.
(2) polymerization process of polycarbonate oligomer
To having plate washer, 2 of oar formula paddles and cooling with adding 5.4 milliliters of 12 liters of above-mentioned oligomer solutions, 9.3 liters of methylene dichloride, long-chain monoalkyl phenol (a) 352g, triethylamine in the 50 liter tank reactors of chuck, under agitation in reactor, add the aqueous sodium hydroxide solution 1720g that is dissolved with V-Brite B 6.4 quality %, carry out reaction in 20 minutes.
Then, add the aqueous sodium hydroxide solution (make dihydroxyphenyl propane 992g be dissolved in 9.78 premium on currency solution the aqueous solution in the aqueous solution of NaOH 580g, V-Brite B 1.98g is arranged) of dihydroxyphenyl propane, adopt 300rpm to carry out 40 minutes polyreactions while stirring.
Then, add 10 liters of the methylene dichloride of dilution usefulness after, become to contain the organic phase of polycarbonate resin and contain the excessive dihydroxyphenyl propane and the water of sodium hydroxide by standing separation, extract organic phase out from reactor lower part and separate.
(3) washing procedure
The dichloromethane solution of the polycarbonate resin that makes like this, sequentially adopt the 0.03 mol aqueous sodium hydroxide solution of 15 volume %, the hydrochloric acid of 0.2 regulation to wash with respect to this solution, the specific conductivity of using pure water to wash repeatedly up to washing back aqueous phase then is below the 0.1 μ S/m.
(4) sheet chemical industry preface
The dichloromethane solution of the polycarbonate resin after washing finished is concentrated to after 150~170g/ rises, and adds the normal hexane of 20 volume %, filters the precipitation that generates, and drying makes polycarbonate resin plate.
To the amount of this resin sheet mensuration viscosity-average molecular weight, Q value, unreacted long-chain monoalkyl phenol, the results are shown in the 1st table.
Embodiment 2
In embodiment 1, except using long-chain monoalkyl phenol (b) 365g replacement long-chain monoalkyl phenol (a), other similarly prepare polycarbonate resin plate.
Measure the amount of viscosity-average molecular weight, Q value, unreacted long-chain monoalkyl phenol similarly to Example 1.The results are shown in the 1st table.
Comparative example 1
Among the embodiment 1, except using lauroyl chloride 198g replacement long-chain monoalkyl phenol (a), other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin similarly to Example 1.The results are shown in the 1st table.
Comparative example 2
In embodiment 1, except using palmityl chloride 249g replacement long-chain monoalkyl phenol (a), other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin similarly to Example 1.The results are shown in the 1st table.
Comparative example 3
Among the embodiment 1, except using stearyl chloride 270g replacement long-chain monoalkyl phenol (a), other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin similarly to Example 1.The results are shown in the 1st table.
Comparative example 4
Among the embodiment 1, except using 18 octyl phenol 314g replacement long-chain monoalkyl phenol (a), other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin similarly to Example 1.The results are shown in the 1st table.
Embodiment 3
Among the embodiment 1, except the addition of long-chain monoalkyl phenol (a) was 292g, other similarly prepared polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin, the amount of unreacted long-chain monoalkyl phenol similarly to Example 1.The results are shown in the 1st table.
Embodiment 4
Among the embodiment 1, except using long-chain monoalkyl phenol (b) 303g replacement long-chain monoalkyl phenol (a), other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin, the amount of unreacted long-chain monoalkyl phenol similarly to Example 1.The results are shown in the 1st table.
Comparative example 5
Among the embodiment 1, except using P-hydroxybenzoic acid dodecane ester 234g replacement long-chain monoalkyl phenol (a), other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin similarly to Example 1.The results are shown in the 1st table.
Comparative example 6
Among the embodiment 1, except using palmityl chloride 210g replacement long-chain monoalkyl phenol (a), other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin similarly to Example 1.The results are shown in the 1st table.
Comparative example 7
Among the embodiment 1, except using 18 octyl phenol 262g replacement long-chain monoalkyl phenol (a), other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin similarly to Example 1.The results are shown in the 1st table.
Embodiment 5
Among the embodiment 1, except the addition of long-chain monoalkyl phenol (a) was 266g, other similarly prepared polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin, the amount of unreacted long-chain monoalkyl phenol similarly to Example 1.The results are shown in the 1st table.
Embodiment 6
Among the embodiment 1, except using long-chain monoalkyl phenol (b) 276g replacement long-chain monoalkyl phenol (a), other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin, the amount of unreacted long-chain monoalkyl phenol similarly to Example 1.The results are shown in the 1st table.
Comparative example 8
Among the embodiment 1, except using lauroyl chloride 146g replacement long-chain monoalkyl phenol (a), other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin similarly to Example 1.The results are shown in the 1st table.
Comparative example 9
Among the embodiment 1, except using palmityl chloride 184g replacement long-chain monoalkyl phenol (a), other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin similarly to Example 1.The results are shown in the 1st table.
Comparative example 10
Among the embodiment 1, except using stearyl chloride 199g replacement long-chain monoalkyl phenol (a), other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin similarly to Example 1.The results are shown in the 1st table.
Comparative example 11
Among the embodiment 1, after adding normal hexane, do not filter and direct concentrating, the gained solid part is carried out outside the drying, other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin, the amount of unreacted long-chain monoalkyl phenol similarly to Example 1.The results are shown in the 1st table.
Comparative example 12
In the comparative example 1, except after adding normal hexane, do not filter and directly concentrate, the gained solid part is carried out outside the drying, other similarly prepare polycarbonate resin plate.
Measure viscosity-average molecular weight, the Q value of resin, the amount of unreacted long-chain monoalkyl phenol similarly to Example 1.The results are shown in the 1st table.
During the injection molding of<polycarbonate resin to the adhesion of mould
In the polycarbonate resin plate that embodiment 1~6 and comparative example 11,12 make, adding phosphorus is oxidation inhibitor (Irgafos 168) [Chiba speciality chemical corporate system, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester] 50ppm, makes pellet 270 ℃ of granulations.
Use 45 tons of injection moulding machines (Toshiba Machine Co. Ltd's system, IS45PV), with the gained pellet at barrel temperature: 320 ℃, die temperature: carry out injection molding under 50 ℃, the condition of injection pressure: 7.84MPa, inject the matrix band that makes the thick 3mm of 35 * 25mm for 300 times continuously.
Then, the visual observation mould has or not bur.
The 1st table
The average carbon number of alkyl Viscosity-average molecular weight Q value (cc/sec) Alkylphenol unreacted amount (ppm)
Embodiment 1 21 14800 98×10 -2 100>
Embodiment 2 22 14900 104×10 -2 100>
Comparative example 1 11 15100 68×10 -2 -
Comparative example 2 15 14800 72×10 -2 -
Comparative example 3 17 14500 76×10 -2 -
Comparative example 4 18 14500 78×10 -2 -
Embodiment 3 21 17300 50×10 -2 100>
Embodiment 4 22 17300 59×10 -2 100>
Comparative example 5 12 17400 32×10 -2 -
Comparative example 6 15 17100 34×10 -2 -
Comparative example 7 18 17300 37×10 -2 -
Embodiment 5 21 18700 26×10 -2 100>
Embodiment 6 22 19000 30×10 -2 100>
Comparative example 8 11 19500 14×10 -2 -
Comparative example 9 15 19500 18×10 -2 -
Comparative example 10 17 19300 21×10 -2 -
Comparative example 11 21 14800 107×10 -2 340
Comparative example 12 11 15100 68×10 -2 350
<unreacted long-chain monoalkyl phenol (a) and mensuration (b) 〉
Polycarbonate resin plate 2g is dissolved in 50 milliliters of the methylene dichloride, adds acetone then bit by bit and 250 milliliters polymkeric substance is separated out.
Behind this system suction filtration, concentrate, use 20 milliliters of normal hexanes with behind this concentrated solution constant volume, adopt gas-chromatography (GC) to carry out quantitatively.
Condition determination is as follows.
GC body: HEWLETT PACKARD HP 6890
Spectrum post: J﹠amp; W SCIENTIFIC corporate system, DB-1 (15m * 0.53mm φ * 0.15 μ m)
Temperature curve: 40 ℃/keep 1 minute → 40 ℃ of/minute → 120 ℃/maintenance 7 minutes → 10 minutes that heats up/intensifications to keep 5 minutes for → 330 ℃
Carrier gas: helium (40cm 3/ second, constant flow rate)
Inject: do not decompose (2.0 μ l)
Implantation temperature: 350 ℃
FID Detector temperature: 350 ℃
By above mensuration, at the polycarbonate resin plate that uses embodiment 1~6 to make during as the pellet of raw material, there is not bur on the mould, and the outward appearance of moulding product is good, and when using polycarbonate resin plate that comparative example 11,12 makes as the pellet of raw material, the buttery bur is arranged on the mould, and moulding product surfaces is dapple can not present even and level and smooth outward appearance.
