CN1105126C - Process for producing stabilized oxymethylene copolymer - Google Patents
Process for producing stabilized oxymethylene copolymer Download PDFInfo
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- CN1105126C CN1105126C CN97125490A CN97125490A CN1105126C CN 1105126 C CN1105126 C CN 1105126C CN 97125490 A CN97125490 A CN 97125490A CN 97125490 A CN97125490 A CN 97125490A CN 1105126 C CN1105126 C CN 1105126C
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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
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/30—Chemical modification by after-treatment
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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
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/10—Polymerisation of cyclic oligomers of formaldehyde
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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
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/28—Post-polymerisation treatments
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Abstract
To economically produce an oxymethylene copolymer having an excellent thermal stability. A stabilized copolyoxymethylene is obtained from a copolyoxymethylene having unstable terminals by using as the copolyoxymethylene having unstable terminals a copolymer obtained by adding a sterically hindered phenol to a monomer mixture in an amount of 0.01 to 2.0% by weight based on all monomers, polymerizing the monomer mixture, pulverizing the resulting crude polyoxymethylene into a powder having a specific particle diameter distribution, and deactivating the polymerization catalyst contained therein, and adding a stabilizer to the copolyoxymethylene as the raw material together with water and degassing the mixture in a molten state in a vacuum to stabilize the raw material. And stabilized copolyoxymethylene is obtained from copolyoxymethylene having unstable terminals.
Description
The present invention relates to prepare the method for the economy of copolyoxymethylenes with superior thermostability.
Because polyacetal copolymer (hereinafter being abbreviated as " POM multipolymer ") has superior mechanical property, thermotolerance, chemical resistant properties, electrical property and sliding capability, have superior mouldability or formability simultaneously, so, it is used for purposes widely as engineering plastics, for example in mechanical part, trolley part or the electrical/electronic element.
The stable POM multipolymer that being known as practical application provides generally prepares according to following method.
At first, use as the cyclic acetal of principal monomer trioxane and obtain POM multipolymer crude product for example as the cyclic acetal with adjacent carbons or the cyclic ethers of comonomer; According to its purpose, add chain-transfer agent so that regulate the polymerization degree; Then, in the presence of the cation activity catalyzer, make formed mixture copolymerization.In general, this POM multipolymer crude product comprises a large amount of unsettled end groups.When to described multipolymer (polymerizing catalyst that is included in wherein still keeps active) heating, this multipolymer generation unzipping or unstable end group increase.
Therefore, after for example the oxyhydroxide of alkylamine, alkoxylamine or hindered amine or basic metal or alkaline-earth metal makes the catalyzer neutralization or inerting that is included in the described multipolymer with the organic or inorganic basic cpd, provide the POM multipolymer crude product of polymerisate for the process of decomposing and remove described unsettled end group.Then, compound and water that the multipolymer that makes processing like this is enumerated more than for example at basic cpd maybe heat in the presence of the alcohol that is used in combination with basic cpd when needing, thereby, remove unsettled end group by decomposition.
Then, different additive addings is therefrom removed in the POM multipolymer of unstable end group by decomposing, so that this multipolymer has thermostability and permanent stability etc., in addition, add various additives or toughener when needing,, then knead by melt so that make this multipolymer have needed character, thereby preparation is fit to the stable POM multipolymer of practical application.
Various researchs have been carried out so that prepare stable POM multipolymer more economically.The example of currently known methods that is used for the production of described economy is included in and improves polymeric kettle, polymerizing catalyst etc. in the polymerization process, in catalyzer inerting process, in the improvement of aspects such as inerting agent, inerting method with decomposing and removing in the process of unsettled end group improvement at aspects such as decomposition accelerating agent, decomposition and removal equipment.
Above-mentioned any method only is used for specific process, so that described innovative approach all has limitation.Therefore, require to consider under the prerequisite of the stable whole process that is aggregated to the POM multipolymer, providing more economical being used to produce the method for POM multipolymer.Especially in said process, be used to decompose and the heavy operation and the lot of energy of process need of removing unsettled end group handled.If the POM multipolymer is offered basically without the final stabilization process of decomposing and remove step, will help carrying out economic production.For this reason, need be at described polymerization process and/or the high-quality POM multipolymer of catalyzer inerting process of preparing crude product.
