CN1454239A - Polycarbonate having excellent hydrolytic stability - Google Patents
Polycarbonate having excellent hydrolytic stability Download PDFInfo
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- CN1454239A CN1454239A CN 00819635 CN00819635A CN1454239A CN 1454239 A CN1454239 A CN 1454239A CN 00819635 CN00819635 CN 00819635 CN 00819635 A CN00819635 A CN 00819635A CN 1454239 A CN1454239 A CN 1454239A
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
- C08G64/14—Aromatic polycarbonates not containing aliphatic unsaturation containing a chain-terminating or -crosslinking agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
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Abstract
This invention is related to polycarbonate produced by the melt process having excellent hydrolytic stability. The invention further relates to a method for preparing polycarbonate having improved hydrolytic stability, and articles made from the polycarbonate having improved hydrolytic stability.
Description
Invention field
The present invention relates to polycarbonate with excellent hydrolytic stability by the scorification preparation.The invention still further relates to a kind of method that is used to prepare polycarbonate with improvement stability to hydrolysis, and from described goods with polycarbonate of improvement stability to hydrolysis.
Background of invention
Conventional factory is mixed together polycarbonate synthesis by the aqueous solution that makes dihydroxy compound (as bisphenol-A) and the organic solvent (as methylene dichloride) that contains carbonylic halide (as phosgene).When mixing immiscible organic phase and water, described dihydroxy compound reacts at phase interface place and described carbonylic halide.Usually phase-transfer catalyst (as tertiary amine) is joined aqueous phase in order to strengthen this reaction.This synthetic method is usually " interface " synthesis method that is used to prepare polycarbonate known to us.
The described interfacial process that is used to prepare polycarbonate has several inherent shortcomings.One of shortcoming is to need process that requires phosgene as reagent of operation, and this will cause tangible security concerns.Two of shortcoming is to need process that requires a large amount of organic solvents of operation, must take the preventive measures of various costlinesses in order to prevent any hostile environment influence.Three of shortcoming is that described interfacial needs relatively large device and capital investment.Four of shortcoming is to have the particle of unsettled color, higher level content and the chlorine that can cause the corrosive high level easily by the prepared polycarbonate of interfacial.
Some new polycarbonate factories promptly come polycarbonate synthesis by the diester (as dipheryl carbonate base ester) that adopts dihydroxy compound (as bisphenol-A) condensation carbonic acid by transesterification reaction.This reaction need not be adopted solvent, and by mixing all ingredients phenol that distillation reaction produced simultaneously reaction is accomplished under decompression and high temperature.This synthetic technology is commonly referred to " fusion " technology.Fusion technology is superior to the interface tech part and is not adopt phosgene, does not need solvent, and needs less device.In addition, the polycarbonate of being produced by scorification does not contain the cl contaminant from all ingredients, and granule content is lower, and color is more stable.Therefore, people more need to adopt fusion technology in industrial manufacture process.
Producing in the polycarbonate by melt phase polycondensation, alkali metal hydroxide, particularly sodium hydroxide is commonly used for polymerizing catalyst.Though alkali metal hydroxide can be used as polymerizing catalyst, they also cause obtaining the side reaction of branching side reaction product.This will cause the change of the melting characteristic of polycarbonate, and then make processing become difficult.
To be the catalyzer that remains in the gained polycarbonate have a negative impact to the performance of polycarbonate another shortcoming of using basic catalyst.Particularly, the stability to hydrolysis of polycarbonate will be subjected to the influence of residual catalyst.
Can be different to its desired stability to hydrolysis of a given application.For some application, for example to produce in the flaky resin of double-walled (twin wall) sheet material can be used for, it is more crucial that the stability to hydrolysis of polycarbonate becomes.
US5,606,607 disclose a kind of method that is used to prepare aromatic polycarbonate, wherein add epoxide in the presence of the acidic components of sulfur-bearing.But the not mentioned influence that joins the various additives of polycarbonate to stability to hydrolysis of the document.
For the requirement that for the polycarbonate of scorification preparation, exists its stability to hydrolysis of improvement.Particularly, need a kind of polycarbonate that the stability to hydrolysis that can be used for producing flaky resin (being used for the double-walled sheet material) obtains improveing that have.
Summary of the invention
One aspect of the present invention relates to a kind of polycarbonate compositions of hydrolysis-stable, the polycarbonate compositions of described hydrolysis-stable has and is lower than about 98% mole terminal aryl carbonates group and 2% mole or above terminal hydroxyl (total mole number based on all end groups of polycarbonate calculates), the polycarbonate of described hydrolysis-stable also comprises about 3.6ppm or following catalyst quenchers, about 1,000ppm or following phosphorous acid ester component and about 200ppm or following epoxide hydrolysis stabilizer.