Production Example 3 and 4 (manufacturing of PDDP-(c) and PDDP-(d))
In the 260 liter reactive tanks that have whipping appts, add the tetrameric dodecylene 32kg of propylene, phenol 70kg and as the ガ レ オ Na イ ト #136[marshy land chemical industrial company system of catalyzer] 7kg, under nitrogen environment atmosphere, 145 ℃ are reacted while stirring.
After reaction finishes, behind the filtering separation catalyzer, adopt underpressure distillation from the lightweight of phenol etc. divide and heavy such as dioxane matrix divide fractionation make with extra care out 4-dodecylphenol (PDDP).
Result to purified PDDP employing gas chromatographic analysis does not detect the dioxane matrix fully.
In addition, following embodiment 8 and 9 and the PDDP that uses of comparative example 14, longer than common alkylated reaction time and isomerization reaction time, and carry out the containing ratio of precise distillation reduction impurity ortho position body.
Like this, obtain the PDDP-(c) of 1.5 moles of % of ortho position body containing ratio and the PDDP-(d) of 0.8 mole of %.
Embodiment 7
(1) preparation section of polycarbonate oligomer
Dihydroxyphenyl propane is dissolved in the 5.6 weight % aqueous sodium hydroxide solutions, and making bisphenol A concentration is 13.5 weight %, the aqueous sodium hydroxide solution of preparation dihydroxyphenyl propane.
In the tube-type reactor of internal diameter 6mm, pipe range 30m, feed the flow of 15 liters/hour of 40 liters/hour of the aqueous sodium hydroxide solutions of above-mentioned dihydroxyphenyl propane and methylene dichloride continuously, feed phosgene 4.0kg/ hour flow simultaneously continuously.
Tube-type reactor has the chuck part, and the feeding water coolant remains on the temperature of reaction solution below 40 ℃ in chuck.
Be imported into the band plate washer tank reactor of internal volume 40 liters that have swept-back wing continuously from the effusive reaction solution of tube-type reactor, to 2.15 liters/hour of the dichloromethane solutions of PDDP-(a) (oiling ス ケ ネ Network デ イ corporate system) the 7.0 weight % of this reactor supply flow rate be dihydroxyphenyl propane 17 liters/hour in 2.8 liters/hour of aqueous sodium hydroxide solutions, 25 0.07 liter/hour of weight % aqueous sodium hydroxide solution, water, 1 0.64 liter/hour of weight % triethylamine aqueous solution and 2.7 moles of % of ortho position body containing ratio, react again at 29~32 ℃.
Leave standstill by from this tank reactor, extracting reaction solution continuously out, separate and remove water, get the methylene dichloride phase.
The polycarbonate oligomer strength of solution that makes like this is the 323g/ liter, and carbonochloridic acid ester group concentration is 0.69 mol.
(2) polymerization process of polycarbonate oligomer
3.84 milliliters of adding above-mentioned (1) operation makes in having plate washer, 2 of oar formula paddles and cooling off with 50 liter tank reactors of chuck 6.15 liters of 10 liters of oligomer solutions, methylene dichloride, PDDP-(a) 76.3g, triethylamines, under agitation in reactor, add the 6.4 weight % aqueous sodium hydroxide solution 1720g that are dissolved with V-Brite B 262mg again, carry out reaction in 20 minutes.
In this reaction process, be no more than 20 ℃ by the cooling control reaction temperature.
Then, the aqueous sodium hydroxide solution that adds dihydroxyphenyl propane makes dihydroxyphenyl propane 660g be dissolved in the aqueous solution in the aqueous solution that is dissolved with NaOH 331g, V-Brite B 1.32g in 4.84 liters in water).Adopt the stirring of 300rpm limit, limit 25~32 ℃ of polymerizations 40 minutes.
After in the polymer fluid that makes like this, adding 10 liters of methylene dichloride, the organic phase that becomes to contain polycarbonate resin by standing separation with contain excessive dihydroxyphenyl propane and the water of NaOH, extract organic phase out from reactor lower part and separate.
(3) washing procedure
The dichloromethane solution of the polycarbonate resin that above-mentioned (2) operation is made, sequentially adopt the 0.03 mol NaOH aqueous solution, the 0.2 mol hydrochloric acid of 15 volume % to wash with respect to this solution, with pure water washing 2 times, confirm that the specific conductivity of washing back water is below the 0.01 μ S/m then.
(4) sheet chemical industry preface
The dichloromethane solution of the polycarbonate resin after above-mentioned (3) operation carrying out washing treatment is concentrated to after 150~170g/ rises, adds normal hexane 20 volume %, filter the precipitation that generates, the resin sheet that makes under reduced pressure 100 ℃ carry out drying treatment.
Have or not bur to be shown in the 2nd table during the performance of polycarbonate resin and injection molding on the mould.
Embodiment 8
Among the embodiment 7, except the PDDP-(c) that uses 1.5 moles of % of ortho position body containing ratio replaced PDDP-(a), other were implemented similarly to Example 7.
Have or not bur to be shown in the 2nd table during the performance of polycarbonate resin and injection molding on the mould.
Embodiment 9
Among the embodiment 7, except the PDDP-(d) that uses 0.8 mole of % of ortho position body containing ratio replaced PDDP-(a), other were implemented similarly to Example 7.
Have or not bur to be shown in the 2nd table during the performance of polycarbonate resin and injection molding on the mould.
Comparative example 13
Among the embodiment 7, except the PDDP-(b) (oiling ス ケ ネ Network デ イ corporate system) that uses 3.5 moles of % of ortho position body containing ratio replaces PDDP-(a) and does not add normal hexane and direct concentrating in sheet chemical industry preface, the solid part that makes is carried out beyond the drying treatment, and other are implemented similarly to Example 7.Have or not bur to be shown in the 2nd table during the performance of polycarbonate resin and injection molding on the mould.
Comparative example 14
Among the embodiment 7, except PDDP-(d) the replacement PDDP-(a) of 0.8 mole of % of use ortho position body containing ratio and in sheet chemical industry preface, do not add normal hexane and directly concentrate, the solid part that makes is carried out beyond the drying treatment, other are implemented similarly to Example 7.
Have or not bur to be shown in the 2nd table during the performance of polycarbonate resin and injection molding on the mould.
Comparative example 15
In embodiment 7 in the preparation section of the polycarbonate oligomer of (1), the 7.0 weight % dichloromethane solutions that replace PDDP-(a) except the 24 weight % dichloromethane solutions that use PTBP (oiling ス ケ ネ Network デ イ corporate system), and in the polymerization process of (2) polycarbonate oligomer, use PTBP 44.0g to replace PDDP-(a) 76.3g, and in the sheet chemical industry preface of (4), do not add normal hexane, directly concentrate beyond, other are implemented similarly to Example 7.
Have or not bur to be shown in the 2nd table during the performance of polycarbonate resin and injection molding on the mould.
During the injection molding of<polycarbonate resin to the adhesion of mould
Adding phosphorus in polycarbonate resin plate is oxidation inhibitor Irgafos168[Chiba speciality chemical corporate system, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester] 50ppm, make pellet 270 ℃ of granulations.
Use 45 tons of injection moulding machines (Toshiba Machine Co. Ltd's system, IS45PV), at barrel temperature: 320 ℃, die temperature: under 50 ℃, the condition of injection pressure: 7.84MPa, the pellet that makes is carried out injection molding, inject continuously 300 times, make the matrix band of the thick 3mm of 35 * 25mm.
Then, the visual observation mould has or not bur.
The 2nd table-1
Embodiment 7 Embodiment 8 Embodiment 9
End-capping reagent Kind PDDP-(a) PDDP-(c) PDDP-(d)
Ortho position body burden (mole %) 2.7 1.5 0.8
Polycarbonate Viscosity number [VN] 47.5 47.5 47.5
Viscosity-average molecular weight [MV] 18400 18400 18400
Unreacted 4-dodecylphenol (ppm) 120 <100 <100
Q value (yield point value) 16 16 16
Initial stage YI 1.5 1.5 1.4
ΔYI 0.7 0.7 0.7
Adhesion to mould Do not have Do not have Do not have
The 2nd table-2
Comparative example 13 Comparative example 14 Comparative example 15
End-capping reagent Kind PDDP-(b) PDDP-(d) PTBP
Ortho position body burden (mole %) 3.5 0.8 -
Polycarbonate Viscosity number [VN] 47.5 47.5 47.5
Viscosity-average molecular weight [MV] 18400 18400 18500
Unreacted 4-dodecylphenol (ppm) 1100 400 <100*
Q value (yield point value) 16 16 11
Initial stage YI 1.7 1.5 1.3
ΔYI 1.1 0.7 0.3
Adhesion to mould Have Have Do not have
*: unreacted PTBP (ppm)
The mensuration of the amount of<unreacted adjacent 4-dodecylphenol 〉
After making resin sheet 2g be dissolved in 15 milliliters of the methylene dichloride, carry out redeposition for 25 milliliters, use chromatodisk (25P) to filter then, adopt liquid chromatography to carry out quantitatively with normal hexane.The condition determination of liquid chromatography such as following.
