CN101001914A - Thermoplastic resin composition and molded object - Google Patents
Thermoplastic resin composition and molded object Download PDFInfo
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- CN101001914A CN101001914A CNA2005800195649A CN200580019564A CN101001914A CN 101001914 A CN101001914 A CN 101001914A CN A2005800195649 A CNA2005800195649 A CN A2005800195649A CN 200580019564 A CN200580019564 A CN 200580019564A CN 101001914 A CN101001914 A CN 101001914A
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- polybutylene terephthalate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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Abstract
A thermoplastic resin composition which is excellent in color tone, mechanical properties, thermal stability, moldability, chemical resistance, and dimensional stability and is inhibited from generating a gas during production or molding. The thermoplastic resin composition comprises a polybutylene terephthalate (A) and an aromatic polycarbonate (B) in a proportion of from 1/19 to 19/1 (by weight), wherein the polybutylene terephthalate (A) is a polybutylene terephthalate having a titanium content of 33-75 ppm, excluding 33 ppm, in terms of titanium atom amount. A preferred embodiment of the thermoplastic resin composition further contains a fibrous reinforcing filler in an amount of 0.1-150 parts by weight per 100 parts by weight of the sum of the polybutylene terephthalate (A) and the aromatic polycarbonate (B).
Description
Technical field
The present invention relates to tone, hydrolytic resistance, thermostability, formability, shock-resistance, resistance to chemical reagents, excellent in dimensional stability, and painted in the time of can suppressing to make or during moulding reduces the thermoplastic resin composition of the warpage after the moulding and contains this thermoplastic resin composition's formed body.
Background technology
In thermoplastic polyester, as the polybutylene terephthalate of the engineering plastics of representative since forming process easily, physics, the chemical property excellence of mechanical properties, thermotolerance, resistance to chemical reagents, fragrance protectiveness etc., therefore, be widely used in injection moulded products such as trolley part, electrical and electronic parts, precision instrument parts.On the other hand, aromatic copolycarbonate is also as the engineering plastics of excellences such as shock-resistance, thermotolerance, dimensional stability, low warpage properties, flame retardant resistance and be widely used in OA parts, trolley part, material of construction etc.
But, though polybutylene terephthalate have shortcoming on aspects such as shock-resistance, dimensional stability, low warpage properties, and aromatic polycarbonate resin has shortcoming at aspects such as resistance to chemical reagents, formabilities having above-mentioned various advantage.Therefore, in order to remedy such weakness mutually and effectively to utilize its advantage, carried out that extensively the two is mixed and made into so-called polymer alloy under molten state and used (for example, non-patent literature 1).
Known in polymer alloy, mutually fully during uniform mixing, excellent separately character disappears resin, on the contrary, when admixture is insufficient, produces and to cause significantly bad phenomenon such as reductions of physical strength, thus do not losing each resin excellence character and remedy the effort of shortcoming.
Under the situation of the polymer alloy that comprises polybutylene terephthalate and aromatic copolycarbonate, guarantee the consistency of each resin, it is particularly important that each resin differential is loose, usually, the melting mixing of the two can apply to shear on one side with forcing machine on one side carries out, but has following awkward situation.
That is, better in order to make dispersion, when the rotation number that improves forcing machine or when reducing the amount of resin that the unit time handles, generate heat owing to shearing, the transesterification reaction of each resin is excessively carried out, and excessive homogenizing, perhaps, decomposition reaction is excessively carried out, and molecular weight reduces.Consequently, can not obtain the polymers of excellent properties alloy.On the contrary, when weakening the shearing of forcing machine, dispersion state extremely worsens, the performance that can not obtain expecting.
In order to address the above problem, proposed to use polybutylene terephthalate (patent documentation 1) with particular end radical concentration.But there is following problem in the concentration of only regulating end group simply.
Promptly, because the catalyzer (titanium catalyst etc.) that contains in the polybutylene terephthalate is many, therefore, the speed of transesterification reaction is excessive, from improving these viewpoints of security dispersed and control transesterification reaction and product property, be unsafty, in addition, also have following problem, produce the gas of tetrahydrofuran (THF) etc. when mixing or during moulding, in addition, produce paintedly, or promote molecular weight to reduce.
Non-patent literature 1: the engineering plastics topical reference book (Yi Baonei compiles, distribution on December 15th, 1988, and skill newspaper hall is published Co., Ltd., P.200)
Patent documentation 1: the spy opens the 2004-18558 communique
Summary of the invention
The problem that invention will solve
The present invention carries out in view of above practical situation, its purpose is, tone, mechanical properties, thermostability, formability, resistance to chemical reagents, excellent in dimensional stability are provided, and produce the thermoplastic resin composition of gas can suppress to make the time or during moulding.
The method of dealing with problems
The inventor etc. are controlled at specific scope for solving found that above-mentioned problem furthers investigate repeatedly by the content with the titanium catalyst in the polybutylene terephthalate, can easily solve above-mentioned problem, so that finished the present invention.
Promptly, the 1st main points of the present invention are, a kind of thermoplastic resin composition, it is the polybutylene terephthalate (A) and the aromatic copolycarbonate (B) of 1/19～19/1 (weight ratio) that said composition contains proportional, wherein, use titanium content to be higher than 33ppm in titanium atom and as the polybutylene terephthalate below the 75ppm as polybutylene terephthalate (A).
And, in thermoplastic resin composition preferred embodiment of the present invention, also contain fibee reinforced packing material, its ratio is 0.1～150 weight part with respect to total amount 100 weight parts of polybutylene terephthalate (A) and aromatic copolycarbonate (B).
In addition, the 2nd main points of the present invention are, a kind of formed body, and this formed body comprises above-mentioned thermoplastic resin composition.
The effect of invention
According to the present invention, tone, mechanical properties, thermostability, formability, shock-resistance, resistance to chemical reagents, excellent in dimensional stability can be provided, and produce the thermoplastic resin composition of gas can suppress to make the time or during moulding.
Description of drawings
[Fig. 1] is the explanatory view of an example of the esterification operation that adopts of the present invention or transesterification reaction operation.
[Fig. 2] is the explanatory view of an example of the polycondensation step that adopts of the present invention.
Nomenclature
1: the raw material supplying pipeline
2: recirculation line
3: the catalyzer supply line
4: extract pipeline out
5: distillate pipeline
6: extract pipeline out
7: circulation line
8: extract pipeline out
9: gas is extracted pipeline out
10: the phlegma pipeline
11: extract pipeline out
12: circulation line
13: extract pipeline out
14: ventilation line
A: reactive tank
B: extractor pump
C: rectifying tower
D, E: pump
F: container
G: condenser
L1: extract pipeline out
L3, L5: extract pipeline out
L2, L4, L6: ventilation line
A: the 1st polycondensation groove
D: the 2nd polycondensation groove
K: the 3rd polycondensation groove
C, e, m: extract out and use toothed gear pump
G: die head
H: rotary cutter
Embodiment
Below, describe the present invention in detail, but the explanation of the constitutive requirements of following record being the representation example of embodiments of the present invention, the present invention is not limited to these contents.
At first, the polybutylene terephthalate (A) that uses among the present invention (below, abbreviate PBT sometimes as) is described.Be meant to have terephthalic acid units and 1 as the PBT that uses in the present invention, 4-butyleneglycol unit forms the structure of ester bond, and 50 moles of % of dicarboxylic acid units are above to be made of terephthalic acid units, and 50 moles of % of diol units are above by 1, the polymer that 4-butyleneglycol unit constitutes.All the ratio of the terephthalic acid units in the dicarboxylic acid units is preferred 70 moles more than the %, be more preferably 80 moles more than the %, preferred especially 95 moles more than the %, in whole diol units 1, preferred 70 moles more than the % of the unitary ratio of 4-butyleneglycol, be more preferably 80 moles more than the %, preferred especially 95 moles more than the %.Terephthalic acid units or 1,4-butyleneglycol unit than 50 moles of % after a little while, the crystallization speed of PBT reduces, and causes formability to worsen.
