CN100572418C - Aromatic dihydroxy compound and carbonic diester prepare polycarbonate catalyzer neutralizing treatment method and employed neutralizing agent - Google Patents
Aromatic dihydroxy compound and carbonic diester prepare polycarbonate catalyzer neutralizing treatment method and employed neutralizing agent Download PDFInfo
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- CN100572418C CN100572418C CNB2007100586056A CN200710058605A CN100572418C CN 100572418 C CN100572418 C CN 100572418C CN B2007100586056 A CNB2007100586056 A CN B2007100586056A CN 200710058605 A CN200710058605 A CN 200710058605A CN 100572418 C CN100572418 C CN 100572418C
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- neutralizing agent
- catalyzer
- ester compounds
- aromatic dihydroxy
- organophosphorus ester
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Abstract
The present invention relates to a kind of aromatic dihydroxy compound and carbonic diester and prepare polycarbonate, belong to the polycarbonate technical field with catalyzer neutralizing treatment method and employed neutralizing agent.Be used for the preparation polycarbonate catalyst is carried out the neutral neutralizing agent, it is characterized in that this neutralizing agent comprises a kind of organophosphorus ester compounds at least, this compound has following general formula: wherein R, R
1, R
2Be H or trimethyl silyl-Si (CH
3)
3, n=0～50, m=0～50.A kind of to the preparation polycarbonate catalyst carry out the neutral method, reactant is aromatic dihydroxy compound and carbonic diester, catalyzer is acetylacetone based metal complexes and nitrogenous basic cpd, reaction finishes back adding neutralizing agent basic catalyst is neutralized, and this neutralizing agent is above-mentioned neutralizing agent.By to the remainder catalyst neutralization, can obtain having the stable polycarbonate of cycling processability.
Description
Technical field
The invention belongs to the polycarbonate technical field, further relate to a kind of aromatic dihydroxy compound and carbonic diester and prepare polycarbonate catalyzer neutralizing treatment method and employed neutralizing agent.
Background technology
Polycarbonate is celebrated with its good transparency, shock-resistance, thermotolerance, dimensional stability, nontoxicity, weathering resistance, electrical insulating property, anti-gamma ray sterilization and mechanical property, is the very good thermoplastic engineering plastic of over-all properties.
Polycarbonate directly carries out melting state transesterification reaction by dihydroxyphenyl propane and diphenyl carbonate and prepares under the basic catalyst effect, compare with traditional phosgenation, avoid using the phosgene and the methylene chloride of severe toxicity, no desolventizing and water elution salt operation, flow process is simple, greatly reduces the pollution level to environment.Although this method is comparatively harsh in the requirement of aspects such as material purity, production unit, Technology, the plurality of advantages that is had because of itself has become current polycarbonate industrialization direction.
In this polycarbonate finished product remaining catalyzer, be extruded or during post-treatment, tending to has disadvantageous effect to polycarbonate finished product quality at polycarbonate, worsen and transparency reduction etc. as polymer molecule degraded, form and aspect.Therefore, after catalyzer is finished katalysis, be desirable to provide a kind of method, it is minimum by neutralization or passivation residual quantity to be reduced to the remainder catalyst in the finished product polycarbonate, comes maximum inhibition or effectively prevents the disadvantageous effect of catalyzer to finished product polycarbonate post-treatment.
Summary of the invention
One of purpose of the present invention is: for the catalyzer that method adopted that carries out melting state transesterification reaction production polycarbonate by aromatic dihydroxy compound and carbonic diester provides efficient neutralizing agent.
Two of purpose of the present invention is: for the catalyzer that method adopted that carries out melting state transesterification reaction production polycarbonate by aromatic dihydroxy compound and carbonic diester provides neutralization method.
The present invention is achieved through the following technical solutions.
Related reactant is aromatic dihydroxy compound and carbonic diester.The aromatic dihydroxy compound of one of reactant is preferably dihydroxyphenyl propane, but also available other dihydric phenol or alcohol; The carbonic diester of one of reactant is preferably diphenyl carbonate, but not should be understood that and should only limit to diphenyl carbonate.