The spectrum post: Whatman Partisil 10 PAC (4.6 φ mm * 250mm)
Elutriant (1.0ml/ branch): octane-iso/2-propyl alcohol (98/2)+0.1 aceticanhydride is measured wavelength: 280nm
By the 2nd table as can be seen, the residual quantity of unreacted adjacent 4-dodecylphenol is all below 300ppm in the polycarbonate resin among the embodiment 7~9, and Δ YI value is little, is 0.7, and the Q value greatly, good fluidity, and do not have the formation of bur on the mould.
On the contrary, in the comparative example 13, the residual quantity of unreacted adjacent 4-dodecylphenol is many, and the formation of bur is arranged on the mould, and Δ YI is big.
In the comparative example 14, Δ YI is little, but the formation of bur is arranged on the mould, in the comparative example 15, and the less residue of unreacted PTBP, YI is also little for Δ, but the Q value is little, and mobile bad.
Production Example 5 (manufacturing of long-chain monoalkyl phenol AP-1)
In 260 liters of reactors that have whipping appts, add mixture (mol ratio 53.3: 40.2: 6.5) 57.3kg, the phenol 70kg of 1-eicosylene, 1-two dodecylenes and 1-tetracosene and as (ガ レ オ Na イ ト #136) (marshy land chemical industrial company system) 7kg of catalyzer, under nitrogen environment atmosphere, 145 ℃, carry out while stirring 80 minutes the reaction.
After reaction finishes, behind the filtering separation catalyzer, adopt underpressure distillation that the lightweight of phenol etc. is divided and the heavy fractionation of dioxane matrix etc., refining long-chain monoalkyl phenol AP-1.
To the result of purified AP-1 employing gas chromatographic analysis, the phenol amount is 500ppm, does not detect the dioxane matrix fully.In addition, adjacent, be 50: 48: 2 to the ratio of, a position body.
Moreover the average carbon number of alkyl is 21 among the AP-1.
Preserve this AP-1 by changing the shelf time, the APHA under obtaining 50 ℃ is respectively 10 AP-1-(a), 15 AP-1-(b) and 40 AP-1-(d).
In addition, by the underpressure distillation condition after changing catalyzer after reaction finished and filtering, the amount that obtains the dioxane matrix is 1.2%, APHA is 15 AP-1-(e).
Production Example 6 (manufacturing of long-chain monoalkyl phenol AP-2)
In the Production Example 5, except replace the mixture 57.3kg of 1-eicosylene, 1-two dodecylenes and 1-tetracosene with cetene 41.7kg, other and Production Example 5 are similarly reacted, refining long-chain monoalkyl phenol AP-2.
To the result of purified AP-2 employing gas chromatographic analysis, the phenol amount is 500ppm, does not detect the dioxane matrix fully.In addition, adjacent, be 51: 47: 2 to the ratio of, a position body.
Preserve this AP-2 by changing the shelf time, the APHA under obtaining 50 ℃ is respectively 10 AP-2-(a), reaches 40 AP-2-(b).
Production Example 7 (manufacturing of long-chain monoalkyl phenol AP-3)
In the Production Example 5, except the mixture 57.3kg that uses dodecylene 32.0kg replacement 1-eicosylene, 1-two dodecylenes and 1-tetracosene, other and Production Example 5 are similarly reacted, refining long-chain monoalkyl phenol AP-3.
To the result of purified AP-3 employing gas chromatographic analysis, the phenol amount is 500ppm, does not detect the dioxane matrix fully.In addition, adjacent, be 52: 46: 2 to the ratio of, a position body.
Preserve this AP-3 by changing the shelf time, obtain APHA 50 ℃ under and be respectively 10 AP-3-(a), reach 40 AP-3-(c).
Among the following embodiment 10~12 and comparative example 16~22, the long-chain monoalkyl phenol AP-1~AP-3 that uses above-mentioned Production Example 5~7 to make.
Embodiment 10
(1) preparation section of polycarbonate oligomer
In 5.6 weight % aqueous sodium hydroxide solutions, adding with respect to back dissolved dihydroxyphenyl propane is the V-Brite B of 2000ppm, and dihydroxyphenyl propane being dissolved in making bisphenol A concentration in this solution again is 13.5 weight %, the aqueous sodium hydroxide solution of preparation dihydroxyphenyl propane.
The absorbancy of this aqueous solution under 380nm is 0.030.
In the tube-type reactor of internal diameter 6mm, pipe range 30m, feed flow continuously and be 15 liters/hour of 40 liters/hour of the aqueous sodium hydroxide solutions of above-mentioned dihydroxyphenyl propane and methylene dichloride, feeding flow continuously simultaneously is phosgene 4.0kg/ hour.
Tube-type reactor has the chuck part, feeds water coolant to chuck, and the temperature of reaction solution is remained on below 40 ℃.
The effusive reaction solution of tube-type reactor is imported the tank reactor of the internal volume 40 liter band plate washers that have swept-back wing continuously, in this reactor, supply with the flow of 2.15 liters/hour of 10.3 weight % dichloromethane solutions of 17 liters/hour in 2.8 liters/hour of aqueous sodium hydroxide solutions, 25 0.07 liter/hour of weight % aqueous sodium hydroxide solution, water, 1 0.64 liter/hour of weight % triethylamine aqueous solution and the AP-1-(a) of dihydroxyphenyl propane again, react at 29~32 ℃.
Extract reaction solution continuously out from this tank reactor, remove water, gather the methylene dichloride phase by standing separation.The absorbancy of water under 380nm is 0.009.
The polycarbonate oligomer solution that makes like this, oligomer concentrations are the 323g/ liters, and carbonochloridic acid ester group concentration is 0.69 mol.
(2) polymerization process of polycarbonate oligomer
3.84 milliliters of adding above-mentioned (1) operation makes in having plate washer, 2 of oar type paddles and cooling off with 50 liter tank reactors of chuck 6.15 liters of 10 liters of oligomer solutions, methylene dichloride, AP-1-(a) 113g, triethylamines, under agitation add the 6.4 weight % aqueous sodium hydroxide solution 1720g that are dissolved with V-Brite B 226mg then, carry out reaction in 20 minutes.
In this reaction process, be no more than 20 ℃ (pre-polymerizations) by the cooling control reaction temperature.
In order to measure this moment water in the absorbancy of 380nm, get a part of reaction solution, by centrifugation water and organic phase, measuring water is 0.013 in the absorbancy of 380nm.
Then, add the aqueous sodium hydroxide solution (making dihydroxyphenyl propane 660g be dissolved in the aqueous solution in the aqueous solution that in 4.84 premium on currency, is dissolved with NaOH 331g, V-Brite B 1.32g) of dihydroxyphenyl propane, implement 1 hour polyreaction (post polymerization).
After in the polymer fluid that makes like this, adding 10 liters of methylene dichloride,, tell organic phase from reactor lower part and separate by leaving standstill, be separated into organic phase that contains polycarbonate resin and the water that contains excessive dihydroxyphenyl propane and NaOH.
At this moment, the absorbancy of water under 380nm is 0.007.
(3) washing procedure
The dichloromethane solution of the polycarbonate resin that above-mentioned (2) operation is made is with respect to this solution, sequentially adopt the 0.03 mol NaOH aqueous solution, the 0.2 mol hydrochloric acid of 15 volume % to wash.The specific conductivity of washing repeatedly up to washing back water with pure water is below the 0.01 μ S/m then.
(4) sheet chemical industry preface
The dichloromethane solution of the polycarbonate resin of the carrying out washing treatment that above-mentioned (3) operation is made concentrates, pulverizes, and under reduced pressure 110 ℃ of resin sheets with gained carry out drying treatment.
These results are shown in the 3rd table with the performance of polycarbonate resin.
Embodiment 11
In the preparation section except (1) polycarbonate oligomer among the embodiment 10, in the 10.3 weight % dichloromethane solutions of the 8.4 weight % dichloromethane solutions replacement AP-1-(a) of use AP-2-(a) and the polymerization process of (2) polycarbonate oligomer, use AP-2-(a) 92.6g to replace beyond AP-1-(a) 113g, other are implemented similarly to Example 10.