In the PBT that the present invention uses, dicarboxylic acid composition beyond the terephthalic acid has no particular limits, can enumerate, for example, phthalic acid, m-phthalic acid, 4,4 '-diphenyldicarboxylic acid, 4,4 '-phenyl ether dicarboxylic acid, 4,4 '-benzophenone dicarboxylic acid, 4,4 '-biphenoxyl ethane dicarboxylic acid, 4,4 '-sulfobenzide dicarboxylic acid, 2, aromatic dicarboxylic acids such as 6-naphthalene dicarboxylic acids, 1, the 2-cyclohexane dicarboxylic acid, 1, the 3-cyclohexane dicarboxylic acid, 1, ester ring type dicarboxylic acid such as 4-cyclohexane dicarboxylic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, aliphatic dicarboxylic acids such as sebacic acid etc.These dicarboxylic acid compositions can use dicarboxylic acid or dicarboxylic acid derivatives such as dicarboxylic ester, dicarboxylic acid halogenide to import in the polymer backbone as raw material.
In the PBT that the present invention uses, 1, diol component beyond the 4-butyleneglycol has no particular limits, can enumerate, for example, ethylene glycol, glycol ether, polyoxyethylene glycol, 1, the 2-propylene glycol, 1, ammediol, polypropylene glycol, polytetramethylene glycol, one dibutylene glycol that contracts, 1, the 5-pentanediol, neopentyl glycol, 1, the 6-hexylene glycol, 1, aliphatic diols such as 8-ethohexadiol, 1, the 2-cyclohexane diol, 1, the 4-cyclohexane diol, 1, the 1-hydroxymethyl-cyclohexane, 1, ester ring type glycol such as 4-hydroxymethyl-cyclohexane, the xylylene glycol, 4,4 '-dihydroxybiphenyl, 2, two (4-hydroxyphenyl) propane of 2-, aromatic diols such as two (4-hydroxyphenyl) sulfone etc.
In the PBT that the present invention uses, can also be with simple function compositions such as lactic acid, oxyacetic acid, m-Salicylic acid, P-hydroxybenzoic acid, 6-hydroxyl-2-naphthalene monocarboxylic acid, right-hydroxycarboxylic acids such as beta-hydroxy ethoxybenzoic acid, alkoxyl group carboxylic acid, stearyl alcohol, benzylalcohol, stearic acid, phenylformic acid, p t butylbenzoic acid, benzoyl phenylformic acid, all the multifunctional one-tenth more than the trifunctional such as propanetricarboxylic acid, trimellitic acid, trimesic acid, pyromellitic acid, trihydroxybenzoic acid, trimethylolethane, TriMethylolPropane(TMP), glycerine, tetramethylolmethane grade and use as copolymer composition.
The PBT that the present invention uses is to use 1, and 4-butyleneglycol and terephthalic acid (or dimethyl terephthalate ester) use titanium compound to obtain as catalyzer as raw material.
As the object lesson of titanium catalyst, can enumerate phenoxide titaniums such as titan-alkoxides such as inorganic titanium compounds such as titanium oxide, titanium tetrachloride, tetramethyl-titanic acid ester, tetra isopropyl titanate, tetrabutyl titanate ester, tetraphenyl titanic acid ester etc.In the middle of these, preferred tetraalkyl titanate, wherein, more preferred tetrabutyl titanate ester.
Except titanium, can also use tin as catalyzer.Tin uses with tin compound usually, as its object lesson, can enumerate dibutyltin oxide, oxidation methyl phenyltin, tin tetraethyl, oxidation triethyltin, oxidation six cyclohexyl two tin (cyclohexahexyl ditin oxide), oxidation two (dodecyl) tin, triethyl hydroxyl tin, triphenyl hydroxyl tin, acetate triisobutyl tin, dibutyltin diacetate, two lauric acid tin diphenyls, tri-chlorination Monobutyltin, tributyltin chloride, butyl disulfide tin, oxidation butylhydroxy tin, stannoacetic acid, ethyl stannonic acid, butyl stannonic acid etc.
Because tin can make the tone of polybutylene terephthalate worsen, its addition is generally below the 200ppm in tin atom, below the preferred 100ppm, is more preferably below the 10ppm, wherein, does not preferably add.
In addition, except that titanium, can also use calcium cpds such as magnesium compounds such as magnesium acetate, magnesium hydroxide, magnesiumcarbonate, magnesium oxide, alkanol magnesium, secondary magnesium phosphate, calcium acetate, calcium hydroxide, lime carbonate, calcium oxide, alkanol calcium, secondary calcium phosphate, and germanium compounds such as antimony compounds, germanium dioxide, four germanium oxides such as ANTIMONY TRIOXIDE SB 203 99.8 PCT, manganic compound, zn cpds, zirconium compounds, cobalt compound, ortho-phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, Tripyrophosphoric acid, their ester or reaction promoters such as phosphorus compound, sodium hydroxide, Sodium Benzoate such as metal-salt.
The feature of the PBT that uses among the present invention is that titanium content is higher than 33ppm in titanium atom and is below the 75ppm.Above-mentioned value is the atomic wts ratio with respect to PBT.
The preferred 35ppm of the lower limit of above-mentioned titanium content is more preferably 40ppm, and the preferred 60ppm of the upper limit is more preferably 50ppm.When the content of titanium is very few, the polymerization rate of PBT reduces, therefore have under high temperature is long-time, carry out polyreaction, this not only can promote the tone of PBT to worsen or the thermal degradation when reaction, and do not carry out carrying out mixing time reaction with aromatic copolycarbonate, cause the mechanical properties of polymer alloy to reduce.On the other hand, when titanium content is too much, not only can cause when mixing or produce gas during moulding or thermostability worsens, and be difficult to control transesterification reaction, and cause that rerum natura instability, thermostability with the polymer alloy of aromatic copolycarbonate worsens, mechanical properties reduces.In addition, therefore painted tendency also causes tone to worsen owing to there is the hydroxyl reaction of titanium compound and aromatic copolycarbonate.
The content of atoms metals such as titanium atom can be after the metal that reclaims with methods such as wet type ashing in the polymkeric substance, use that atom is luminous, atom extinction, inductively coupled plasma (Inductively CoupledPlasma) (ICP) etc. method measure.
The end carboxy concentration of the PBT that uses among the present invention is generally below the 50 μ eq/g, and preferred 1～40 μ eq/g is more preferably 1～30 μ eq/g, preferred especially 10～25 μ eq/g.When end carboxy concentration is too high, exist hydrolytic resistance to worsen, perhaps the tendency that worsens with the consistency of aromatic copolycarbonate.
The end carboxy concentration of PBT can be by being dissolved in PBT in the organic solvent etc., uses alkaline solution such as sodium hydroxide solution to carry out titration and obtain.
In addition, the terminal ethylenyl groups concentration of the PBT that the present invention uses is generally 0.1～15 μ eq/g, and preferred 0.5～10 μ eq/g is more preferably 1～8 μ eq/g.During the terminal ethylenyl groups excessive concentration, become the reason that tone worsens.The thermal history of terminal ethylenyl groups concentration during owing to moulding has the tendency of further rising, and therefore, when mold temperature was high, perhaps in having the manufacture method of recycling operation, tone worsened more remarkable.
Beyond the terminal hydroxyl-removal of PBT, carboxyl, the vinyl, the residual sometimes methoxycarbonyl that has from raw material, particularly residual more when being raw material with the dimethyl terephthalate (DMT).But the terminal heat that produces during owing to moulding of methoxycarbonyl produces has toxic methyl alcohol, formaldehyde, formic acid.In addition, formic acid can damage the forming machine of metal manufacturing or be attached to its machine relevant with vacuum etc.Therefore, the terminal methoxycarbonyl concentration among the PBT that uses among the present invention is preferably below the 0.5 μ eq/g, is more preferably below the 0.3 μ eq/g, below the preferred especially 0.2 μ eq/g, most preferably below the 0.1 μ eq/g.
The concentration of each above-mentioned end group can be by measuring in the mixed solvent that PBT is dissolved in deuterochloroform/hexafluoroisopropanol=7/3 (volume ratio)
1H-NMR comes quantitatively.At this moment, for preventing overlapping with solvents signals, also can add the alkaline components such as deuterated pyridine of minute quantity etc.
The limiting viscosity of the PBT that uses among the present invention is generally 0.60～2.50dL/g, and preferred 0.70～2.00dL/g is more preferably 0.80～1.20dL/g, preferred especially 0.80～1.10dL/g.During limiting viscosity deficiency 0.60dL/g, the physical strength of moulded products is insufficient, when surpassing 2.50dL/g, exists melt viscosity to uprise, the mobile deterioration, the tendency that the superficiality of formability or goods worsens.In addition, the tendency that the dispersiveness that the limiting viscosity of PBT is too high or too low all can exist with the aromatic copolycarbonate melting mixing time worsens.Above-mentioned limiting viscosity is to use the mixed solvent of phenol/tetrachloroethane (weight ratio 1/1) 30 ℃ of values of measuring down.