The invention still further relates to from the prepared goods of the polycarbonate of described hydrolysis-stable.In one embodiment, formed goods are sheet material, and in another embodiment, described goods are the double-walled sheet material.
The present invention relates to the method that a kind of preparation has the polycarbonate compositions of the hydrolysis-stable that is lower than about 98% mole terminal aryl carbonates group and 2% mole or above terminal hydroxyl (total mole number based on all end groups of polycarbonate calculates) in yet another aspect, and described method comprises following each step: the content with catalyst quenchers during the preparation of the polycarbonate of hydrolysis-stable and processing remains on 3.6ppm or following; The phosphorous acid ester components contents is maintained at about 1,000ppm or following; Be maintained at about 200ppm or following with content with the epoxide hydrolysis stabilizer.
The present invention also aspect relates to a kind of method that is used to prepare the polycarbonate of hydrolysis-stable, said method comprising the steps of:
A) polycarbonate based on the scorification preparation calculates, and adds the catalyst quenchers that reaches as high as about 3.6ppm;
B) polycarbonate based on the scorification preparation calculates, and adds the phosphorous acid ester component that reaches as high as about 1000ppm; With
C) polycarbonate based on the scorification preparation calculates, and adds the epoxide hydrolysis stabilizer that reaches as high as about 200ppm
Wherein component a), b) or c) at least a amount greater than 0ppm, and wherein in the steam autoclave of 120 ℃ and 100% relative humidity, the loss of molecular weight of the polycarbonate of described hydrolysis-stable is less than about 30%.The present invention describes
The present invention is devoted to address these problems and provide other surprising performance.
By can more easily understanding the present invention to the preferred embodiments of the invention and the detailed description that is included in embodiment wherein with reference to following.
Before open and description present composition content and method, should understand that the present invention is not limited to concrete synthetic method or is confined to concrete prescription, because these methods and prescription can change.It is also to be understood that term used herein only to be used to describe specific embodiment simultaneously and be not to be limited.
In the following description book, with reference to many terms that are defined as with following meaning:
Set forth unless have in the text clearly, otherwise the object that " " of singulative and " described " modifies comprises its plural form.
" optional " or " randomly " refers to that described subsequently incident or situation may take place, and also may not take place, and comprises the example that example that incident takes place and incident do not take place simultaneously.
Term used herein " scorification polycarbonate " is meant the polycarbonate that is made by carbonic diester and dihydroxy compound generation transesterification reaction.
" BPA " is defined as dihydroxyphenyl propane or 2 herein, two (4-hydroxy phenyl) propane of 2-.
Term used herein " diphenol " and " dihydric phenol " are synonym.
Term used herein " acidic substance " is meant that the pKa value is not more than 4.0 component in 25 ℃ water.
The polycarbonate that term used herein " hydrolysis-stable " is meant scorification preparation in the steam autoclave of 120 ℃ and 100% relative humidity after 120 hours its loss of molecular weight less than about 30%.
In the present invention, we are surprised to find that the content of the various conventional additives that join the polycarbonate for preparing by scorification influences each other, and produces variety of issue to the stability of scorification polycarbonate, particularly stability to hydrolysis.The threshold value of stability to hydrolysis depends on the intended purpose of polycarbonate.The content of some content of additive, particularly catalyst quenchers, phosphorous acid ester component and epoxide hydrolysis stabilizer by will joining the scorification polycarbonate remains on the stability to hydrolysis that can significantly improve polycarbonate in certain critical range.Polycarbonate with improvement stability to hydrolysis is applicable in the flaky resin (can be used for the double-walled sheet material).
Particularly, the invention provides the polycarbonate of hydrolysis-stable, this class polycarbonate can be used in the past because hydrolytic stability issues and in the various application that the polycarbonate of scorification preparation can't be suitable for.For example, in one embodiment, the polycarbonate of the hydrolysis-stable by scorification preparation can be used for sheet material, as the double-walled sheet material in the greenhouse.
The polycarbonate of the polycarbonate of interfacial preparation and scorification preparation requires to add some additive usually so that stablize the product of gained after preparation.Yet the difference of the additive that the polycarbonate of the polycarbonate of interfacial preparation and scorification preparation is required is that the polycarbonate of scorification preparation need add catalyst quenchers with the remaining alkaline matter that neutralizes, as basic metal or the alkaline earth salt of remnants.The common additives that is used for this purpose comprises, for example sulfuric acid (" S " acid) or phosphoric acid (" P " acid) and corresponding ester thereof.
Polycarbonate by the interfacial process preparation contains usually above about 98% mole terminal aryl carbonates (based on the total mole number meter of all end groups of polycarbonate).Polycarbonate by scorification preparation contains and is less than about 98% mole terminal aryl carbonates group and 2% mole or above terminal hydroxyl (based on the total mole number meter of all end groups of polycarbonate).This will bring the problem of aspect of performance in some applications, and partly cause is that the hydrolysis of the terminal hydroxyl that exists in the polycarbonate causes.In addition, in melting method, generally include and add phosphoric acid so that the protection to the randomness iron pollution that causes because of the equipment seepage to be provided, thereby prevent to form color.