The result is shown in the 3rd table with the performance of polycarbonate resin.
Embodiment 12
In the preparation section except (1) polycarbonate oligomer among the embodiment 10, in the 10.3 weight % dichloromethane solutions of the 7.0 weight % dichloromethane solutions replacement AP-1-(a) of use AP-3-(a) and the polymerization process of (2) polycarbonate oligomer, use AP-3-(a) 76.3g to replace beyond AP-1-(a) 113g, other are implemented similarly to Example 10.
The result is shown in the 3rd table with the performance of polycarbonate resin.
Comparative example 16
Among the embodiment 10, except using AP-1-(e) replacement AP-1-(a), other are implemented similarly to Example 10.
The result is shown in the 3rd table with the performance of polycarbonate resin.
Comparative example 17
In the polymerization process of the polycarbonate oligomer in the comparative example 16, except using the 6.4 weight % aqueous sodium hydroxide solution 1720g do not add V-Brite B to replace being dissolved with the 6.4 weight % aqueous sodium hydroxide solution 1720g of V-Brite B 226mg, other and comparative example 16 are similarly implemented.
The result is shown in the 3rd table with the performance of polycarbonate resin.
Comparative example 18
Among the embodiment 10, except using AP-1-(d) replacement AP-1-(a), other are implemented similarly to Example 10.
The result is shown in the 3rd table with the performance of polycarbonate resin.
Comparative example 19
Embodiment 11, and except using AP-2-(b) replacement AP-2-(a), other are implemented similarly to Example 11.
The result is shown in the 3rd table with the performance of polycarbonate resin.
Comparative example 20
Among the embodiment 12, replace the AP-3-(a) except using AP-3-(c), other with
Embodiment 12 similarly implements.
The result is shown in the 3rd table with the performance of polycarbonate resin.
Comparative example 21
Among the embodiment 12, (commercially available product: the propylene tetramer and phenol addition make except using PDDP, APHA under 50 ℃ is 10, the mol ratio of ortho position, contraposition, a position body is 0.8: 99.2 :-, do not detect the dioxane matrix), and use during sheet to filter behind the hexane redeposition to make beyond the resin sheet, other are implemented similarly to Example 12.
The result is shown in the 3rd table with the performance of polycarbonate resin.
Comparative example 22
In the preparation section except (1) polycarbonate oligomer among the embodiment 10, in the polymerization process of the 10.3 weight % dichloromethane solutions of the 24 weight % dichloromethane solutions replacement AP-1-(a) of use PTBP (commercially available product: the not enough 10ppm of dioxane matrix, the not enough 10ppm of ortho position body) and the polycarbonate oligomer of (2), use PTBP 43.7g to replace beyond AP-1-(a) 113g, other are implemented similarly to Example 10.
The result is shown in the 3rd table with the performance of polycarbonate resin.
The 3rd table-1
Embodiment Comparative example
10 11 12 16 17
End-capping reagent Kind AP-1-(a) AP-2-(a) AP-3-(a) AP-1-(e) AP-1-(e)
APHA 10 10 10 15 15
The absorbancy of water [380nm] behind the pre-polymerization 0.013 0.012 0.013 0.012 0.004
The absorbancy of water [380nm] behind the post polymerization 0.007 0.006 0.017 0.006 0.004
The performance of polycarbonate Unreacted (ppm) 100> 100> 100> 100> 100>
YIs 0.6 0.7 0.7 1.4 2.2
YIp 1.3 1.3 1.3 2.0 4.0
The Q value 29 21 16 28 29
VN 47.5 47.7 47.7 47.5 47.5
Mv 18400 18500 18500 18400 18400
Unreacted: the residual quantity of end-capping reagent
The 3rd table-2
Comparative example
18 19 20 21 22
End-capping reagent Kind AP-1-(d) AP-2-(b) AP-3-(c) PDDP PTBP
APHA 40 40 40 10 -
The absorbancy of water [380nm] behind the pre-polymerization 0.014 0.013 0.012 0.013 0.011
The absorbancy of water [380nm] behind the post polymerization 0.007 0.006 0.007 0.007 0.006
The performance of polycarbonate Unreacted (ppm) 100> 100> 100> 100> 100>
YIs 1.2 1.2 1.2 1.5 0.7
YIp 1.5 1.6 1.6 1.7 1.3
The Q value 28 21 16 16 11
VN 47.5 47.7 47.7 47.5 47.7
Mv 18400 18500 18500 18400 18500
Unreacted: the residual quantity of end-capping reagent
YIs, YIp: the value that adopts the method described in the specification sheets to measure.
The mensuration of<unreacted long-chain monoalkyl phenol AP-1~AP-3 〉
Accurately measure 15 milliliters of the polycarbonate resin solutions of carrying out washing treatment, in this solution, add 25 milliliters of hexanes and make the component of polymer precipitation, use chromatodisk (25P) filtering supernatant, carry out gas chromatographic analysis, the amount of the chain monoalkyl phenol of rectificating.
By the amount of this long-chain monoalkyl phenol with measure the polycarbonate resin lipid concentration of employed polycarbonate resin solution, calculate the amount of unreacted long-chain monoalkyl phenol in the polycarbonate resin.
In addition, the condition of gas-chromatography such as following.
GC body: HEWLETT PACKARD HP 6890
Spectrum post: J﹠amp; W SCIENTIFIC system, DB-1 (15m * 0.53mm φ * 0.15 μ m)
Temperature curve: 150 ℃/keep 2 minutes → 20 ℃/minute to heat up → 360 ℃
Carrier gas: He (40cm/ second, constant flow rate)
Inject: do not decompose (1.0 microlitre)
Implantation temperature: 175 ℃
FID Detector temperature: 350 ℃
Find out the polycarbonate resin that embodiment makes by the 3rd table, having with PTBP is the tone that the polycarbonate resin of end group is equal to mutually, and mobile is that the polycarbonate resin of end group is good than PTBP also.
Production Example 8 (manufacturing of long-chain monoalkyl phenol AP-4)
In the Production Example 5, except the mixture 57.3kg that uses 1-two dodecylene 78.3kg replacement 1-eicosylene, 1-two dodecylenes and 1-tetracosene, other and Production Example 5 are similarly reacted, refining long-chain monoalkyl phenol AP-4.
To the result of purified AP-4 employing gas chromatographic analysis, the phenol amount is 500ppm, does not detect the dioxane matrix fully.
In addition, form and aspect are to be 15 with APHA, and are adjacent, be 50: 48: 2 to the ratio of, a position body with mol ratio.
Following embodiment 13~17 and comparative example 23~27, long-chain monoalkyl phenol AP-1 and AP-4 that above-mentioned Production Example 5 and 8 is made.
Embodiment 13
(1) preparation section of polycarbonate oligomer
Dihydroxyphenyl propane is dissolved in the 5.6 weight % aqueous sodium hydroxide solutions, and making bisphenol A concentration is 13.5 weight %, the aqueous sodium hydroxide solution of preparation dihydroxyphenyl propane.
In the tube-type reactor of internal diameter 6mm, pipe range 30m, feed 15 liters/hour of 40 liters/hour of the aqueous sodium hydroxide solutions of above-mentioned dihydroxyphenyl propane and methylene dichloride by flow continuously, press flow feeding phosgene simultaneously continuously 4.0kg/ hour.Tube-type reactor has the chuck part, and the feeding water coolant remains on the temperature of reaction solution below 40 ℃ in chuck.
The effusive reaction solution of tube-type reactor is imported the band plate washer tank reactor of internal volume 40 liters that have swept-back wing continuously, again in this reactor, supply with 2.15 liters/hour of the 10.3 weight % dichloromethane solutions of the AP-1-(a) that 17 liters/hour in 2.8 liters/hour of aqueous onium hydroxide solutions, 25 0.07 liter/hour of weight % aqueous sodium hydroxide solution, water, 1 0.64 liter/hour of weight % triethylamine aqueous solution and the Production Example 5 of dihydroxyphenyl propane make by flow, react at 29~32 ℃.
Extract reaction solution out from this tank reactor continuously, remove water, tell the methylene dichloride phase by standing separation.
The polycarbonate oligomer solution that makes like this, oligomer concentrations are the 323g/ liters, and chloroformic acid ester group concentration is 0.69 mol.
(2) polymerization process of polycarbonate oligomer
1. prepolymerization
To having 4 piece baffles, 2 oar type paddles and cooling off with in the 50 liter tank reactors of chuck, add 10 liters of oligomer solutions, 6.15 liters of methylene dichloride that above-mentioned (1) operation makes, be cooled to 5 ℃.