Related catalyzer is acetylacetone based metal complexes and nitrogenous basic cpd.One of composite catalyst is acetylacetone based metal complexes, preferably any in methyl ethyl diketone lanthanum, methyl ethyl diketone cerium, methyl ethyl diketone samarium and methyl ethyl diketone europium; With acetylacetone based another catalyzer of metal complexes compound be nitrogenous basic cpd, preferred any in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TBAH, hydroboration tetramethylammonium, hydroboration four butylamine, tetraphenyl borate tetramethylammonium, tetraphenyl borate four fourth methylamines.
The neutralizing agent that is suitable for for comprise at least a kind of organophosphorus ester compounds mixture.Above-mentioned organophosphorus ester compounds has following general formula:
Wherein R, R
1, R
2Be H or trimethyl silyl-Si (CH
3)
3, n=0～50, m=0～50.
The preferred situation of this neutralizing agent is: comprise any in following three kinds of organophosphorus ester compounds at least,
First kind of organophosphorus ester compounds, R=H in this compound general formula, R
1=H, R
2=-Si (CH
3)
3, n=0, m=0;
Second kind of organophosphorus ester compounds, R=H in this compound general formula, R
1=-Si (CH
3)
3, R
2=-Si (CH
3)
3, n=0, m=0;
The third organophosphorus ester compounds, R=-Si (CH in this compound general formula
3)
3, R
1=-Si (CH
3)
3, R
2=-Si (CH
3)
3, n=0, m=0.
The further preferred situation of this neutralizing agent is: comprise above-mentioned three kinds of organophosphorus ester compounds, and the weight percent content of three kinds of organophosphorus ester compounds is respectively:
First kind of organophosphorus ester compounds: 10%-30%;
Second kind of organophosphorus ester compounds: 65%-85%;
The third organophosphorus ester compounds: 2%-7%.
The add-on of organophosphorus ester class mixture neutralizing agent determines that according to the amount of acetylacetone based metal complexes add-on is 3 to 8 times of molar weight meters of acetylacetone based metal complexes, preferred 4 to 6 times of molar weights.
Usually neutralizing agent uses with the form that is made into certain density solution, and the solvent in the solution mainly serves as diluent functions, helps a small amount of neutralizing agent is joined in the product of melt polymerization equably.Contain the high solution of neutralizing agent concentration and can add more on a small quantity, the solution that concentration is low can add more amount, and strength of solution should finally be removed and is as the criterion to help neutralizing agent homodisperse and solvent.Usually, neutralizing agent concentration is pressed 1mg-20mg/100mL configuration, preferably about 10mg/100mL.
By preparing remainder catalyst in the polycarbonate with the neutralization of organophosphorus ester class mixture neutralizing agent, can obtain having the stable polycarbonate of cycling processability to carry out melting state transesterification reaction by aromatic dihydroxy compound and carbonic diester.
Embodiment
Embodiment 1
Melting state transesterification reaction carries out in the successive reactor usually stage by stage.At first dihydroxyphenyl propane and diphenyl carbonate and catalyzer are mixed under the fusion in reactor, in the fs of reaction, temperature of reaction is at 250 ℃ or more carry out about 10 millibars from barometric point to absolute pressure of pressure under the low temperature, time is about 1 hour to 3 hours, preferred 1.5 hours to 2.5 hours; The reaction subordinate phase in, temperature of reaction is being carried out more than 250 ℃, the pressure absolute pressure about 1 millibar or below, the time is about 1 hour to 3 hours, preferred 1.5 hours to 2.5 hours.Behind the finished product polycarbonate that reaches needed target molecular weight, add that above neutralizing agent neutralizes fully or the passivation reaction catalyzer, industrial can be with the finished product by the forcing machine granulation or through handling in addition.
Be reflected to be furnished with in the non-leakage magnetic coupled driving stirring nickel system metal reaction still and carry out.Vacuum system steams condenser by phenol receiving flask and phenol and links to each other with reactor, reacting system pressure is jointly controlled by vacuum pump that is incorporated into phenol receiving flask downstream and nitrogen steel cylinder, adopt U type mercury manometr to measure during high pressure (barometric point to 50 millibar), measure with Maxwell rotary type vacuumometer during low pressure (50 millibars to 1.333 millibars and following).The reactive system temperature adopts heating of circulating heat conduction oil and control.The reactor bottom sets out the material mouth.