One aspect of the present invention relates to the polycarbonate of the hydrolysis-stable for preparing in the melt polymerization system, dihydric phenol and carbonic diester react in described polymerization system.The dihydric phenol that can be used for preparing polycarbonate of the present invention is represented by following general formula:
Wherein:
R independently is selected from halogen, monovalence alkyl and monovalence-oxyl;
R
1Independently be selected from halogen, monovalence hydrocarbon and monovalence-oxyl;
W be selected from bivalent hydrocarbon radical ,-S-,-S-S-,-O-,
With
N and n
1Independently be selected from the integer (comprising 0 and 4) of 0-4; With
B is 0 or 1.
By R and R
1Represented monovalence alkyl comprises alkyl, cycloalkyl, aryl, aralkyl and alkaryl.Preferred alkyl is to contain 1 alkyl to about 12 carbon atoms.Preferred cycloalkyl is to contain 4 groups to about 8 ring carbon atoms.Preferred aryl groups is the group that contains 6 to 12 ring carbon atoms, i.e. phenyl, naphthyl and xenyl.Preferred alkaryl and aralkyl are to contain 7 groups to about 14 carbon atoms.
By R and R
1Represented preferred halogen group is chlorine and bromine.
Shown in bivalent hydrocarbon radical comprise alkylidene group (alkylene base alkylene), alkylidene group (alkylidene), ring alkylidene group (ring alkylene base) and encircle alkylidene group.Preferred alkylidene group (alkylene base) is for containing 2 groups to about 30 carbon atoms.Preferred alkylidene group is to contain 1 group to about 30 carbon atoms.Preferred ring alkylidene group (ring alkylene base) and ring alkylidene group are to contain 6 groups to about 16 ring carbon atoms.
By R and R
1Represented monovalence-oxyl can be by formula-OR
2Expression, wherein R
2Be the monovalence alkyl of described type before this.Preferred monovalence-oxyl is alkoxyl group and aryloxy.
Suitable dihydric phenol includes, but is not limited to BPA, 2,2-two (3,5-two bromo-4-hydroxy phenyls) propane, 2,2-two (3,5-dimethyl-4-hydroxy phenyl) propane, 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1,1-two (3,5-dimethyl-4-hydroxy phenyl) hexanaphthene, 1, two (4-hydroxy phenyl) decane of 1-, 1, two (4-hydroxy phenyl) propane of 1-, 1, two (4-hydroxy phenyl) cyclodecane of 1-, 1,1-two (3,5-dimethyl-4-hydroxy phenyl) cyclododecane, 4,4-dihydroxy phenyl ether, 4,4-sulfo-biphenol, 4,4-dihydroxyl-3, the 3-dichloro-diphenyl ether, 4,4-sulfo-biphenol, 4,4-dihydroxyl-3, the 3-dichloro-diphenyl ether, 4,4-dihydroxyl-2, the 5-dihydroxy diphenyl ether, BPI, 1, two (4-the hydroxy phenyl)-1-phenylethanes of 1-, 1, two (3-methyl-4-the hydroxy phenyl)-1-phenylethanes of 1-, and various mixture.In one embodiment, the remaining dihydric phenol in the polycarbonate comprises 100% mole of resistates derived from BPA.
Choose wantonly and can utilize the polyfunctional compound.The suitable polyfunctional compound who is used for the branching polycarbonate polymerization includes, but is not limited to:
1,1,1-three (4-hydroxy phenyl) ethane;
4-[4-[1, two (4-the hydroxy phenyl)-ethyls of 1-]-dimethyl benzyl (bennzyl)];
1,2, the 4-benzenetricarboxylic anhydride;
1,2,4-benzenetricarboxylic acid, or its various chloride derivatives.
Available all cpds is as carbonic diester, and these compounds include, but is not limited to diaryl carbonates ester cpds, dialkyl carbonate ester cpds and carbonate alkyl aryl ester compound.Suitable carbonic diester includes, but is not limited to diphenyl carbonate, two (4-tert-butyl-phenyl) esters of carbonic acid, carbonic acid two (2, the 4-dichlorophenyl) ester, carbonic acid two (2,4, the 6-trichlorophenyl) between two (2-cyano-phenyl) esters of ester, carbonic acid, two (o-nitrophenyl) esters of carbonic acid, carboxylol base ester, carbonic acid-cresols ester, carbonic acid dinaphthyl ester, carbonic acid two (biphenyl) ester (bis (diphenyl) carbonate), carbonic acid diethyl ester, dimethyl carbonate, carbonic acid dibutyl ester, carbonic acid dicyclohexyl ester, and various mixture.Wherein preferred dipheryl carbonate base ester.If use two or more these compounds, then preferably wherein a kind of is dipheryl carbonate base ester.