Then, 3.84 milliliters of AP-1-(a) 140g, triethylamines that adding Production Example 5 makes, again the 6.4 weight % aqueous sodium hydroxide solution 1720g that are dissolved with V-Brite B 226mg are cooled to 7 ℃ the aqueous solution and under agitation add reactor to, the limit is controlled at 10~12 ℃ with temperature of reaction, and reaction in 20 minutes is carried out on the limit.
2. this polymerization
Then, add dihydroxyphenyl propane aqueous sodium hydroxide solution (making dihydroxyphenyl propane 660g be dissolved in the aqueous solution in the aqueous solution that in 4.84 premium on currency, is dissolved with NaOH 331g, V-Brite B 1.32g), adopt that stir on the 300rpm limit, 40 minutes polyreactions are implemented at 25~32 ℃ in the limit.
(3) washing procedure
After in the reaction solution that above-mentioned (2) operation makes, adding 10 liters of methylene dichloride, stirs and make it to leave standstill after 20 minutes, be separated into the organic phase that contains polycarbonate resin and contain excessive dihydroxyphenyl propane and the water of NaOH, tell organic phase from reactor lower part and separate.
Dichloromethane solution with this polycarbonate resin, after sequentially washing with respect to this solution with the hydrochloric acid of the NaOH aqueous solution of 0.03 mol of 15 volume %, 0.2 mol, with pure water washing 2 times, confirm that the specific conductivity of washing back water is below the 0.01 μ S/m.
(4) sheet chemical industry preface
The dichloromethane solution of the polycarbonate resin that above-mentioned (3) operation is made concentrates, pulverizes, and under reduced pressure 110 ℃ are carried out drying treatment with the resin sheet that makes.
The performance of reaction conditions and the polycarbonate resin that makes is shown in the 4th table.
Embodiment 14
Among the embodiment 13, except prepolymerized temperature of reaction in (2) operation is controlled at 15~17 ℃, other are implemented similarly to Example 13.
The performance of reaction conditions and the polycarbonate resin that makes is shown in the 4th table.
Embodiment 15
Among the embodiment 13, except prepolymerized temperature of reaction in (2) operation is controlled at 20~22 ℃, other are implemented similarly to Example 13.
The performance of reaction conditions and the polycarbonate resin that makes is shown in the 4th table.
Embodiment 16
Among the embodiment 13, except the 10.7 weight % dichloromethane solutions that use the AP-4 that Production Example 8 makes replace AP-1 (a) 10.3 weight % dichloromethane solutions in (1) operation, and, beyond AP-(a) 140g in AP-4 replacement (2) operation of use 144g, other are implemented similarly to Example 13.
The performance of reaction conditions and the polycarbonate resin that makes is shown in the 4th table.
Embodiment 17
Among the embodiment 13, except the addition with the triethylamine in the prepolymerization in (2) operation changes over 5.76 milliliters, other are implemented similarly to Example 13.
The performance of reaction conditions and the polycarbonate resin that makes is shown in the 4th table.
Comparative example 23
To having 4 piece baffles, 2 oar type paddles and cool off, 3.84 milliliters of 6.15 liters of 10 liters of oligomer solutions, the methylene dichloride of adding embodiment 13 (1) preparations, AP-1 (a) 140g, the triethylamines that Production Example 5 makes with in the 50 liter tank reactors of chuck.
Then, under agitation add the aqueous sodium hydroxide solution (making dihydroxyphenyl propane 708g be dissolved in the aqueous solution in the aqueous solution that is dissolved with NaOH 414g, V-Brite B 1.42g in 6.05 premium on currency) of dihydroxyphenyl propane, adopt the stirring of 300rpm limit, limit control reaction temperature to be no more than 32 ℃, implement 60 minutes polyreactions at 25~32 ℃.
Then, implement washing procedure and sheet chemical industry preface similarly to Example 13.
The performance of reaction conditions and the polycarbonate resin that makes is shown in the 4th table.
Comparative example 24
To having 4 piece baffles, 2 oar type paddles and cooling off with in the 50 liter tank reactors of chuck, 6.15 liters of 10 liters of the oligomer solutions of adding embodiment 13 (1) preparations and methylene dichloride are cooled to 5 ℃ with solution.Then, add 3.84 milliliters of AP-1 (a) 140g that Production Example 5 makes and triethylamines.
Then, under agitation add the aqueous sodium hydroxide solution (making dihydroxyphenyl propane 708g be dissolved in the aqueous solution in the aqueous solution that is dissolved with NaOH 414g, V-Brite B 1.42g in 6.05 premium on currency) of the dihydroxyphenyl propane be cooled to 10 ℃, adopt the 300rpm limit to stir, 90 minutes polyreactions are implemented at 10~17 ℃ in the limit.
Then, implement washing procedure and sheet chemical industry preface similarly to Example 13.
The performance of reaction conditions and the polycarbonate resin that makes is shown in the 4th table.
Comparative example 25
Among the embodiment 13, except prepolymerized temperature of reaction in (2) operation is controlled at 28~30 ℃, other are implemented similarly to Example 13.
The performance of reaction conditions and the polycarbonate resin that makes is shown in the 4th table.
Comparative example 26
In the comparative example 25, except the AP-4 that uses 144g replaced AP-1 (a) 140g, other and comparative example 25 were similarly implemented.
The performance of reaction conditions and the polycarbonate resin that makes is shown in the 4th table.
Comparative example 27
Among the embodiment 13, when the interpolation of the methylene dichloride that adds when making prepolymerization in (2) operation changes the beginning of post polymerization into period, and pass through at stylish adding 3 premium on currency of prepolymerization, beyond reacting under the oil droplet dispersion state in water in prepolymerization, other are implemented similarly to Example 13.
The performance of reaction conditions and the polycarbonate resin that makes is shown in the 4th table.
During the injection molding of<polycarbonate resin to the adhesion of mould
In the polycarbonate resin plate that embodiment 13~17 and comparative example 23~27 make, add リ ケ マ one Le S-100A[reason and grind the VITAMIN corporate system, glyceryl monostearate] 100ppm (weight), (Irgafos168) [Chiba speciality chemical corporate system, tricresyl phosphite (2,4-two uncles base phenyl) ester] 50ppm (weight), make pellet 270 ℃ of granulations.
Each pellet that use makes is injected after 300 injection molding makes the formed body of 35 * 25 * 3mm continuously, and the visual observation mould has or not the outward appearance of bur and formed body.The results are shown in the 4th table.
Moreover, injection molding condition such as following.
Shaper: the IS45PV of Toshiba
Grain tube temperature: 320 ℃
Die temperature: 50 ℃
Injection pressure: 8MPa
The 4th table-1
Embodiment
13 14 15 16 17
The kind of end-capping reagent AP-1(a) AP-1(a) AP-1(a) AP-4 AP-1(a)
Prepolymerization Polymerization temperature (℃) 10~12 15~17 20~22 15~17 15~17
The TEA/CF mol ratio 0.004 0.004 0.004 0.004 0.006
The phase state W/O W/O W/O W/O W/O
This polymerization temperature (℃) 25~32 25~32 25~32 25~32 25~32
Unreacted alkylphenol (ppm) 100> 100> 120 100> 100>
Polycarbonate Viscosity number [VN] (viscosity-average molecular weight [Mv]) 45.1 (17400) 44.8 (17300) 44.1 (17000) 45.1 (17400) 44.8 (17300)
The Q value 50 50 52 57 50
Tg (℃) 119 118 118 119 118
Formed body Dirt settling to mould Do not have Do not have Do not have Do not have Do not have
Outward appearance Well Well Well Well Well
Viscosity number [VN]=reducing viscosity [η Sp/ c]
TEA/CF: triethylamine/carbonochloridic acid ester group
The 4th table-2
Comparative example
23 24 25 26 27
The kind of end-capping reagent AP-1(a) AP-1(a) AP-1(a) AP-4 AP-1(a)
Prepolymerization Polymerization temperature (℃) - - 28~30 28~30 15~17
The TEA/CF mol ratio - - 0.004 0.004 0.004
The phase state - - W/O W/O O/W
This polymerization temperature (℃) 25~32 10~17 25~32 25~32 25~32
Unreacted alkylphenol (ppm) 550 470 330 330 630
Polycarbonate Viscosity number [VN] (viscosity-average molecular weight [Mv]) 44.3 (17100) 44.4 (17100) 44.8 (17300) 44.9 (17300) 44.1 (17000)
The Q value 52 52 51 57 53
Tg (℃) 118 118 118 118 118
Formed body Dirt settling to mould Oily matter is arranged Oily matter is arranged Oily matter is arranged Oily matter is arranged Oily matter is arranged
Outward appearance The surface is dapple The surface is dapple The surface is dapple The surface is dapple The surface is dapple
Viscosity number [VN]=reducing viscosity [η Sp/ c]
TEA/CF: triethylamine/carbonochloridic acid ester group
The mensuration of<unreacted long-chain monoalkyl phenol AP-1 and AP-4 〉
Accurately measure 15 milliliters of polycarbonate resin solutions after the carrying out washing treatment, add 25 milliliters of hexanes then and make the component of polymer precipitation,, carry out gas chromatographic analysis, obtain the amount of long-chain monoalkyl phenol with chromatodisk (25P) filtering supernatant.