In reactor, add solid dihydroxyphenyl propane (Japanese GE Plastics Company) 600.0g (2.628mol) successively, solid carbonic acid diphenyl ester (Shen, Shanghai dimerization factory) 602.4g (2.812mol), diphenyl carbonate/dihydroxyphenyl propane=1.07 (mol/mol), subsequently that kettle cover and kettle is closely linked, near or be lower than slightly under the barometric point, the heating thermal oil heats up reaction mass gradually, starts stirring after 120 ℃, adds in the time of 180 ℃ and contains catalyzer TMAH and La (acac)
3Water or water-ethanol solution.In 5 minutes pressure is reduced to 133.3 millibars, temperature of reaction rises to or maintains 180 ℃, picks up counting, and continues 60 minutes, has phenol constantly to distillate during this; In 5 minutes temperature is risen to 220 ℃ then, pressure is reduced to 40.0 millibars, keeps 60 minutes; In 5 minutes temperature is risen to 260 ℃ more afterwards, pressure is reduced to 20.0 millibars, keeps 60 minutes; In 5 minutes temperature is risen to 280 ℃ at last, pressure is reduced to about 1.0 millibars, keeps 30 minutes, and polyreaction finishes, and adds and contains the solution that neutralizing agent is preferred organophosphorus ester mixture, and the organophosphorus ester usage quantity is 5 times of catalyzer La (acac)
3Amount (mol ratio) stirred 15 to 20 minutes, and pressure is reduced to about 1.0 millibars, till solvent is steamed fully.Blowing under the discharge port nitrogen atmosphere protection under the still.
The polymeric articles of being emitted, a part are used for molecular weight and Hue index analysis; Another part sample is added in the barrel of melt indexer, will expect that bar inserts barrel, preheating 4min under 300 ℃, then the 1.2kg counterweight is joined material masthead end, after keeping 1min, open the die orifice plug, effusive polymkeric substance is used for molecular weight and Hue index analysis equally.Molecular weight and Hue index variation are measured neutralization before and after the heating.
In an embodiment, resulting polycarbonate carries out measuring physical properties by following method.
(1) viscosity-average molecular weight
At 20 ℃ of methylene dichloride is to use determination of ubbelohde viscometer in (0.5g/dL), viscosity-average molecular weight M
vCalculation formula is
[η]＝1.11×10
-4M
v 0.82
(2) form and aspect
With Hue exponential representation.Utilize day island proper Tianjin UV-160A ultraviolet spectrophotometer, under wavelength 380nm, the long 10mm of cuvette, the absorbance A of the dichloromethane solution (1g/10mL) of mensuration polycarbonate
380, deduct its absorbance A at 580nm
580, estimate the coloring degree of polycarbonate, that is: Hue index=A
380-A
580
Embodiment 2
Except using 3 times of catalyzer La of preferred organophosphorus ester mixture (acac)
3Amount (mol than) is as outside the neutralizing agent, carries out the process identical with embodiment 1 with the preparation polycarbonate and carry out the neutralization analysis of similar process.
Embodiment 3
Except using 8 times of catalyzer La of preferred organophosphorus ester mixture (acac)
3Amount (mol than) is as outside the neutralizing agent, carries out the process identical with embodiment 1 with the preparation polycarbonate and carry out the neutralization analysis of similar process.
The comparative example
Except not using the organophosphorus ester mixture as neutralizing agent, only add and do not contain outside the equivalent solvent of neutralizing agent, carry out the process identical with the preparation polycarbonate and carry out the neutralization analysis of similar process with embodiment 1.
By molecular weight before and after the polycarbonate for preparing among embodiment 1～3 and the comparative example is heated and Hue index variation, determine neutralization.The results are shown in the following table 1.