In the method for the invention, can choose the use end-capping reagent wantonly.Suitable end-capping reagent comprises haloformate derivative, a divalent carboxylic acid of monovalence aromatic hydroxy compound, monovalence aromatic hydroxy compound, the halide derivative of a divalent carboxylic acid, and various mixture.
Suitable end-capping reagent includes, but is not limited to phenol, p-tert-butylphenol, right-cumyl phenol, right-the cumyl phenol carbonic ether, undecanoic acid, lauric acid, stearic acid, carbonochloridic acid phenylester, carbonochloridic acid tert-butyl phenylester, carbonochloridic acid right-cumyl ester, coumaran carbonochloridic acid ester, carbonochloridic acid octyl phenyl ester, carbonochloridic acid nonyl phenylester, or its various mixtures.
If there is end-capping reagent, then preferred its amount is about 0.01 mole to about 0.20 mole of every mole of dihydric phenol, preferably about 0.02 mole to about 0.15 mole even more preferably from about 0.02 mole to about 0.10 mole.
In the method for the invention, catalyst system comprises at least a basic metal and/or alkaline earth metal compound.Preferred these compounds use with the form of basic metal and alkaline earth metal derivative (as organic hydrochlorate, inorganic acid salt, oxide compound, oxyhydroxide, hydride, alcoholate, or its mixture).
The suitable alkali metal compound of useful as catalysts includes, but is not limited to sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, saleratus, lithium bicarbonate, yellow soda ash, salt of wormwood, Quilonum Retard, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, and various mixture.
The suitable alkaline earth metal compound of useful as catalysts includes, but is not limited to calcium hydroxide, hydrated barta, magnesium hydroxide, strontium hydroxide, Calcium hydrogen carbonate, barium bicarbonate, Magnesium hydrogen carbonate, strontium bicarbonate, lime carbonate, barium carbonate, magnesiumcarbonate, Strontium carbonate powder, lime acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, Magnesium Stearate, strontium stearate, and various mixture.
The preferable amount of catalyzer or its mixture is 10
-8To 10
-3Mol catalyst/mole dihydric phenolic compounds, more preferably 10
-7To 10
-5Mol catalyst/mole dihydric phenolic compounds.When its amount is lower than 10
-8During mole, activity of such catalysts possibly can't embody.When it is measured greater than 10
-3During the moles/mole dihydric phenol, the performance of final polycarbonate product will affect adversely.
Except above-mentioned catalyzer, described catalyst system can be chosen wantonly and comprise quaternary ammonium salt and/or phosphorus catalyst.The example of suitable quaternary ammonium salt includes, but is not limited to have alkyl, the ammonium hydroxide of aryl and alkaryl, as tetramethylammonium hydroxide (TMAH) and tetrabutylammonium hydroxide (TBAH).Suitable phosphorus includes, but is not limited to hydroxide tetraethyl-phosphorus and tetrabutylphosphoniuhydroxide hydroxide phosphorus.
Except an alkali metal salt of sequestrant and/or alkaline earth salt and optional alkali metal hydroxide, if having quaternary ammonium salt and/or phosphorus catalyst, then preferred its consumption is 10
-2To about 10
-6, more preferably 10
-2To 10
-5The moles/mole dihydric phenolic compounds.
The reaction conditions of melt polymerization is not subjected to special qualification, and melt polymerization can carry out under the operational condition of broad.Range of reaction temperature is generally about 100 ℃ to about 350 ℃, more preferably at about 180 ℃ to about 310 ℃.Pressure can be normal atmosphere, or is forced into about 15 holders in the starting stage of reaction from normal atmosphere, reduces pressure in the stage afterwards, and pressure range is for for example about 0.2 to about 15 holding in the palm.Reaction times was generally about 0.1 hour to about 10 hours.
The polycarbonate of hydrolysis-stable of the present invention shows the stability to hydrolysis of remarkable improvement in accelerated weathering test.As mentioned above, the threshold value of stability to hydrolysis depends on the intended purpose of polycarbonate.In some applications, stability to hydrolysis becomes more crucial.For example, in sheet applications, as the double-walled sheet material in the greenhouse, the requirement that the requirement comparison of the stability to hydrolysis that is exposed to the polycarbonate in rainwater and the sunlight is used for the required stability to hydrolysis of indoor polycarbonate wants high.
The polycarbonate of hydrolysis-stable of the present invention in the steam autoclave of 120 ℃ and 100% relative humidity after 120 hours its loss of molecular weight less than about 30%, more preferably in the steam autoclave of 120 ℃ and 100% relative humidity after 120 hours its loss of molecular weight less than about 20%, even more preferably in the steam autoclave of 120 ℃ and 100% relative humidity after 120 hours its loss of molecular weight less than about 10%.