By the amount of this long-chain monoalkyl phenol with measure in the polycarbonate resin lipid concentration of the polycarbonate resin solution that uses, calculate the amount of the unreacted long-chain monoalkyl phenol in the polycarbonate resin.
In addition, the condition of gas-chromatography such as following.
GC body: HEWLETT PACKARD HP 6890
Spectrum post: J﹠amp; W SCIENTIFIC system, DB-1 (15m * φ 0.53mm * 0.15 μ m)
Temperature curve: 150 ℃/keep 2 minutes → 20 ℃/minute to heat up → 350 ℃
Carrier gas: He (40cm/ second, constant flow rate)
Inject: do not decompose (1.0 microlitre)
Implantation temperature: 175 ℃
FID Detector temperature: 350 ℃
Secondly, among the following embodiment 18~23 and comparative example 28~32, the long-chain monoalkyl phenol AP-1~AP-3 that uses above-mentioned Production Example 5~7 to make reaches 4-dodecylphenol (PDDP).
Moreover though avoid contacting oxygen or light in the preservation, the long-chain monoalkyl phenol in elapsed time is as seen painted after making with extra care or buying.
In the 5th table, the long-chain monoalkyl phenol that uses in expression embodiment 18~23 and the comparative example 28~32.
The 5th table
APHA Preservation fate after distillation is made with extra care or bought
AP-1-(a) 10 20 days
AP-1-(b) 15 3 months
AP-1-(c) 35 6 months 1.
AP-1-(d) 40 6 months 2.
AP-2-(a) 10 7 days
AP-2-(b) 40 6 months
AP-3-(a) 10 7 days
AP-3-(b) 20 3 months
AP-3-(c) 40 6 months
PDDP-(e) 10 1 month
PDDP-(f) 35 1 year
APHA: in 50 ℃ of values of measuring down of temperature.
In addition, in the 6th table expression to long-chain monoalkyl phenol with production day of polycarbonate resin on the same day or the analytical results of the gas-chromatography of carrying out the day before yesterday, the analysis condition of the above-mentioned gas-chromatography of expression in the 7th table.
The 6th table
The gas chromatographic analysis result
The dioxane matrix Adjacent, to the mol ratio of, a position body
AP-1-(a) n.d. 50∶48∶2
AP-1-(b) n.d. 50∶48∶2
AP-1-(c) n.d. 50∶48∶2
AP-1-(d) n.d. 50∶48∶2
AP-2-(a) n.d. 51∶47∶2
AP-2-(b) n.d. 51∶47∶2
AP-3-(a) n.d. 52∶46∶2
AP-3-(b) n.d. 52∶46∶2
AP-3-(c) n.d. 52∶46∶2
PDDP-(e) n.d. 4∶96∶0
PDDP-(f) n.d. 4∶96∶0
(n.d.: do not detect)
The 7th table
AP-1 AP-2 AP-3 PDDP
Dilution process Constant volume 0.1g in the 50ml chloroform Constant volume 0.1g in the 50ml hexane Constant volume 0.1g in the 50ml hexane Constant volume 0.1g in the 50ml hexane
Post HP-1 0.53mm * 15m thickness 0.15 μ m DB-1 0.53mm * 15m thickness 0.15 μ m DB-1 0.53mm * 15m thickness 0.15 μ m DB-1 0.53mm * 15m thickness 0.15 μ m
Column temperature ①50(0min) ②5℃/min ③400℃(20min) ①50(1min) ②5℃/min ③320℃(5min) ①50(1min) ②20℃/min ③300℃(15min) ①50(1min) ②20℃/min ③300℃(15min)
Carrier gas He 21kPa He 21kPa He 21kPa He 21kPa
Inlet Do not shunt 200 ℃ Do not shunt 175 ℃ Do not shunt 175 ℃ Do not shunt 175 ℃
Detector 350℃ 350℃ 350℃ 350℃
Injection rate 1.0μL 1.0μL 1.0μL 1.0μL
Embodiment 18
(1) preparation section of polycarbonate oligomer
Dihydroxyphenyl propane is dissolved in the 5.6 weight % aqueous sodium hydroxide solutions, and making bisphenol A concentration is 13.5 weight %, the aqueous sodium hydroxide solution of preparation dihydroxyphenyl propane.
In the tube-type reactor of internal diameter 6mm, pipe range 30m, feed 15 liters/hour of 40 liters/hour of the aqueous sodium hydroxide solutions of above-mentioned dihydroxyphenyl propane and methylene dichloride by flow continuously, press flow feeding phosgene simultaneously continuously 4.0kg/ hour.The cast reaction tubes has the chuck part, and the feeding water coolant remains on the temperature of reaction solution below 40 ℃ in chuck.
The effusive reaction solution of tube-type reactor is imported the internal volume 40 liter band plate washer tank reactors that have swept-back wing continuously, in reactor, press flow again and supply with 2.15 liters/hour of the dichloromethane solutions of 10.3 weight % of 17 liters/hour in 2.8 liters/hour of aqueous sodium hydroxide solutions, 25 0.07 liter/hour of weight % aqueous sodium hydroxide solution, water, 1 0.64 liter/hour of weight % triethylamine aqueous solution and the AP-1-(a) of dihydroxyphenyl propane, react at 29~32 ℃.
Extract reaction solution continuously out from this tank reactor, remove water, get the methylene dichloride phase by standing separation.
The polycarbonate oligomer solution that makes like this, oligomer concentrations are the 323g/ liters, and carbonochloridic acid ester group concentration is 0.69 mol.
(2) polymerization process of polycarbonate oligomer
To having plate washer, 2 of oar formula paddles and cooling with in the 50 liter tank reactors of chuck, add 3.84 milliliters of 6.15 liters of 10 liters of oligomer solutions, methylene dichloride, AP-1-(a) 113g, triethylamines that above-mentioned (1) operation makes, then, under agitation add the 6.4 weight % aqueous sodium hydroxide solution 1720g that are dissolved with V-Brite B 226mg, carry out reaction in 20 minutes.
In this reaction process, adopt the cooling control reaction temperature to be no more than 20 ℃.
Then, add the aqueous sodium hydroxide solution (making dihydroxyphenyl propane 660g be dissolved in the aqueous solution in the aqueous solution that is dissolved with NaOH 331g, V-Brite B 1.32g in 4.84 premium on currency) of dihydroxyphenyl propane, adopt that stir on the 300rpm limit, 40 minutes polyreactions are implemented on the limit.
(3) aqueous phase separation operation
Add 7.0 liters of methylene dichloride in the polymer fluid that above-mentioned (2) operation makes, restir is after 20 minutes, gets a part of emulsion and puts into 200 milliliters of graduated cylinders and leave standstill, and measures disengaging time.
In addition, remaining polymer fluid is told organic phase from reactor lower part and is separated by leaving standstill 30 minutes, and be separated into the organic phase that contains polycarbonate resin and containing excessive dihydroxyphenyl propane and the water of NaOH.
This organic phase is supplied with following neutralizing treatment operation.
(4) neutralizing treatment operation
The isolated organic phase of above-mentioned (3) operation, be added in the 50 above-mentioned liter reactors with the aqueous sodium hydroxide solution that is equivalent to 0.03 mol of 15 volume % with respect to this organic phase, adopt 300rpm to stir after 20 minutes, get the graduated cylinder that 140 milliliters of emulsions are put into 200 milliliters, after appending 40 milliliters of methylene dichloride then and diluting, leave standstill, estimate disengaging time.
In addition, remaining emulsion is by leaving standstill 30 minutes, and be separated into water and the organic phase that contains micro-dihydroxyphenyl propane and NaOH, and organic phase is supplied with following acid elution operation.
(5) acid elution operation
The isolating organic phase of above-mentioned (4) operation, add in the 50 above-mentioned liter reactors with the hydrochloric acid that is equivalent to 0.2 mol of 15 volume % with respect to this organic phase, adopt 300rpm to stir after 20 minutes, get a part of emulsion and put into 200 milliliters of graduated cylinders and leave standstill, measure disengaging time and leave standstill water amount after 20 minutes.
In addition, remaining emulsion is by leaving standstill 30 minutes, and be separated into the hydrochloride that contains triethylamine and water and the organic phase of NaCl, and organic phase is supplied with the first following washing step.