Below, the manufacture method of the PBT that uses among the present invention is described.The manufacture method of PBT is from the raw material aspect, roughly can be divided into using dicarboxylic acid as the so-called direct polymerization method of main raw material with use the ester-interchange method of dicarboxylic acid dialkyl esters as main raw material.Its difference is, generates water in the former esterification in the early stage, generates alcohol in latter's transesterification reaction in the early stage.
In addition, the manufacture method of PBT can roughly be divided into interrupter method and continuous processing according to the output form of raw material supplying or polymkeric substance.Also have the esterification or the transesterification reaction at initial stage to carry out with operate continuously, ensuing polycondensation is carried out with periodical operation, and on the contrary, the esterification at initial stage or transesterification reaction are carried out with periodical operation, the method that ensuing polycondensation is carried out with operate continuously.
In the present invention, from the viewpoint of the improved effect that obtains the former unitary dominance of easy degree, raw material (Gifted position property) that stability, overhead product handles, produces by the present invention of raw material, preferred direct polymerization method.In addition, in the present invention, the viewpoint of the improved effect that produces from the stability of productivity or product property, by the present invention preferably adopts base feed continuously and carries out the method for esterification or transesterification reaction continuously.And, in the present invention, preferably be connected on the so-called continuous processing that the polycondensation afterwards of esterification or transesterification reaction is also carried out continuously.
In the present invention, the preferred operation that adopts is, use the esterification groove, in the presence of titanium catalyst, on one side with at least a portion 1, the 4-butyleneglycol is not with terephthalic acid (or dimethyl terephthalate ester) but be supplied to esterification groove (or transesterification reaction groove) independently, and on one side with terephthalic acid (or dimethyl terephthalate ester) and 1, the 4-butyleneglycol carries out the operation of esterification (or transesterify) continuously.
Promptly, in the present invention, for fog or the impurity that reduces from catalyzer does not make activity of such catalysts reduce, as raw material slurry or solution, be different from terephthalic acid or dimethyl terephthalate ester supply with simultaneously 1, the 4-butyleneglycol is not with terephthalic acid or dimethyl terephthalate ester but independently with 1, the 4-butyleneglycol is supplied in esterification groove or the transesterification reaction groove.The back, sometimes with this 1, the 4-butyleneglycol is called " supply with in addition 1,4-butyleneglycol ".
For above-mentioned " supply with in addition 1,4-butyleneglycol ", can be used as and irrelevant fresh 1 of technology, 4-butyleneglycol.In addition, " 1 of other supply; 4-butyleneglycol ", can be to collect distilled 1 from esterification groove or transesterification reaction groove with condenser, the 4-butyleneglycol directly or in container etc. is back to reactive tank after temporary transient the maintenance again, perhaps also can be separating impurity and purifying, as having improved 1 of purity, the 4-butyleneglycol is supplied with.The back, sometimes will by collect with condenser etc. 1, " supply with in addition 1,4-butyleneglycol " that the 4-butyleneglycol constitutes is called " recirculation 1,4-butyleneglycol ".From the viewpoint of the simplification of resources effective utilization, equipment, preferably " recirculation 1,4-butyleneglycol " is used as " supply with in addition 1,4-butyleneglycol ".
In addition, usually, distilled 1 from esterification groove or transesterification reaction groove, the 4-butyleneglycol removes 1, beyond the 4-butyleneglycol composition, also contains compositions such as water, alcohol, tetrahydrofuran (THF) (THF), dihydrofuran.Therefore, after 1 of above-mentioned overhead product, 4-butyleneglycol are preferably collected with condenser etc., or while collecting and component separating such as water, alcohol, THF, purifying is back in the reactive tank.
And, in the present invention, in " 1 of other supply, 4-butyleneglycol ", directly turn back to reaction solution liquid phase portion more than the preferred 10 weight %.Here, so-called reaction solution liquid phase portion, the liquid side of the liquid-gas interface in expression esterification groove or the transesterification reaction groove, what is called is directly returned reaction solution liquid phase portion, pipe arrangement etc. is used in expression, and " supply with in addition 1,4-butyleneglycol " be not via gas phase portion but directly supply with liquid phase part.Directly return more than the preferred 30 weight % of ratio of reaction solution liquid phase portion, be more preferably more than the 50 weight %, more than the preferred especially 80 weight %, most preferably more than the 90 weight %.After a little while, titanium catalyst has the tendency of inactivation directly to turn back to " supply with in addition 1,4-butyleneglycol " of reaction solution liquid phase portion.
In addition, the temperature of " 1 of other supply, 4-butyleneglycol " during Returning reactor is generally 50～220 ℃, preferred 100～200 ℃, is more preferably 150～190 ℃.When the temperature of " 1 of other supply, 4-butyleneglycol " was too high, the by-product amount of THF had the tendency that becomes many, crossed when hanging down, and owing to thermal load increases, therefore the tendency that causes power loss was arranged.
In addition, in the present invention, for preventing catalyst deactivation, in the titanium catalyst that in esterification (or transesterification reaction), uses, more than the preferred 10 weight % not with terephthalic acid (or dimethyl terephthalate ester) but directly supply to reaction solution liquid phase portion independently.Here, what is called reaction solution liquid phase portion, the liquid side of the liquid-gas interface in expression esterification groove or the transesterification reaction groove, what is called directly supplies to reaction solution liquid phase portion, pipe arrangement etc. is used in expression, and titanium catalyst is without the gas phase portion of reactor but directly supply to liquid phase part.Directly add to more than the preferred 30 weight % of ratio of titanium catalyst of reaction solution liquid phase portion, be more preferably more than the 50 weight %, more than the preferred especially 80 weight %, most preferably more than the 90 weight %.
Above-mentioned titanium catalyst also can be dissolved in solvent etc. or not dissolve but directly supply to the reaction solution liquid phase portion of esterification groove or transesterification reaction groove, but in order to make the feed rate stabilization, alleviate because the detrimentally affects such as sex change that come the thermal conductance of the thermal medium chuck etc. of autoreactor to cause, preferably use 1, the dilution of 4-butyleneglycol equal solvent.The concentration of this moment with the titanium catalyst densitometer all with respect to solution, is generally 0.01～20 weight %, and preferred 0.05～10 weight % is more preferably 0.08～8 weight %.In addition, from reducing the viewpoint of impurity, the moisture concentration in the solution is generally 0.05～1.0 weight %.From preventing inactivation or agglutinative viewpoint, the temperature during preparation solution is generally 20～150 ℃, preferred 30～100 ℃, is more preferably 40～80 ℃.In addition, from preventing deterioration, prevent to separate out, prevent the viewpoint of inactivation, catalyst solution preferably in pipe arrangement etc. with supply with in addition 1, the 4-butyleneglycol supplies in esterification groove or the transesterification reaction groove after mixing.
An example of the continuous processing of employing direct polymerization method is as follows.Promptly, to be the above-mentioned dicarboxylic acid composition of main component and with the terephthalic acid with 1, the 4-butyleneglycol is that the above-mentioned diol component of main component mixes in the raw material tempering tank, make slurry, in single or multiple esterification grooves, in the presence of titanium catalyst, be generally 180～260 ℃, preferred 200～245 ℃, be more preferably under 210～235 ℃ the temperature, be generally 10～133kPa in addition, preferred 13～101kPa, be more preferably (absolute pressure under the pressure of 60～90kPa, down together), be generally 0.5～10 hour continuously, preferred 1～6 hour esterification, to be transferred to the polycondensation groove as the oligopolymer of the esterification reaction product that obtains, in single or multiple polycondensation grooves, in the presence of polycondensation catalyst, preferably be generally 210～280 ℃ continuously, preferred 220～260 ℃, be more preferably under 230～250 ℃ the temperature, in at least 1 polycondensation groove, be generally below the 20kPa, below the preferred 10kPa, be more preferably under the following decompression of 5kPa and under agitation carried out preferred 3～10 hours polycondensation common 2～15 hours.By the polymkeric substance that polycondensation obtains, common bottom from the polycondensation groove is extracted polymkeric substance out, transfers in the die head, extracts out to be strip, in the time of water-cooled or after the water-cooled, cuts off with cutter, makes particulate state, shred even-granular body.