In the present invention, require the content of careful control catalyst quencher, phosphorous acid ester component and epoxide hydrolysis stabilizer.We are surprised to find that in the polycarbonate Central Asia phosphate ester components of scorification preparation and acidic substance and interact that the result has reduced the stability to hydrolysis of scorification polycarbonate.Usually the hydrolysis of the catalyst quenchers of the additive of the polycarbonate that makes as melt transesterification will produce acidic substance, and catalyst quenchers can be acidic substance, and acidic substance also can be to add for other purpose.Toluenesulphonic acids butyl ester (catalyst quenchers commonly used) can hydrolysis form toluenesulphonic acids in polycarbonate, formed toluenesulphonic acids is used as catalyst quenchers in polycarbonate.The phosphoric acid or derivatives thereof is the useful as catalysts quencher also.We find can prepare the polycarbonate with higher stability to hydrolysis by the content of careful control polycarbonate Central Asia phosphate ester components and catalyst quenchers.In addition, preferably the concentration of other acidic substance in the polycarbonate is remained on minimum value.Particularly, preferably will be maintained at about 3.6ppm or following level as catalyst quenchers or the total amount of acidic substance in polycarbonate resin that adds for other purpose.We also find to add the stability to hydrolysis that suitable epoxide hydrolysis stabilizer will further strengthen the polycarbonate for preparing by scorification.
The suitable catalyst quenchers that can be used for preparing the polycarbonate of hydrolysis-stable includes, but is not limited to sulfuric acid and phosphoric acid and ester thereof; The alkyl ester of preferably sulfuric acid and phosphoric acid; More preferably toluenesulphonic acids alkyl ester is as toluenesulphonic acids butyl ester and the positive butyl ester of toluenesulphonic acids.The suitable phosphorous acid ester that can be used for preparing the polycarbonate of hydrolysis-stable includes, but is not limited to triphenyl phosphite, phosphorous acid 2,4-di tert butyl carbonate, tricresyl phosphite (nonyl phenyl) ester, triisodecyl phosphite ester, and various mixtures, preferred triphenyl phosphite.The suitable epoxide hydrolysis stabilizer that can be used for preparing the polycarbonate of hydrolysis-stable includes, but is not limited to contain the fat of epoxy group(ing) and oil, glycidyl compound (as phenyl glycidyl ether), epoxy cyclohexane compound, tetraphenyl oxyethylene.
The total amount of the acidic substance that should use, phosphorous acid ester component and epoxide hydrolysis stabilizer should be and is enough to make polycarbonate to stablize nondiscoloration in intended purpose and has the improvement stability to hydrolysis, keeps the total amount of superperformance simultaneously.This amount depends on from the condition of formed goods of described polycarbonate and use polycarbonate.
The amount of catalyst quenchers in the polycarbonate of hydrolysis-stable be about 0 to about 3.6ppm, be preferably about 0.5 to about 2.0ppm, more preferably about 0 to about 1.0ppm (calculating based on polycarbonate).The amount of phosphorous acid ester component is about 0 to about 1,000ppm, more preferably about 50 to 700ppm even more preferably about 100 to 500ppm (calculating based on polycarbonate weight).The amount of epoxide hydrolysis stabilizer is about 0 to about 200ppm even more preferably about 100 to 200ppm (calculating based on polycarbonate weight).As mentioned above, the amount of additive depends on the intended purpose of polycarbonate.
(as indoor application, as in the situation of compression magnetic disc) in some applications, the concentration of catalyst quenchers, phosphorous acid ester and epoxide hydrolysis stabilizer may be lower.In other is used (as be exposed in rainwater and the sunlight sheet material), its concentration needs higher.In one embodiment, will make the double-walled sheet material that is used for the greenhouse by the polycarbonate of scorification preparation.
In one embodiment, according to the material of the sheet material grade of hydrolysis-stable of the present invention contain 0.5 to about 3.6ppm, more preferably 0.5 to 2.0 catalyst quenchers; About 50 to about 700ppm, more preferably 50 to 500ppm even more preferably 50 to 250ppm phosphorous acid ester component; With about 100 to 200ppm epoxide hydrolysis stabilizer.Also preferably will exist or the total amount of acidic substance in the sheet material grade material of hydrolysis-stable that add for other purpose is maintained at about 3.6ppm or following level as catalyst quenchers.
Can after polycondensation, catalyst quenchers, phosphorous acid ester and epoxide hydrolysis stabilizer be joined in the polycarbonate of the molten state in reactor or the forcing machine, subsequently by mediating or various additives being incorporated in the polycarbonate material by other known technology.Also the form of various additives with Powdered enriched material can be incorporated in the identical or different polycarbonate.The weight-average molecular weight of polycarbonate is about 1,000 to about 300,000.Preferred molecular weight will depend on the intended purpose of polycarbonate.For example, for sheet applications, preferred molecular weight ranges is about 10,000 to about 80,000 even more preferably about 18,000 to about 50,000.