(6) first washing steps
The isolating organic phase of above-mentioned (5) operation, be equivalent to the pure water of 15 volume % with respect to this organic phase, add in the 50 above-mentioned liter reactors, adopt 300rpm to stir after 20 minutes, get a part of emulsion and put into 200 milliliters graduated cylinder and leave standstill, measure disengaging time and leave standstill water amount after 20 minutes.
In addition, remaining emulsion left standstill 30 minutes, was separated into water and organic phase, and organic phase is supplied with the second following washing step.
(7) second washing steps
The isolating organic phase of above-mentioned (6) operation, be equivalent to the pure water of 15 volume % with respect to this organic phase, adds in the 50 above-mentioned liter reactors, adopt 300rpm to stir after 20 minutes, standing separation water and organic phase, the specific conductivity of mensuration water.
(8) the 3rd washing steps
The specific conductivity of water is when 0.01 μ S/m is not following in above-mentioned (7) second washing steps, add in the 50 above-mentioned liter reactors with organic phase with respect to the pure water that this organic phase is equivalent to 15 volume % again, adopt 300rpm to stir after 20 minutes, standing separation water and organic phase, the specific conductivity of mensuration water.
(9) sheet chemical industry preface
The dichloromethane solution of the polycarbonate resin that carrying out washing treatment is obtained concentrates, pulverizes, and under reduced pressure 100 ℃ of resin sheets with gained carry out drying treatment.
These results are shown in the 8th table with the molecular weight of polycarbonate resin.
Embodiment 19
Among the embodiment 18, except using AP-1-(b) replacement AP-1-(a), other are implemented similarly to Example 18.
The result is shown in the 8th table with the molecular weight of polycarbonate resin.
Embodiment 20
Among the embodiment 18, in the preparation section except (1) polycarbonate oligomer, in the 10.3 weight % dichloromethane solutions of the 8.4 weight % dichloromethane solutions replacement AP-1-(a) of use AP-2-(a) and the polymerization process of (2) polycarbonate oligomer, use AP-2-(a) 92.6g to replace beyond AP-1-(a) 113g, other are implemented similarly to Example 18.
The result is shown in the 8th table with the molecular weight of polycarbonate resin.
Embodiment 21
Among the embodiment 18, in the polycarbonate oligomer preparation section except (1), in the polymerization process of the 10.3 weight % dichloromethane solutions of the 7.0 weight % dichloromethane solutions replacement AP-1-(a) of use AP-3-(a) and the polycarbonate oligomer of (2), use AP-3-(a) 76.3g to replace beyond AP-1-(a) 113g, other are implemented similarly to Example 18.
The result is shown in the 8th table with the molecular weight of polycarbonate resin.
Embodiment 22
Among the embodiment 21, except using AP-3-(b) replacement AP-3-(a), other are implemented similarly to Example 21.
The result is shown in the 8th table with the molecular weight of polycarbonate resin.
Embodiment 23
Among the embodiment 21, except using PDDP-(a) replacement AP-3-(a), other are implemented similarly to Example 21.
The result is shown in the 8th table with the molecular weight of polycarbonate resin.
Comparative example 28
Among the embodiment 18, use AP-1-(c) to replace AP-1-(a), the preparation section of implementing the oligopolymer of (1) similarly to Example 18 reaches the polymerization process of the oligopolymer of (2).
In the standing separation after the washing of neutralizing treatment, acid elution and first each operation of washing, even leave standstill 30 minutes, also because water is slow with separating of organic phase, so adopt separating centrifuge to carry out the separation of water.
The result is shown in the 8th table with the molecular weight of polycarbonate resin.
Comparative example 29
Among the embodiment 18, use AP-1-(d) to replace AP-1-(a), the preparation section of implementing the oligopolymer of (1) similarly to Example 18 reaches the polymerization process of the oligopolymer of (2).
In the standing separation after the washing of neutralizing treatment, acid elution and first each operation of washing, even leave standstill 30 minutes, also because water is slow with separating of organic phase, so use separating centrifuge to carry out the separation of water.
The result is shown in the 8th table with the molecular weight of polycarbonate resin.
Comparative example 30
Among the embodiment 20, use AP-2-(b) to replace AP-2-(a), the preparation section of implementing the oligopolymer of (1) similarly to Example 20 reaches the polymerization process of the oligopolymer of (2).
In the standing separation after the washing of neutralizing treatment, acid elution and first each operation of washing, even leave standstill 30 minutes, also because water is slow with separating of organic phase, so use separating centrifuge to carry out the separation of water.
The result is shown in the 8th table with the molecular weight of polycarbonate resin.
Comparative example 31
Among the embodiment 21, use AP-3-(c) to replace AP-3-(a), the preparation section of implementing the oligopolymer of (1) similarly to Example 21 reaches the polymerization process of the oligopolymer of (2).
In the standing separation after the washing of neutralizing treatment, acid elution and first each operation of washing, even leave standstill 30 minutes, also because water is slow with separating of organic phase, so use separating centrifuge to carry out the separation of water.
The result is shown in the 8th table with the molecular weight of polycarbonate resin.
Comparative example 32
Among the embodiment 23, use PDDP-(b) to replace PDDP-(a), the preparation section of implementing the oligopolymer of (1) similarly to Example 23 reaches the polymerization process of the oligopolymer of (2).
In the standing separation after the washing of neutralizing treatment, acid elution and first each operation of washing, even leave standstill 30 minutes, also because water is slow with separating of organic phase, so use separating centrifuge to carry out the separation of water.
The result is shown in the 8th table with the molecular weight of polycarbonate resin.
Reference example
Among the embodiment 18, in the preparation section except (1) polycarbonate oligomer, (oiling ス ケ ネ Network デ イ corporate system, dioxane matrix:<10ppm, ortho position body:<10ppm) 24 weight % dichloromethane solutions replace in the polymerization process of polycarbonate oligomer of the 10.3 weight % dichloromethane solutions of AP-1-(a) and (2) to use PTBP, use PTBP 44.0g to replace beyond AP-1-(a) 113g, other are implemented similarly to Example 18.
The result is shown in the 8th table with the molecular weight of polycarbonate resin.
The 8th table-1
Embodiment
18 19 20
End-capping reagent Kind AP-1-(a) AP-1-(b) AP-2-(a)
APHA(50℃) 10 15 10
Disengaging time (branch) Aqueous phase separation 13 14 14
Alkali cleaning 34 33 35
Pickling 7 7 8
First washing 7 8 9
Water output (ml) Pickling 25 25 25
First washing 25 24 25
The water specific conductivity (μ S/m) of second washing 0.008 0.008 0.008
Polycarbonate Viscosity number [VN] 47.5 47.5 47.7
Viscosity-average molecular weight [Mv] 18400 18400 18500
The 8th table-2
Embodiment
21 22 23
End-capping reagent Kind AP-3-(a) AP-3-(b) PDDP-(e)
APHA(50℃) 10 20 10
Disengaging time (branch) Aqueous phase separation 13 15 13
Alkali cleaning 33 35 33
Pickling 8 8 7
First washing 8 8 9
Water output (ml) Pickling 25 25 25
First washing 25 25 24
The water specific conductivity (μ S/m) of second washing 0.009 0.009 0.008
Polycarbonate Viscosity number [VN] 47.7 47.7 47.5
Viscosity-average molecular weight [Mv] 18500 18500 18400
The 8th table-3
Comparative example
28 29 30
End-capping reagent Kind AP-1-(c) AP-1-(d) AP-2-(b)
APHA(50℃) 35 40 40
Disengaging time (branch) Aqueous phase separation 38 35 40
Alkali cleaning >40 >40 >40
Pickling 8 8 9
First washing 19 20 18
Water output (ml) Pickling 23 20 20
First washing 11 10 10
The water specific conductivity (μ S/m) of second washing 0.06 0.07 0.07
The water specific conductivity (μ S/m) of the 3rd washing 0.008 0.008 0.008
Polycarbonate Viscosity number [VN] 47.5 47.5 47.7
Viscosity-average molecular weight [Mv] 18400 18400 18500
The 8th table-4
Comparative example Reference example
31 32
End-capping reagent Kind AP-3-(c) PDDP-(f) PTBP
APHA(50℃) 40 35 -
Disengaging time (branch) Aqueous phase separation 39 35 13
Alkali cleaning >40 >40 33
Pickling 9 8 8
First washing 20 18 8
Water output (ml) Pickling 20 22 25
First washing 11 12 25
The water specific conductivity (μ S/m) of second washing 0.08 0.06 0.008
The water specific conductivity (μ S/m) of the 3rd washing 0.009 0.008 -
Polycarbonate Viscosity number [VN] 47.7 47.5 47.7
Viscosity-average molecular weight [Mv] 18500 18400 18500
The polymer fluid of embodiment 18~23, any polymer fluid be in when washing, and shown in the separation property (disengaging time, water output) of the 8th table, by emulsification etc., the separation after the washing is not difficult.