Applicant of the present invention had proposed the method that makes the POM multipolymer stable in the past, it is included in before the described polymerization process polymerization, with consumption based on all monomeric 0.001-2.0% (weight), sterically hindered phenol is added the formed mixture of polymerization in the monomer mixture, then, heating and the resulting POM multipolymer of fusion (JP-B-62-13369).Have been found that, in described polymerization process, add sterically hindered phenol, owing to compare the improvement aspect dispersed with the sterically hindered phenol that adds when the melt stabilizing treatment, cause in the melt stabilization process some restraining effect to the oxygenolysis of POM multipolymer, yet the degradation production of the POM that occurs in described melt stabilization process can not fully be removed.
As the method for improving described catalyzer inerting, the angle of known efficient from the efficient that improves the catalyzer inerting and decomposition and the unsettled end group of removal is considered, before inerting, pulverizes described POM multipolymer crude product (polymerisate).From then on viewpoint is set out, and preferably has the pulverizing multipolymer (JP-A-57-80414 and JP-A-58-34819) than small particle size.
Yet, result as research, it has been observed by the present inventors that pulverizing the back inerting handles the quality that described POM multipolymer crude product has improved the POM multipolymer that generates, but, if the POM multipolymer that is generated is offered follow-up stabilization process, wherein, the multipolymer that is generated is added wherein with stablizer, the formed mixture of melt-kneaded then, without the process of decomposing and removing unsettled end group, the POM multipolymer that generates must have remarkable superior operability.
JP-A-233230 has proposed following method, wherein use crude product POM multipolymer as raw material and in the extruding machine that has melt zone, thermally-stabilised section and exhaust section with limited amount unstable end group, in the end group stabilization section, stablizer, water etc. are added wherein.As the result of study of aforesaid method, have been found that described method is produced stable POM reposefully, yet follow economic problem, because described extruding machine is prolonged, so that satisfy described thermally-stabilised section requirement with sufficient length.
The purpose of this invention is to provide the economy and the simple method of producing the stable POM multipolymer that is suitable for practical use, so that overcome the problems referred to above.More precisely, the purpose of this invention is to provide the method that production can provide the stable POM multipolymer of practical use, the process that does not have conventional employed decomposition and remove unsettled end group.Another object of the present invention provides the method for the oxidation of the POM multipolymer (it is the raw material of described stabilization procedures) that suppresses to have unstable end group, thereby, preparation can provide the stable POM multipolymer of practical use, in the case, because factors such as transportation, storages, described raw material POM multipolymer needs the regular hour to offer the described stabilization stage.
In order to achieve the above object, the present inventor has done the comprehensive research from the polymerization process of POM multipolymer to stabilization procedures.The result has been found that in described polymerization process, will add with sterically hindered phenol as the POM multipolymer with unstable end group of stabilization procedures raw material; When pulverizing this polymkeric substance, its size distribution of appropriateness control; And by less water being added in the described raw material or after making described raw material melt is plasticated in stabilization procedures, adding entry, be suppressed at oxidation and decomposition as the POM multipolymer of raw material, the problem that has overcome the operability aspect is for example corroded roll neck (biting neck) and is passed through exhaust in a vacuum in stabilization procedures, can easily remove the degradation production of the formed POM multipolymer of thermolysis when fusion, thereby finish the present invention.
Also have been found that, under described situation, the POM multipolymer with unstable end group as raw material in the described stabilization procedures has the unstable end group of fixed amount and has the size distribution of appropriateness control, less water added in the described raw material or after making described raw material melt is plasticated in stabilization procedures, add entry, can suppress oxidation and decomposition as the POM multipolymer of raw material, in addition, the problem that has overcome the operability aspect is for example corroded roll neck in stabilization procedures, thereby by exhaust in a vacuum, can easily remove the degradation production of the formed POM multipolymer of thermolysis when fusion, thereby finish the present invention.