In the occasion of direct polymerization method, terephthalic acid and 1, the mol ratio of 4-butyleneglycol preferably satisfies following formula (I).
[several 1]
B/TPA＝1.1～5.0(mol/mol) …(I)
(here, B represents that time per unit supplies to 1 the esterification groove from the outside, and the mole number of 4-butyleneglycol, TPA represent that time per unit supplies to the mole number of the terephthalic acid the esterification groove from the outside).
Above-mentioned what is called " supplies to 1 the esterification groove; the 4-butyleneglycol " from the outside be to make raw material slurry or solution, with terephthalic acid or dimethyl terephthalate ester supply with 1, the 4-butyleneglycol, and supply with not with them but independently 1, the 4-butyleneglycol, as the solvent of catalyzer use 1,4-butyleneglycols etc. enter into 1 in the reactive tank, the summation of 4-butyleneglycol from the reactive tank outside.
The value of above-mentioned B/TPA is than 1.1 hours, causes transformation efficiency to reduce or catalyst deactivation, and when bigger than 5.0, not only thermo-efficiency reduces, and by product such as THF has the tendency of increase.The value of B/TPA is preferred 1.5～4.5, is more preferably 2.0～4.0, preferred especially 3.1～3.8.
For example descend as one of the continuous processing that adopts ester-interchange method.Promptly, in single or multiple transesterification reaction grooves, in the presence of titanium catalyst, usually at 110～260 ℃, preferred 140～245 ℃, be more preferably under 180～220 ℃ the temperature, and usually at 10～133kPa, preferred 13～120kPa is more preferably under the pressure of 60～101kPa, is generally 0.5～5 hour, preferred 1～3 hour successive transesterification reaction, to transfer in the polycondensation groove as the oligopolymer of the transesterification reaction resultant that obtains, in single or multiple polycondensation grooves, in the presence of polycondensation catalyst, preferably be generally 210～280 ℃ continuously, preferred 220～260 ℃, be more preferably under 230～250 ℃ the temperature, at least 1 polycondensation groove, usually below the 20kPa, below the preferred 10kPa, under the decompression below the more preferred 5kPa, under agitation carried out preferred 3～10 hours polycondensation common 2～15 hours.
In the occasion of ester-interchange method, the formula (II) below dimethyl terephthalate ester and 1, the mol ratio of 4-butyleneglycol preferably satisfy.
[several 2]
B/DAT＝1.1～2.5(mol/mol) …(II)
(here, B represents that time per unit supplies to 1 the transesterification reaction groove from the outside, and the mole number of 4-butyleneglycol, DAT represent that time per unit supplies to the mole number of the dimethyl terephthalate ester the transesterification reaction groove from the outside.)
The value of above-mentioned B/DAT is than 1.1 hours, causes transformation efficiency to reduce or the reduction of catalyst activity, and when bigger than 2.5, not only thermo-efficiency reduces, and by product such as THF has the tendency of increase.The value of B/DAT is preferred 1.1～1.8, is more preferably 1.2～1.5.
In the present invention, for shortening the reaction times, esterification or transesterification reaction are carried out under the temperature more than the boiling point of 4-butyleneglycol preferably 1.1, the boiling point of 4-butyleneglycol depends on the pressure of reaction, is 230 ℃ under 101.1kPa (normal atmosphere), is 205 ℃ under 50kPa.
As esterification groove or transesterification reaction groove, can use known reactive tank, can be any patterns such as the complete tempering tank of vertical stirring, vertical thermal convection formula tempering tank, tower successive reaction groove, in addition, can be single groove, also can be a plurality of grooves of groove serial or parallel connection of the same race or not of the same race.Wherein, the reactive tank that preferably has whipping appts, as whipping appts, except that the common type that comprises power section, bearing, axle, agitating wing, the type that can also use turbine guide vane type high-speed rotary stirrer, disk crush type stirrer, roll-type abrasive type stirrer etc. to rotate at a high speed.
The form that stirs has no particular limits, except that the common stirring means that can adopt top from reactive tank, bottom, sidepiece etc. that the reaction solution the reactive tank is directly stirred, can also adopt the outside that the part of reaction solution is exported to reactor with pipe arrangement etc., with stirrings such as line mixer, make reaction solution round-robin method.
The kind of agitating wing can be selected known agitating wing, particularly, can enumerate spiral paddle, screw wing, the turbine wing, the flabellum turbine wing, the disc turbine wing, the three leaf palintrope wings, the general energy wing, the maximum blade wing etc.
In the manufacturing of PBT, use a plurality of reactive tanks usually, preferably use 2～5 reactive tanks, molecular weight is risen successively.Usually after the esterification or transesterification reaction in the early stage, proceed polycondensation.
The polycondensation operation of PBT can be used single reactive tank, also can use a plurality of reactive tanks, but preferably uses a plurality of reactive tanks.The form of reactive tank can be any patterns such as the complete tempering tank of vertical stirring, vertical thermal convection formula tempering tank, tower successive reaction groove, in addition, also they can be made up.Wherein, the reactive tank that preferably has whipping appts, as whipping appts, except that the common type that comprises power section, bearing, axle, agitating wing, the type that can also use turborotor type high-speed rotary stirrer, disk crush type stirrer, roll-type abrasive type stirrer etc. to rotate at a high speed.
The form that stirs has no particular limits, except that the common stirring means that can adopt top from reactive tank, bottom, sidepiece etc. that the reaction solution the reactive tank is directly stirred, can also adopt the outside that the part of reaction solution is exported to reactor with pipe arrangement etc., with stirrings such as line mixer, make reaction solution round-robin method.Wherein, recommend the horizontal reactor that has the Surface Renewal and the self-stip excellence of turning axle on the usage level direction in the polycondensation groove at least.
In addition, for suppressing painted or deterioration, the increase that ethene suppressing base etc. are terminal, can be at least in a reactive tank, usually below 1.3kPa, preferably below 0.5kPa, under the more preferred high vacuum below 0.3kPa, usually at 225～255 ℃,, more preferably under 233～245 ℃ temperature, carry out preferably at 230～250 ℃.
Have again, the polycondensation operation of PBT, it is less, for example at first to produce molecular weight ratio in melt phase polycondensation, and limiting viscosity is after about 0.1～1.0 the PBT, then, can carry out solid phase polycondensation (solid state polymerization) under the temperature below the fusing point of PBT.
Below, based on accompanying drawing, the preferred implementation of the manufacture method of PBT is described.Fig. 1 is the explanatory view of an example of the esterification operation that adopts of the present invention or transesterification reaction operation, and Fig. 2 is the explanatory view of an example of the polycondensation step that adopts of the present invention.
In Fig. 1, the raw material terephthalic acid usually in raw material tempering tank (not shown) with 1, the 4-butyleneglycol mixes, supply to the reactive tank (A) from the form of raw material supplying pipeline (1) with slurry, when raw material is dimethyl terephthalate ester, supply in the reactive tank (A) with the fused liquid state usually.On the other hand, titanium catalyst is preferably adjusted in the groove (not shown) at catalyzer and is made 1, behind the solution of 4-butyleneglycol, supplies with from catalyzer supply line (3).Figure 1 illustrates catalyzer supply line (3) and be connected recirculation 1, on the recirculation line of 4-butyleneglycol (2), after the two mixes, supply to the mode of the liquid phase portion of reactive tank (A).
Rectifying tower (C), be separated into high boiling point composition and low boiling point component through distillating pipeline (5) from reactive tank (A) distilled gas.Usually, the main component of high boiling point composition is 1, the 4-butyleneglycol, and the main component of low boiling point component is water and THF when the direct polymerization method, is alcohol, THF, water when ester-interchange method.
Isolating high boiling point composition is extracted out from extracting pipeline (6) out in rectifying tower (C), and through pump (D), a part is circulated to the reactive tank (A) from recirculation line (2), and a part is returned rectifying tower (C) from circulation line (7).In addition, remainder is drawn to the outside from extracting pipeline (8) out.On the other hand, the isolating composition that gently boils is extracted pipeline (9) extraction out from gas in rectifying tower (C), condensation in condenser (G), and process phlegma pipeline (10) temporary storage is in container (F).The part of the volatile component that compiles in the container (F) (composition gently boils) is returned rectifying tower (C) through extracting pipeline (11), pump (E) and circulation line (12) out, and remainder is evacuated to the outside through extracting pipeline (13) out.Condenser (G) connects gas barrier (not shown) through ventilation line (14).The oligopolymer that generates in reactive tank (A) is through extractor pump (B) and extract pipeline (4) extraction out.