As mentioned in one embodiment of the invention, the polycarbonate that comprises resin quencher composition can be made the form of sheet material.In a concrete application, polycarbonate can be made the double-walled sheet material that is used to construct the greenhouse.Can directly from polymer melt, polycarbonate be made sheet material, also can from melt, it be made easy to handle form (as particle), make sheet material subsequently again.Can pass through the whole bag of tricks known in the art, include, but is not limited to extrusion molding, solution stream casting or injection moulding and make sheet material of the present invention.
It also other additive can be joined in the polycarbonate product, as long as can not cause disadvantageous effect to the performance of product.These additives comprise the conventional various materials that join for various purposes in the polycarbonate.Concrete example comprises thermo-stabilizer, epoxy compounds, uv-absorbing agent, releasing agent, tinting material, static inhibitor, slip(ping)agent, antitack agent, lubricant, antifogging agent, natural oil, synthetic oil, wax, organic filler, fire retardant, mineral filler and any other known additive.
Reaction can be intermittently or successive technology carry out.Any required equipment can be used for this reaction.Be used for reactor material of the present invention and structure and be not subjected to special qualification, as long as reactor has conventional stirring capacity.Because the viscosity of reaction system increases in the latter stage of reaction, so preferred reactor can stir under full-bodied condition.
The polycarbonate compositions of hydrolysis-stable of the present invention can be mixed with various additives commonly used (as softening agent, pigment, lubricant, releasing agent, stablizer and organic filler).Releasing agent is a preferred additives.We find that also releasing agent (as pentaerythritol tetrastearate) does not have negative impact to the stability to hydrolysis of the polycarbonate of hydrolysis-stable of the present invention.
Except above-mentioned various uses, the polycarbonate of hydrolysis-stable of the present invention can be used for outdoor applications, as the shell and the optical goods (as lens and compression magnetic disc) of auto parts, various devices.As mentioned in one embodiment, the polycarbonate of hydrolysis-stable is used to prepare the double-walled sheet material in greenhouse.
Also polycarbonate and other polymkeric substance can be included, but is not limited to polyolefine, polystyrene, polysulfonates, polymeric amide and polyphenylene oxide, together fusion.
Embodiment
Following embodiment is used to those skilled in the art to provide complete about how preparing and assess that composition required for protection is formed and the description of method herein, and these descriptions are not used for limiting the category of the inventor about its invention.Try hard to be and guarantee accuracy at quantitative aspects (as amount, temperature etc.), but should be taken into account some errors and deviation.Except as otherwise noted, otherwise umber is a weight part, and temperature is ℃.
Molecular weight is with the form report of number-average molecular weight (Mw), and the employing polystyrene standards, measures by the polycarbonate of melt phase polycondensation preparation by gpc analysis.
In following examples, illustrated by interfacial and the prepared polycarbonate of scorification.It is LEXAN LF100 grade resin that used interfacial prepares polycarbonate, can be available from General Electric Company.It is the LEXANLX140 grade resin that used scorification prepares polycarbonate, can be available from General Electric Company.
Polycarbonate (adopting 100 grades LEXAN LF) is mixed with additive with the form of enriched material charging, and the blended ratio of wherein overall charging and enriched material charging is 95: 5 (weight ratio).Adopt 1 gallon Henschel mixing tank to make additive and Powdered enriched material fusion.Adopt twin screw extruder to mix various materials then, the temperature that is provided with of machine barrel is 280 ℃, and feeding rate is 25lbs/h, and screw speed is 350-400 rev/min (rpms).
In autoclave in the forming step, in Nissei FE160 injector,, and under the steam of 120 ℃ and 15psi, carried out hot-forming 5 days dynatup dish molding.Take out sample (1-5) every day, at first autoclave is cooled to room temperature, then remove video disc, the video disc that cuts a part of molding is to measure its molecular weight.Remaining dish is put back in the baking oven.Measure every day in this way, carried out altogether 5 days.
Adopt the relative stability to hydrolysis of determining sample by the prepared rate of curve of loss of molecular weight of corresponding time then.In table 1, illustrated the result wherein these slopes to be expressed as " log Mw/ (T/1000) " or " K slope ".Preferred sample of the present invention-the K slope is lower than about 1.615.
Used phosphorous acid ester is the IRGAPHOS 168 that Ciba-Geigy produces, and used catalyst quenchers is the positive butyl ester of toluenesulphonic acids, the ERL-4221 that used epoxide hydrolysis stabilizer is produced for Union Carbide.Releasing agent is a pentaerythritol tetrastearate, and the UV stablizer is the CYASORB 5411 that Ciba-Geigy produces.Concentration shown in the table 1 is 1,000,000/(ppm).