Thereby, provide in the present invention:
1. by the copolymerized methanal with unstable end group being stablized prepare the method for stable copolymerized methanal, it is characterized in that:
(A) use is passed through with the consumption based on all monomeric 0.001-2.0% (weight), sterically hindered phenol added the multipolymer that obtains in the monomer mixture as copolymerized methanal with unstable end group, make described monomer mixture polymerization, to be ground into powder by the crude product polyoxymethylene that described polymerization process forms with the size distribution that satisfies following (1)-(4) item, and make the polymerizing catalyst inerting that is contained in the described crude product polyoxymethylene and
(B) stablizer is added in the copolymerized methanal as raw material with water, and in a vacuum with the mixture exhaust of molten state:
(1) median size is 0.3-0.7mm,
(2) having diameter is 3-20% (weight) greater than the content of the particle of 1.0mm,
(3) have content that diameter is not less than 0.18mm and is not more than the particle of 1.0mm be 50-97% (weight) and
(4) having diameter is 0-30% (weight) [the supposition total amount is 100% (weight)] less than the content of the particle of 0.18mm;
2. by the copolymerized methanal with unstable end group being stablized prepare the method for stable copolymerized methanal, it is characterized in that:
(A) use the powdery copolymer conduct contain the unstable end group (based on described multipolymer) of 0.3-0.8% (weight) and to have a size distribution that satisfies following (1)-(4) have unstable end group copolymerized methanal and
(B) stablizer is added in the copolymerized methanal as raw material with water, and in a vacuum with the mixture exhaust of molten state:
(1) median size is 0.3-0.7mm,
(2) having diameter is 3-20% (weight) greater than the content of the particle of 1.0mm,
(3) have content that diameter is not less than 0.18mm and is not more than the particle of 1.0mm be 50-97% (weight) and
(4) having diameter is 0-30% (weight) [the supposition total amount is 100% (weight)] less than the content of the particle of 0.18mm;
3. the method for preparing the stable copolymerized methanal described in 1 or 2, wherein, with described water and copolymerized methanal raw material pre-mixing with unstable end group;
4. the method for the stable copolymerized methanal described in the preparation as 1 or 2 wherein, after described copolymerized methanal raw material melt with unstable end group is plasticated, adds described water;
5. preparation is as the method for each described stable copolymerized methanal among the 1-3, wherein, and with described water and stablizer and have the copolymerized methanal raw material pre-mixing of unstable end group;
6. the method for stable copolymerized methanal described in the preparation as 1,2 or 4, wherein, with described stablizer with have the copolymerized methanal raw material pre-mixing of unstable end group, and after described copolymerized methanal raw material melt with unstable end group is plasticated, add described water; With
7. the method for the stable copolymerized methanal described in the preparation as 1,2 or 4 wherein, after described copolymerized methanal raw material melt with unstable end group is plasticated, adds described water and stablizer.
As seen, the method according to this invention can prepare stable POM multipolymer economically from the result of following embodiment.
To introduce the present invention in more detail hereinafter.
Utilizing described (crude product) of the present invention copolyoxymethylenes (POM multipolymer) is by as the cyclic acetal of principal monomer trioxane and obtain as the cyclic ethers or the copolymerization of cyclic formals in the presence of the cation activity catalyzer of comonomer for example.
Is to comprise the carbon atom of at least one pair of coupling (coupling) and the ring compound of Sauerstoffatom at this as cyclic ethers or cyclic formals that following comonomer uses.The example comprises oxyethane, 1,3-dioxolane, 1,3,5-trioxetane, glycol ether formal, 1,4-butyleneglycol formal, 1,3-diox and propylene oxide.Wherein, preferred comonomer is an oxyethane, 1,3-dioxolane, glycol ether formal and 1,4-butyleneglycol formal.The consumption of described comonomer is 0.1-20% (mole) based on as principal monomer De trioxane, preferred 0.2-10% (mole).