In operation shown in Figure 1, catalyzer supply line (3) is connected on the recirculation line (2), but the two also can be independently.In addition, raw material supplying pipeline (1) also can be connected with the liquid phase portion of reactive tank (A).
In Fig. 2, the oligopolymer of supplying with from above-mentioned extraction pipeline (4) shown in Figure 1 under reduced pressure carries out the 1st polycondensation groove (a) after polycondensation becomes prepolymer, through extracting out with toothed gear pump (c) and extracting pipeline (L1) out, supply in the 2nd polycondensation groove (d), supply to the 3rd polycondensation groove (k) through extracting out with toothed gear pump (e) and extracting pipeline (L3) out again.The 3rd polycondensation groove (k) is made of a plurality of stirring fins, is the horizontal reacting groove that possesses 2 Self-cleaning type agitating wing.And, in the 2nd polycondensation groove (d), under than the low pressure of the 1st polycondensation groove (a), carry out polycondensation usually, in the 3rd polycondensation groove (k), polycondensation is further carried out and is obtained polymkeric substance.The polymkeric substance that obtains, cuts off with rotary cutter (h) after the cooling such as water through extracting out with toothed gear pump (m) and extracting pipeline (L5) out and extract out with the state of fused bar from die head (g), makes particle.Symbol (L2), (L4), (L6) represent the ventilation line of each polycondensation groove (a), (d), (k).
Below, the aromatic copolycarbonate (B) that uses among the present invention (below, brief note is PC sometimes) is described.The PC that uses among so-called the present invention is by making carbonic diester such as aromatic hydroxy compound and diphenyl carbonate or phosgene react the thermoplasticity aromatic polycarbonate polymers or the multipolymer of making that can have side chain.
As aromatic dihydroxy compound, can enumerate 2, two (4-hydroxyphenyl) propane (=dihydroxyphenyl propane) of 2-, tetramethyl-dihydroxyphenyl propane, two (4-hydroxyphenyl) are to diisopropyl benzene, quinhydrones, Resorcinol, 4,4-dihydroxybiphenyl etc., among these, preferred dihydroxyphenyl propane.From improving the viewpoint of flame retardant resistance, above-mentioned aromatic dihydroxy compound can also have with bromine atoms or has the structure of the group replacement of siloxane structure except that sulfonic acid tetraalkyl .
In order to obtain the ramose aromatic polycarbonate resin, can use Phloroglucinol monomethyl ether, 4,6-dimethyl-2,4,6-three (4-hydroxyphenyl) heptene-2,4,6-dimethyl-2,4,6-three (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-three (4-hydroxyphenyl) teracrylic acid, 1,3,5-three (4-hydroxyphenyl) benzene, 1,1, the polyol of expression such as 1-three (4-hydroxyphenyl) ethane, and 3, two (4-hydroxyaryl) oxyindoles (=isatin bis-phenol) of 3-, the 5-chlorisatide, 5,7-two chlorisatides, 5-bromoisatins etc. are as the part of above-mentioned aromatic dihydroxy compound, and its usage quantity is generally 0.01～10 mole of %, preferred 0.1～2 mole of %.
In addition, to regulate molecular weight or end group is purpose, can also use the monobasic aromatic hydroxy compound, monobasic aromatic hydroxy compound derivatives such as its chloro-formic ester (Network ロ ロ ホ Le メ one ト) body, as its object lesson, can enumerate, phenol, and p-methyl phenol, and n-propyl phenol, p-tert-butylphenol, to alkylphenols such as chain alkyl fortified phenol, their derivative etc.
In order to improve flame retardant resistance, can be on the PC that the present invention uses copolymerization have the polymkeric substance or the oligopolymer of siloxane structure, the flowability when improveing moulding, can be on the PC that the present invention uses derivatives such as copolymerization dicarboxylic acid, dicarboxylic acid acyl chlorides.In addition, can also use PC more than 2 kinds simultaneously.
The terminal hydroxyl concentration of the PC that uses among the present invention is generally below the 60 μ eq/g, and preferred 1～50 μ eq/g is more preferably 5～50 μ eq/g, preferred especially 10～45 μ eq/g, and wherein, 20～40 μ eq/g are the most suitable.When terminal hydroxyl concentration ratio 60 μ eq/g are big, by the titanium from PBT cause painted serious, the thermoplastic resin composition's who obtains mechanical properties has the tendency of reduction.On the other hand, terminal hydroxyl concentration is too small, with the consistency reduction of PBT, the tendency that exists mechanical properties to worsen.
Under the situation of the interfacial polymerization that the aromatic hydroxy compound photoreactive gas is reacted, the terminal hydroxyl concentration of PC can be controlled with for example reaction conditionss such as temperature of reaction, catalyzer, composition, under the situation of the melt phase polycondensation of aromatic hydroxy compound and carbonic diester reaction, can recently control by the composition of for example raw material.
In the present invention, the PC that can use any means in interfacial polymerization and the melt phase polycondensation to obtain, but from being easy to control the viewpoint of terminal hydroxyl concentration, the preferably PC that obtains with melt phase polycondensation.
The molecular weight of the PC of Shi Yonging can adopt the viscosity-average molecular weight of using methylene dichloride to be converted by the soltion viscosity of measuring as solvent under 25 ℃ temperature in the present invention, be generally 14000～40000, preferred 15000～30000, more preferred 15000～23000.
Then, thermoplastic resin composition of the present invention is described.It is the above-mentioned PBT and the PC of 1/19～19/1 (weight ratio) that thermoplastic resin composition of the present invention contains proportional.Two components in proportions are outside the above-mentioned scope time, can not show the characteristic of each composition of performance and the performance of the expectation that obtains.The ratio of PBT and PC (weight ratio) preferred 1/9～9/1, more preferred 1/4～4/1.Thermoplastic resin composition of the present invention can only be made of above-mentioned PBT and PC, but in the scope of not damaging effect of the present invention, can also contain various compositions.
In thermoplastic resin composition preferred embodiment of the present invention, except that above-mentioned PBT and PC, also contain fibee reinforced packing material.
As fibee reinforced packing material, can enumerate, for example, organic fibres such as inorganic fibre, aromatic polyamide fibre, fluororesin fiber such as glass fibre, carbon fiber, silica/alumina fiber, Zirconium oxide fibre, boron fibre, boron nitride fibre, silicon nitride metatitanic acid potassium fiber, steel fiber etc.These fibee reinforced packing materials can make up more than 2 kinds and use.In above-mentioned fibee reinforced packing material, preferably use inorganic filling material, particularly glass fibre.
The average fiber of fibee reinforced packing material directly is generally 1～100 μ m, and preferred 2～50 μ m are more preferably 3～30 μ m, preferred especially 5～20 μ m.In addition, average fiber length is generally 0.1～20mm, preferred 1～10mm.
Be the interfacial adhesion of raising with resin, the fiber strengthening packing material preferably carries out using after the surface treatment with collecting agent or surface treatment agent.As collecting agent or surface treatment agent, can enumerate, for example, functionality compounds such as epoxy compounds, acrylic compounds, isocyanate ester compound, silane compound, titanate ester compound.The fiber strengthening packing material can carry out surface treatment in advance by collecting agent or surface treatment agent, perhaps, also can add collecting agent during the thermoplastic resin composition or surface treatment agent carries out surface treatment in preparation.
With respect to total 100 weight parts of polybutylene terephthalate (A) and aromatic copolycarbonate (B), the ratio of fibee reinforced packing material is generally 0.1～150 weight part, preferred 5～100 weight parts.During ratio less than 0.1 weight part of fibee reinforced packing material, can not show and cooperate the effect that fibee reinforced packing material produced, when surpassing 150 weight parts, difficulty becomes during the forming of melting mixing or resin combination.