Table 1
In an embodiment, determine the preferred catalyst system at this reaction institute, neutralizing agent organophosphorus ester class amount of mixture is catalyzer La (acac)
3During 5 times of molar weights, had neutralization or passivation effect preferably.During the reprocessing of gained polycarbonate products, degraded and form and aspect deterioration degree all are reduced to bottom line, i.e. its viscosity-average molecular weight changes in 0.15% before and after the high-temperature heating processing, and its form and aspect hue index variation is in 0.003.
The foregoing description is explanation or the explanation of wanting the resist technology scheme to of the present invention, but should clear and definite the present invention be not limited to these embodiment, and therefore, protection scope of the present invention still is as the criterion with the technical scheme that claims are described.
Claims (7)
1, a kind ofly aromatic dihydroxy compound and carbonic diester are prepared polycarbonate carries out the neutral method with catalyzer, catalyzer is acetylacetone based metal complexes and nitrogenous basic cpd, it is characterized in that: reaction finishes the back and adds a kind of neutralizing agent, this neutralizing agent comprises a kind of organophosphorus ester compounds at least, and wherein the organophosphorus ester compounds has following general formula:
Wherein R, R
1, R
2Be H or trimethyl silyl-Si (CH
3)
3, n=0～50, m=0～50;
The add-on of neutralizing agent is in 3 to 8 times of molar weights of acetylacetone based metal complexes; Neutralizing agent uses with the form of the solution that is made into 1mg-20mg/100mL concentration.
2, a kind ofly according to claim 1 aromatic dihydroxy compound and carbonic diester are prepared polycarbonate carry out the neutral method with catalyzer, it is characterized in that, the neutralizing agent that is added comprises any in the following organophosphorus ester compounds at least,
First kind of organophosphorus ester compounds, R=H in this compound general formula, R
1=H, R
2=-Si (CH
3)
3, n=0, m=0;
Second kind of organophosphorus ester compounds, R=H in this compound general formula, R
1=-Si (CH
3)
3, R
2=-Si (CH
3)
3, n=0, m=0;
The third organophosphorus ester compounds, R=-Si (CH in this compound general formula
3)
3, R
1=-Si (CH
3)
3, R
2=-Si (CH
3)
3, n=0, m=0.
3, aromatic dihydroxy compound and carbonic diester are prepared polycarbonate carry out the neutral method as a kind of as described in the claim 2 with catalyzer, it is characterized in that, comprise described three kinds of organophosphorus ester compounds, and the content of three kinds of organophosphorus ester compounds is respectively:
First kind of organophosphorus ester compounds: 10%-30%;
Second kind of organophosphorus ester compounds: 65%-85%;
The third organophosphorus ester compounds: 2%-7%.
4, aromatic dihydroxy compound and carbonic diester are prepared polycarbonate carry out the neutral method as claim 1 to 3 is a kind of as described in any one with catalyzer, it is characterized in that the add-on of neutralizing agent is 4 to 6 times of molar weight meters of acetylacetone based metal complexes; Neutralizing agent uses with the form of the solution that is made into 10mg/100mL concentration.
5, aromatic dihydroxy compound and carbonic diester are prepared polycarbonate carry out the neutral method with catalyzer as claim 1 to 3 is a kind of as described in any one, it is characterized in that aromatic dihydroxy compound is a dihydroxyphenyl propane, carbonic diester is a diphenyl carbonate.
6, aromatic dihydroxy compound and carbonic diester are prepared polycarbonate carry out the neutral method as claim 1 to 3 is a kind of as described in any one with catalyzer, it is characterized in that the acetylacetone based metal complexes of one of composite catalyst is selected from any in methyl ethyl diketone lanthanum, methyl ethyl diketone cerium, methyl ethyl diketone samarium and the methyl ethyl diketone europium.
7, aromatic dihydroxy compound and carbonic diester are prepared polycarbonate carry out the neutral method as claim 1 to 3 is a kind of as described in any one with catalyzer, it is characterized in that, be selected from any in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TBAH, hydroboration tetramethylammonium, hydroboration four butylamine, tetraphenyl borate tetramethylammonium, the tetraphenyl borate four fourth methylamines with the nitrogenous basic cpd of acetylacetone based another catalyzer of metal complexes compound.
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