Therefore, the water specific conductivity less than 0.01 μ S/m in second washing step does not need to implement the 3rd washing step.
That is the detergency that is equal to mutually when, the end-capping reagent shown in the reference example shows with PTBP.
The possibility of utilizing on the industry
According to the present invention 1, do not adhere on the mould in the time of can obtaining that flowability is improved and injection moulding thing, the products formed outward appearance might as well straight chain shape Merlon resin.
According to the present invention 2, use, can provide and improve flowability, when having simultaneously good heat resistance and carrying out injection moulding continuously for a long time as end-capping reagent dodecylphenol, the amount that can suppress the adhesion thing on the mould can make the Merlon resin of good appearance formed body.
According to the present invention 3, use has the long-chain monoalkyl phenol of the alkyl that specific average carbon number and skeleton are arranged as end-capping reagent, can provide to improve liquidity, have simultaneously the good tone that is equal to mutually when using PTBP as end-capping reagent, be suitable for the straight chain shape Merlon resin of optical applications.
4 the method according to the present invention, use long-chain monoalkyl phenol as end-capping reagent, can effectively provide and improve liquidity, suppress simultaneously to generate the diphenyl carbonate thing of deriving by long-chain monoalkyl phenol, and unreacted long-chain monoalkyl phenol is residual few, suppresses to produce the straight chain shape Merlon resin of volatilization composition during moulding.
5 the manufacture method according to the present invention, use long-chain monoalkyl phenol as end-capping reagent, when the employing interface polycondensation method straight chain shape Merlon resin that manufacturing improves liquidity can be provided, improve the washing in the washing operation, need not obviously dilute polymerization liquid, or do not increase washing times, do not need the manufacture method to the Merlon resin of washing operation and enrichment process increasing load.

Claims (13)

1. straight chain shape polycarbonate resin, be to use dihydric phenol, carbonic ether raw material and have average carbon number 12~35 alkyl and the amount dioxane matrix be the following long-chain monoalkyl phenol of 1 weight % as the end-capping reagent manufacturing and in the polycarbonate of making the amount of unreacted long-chain monoalkyl phenol be the straight chain shape polycarbonate resin of the viscosity-average molecular weight 13500~30000 below the 300ppm.
2. the described straight chain shape of claim 1 polycarbonate resin, wherein, the average carbon number of the alkyl of long-chain monoalkyl phenol is 19~35.
3. the described straight chain shape of claim 2 polycarbonate resin, wherein, the average carbon number of the alkyl of long-chain monoalkyl phenol is 21~25.
4. the described straight chain shape of claim 1 polycarbonate resin, wherein, the APHA of long-chain monoalkyl phenol under 50 ℃ is below 30.
5. the described straight chain shape of claim 1 polycarbonate resin, wherein, long-chain monoalkyl phenol is to 4-dodecylphenol, the containing ratio of the ortho position body of this phenol is that the following and unreacted 4-dodecylphenol of 3 moles of % is the ortho position body.
6. the described straight chain shape of claim 1 polycarbonate resin, wherein, dihydric phenol is 2, two (4-hydroxy phenyl) propane of 2-.
7. the described straight chain shape of claim 1 polycarbonate resin, wherein, viscosity-average molecular weight is 14000~30000.
8. the described straight chain shape of claim 1 polycarbonate resin, wherein, the YIs value of formula (IV) expression is below 1.0:
YIs=(YIa-YIb)×0.76+0.11 (IV)
In the formula, YIa is dissolved in polycarbonate resin plate 3g among the methylene dichloride 34.5g, this solution is added the YI value of measuring in the silica glass rounding cartridge type pond of optical length 50mm, internal diameter 25mm, and YIb adds the YI value of measuring in the above-mentioned silica glass rounding cartridge type pond with methylene dichloride.
9. the described straight chain shape of claim 1 polycarbonate resin wherein, is below 1.5 in the YI value of the matrix band of 340 ℃ of injection molding thick 3.2mm, and wherein matrix band is 80 * 40 * 2mm.
10. claim 8 or 9 described straight chain shape polycarbonate, wherein, be adopt behind the polycarbonate of interfacial polycondensation manufacturing and the pre-polymerization and behind the post polymerization absorbancy of the 380nm of water be respectively more than 0.005.
11. the manufacture method of the described polycarbonate resin of claim 1, wherein, use has average carbon number 12~35 alkyl and the amount dioxane matrix is that the following long-chain monoalkyl phenol of 1 weight % is as end-capping reagent, when making dihydric phenol and carbonic ether raw material carry out interfacial polycondensation manufacturing straight chain shape polycarbonate resin, implementing (A) makes dihydric phenol and carbonic ether raw material carry out the dihydric phenol polycarbonate oligomer that the interfacial polycondensation manufacturing contains the chloroformic acid ester group, (B1) make the long-chain monoalkyl phenol of oligopolymer that above-mentioned (A) operation makes and total at least usage quantity 50% at organic solvent, under the existence of alkali aqueous solution and catalyzer, be W/O and disperse state, the operation that temperature below 25 ℃ is reacted, and (B2) in the reaction solution that above-mentioned (B1) operation makes, add dihydric phenol, carry out the operation of interfacial polycondensation again.
12. the manufacture method of the described straight chain shape of claim 11 polycarbonate resin, wherein, in (B1) operation, the addition of catalyzer is for the amount of [A] mole, the carbonochloridic acid ester group that contains of oligopolymer during for [B] mole, and [A]/[B] is in 0.0001~0.02 scope.
13. the manufacture method of claim 1,8 or 9 described straight chain shape polycarbonate resins, wherein, use has average carbon number 12~35 alkyl and the amount dioxane matrix is that the following long-chain monoalkyl phenol of 1 weight % is as end-capping reagent, when making dihydric phenol and carbonic ether raw material carry out interfacial polycondensation manufacturing straight chain shape polycarbonate resin, as long-chain monoalkyl phenol, the APHA of use tone under 50 ℃ is the long-chain monoalkyl phenol below 30.
CN 02818104 2001-09-27 2002-09-26 Polycarbonate resin and method for producing same Expired - Fee Related CN1281655C (en)

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JP295483/2001 2001-09-27
JP2001295483A JP2003096180A (en) 2001-09-27 2001-09-27 Straight-chain polycarbonate
JP2002026667A JP3995945B2 (en) 2002-02-04 2002-02-04 Method for producing linear polycarbonate
JP026667/2002 2002-02-04
JP2002026669A JP4025083B2 (en) 2002-02-04 2002-02-04 Linear polycarbonate
JP2002026668A JP2003226750A (en) 2002-02-04 2002-02-04 Method for producing straight-chain polycarbonate
JP026669/2002 2002-02-04
JP026668/2002 2002-02-04
JP2002029175A JP4104873B2 (en) 2002-02-06 2002-02-06 Polycarbonate resin
JP029175/2002 2002-02-06

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JP5544681B2 (en) * 2007-10-19 2014-07-09 三菱瓦斯化学株式会社 Method for producing polycarbonate
JP5775345B2 (en) * 2011-03-31 2015-09-09 出光興産株式会社 Control method for continuous production of polycarbonate oligomer
JP5775347B2 (en) * 2011-03-31 2015-09-09 出光興産株式会社 Control method for continuous production of polycarbonate oligomer
CN103274905A (en) * 2013-06-13 2013-09-04 杨锌荣 Ortho-position monoalkyl phenol and preparation method thereof
WO2016158844A1 (en) * 2015-03-31 2016-10-06 三菱瓦斯化学株式会社 Molded body for light-guiding plate
KR102481043B1 (en) 2015-03-31 2022-12-23 미츠비시 가스 가가쿠 가부시키가이샤 Injection-molded body for vehicle, automobile light guide using same, automobile interior panel, and automobile lamp lens
JP7181006B2 (en) * 2018-06-01 2022-11-30 出光興産株式会社 Polycarbonate resin, method for producing the same, and polycarbonate resin composition

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JPH0725871B2 (en) * 1984-03-28 1995-03-22 三菱瓦斯化学株式会社 Polycarbonate resin optical molded product
WO1999036456A1 (en) * 1998-01-19 1999-07-22 Mitsubishi Chemical Corporation Polycarbonate resin, optical-information recording medium substrate made of the same, and optical-information recording medium
JP2002146006A (en) * 2000-11-13 2002-05-22 Idemitsu Petrochem Co Ltd Linear polycarbonate

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