The packing material that can also in thermoplastic resin composition of the present invention, cooperate other.As other packing materials that cooperate, can enumerate, for example, tabular inorganic filling material, ceramic bead, asbestos, wollastonite, talcum, potter's clay, mica, zeolite, kaolin, potassium titanate, barium sulfate, titanium oxide, silicon oxide, aluminum oxide, magnesium hydroxide etc.By cooperating tabular inorganic filling material, can reduce the anisotropy and the warpage of moulded products.As tabular inorganic filling material, can enumerate, for example, sheet glass, mica, tinsel etc.Among these, preferably use sheet glass.With respect to total 100 weight parts of polybutylene terephthalate (A) and aromatic copolycarbonate (B), the usage quantity of these packing materials is generally 1～100 weight part, preferred 5～50 weight parts.
Can also in thermoplastic resin composition of the present invention, add 2,6-di-t-butyl-4-octyl phenol, [3-(3 ' for tetramethylolmethane four, 5 '-tertiary butyl-4 '-hydroxy phenyl) propionic ester] etc. phenolic compound, dilauryl-3,3 '-thiodipropionate, tetramethylolmethane four sulfide compounds such as (3-lauryl thiodipropionates), triphenylphosphate, tricresyl phosphate (nonyl phenyl ester), tricresyl phosphate oxidation inhibitor such as phosphorus compound such as (2,4-di-t-butyl phenyl ester), paraffin, Microcrystalline Wax, polyethylene wax, montanic acid or montanate are the longer chain fatty acid and the ester thereof of representative, releasing agents such as silicone oil etc.
In order to give flame retardant resistance, can in thermoplastic resin composition of the present invention, cooperate fire retardant.As fire retardant, have no particular limits, can enumerate, for example, organohalogen compound, antimony compounds, phosphorus compound, polysiloxane compound, other organic fire-retardant, inorganic combustion inhibitor etc.As organohalogen compound, can enumerate, for example, bromo polycarbonate, brominated epoxy resin, bromo phenoxy resin, bromo polyphenylene oxide resin, bromo polyvinyl resin, bromo dihydroxyphenyl propane, polyacrylic acid pentabromo-benzyl ester etc.As antimony compounds, can enumerate, for example, ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, sodium antimonate etc.As phosphorus compound, can enumerate, for example, phosphoric acid ester, Tripyrophosphoric acid, ammonium polyphosphate, red phosphorus etc.As other organic fire-retardant, can enumerate, for example, nitrogen compounds such as melamine, cyanuric acid etc.As other inorganic combustion inhibitor, can enumerate, for example, aluminium hydroxide, magnesium hydroxide, silicon compound, boron compound etc.
Can in thermoplastic resin composition of the present invention, cooperate thermosetting resins such as thermoplastic resins such as polyethylene, polypropylene, polystyrene, polyacrylonitrile, polymethacrylate, ABS resin, polymeric amide, polyphenylene sulfide, polyethylene terephthalate, liquid crystal polyester, polyacetal, polyphenylene oxide, resol, melamine resin, polyorganosiloxane resin, Resins, epoxy.These thermoplastic resins and heat reactive resin also can make up more than 2 kinds and use.
Can in thermoplastic resin composition of the present invention, cooperate additive commonly used etc.As these additives, can enumerate, for example, stablizer such as heat-resisting stabilizing agent and lubricant, catalyst deactivation agent, crystallization nucleating agent, crystallization promotor etc.These additives can add in polymerization process or after the polymerization.In addition, in order to give the performance of expectation, can also cooperate tinting materials such as stablizers such as UV light absorber, weather-proof stablizer, dye pigment, static inhibitor, whipping agent, softening agent, shock-resistance modifying agent etc.
Thermoplastic resin composition of the present invention adopts usually and uses single shaft or biaxial extruder to carry out the method manufacturing of melting mixing, but in order to improve dispersiveness and to seek the raising of mechanical properties, preferably uses biaxial extruder.Wherein, reduce the preferred forcing machine that uses in order to prevent the molecular weight in the melting mixing with ventage type.
The method that PBT and PC is supplied to forcing machine has no particular limits, can enumerate, the method of be pre-mixed the two and method of together supplying with, using a plurality of feed appliances in the hopper of forcing machine, to mix the back to supply with, a kind of resin is supplied in the forcing machine, from the method for supplying with another resin midway of forcing machine, with the method for their combination etc.
In addition, in the present invention, because the catalyst concn among the PBT is controlled in certain scope, therefore, controlled compared with the past being improved largely of the transesterification reaction during melting mixing, controlled in order further to improve transesterification reaction, can use acid phosphites such as phosphoric acid ester, phosphorous acid esters etc., particularly phosphorous acid list (two) alkyl ester as the catalyst deactivation agent.Their addition is generally 0.001～5 weight part, and preferred 0.005～1 weight part is more preferably 0.01～0.5 weight part.
Thermoplastic resin composition's of the present invention method for processing forming has no particular limits, and can use for the normally used method of forming of thermoplastic resin, promptly, the methods of forming such as injection moulding, blow molding, extrusion moulding, extrusion forming.
Thermoplastic resin composition's of the present invention tone, hydrolytic resistance, thermostability, formability, shock-resistance, resistance to chemical reagents, excellent in dimensional stability, and painted can suppress to make the time or during moulding are at industrial utility value height.
Embodiment
Below, by embodiment the present invention is described in more detail, but the present invention is only otherwise exceed its main points, then is not subjected to any qualification of following examples.In addition, the rerum natura that adopts in each example below and the measuring method of assessment item are as follows.
(1) esterification yield:
(III) calculated by acid number and saponification value according to following calculating formula.Acid number uses the KOH/ methanol solution titration of 0.1N to try to achieve by oligopolymer is dissolved in the dimethyl formamide.Saponification value is to make hydrolyzing oligomer in the KOH/ of 0.5N ethanolic soln, tries to achieve with the salt acidometric titration of 0.5N again.
[several 3]
Esterification yield=((saponification value-acid number)/saponification value) * 100 ... (III)
(2) the titanium concentration among the PBT:
With used in electronic industry high purity sulfuric acid and nitric acid the PBT wet type is decomposed, use high de-agglomeration to measure by ICP (inductively coupled plasma)-MS (mass spectrograph) (manufacturing of Thermo-Quest company).
(3) limiting viscosity of PBT ([η]):
Use Ubbelohde type viscometer to obtain according to following main points.That is, use the mixed solvent of phenol/tetrachloroethane (weight ratio 1/1), under 30 ℃, mensuration concentration is the polymers soln of 1.0g/dL and only is second number that falls of solvent that (IV) obtains by following formula.
[several 4]
[η]＝((1+4K
Hη
sp)
0.5-1)/(2K
HC) …(IV)
(wherein, η
Sp=η/η
0-1, η be polymers soln fall a second number, η
0Be second number that falls of solvent, C is polymer solution concentration (g/dL), K
HBe the He Jin constant.K
HAdopt 0.33).
(4) decrease temperature crystalline temperature (Tc):
Use differential scanning calorimeter [パ one キ Application エ Le マ one company, model DSC7], be warmed up to 300 ℃ with the heat-up rate of 20 ℃/min from room temperature after, cool to 80 ℃ with the cooling rate of 20 ℃/min, with the exothermal peak temperature as the decrease temperature crystalline temperature.Tc is high more, and crystallization speed is fast more, and shaping cycle shortens.
(5) end carboxy concentration of PBT:
0.5g PBT or oligopolymer are dissolved in the 25mL benzylalcohol, carry out titration with the benzylalcohol solution of 0.01 mole/L of sodium hydroxide.
(6) terminal methoxycarbonyl concentration and the terminal ethylenyl groups concentration of PBT:
In the mixed solvent of 1mL deuterochloroform/hexafluoroisopropanol=7/3 (volume ratio), dissolve the PBT of about 100mg, add the deuterated pyridine of 36 μ L, measure down at 50 ℃
1H-NMR and trying to achieve." α-400 " or " AL-400 " that the NMR device uses NEC (strain) to make.
(7) particle tone:
The colour-difference meter (Z-300A type) that uses Japanese electric look (strain) to make is estimated with the b value in L, a, the b coloring system.Be worth low more, the expression yellowing low more, tone is good more.
(8) the solution haze value of PBT:
After under 110 ℃ 2.70g PBT being dissolved 30 minutes in the mixed solvent of 20mL phenol/tetrachloroethane=3/2 (weight ratio), cooling is 15 minutes in 30 ℃ Water Tank with Temp.-controlled, use the turbidometer (NDH-300A) of Japanese electric look (strain) manufacturing, measure the turbidity of solution with the pond of long 10mm.It is good more to be worth the low more expression transparency.