Table 1
| Sample | Phosphorous acid ester | Releasing agent | The UV stablizer | Catalyst quenchers | H 3PO 3 | Epoxide stabilizer | -K slope | Mw after 120 hours |
| The LF resin | ||||||||
| ?1 | Pure | ?0.54 | ?42950 | |||||
| ?2 | ?500 | ?1000 | ?700 | Do not have | Do not have | Do not have | ?1.55 | |
| ?3 | ?500 | ?1000 | ?700 | ?3.6 | 2.0 | Do not have | ?2.20 | ?27255 |
| The LX resin | ||||||||
| ?4 | Pure | ?1.12 | ?36691 | |||||
| ?5 | ?500 | ?1000 | ?700 | ?3.6 | 2.0 | Do not have | ?7.63 | ?6072 |
| ?6 | ?250 | ?1000 | ?1500 | ?1.0 | Do not have | Do not have | ?2.04 | ?28455 |
| ?7 | ?250 | ?1000 | ?1500 | ?1.0 | Do not have | 200 | ?1.24 | ?35495 |
| ?8 | ?500 | ?1000 | ?1500 | ?1.0 | Do not have | Do not have | ?2.46 | ?25337 |
| ?9 | ?500 | ?1000 | ?2000 | ?1.0 | Do not have | 200 | ?1.13 | ?36590 |
| ?10 | ?250 | ?1000 | ?2000 | ?1.0 | Do not have | 200 | ?1.27 | ?35202 |
The present invention specifically is described in detail with reference to its preferred embodiment, but still should be clear that in the present invention spirit and category and can carry out various changes and modification.
Claims (14)
1. the polycarbonate compositions of a hydrolysis-stable, the polycarbonate compositions of described hydrolysis-stable has and is lower than about 98% mole terminal aryl carbonates group and 2% mole or above terminal hydroxyl, total mole number based on described all end groups of polycarbonate calculates, the polycarbonate of described hydrolysis-stable also comprises about 3.6ppm or following catalyst quenchers and about 1,000ppm or following phosphorous acid ester component.
2. the polycarbonate of the hydrolysis-stable of claim 1, described polycarbonate also comprises about 200ppm or following epoxide hydrolysis stabilizer.
3. sheet material that makes by the polycarbonate of the hydrolysis-stable of claim 1.
4. double-walled sheet material that makes by the polycarbonate of the hydrolysis-stable of claim 1.
5. the polycarbonate of the hydrolysis-stable of claim 1, wherein said catalyst quenchers is the positive butyl ester of toluenesulphonic acids.
6. the polycarbonate of the hydrolysis-stable of claim 1, wherein said phosphorous acid ester component is a triphenyl phosphite.
7. the polycarbonate of the hydrolysis-stable of claim 1, described polycarbonate comprises the acidic substance that are lower than about 4ppm.
8. method for preparing the polycarbonate of hydrolysis-stable said method comprising the steps of:
A) polycarbonate based on described scorification preparation calculates, and adds the catalyst quenchers that reaches as high as about 3.6ppm;
B) polycarbonate based on described scorification preparation calculates, and adds the phosphorous acid ester component that reaches as high as about 1000ppm; With
C) polycarbonate based on described scorification preparation calculates, and adds the epoxide hydrolysis stabilizer that reaches as high as about 200ppm;
Wherein component a), b) or c) at least a amount greater than 0ppm, and wherein in the steam autoclave of 120 ℃ and 100% relative humidity, the loss of molecular weight of the polycarbonate of described hydrolysis-stable is less than about 30%.
9. method for preparing the polycarbonate of hydrolysis-stable said method comprising the steps of:
A) calculate based on polycarbonate, the content of catalyst quenchers is maintained at about 3.6ppm or following;
B) calculate based on polycarbonate, the phosphorous acid ester components contents is maintained at about 1,000ppm or following; With
C) calculate based on polycarbonate, the content of epoxide hydrolysis stabilizer is maintained at about 200ppm or following.
10. sheet material that comprises the hydrolysis-stable of polycarbonate with at least 2% terminal hydroxyl.
11. double-walled sheet material that comprises the hydrolysis-stable of polycarbonate with at least 2% terminal hydroxyl.
12. sheet material that comprises the hydrolysis-stable of polycarbonate with at least 5% terminal hydroxyl.
13. resin quencher composition of being formed by catalyst quenchers, phosphorous acid ester and epoxide hydrolysis stabilizer basically.