(9) viscosity-average molecular weight of PC (Mv)
Use the dichloromethane solution of the concentration (C) of aromatic copolycarbonate, by the specific viscosity (η that uses the Ubbelohde viscometer determining down at 20 ℃ as 0.6g/dL
Sp) use following formula V and (VI) calculate.
η
sp/C＝[η]×(1+0.28η
sp) (V)
[η]＝1.23×10
-4×(Mv)
0.83 (VI)
(10) the terminal hydroxyl concentration of PC
Carry out colorimetric assay by titanium tetrachloride/method of acetic acid (Makromol.Chem.88 215 (1965)).
(11) stretching and pendulum impact test
The injection moulding machine (model SG-75MIII) that uses Sumitomo heavy-duty machine tool (strain) to make is 250 ℃ at barrel temperature, and die temperature is that according to ISO294-1, moulding is used for the ISO test film that mechanical properties is measured, and carries out performance evaluation under 80 ℃ the condition.Tension test is carried out according to the ISO527 standard.The unit of intensity and elongation is respectively " MPa " and " % ".In addition, pendulum impact test is carried out according to the ISO179 standard.Measure nicked intensity, its unit is " kJ/m
2".
(12) dissolving viscosity reduces ratio
Measure with filler particles in the barrel at the melt viscosity of the キ ヤ ピ ロ グ ラ Off (model 1B) that the smart machine of Japan (strain) is made, after 5 minutes, measuring velocity of shear is 91 (see 270 ℃ of following preheatings
-1) under melt viscosity (melt viscosity A), after keeping 30 minutes under this temperature, measure melt viscosity (melt viscosity B) once more, calculate their ratio (melt viscosity B/ melt viscosity A).Be worth big more, the expression melt stability excellent more.
Embodiment 1
By esterification step shown in Figure 1 and polycondensation step shown in Figure 2, carry out the manufacturing of PBT according to following main points.At first, will be with respect to 1.00 moles of terephthalic acids, with 1,60 ℃ slurry of the mixed that the 4-butyleneglycol is 1.80 moles supplies to continuously with the speed of 40.0kg/h by raw material supplying pipeline (1) from the pulp preparation groove and has been pre-charged with the reactive tank that is used for esterification (A) with propeller-type stirrer that esterification yield is 99% PBT oligopolymer.Simultaneously, supply with composition at the bottom of 185 ℃ the tower of rectifying tower (C) with the speed of 18.4kg/h from recirculation line (2), supply with as 1 of 6.0 weight % of 65 ℃ tetrabutyl titanate ester of catalyzer, 4-butanediol solution (is 40ppm with respect to theoretical polymkeric substance receipts amount) with the speed of 127g/h from catalyzer supply line (3).Moisture in this solution is 0.20 weight %.
The internal temperature of reactive tank (A) is 230 ℃, and pressure is 78kPa, and with the water that generates and THF and remaining 1, the 4-butyleneglycol distillates from distillating pipeline (5), is separated into high boiling point composition and low boiling point component in rectifying tower (C).More than the 98 weight % of the high boiling point composition at the bottom of the tower after system is stable is 1, and the 4-butyleneglycol for the liquid level that makes rectifying tower (C) is certain, is drawn to the outside by extracting pipeline (8) out with its part.On the other hand, low boiling point component is extracted out with gas form from cat head, and condensation in condenser (G) for the liquid level that keeps container (F) is certain, is drawn to the outside by extracting pipeline (13) out.
Certain amount of the oligopolymer that generates in reactive tank (A) uses pump (B) to extract out from extracting pipeline (4) out, and the control liquid level is so that the average retention time of the interior liquid of reactive tank (A) is 3.0 hours.Supply to the 1st polycondensation groove (a) continuously from the oligopolymer of extracting pipeline 4 extractions out.After system was stable, the esterification yield of the oligopolymer that collects in the outlet of reactive tank (A) was 97.4%.
The internal temperature of the 1st polycondensation groove (a) is 240 ℃, and pressure is 2.7kPa, carries out tank level control so that the residence time is 120 minutes.Extract water, THF, 1 out from the ventilation line (L2) that is connected on the negative booster (not shown), the 4-butyleneglycol carries out the initial stage polycondensation simultaneously.The reaction solution of extracting out supplies in the 2nd polycondensation groove (d) continuously.
The internal temperature of the 2nd polycondensation groove (d) is 245 ℃, pressure is 140Pa, and the control liquid level is extracted water, THF, 1 so that the residence time is 60 minutes out from the ventilation line (L4) that is connected on the negative booster (not shown), the 4-butyleneglycol further carries out polycondensation simultaneously.The polymkeric substance that obtains supplies in the 3rd polycondensation groove (k) through extracting pipeline (L3) out continuously by extracting out with toothed gear pump (e).The internal temperature of the 3rd polycondensation groove (k) is 239 ℃, and pressure is 600Pa, and the residence time is 80 minutes, further carries out polycondensation.The polymkeric substance that obtains is extracted out continuously from die head (g) and is strip, cuts off with rotary cutter (h).The end carboxy concentration of the PBT that obtains is 22 μ eq/g.The PBT tone excellence that obtains, the solution haze value is low.Analytical value is concluded and is shown in table 1.
With the above-mentioned PBT of the mixed of weight ratio 7 to 3 with the viscosity-average molecular weight that melt phase polycondensation obtains is 21000, terminal hydroxyl concentration is PC (Mitsubishi's engineering plastics (strain) company manufacturing of 31 μ eq/g, trade(brand)name " Pie バ レ ッ Network ス 7022J "), the biaxial extruder (internal diameter 30mm) that uses Japan system steel company to make, at 260 ℃ of following melting mixings, obtain the polymer alloy of PBT and PC.Obtain polymer alloy tone, physical strength, excellent heat stability.The result concludes and is shown in table 1.
Except in embodiment 1, the internal temperature of the 2nd polycondensation groove (d) being set at 246 ℃, pressure is made as 180Pa, residence time was made as 80 minutes, the internal temperature of the 3rd polymerization reaction trough (k) is made as 243 ℃, pressure is made as 900Pa, beyond residence time was made as 90 minutes, carry out similarly to Example 1.Obtaining end carboxy concentration is 35 μ eq/g, tone excellence, the PBT that the solution haze value is low.Use this PBT to obtain polymer alloy similarly to Example 1.Obtain polymer alloy tone, physical strength, excellent heat stability.The result concludes and is shown in table 1.
In embodiment 1, remove using the terminal hydroxyl concentration that is obtained by interfacial polymerization is that the PC (Mitsubishi's engineering plastics (strain) company makes, trade(brand)name " ノ バ レ ッ Network ス 7022J ") of 2 μ eq/g in addition, carries out similarly to Example 1.Obtain the polymer alloy of tone, physical strength, excellent heat stability.The result concludes and is shown in table 1.
Comparative example 1
In embodiment 1, except supplying with catalyst solution with 64g/h, and the internal temperature of the 2nd polycondensation groove (d) is made as 247 ℃, pressure is made as 140Pa, residence time was made as 90 minutes, the internal temperature of the 3rd polycondensation groove (k) is made as 247 ℃, and the residence time was made as outside 90 minutes, carried out similarly to Example 1.The terminal ethylenyl groups concentration height of the PBT that obtains, tone worsens.The tone or the physical strength of the polymer alloy that obtains in addition, also reduce.The result is summarized in table 1.
Comparative example 2
In embodiment 1, except supplying with catalyst solution with 254g/h, and the pressure of the 2nd polycondensation groove (d) is made as 200Pa, the pressure of the 3rd polycondensation groove (k) is made as 650Pa, beyond the residence time was made as 70 minutes, carry out similarly to Example 1.The terminal ethylenyl groups concentration height of the PBT that obtains, the haze value in tone or the solution worsens.Intensity, the thermostability of the tone of the polymer alloy that obtains in addition,, machinery also reduce.The result is summarized in table 1.
Comparative example 3
In the internal capacity with Scroll-type agitating wing is the reaction vessel made of the stainless steel of 200L, add 272.9mol dimethyl terephthalate (DMT) (DMT), 327.5mol 1,4-butyleneglycol, 0.126mol tetrabutyl titanate ester are (in the titanium amount, with respect to the theoretical yield polymkeric substance is 100ppm), fully carry out nitrogen replacement.Then, system is heated up, after 60 minutes under 210 ℃ of temperature, nitrogen, normal atmosphere, with the methyl alcohol, 1 that generates, 4-butyleneglycol, THF distillate outside the system, carry out 2 hours transesterification reaction (the reaction time opening is the moment that reaches specified temperature, specified pressure) simultaneously.
With the above-mentioned oligopolymer that obtains transfer to the internal capacity with ventpipe and double helical form agitating wing be in the reaction vessel made of the stainless steel of 200L after, reached 245 ℃ of temperature, pressure 100Pa through 60 minutes, directly carry out 2.5 hours polycondensation with this state.After reaction finishes, polymkeric substance is extracted out to strip, cut into particulate state.The PBT end carboxy concentration that obtains is 44 μ eq/g, and terminal methoxycarbonyl concentration is 2.0 μ eq/g.
Use above-mentioned PBT, obtain polymer alloy similarly to Example 1.The physical strength of the polymer alloy that obtains is low, and thermostability also reduces.The result concludes and is shown in table 1.
[table 1]
| Embodiment | Comparative example | ||||||
| 1 | 2 | 3 | 1 | 2 | 3 | ||
| Raw material PBT | [Ti](ppm) | 40 | 40 | 40 | 20 | 80 | 100 |
| [η] | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | |
| Tc(℃) | 178 | 179 | 178 | 177 | 178 | 168 | |
| End carboxy concentration (μ eq/g) | 22 | 35 | 22 | 25 | 27 | 44 | |
| Terminal methoxycarbonyl concentration (μ eq/g) | ≤0.1 | ≤0.1 | ≤0.1 | ≤0.1 | ≤0.1 | 2.0 | |
| Terminal ethylenyl groups concentration (μ eq/g) | 7 | 10 | 7 | 12 | 9 | 8 | |
| Particle tone (b value) | -1.2 | -0.2 | -1.2 | 0.4 | 0.5 | -1.0 | |
| Solution haze value (%) | ≤0.3 | ≤0.3 | ≤0.3 | ≤0.3 | 5.5 | ≤0.3 | |
| Raw material PC | Mv | 21000 | 21000 | 21000 | 21000 | 21000 | 21000 |
| Terminal hydroxyl concentration (μ eq/g) | 31 | 31 | 2 | 31 | 31 | 31 | |
| PBT/PC | Particle tone (b value) | 7 | 9 | 8 | 10 | 13 | 12 |
| Tensile strength (Mpa) | 55 | 54 | 52 | 49 | 48 | 48 | |
| Tensile elongation (%) | 14 | 12 | 12 | 9 | 7 | 6 | |
| Pendulum bell impact value (kJ/m 2) | 6.2 | 5.9 | 5.7 | 4.9 | 4.8 | 4.7 | |
| Melt viscosity reduces ratio (%) | 55 | 54 | 50 | 55 | 42 | 39 | |
Similarly to Example 1, be that 7 to 3 PBT and PC together put in the hopper of forcing machine with the weight ratio of 100 weight parts, after the fusion, add 30 weight part glass fibre from other feeders, obtain glass fiber-reinforced polymer alloy.The result of the glass fiber-reinforced polymer alloy that obtains is recorded in table 2.The commodity that glass fibre uses NEG company to make are called the glass fibre of " T-187 " (diameter 13 μ m, length 3mm).
Comparative example 4
Use the PBT and the PC that use in the comparative example 1, the method by identical with embodiment 4 obtains glass fiber-reinforced polymer alloy.The result of the glass fiber-reinforced polymer alloy that obtains is recorded in table 2.Tone or physical strength worsen.
Comparative example 5
Use the PBT and the PC that use in the comparative example 3, the method by identical with embodiment 4 obtains glass fiber-reinforced polymer alloy.The result of the glass fiber-reinforced polymer alloy that obtains is recorded in table 2.Tone or physical strength, thermostability worsen.
[table 2]
| |
Comparative example 4 | Comparative example 5 | |
| The |
9 | 11 | 13 |
| Tensile strength (MPa) | 131 | 121 | 122 |
| Tensile elongation (%) | 2.5 | 2.4 | 2.3 |
| Pendulum impact value (kJ/m 2) | 9.2 | 8.2 | 8.1 |
| Melt viscosity reduces ratio (%) | 48 | 47 | 39 |
Claims (9)
1. thermoplastic resin composition, it is the polybutylene terephthalate (A) and the aromatic copolycarbonate (B) of 1/19～19/1 (weight ratio) that said composition contains proportional, wherein, use titanium content to be higher than 33ppm in titanium atom and as the polybutylene terephthalate below the 75ppm as polybutylene terephthalate (A).
2. the described thermoplastic resin composition of claim 1, wherein, the terminal hydroxyl concentration of aromatic copolycarbonate (B) is 5～50 μ eq/g.
3. claim 1 or 2 described thermoplastic resin compositions, wherein, the terminal methoxycarbonyl concentration of polybutylene terephthalate (A) is below the 0.5 μ eq/g.
4. any described thermoplastic resin composition in the claim 1～3, wherein, the terminal ethylenyl groups concentration of polybutylene terephthalate (A) is 0.5～10 μ eq/g.
5. any described thermoplastic resin composition in the claim 1～4, wherein, the titanium content of polybutylene terephthalate (A) is 40～60ppm.
6. any described thermoplastic resin composition in the claim 1～5, wherein, the end carboxy concentration of polybutylene terephthalate (A) is 1～30 μ eq/g.
7. any described thermoplastic resin composition in the claim 1～6, wherein, the viscosity-average molecular weight of aromatic copolycarbonate (B) is 15000～23000.
8. any described thermoplastic resin composition in the claim 1～7, wherein, also contain fibee reinforced packing material, its ratio is 0.1～150 weight part with respect to total amount 100 weight parts of polybutylene terephthalate (A) and aromatic copolycarbonate (B).
9. formed body, this formed body comprises any described thermoplastic resin composition in the claim 1～8.
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| CN104379669A (en) * | 2012-06-18 | 2015-02-25 | 巴斯夫欧洲公司 | Flame-proof polyester comprising polyacrylonitrile homopolymerisates |
| CN112625404A (en) * | 2020-11-25 | 2021-04-09 | 金发科技股份有限公司 | Glass fiber reinforced PBT/PC alloy with high strength, low warpage and high thermal deformation temperature, and preparation method and application thereof |
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| WO2007074603A1 (en) * | 2005-12-27 | 2007-07-05 | Mitsubishi Chemical Corporation | Aromatic polycarbonate resin composition and molded resin |
| JP2007176969A (en) * | 2005-12-27 | 2007-07-12 | Mitsubishi Chemicals Corp | Aromatic polycarbonate resin composition and resin molded product |
| JP2007176970A (en) * | 2005-12-27 | 2007-07-12 | Mitsubishi Chemicals Corp | Aromatic polycarbonate resin composition and resin molded product |
| JP5204795B2 (en) * | 2010-01-15 | 2013-06-05 | 帝人化成株式会社 | Polycarbonate resin composition |
| JP5204814B2 (en) * | 2010-08-10 | 2013-06-05 | 帝人化成株式会社 | Thermoplastic resin composition |
| CN102712807B (en) * | 2010-01-15 | 2014-09-03 | 帝人化成株式会社 | Polycarbonate resin composition |
| JP5346994B2 (en) * | 2011-07-11 | 2013-11-20 | 帝人株式会社 | Polycarbonate resin composition and molded article thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104379669A (en) * | 2012-06-18 | 2015-02-25 | 巴斯夫欧洲公司 | Flame-proof polyester comprising polyacrylonitrile homopolymerisates |
| CN112625404A (en) * | 2020-11-25 | 2021-04-09 | 金发科技股份有限公司 | Glass fiber reinforced PBT/PC alloy with high strength, low warpage and high thermal deformation temperature, and preparation method and application thereof |
| CN112625404B (en) * | 2020-11-25 | 2022-03-01 | 金发科技股份有限公司 | Glass fiber reinforced PBT/PC alloy with high strength, low warpage and high thermal deformation temperature, and preparation method and application thereof |
| WO2022110674A1 (en) * | 2020-11-25 | 2022-06-02 | 金发科技股份有限公司 | Glass fiber reinforced pbt/pc alloy with high strength, low warpage and high thermal deformation temperature, preparation method therefor and use thereof |
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