14. the polycarbonate compositions of a hydrolysis-stable, the polycarbonate compositions of described hydrolysis-stable has and is lower than about 98% mole terminal aryl carbonates group and 2% mole or above terminal hydroxyl, total mole number based on described all end groups of polycarbonate calculates, the polycarbonate of described hydrolysis-stable also comprises about 3.6ppm or following catalyst quenchers, about 1,000ppm or following phosphorous acid ester component and about 200ppm or following epoxide hydrolysis stabilizer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US54640500A | 2000-04-10 | 2000-04-10 | |
| US09/546,405 | 2000-04-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1454239A true CN1454239A (en) | 2003-11-05 |
Family
ID=24180288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00819635 Pending CN1454239A (en) | 2000-04-10 | 2000-10-25 | Polycarbonate having excellent hydrolytic stability |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1274798A1 (en) |
| JP (1) | JP2003531926A (en) |
| CN (1) | CN1454239A (en) |
| AU (1) | AU2001212294A1 (en) |
| TW (1) | TW570955B (en) |
| WO (1) | WO2001077227A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317835A (en) * | 2016-09-30 | 2017-01-11 | 福建华塑新材料有限公司 | Hydrolysis-resisting polycarbonate composite material and preparation method thereof |
| CN109265670A (en) * | 2018-08-03 | 2019-01-25 | 宁波浙铁大风化工有限公司 | A kind of preparation process of polycarbonate |
| CN109265951A (en) * | 2018-08-03 | 2019-01-25 | 宁波浙铁大风化工有限公司 | The preparation process of polycarbonate |
| CN110621733A (en) * | 2017-06-16 | 2019-12-27 | 沙特基础工业全球技术有限公司 | Use of sulfonic acids as stabilizers in polycarbonates |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3259301B1 (en) | 2015-02-17 | 2019-03-27 | SABIC Global Technologies B.V. | A method of quenching a melt polycarbonate |
| US11155695B2 (en) | 2015-12-16 | 2021-10-26 | Sabic Global Technologies B.V. | Abusively molded article including UV-stable polycarbonate |
| EP3472236B1 (en) * | 2016-06-17 | 2023-09-06 | SABIC Global Technologies B.V. | Method for forming polycarbonate molded articles |
| KR102194062B1 (en) * | 2018-04-27 | 2020-12-22 | 롯데첨단소재(주) | Thermoplastic resin composition and article including same |
| KR102221622B1 (en) * | 2018-06-29 | 2021-02-26 | 롯데첨단소재(주) | Thermoplastic resin composition and article including same |
| CN113574114B (en) | 2019-03-13 | 2024-05-28 | 帝人株式会社 | Resin composition for infrared shielding transparent member and molded article |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2924985B2 (en) * | 1991-06-28 | 1999-07-26 | 日本ジーイープラスチックス株式会社 | Method for producing polycarbonate |
| SG68668A1 (en) * | 1997-06-16 | 1999-11-16 | Gen Electric | Polycarbonate composition for vented moldings |
| ES2329111T3 (en) * | 1999-05-27 | 2009-11-23 | Teijin Limited | COMPOSITION OF POLYCARBONATE RESIN, OPTICAL RECORDING MEDIA, AND SUBSTRATE FOR THE SAME. |
| IL148251A0 (en) * | 1999-09-01 | 2002-09-12 | Dow Chemical Co | Polycarbonate resin compositions comprising cyanacrylic acid ester stabilizer compounds |
-
2000
- 2000-10-25 AU AU2001212294A patent/AU2001212294A1/en not_active Abandoned
- 2000-10-25 WO PCT/US2000/029343 patent/WO2001077227A1/en not_active Application Discontinuation
- 2000-10-25 EP EP00973827A patent/EP1274798A1/en not_active Withdrawn
- 2000-10-25 JP JP2001575092A patent/JP2003531926A/en not_active Withdrawn
- 2000-10-25 CN CN 00819635 patent/CN1454239A/en active Pending
-
2001
- 2001-03-28 TW TW90107291A patent/TW570955B/en not_active IP Right Cessation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317835A (en) * | 2016-09-30 | 2017-01-11 | 福建华塑新材料有限公司 | Hydrolysis-resisting polycarbonate composite material and preparation method thereof |
| CN110621733A (en) * | 2017-06-16 | 2019-12-27 | 沙特基础工业全球技术有限公司 | Use of sulfonic acids as stabilizers in polycarbonates |
| CN110621733B (en) * | 2017-06-16 | 2021-11-09 | 沙特基础工业全球技术有限公司 | Use of sulfonic acids as stabilizers in polycarbonates |
| CN109265670A (en) * | 2018-08-03 | 2019-01-25 | 宁波浙铁大风化工有限公司 | A kind of preparation process of polycarbonate |
| CN109265951A (en) * | 2018-08-03 | 2019-01-25 | 宁波浙铁大风化工有限公司 | The preparation process of polycarbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2001212294A1 (en) | 2001-10-23 |
| JP2003531926A (en) | 2003-10-28 |
| TW570955B (en) | 2004-01-11 |
| WO2001077227A1 (en) | 2001-10-18 |
| EP1274798A1 (en) | 2003-01-15 |
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