Prepare in the process of described (crude product) POM multipolymer in the copolymerization by described monomer and interpolymer, the general cationic catalyst of using always that uses is as polymerisation catalysts.The example of described cationic catalyst comprises for example boron of Lewis acid; tin; titanium; phosphorus; the muriate of arsenic and antimony; boron trifluoride for example; tin tetrachloride; titanium tetrachloride; phosphorus pentachloride; phosphorus pentafluoride; arsenic pentafluoride and antimony pentafluoride; mixture is mixture or its salt for example; protonic acid is trifluoromethanesulfonic acid and perchloric acid for example; the ester of protonic acid is the ester (for example tert-butyl ester of perchloric acid) of perchloric acid and lower aliphatic alcohols for example; the acid anhydrides of protonic acid is the mixed acid anhydride (for example acetate perchloric acid anhydride) of perchloric acid and lower fatty acid particularly; isopoly-acid; heteropolyacid (for example phospho-molybdic acid); phosphofluoric acid triethyl oxonium salt, hexafluoroarsenate trityl group ester and ethanoyl hexafluoro borate.
In these compounds, the coordination compound of boron trifluoride and boron trifluoride and organism (for example ether) is the catalyzer of normal use.Because protonic acid for example heteropolyacid or isopoly-acid has high reactivity as catalyzer, easily so that high-quality POM multipolymer crude product and inerting easily to be provided in a small amount.So, preferably by preparing POM multipolymer crude product in the polymerization that is selected from the presence of two or more the catalyzer of mixture of at least a this class catalyzer or its.When using Lewis acid for example boron trifluoride is as catalyzer, its preferred add-on is 15-25ppm with respect to described starting monomer.Require to use its water content to be no more than the monomer of 10ppm, so that obtain high quality P OM multipolymer crude product.
In order to regulate the molecular weight of the POM multipolymer crude product that obtains through polymerization, suitable chain-transfer agent that also may be by adding appropriate amount polymerization process as described in for example acetal compound is finished as methylal or dioxy methylene radical dimethyl ether.
By using for example partial or continuous method of known conventional equipment and method, or the method for melt polymerization or melt mass polymerization, can make the copolymerization of described POM multipolymer crude product.From industrialized angle, the general use and the method for continuous bulk polymerization preferably wherein used liquid monomer and along with the carrying out of described polymerization process, obtained the polymkeric substance of pressed powder form.In this case, when needs, described polymerization process also can be carried out in the presence of inert liquid medium.The example that is used for the present invention's polymerization unit comprises worm kneading machine (co-kneader), twin screw continuous extrusion mixing machine and two stirring-type continuous mixer.
The present invention also provides the method for the stable POM multipolymer of preparation, it is characterized in that using POM multipolymer as raw material with unsettled end group, this multipolymer is by pulverizing through adding the crude product POM multipolymer that sterically hindered phenol obtains in the powder with specific size distribution, and inerting is contained in that polymerizing catalyst in the described powder copolymer obtains then; Stablizer is added in the raw material POM multipolymer with water; Then in a vacuum, under molten state, make described mixture exhaust, substantially not end group stabilization processing by decomposing and removing described unstable end group.
In the presence of the sterically hindered phenol (sterically hindered phenolic compound) as oxidation inhibitor, the crude product POM multipolymer that preparation obtains through described copolymerization is necessary.Because described sterically hindered phenol is suppressed at the oxygenolysis that forms the POM multipolymer in the polymerization process and suppresses POM multipolymer oxygenolysis under the high temperature in subsequent step, thereby making to provide high-quality POM multipolymer in final stabilization procedures, and the crude product POM multipolymer that obtains by this method is suitable as the crude product POM multipolymer that the present invention utilizes.
As at the used sterically hindered phenol of the present invention, preferably those have the compound of the structure of following formula representative:
Wherein, R1 and R2 are same to each other or different to each other, and represent the substituting group with at least 4 carbon atoms separately.The example comprises: 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenol); hexylene glycol-two (3; 5-di-t-butyl-4-hydroxyl hydrogenated cinnamate); four [methylene radical (3; 5-di-t-butyl-4-hydroxyl hydrogenated cinnamate)] methane; triethylene glycol-two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; 1; 3; 5-trimethylammonium-2; 4; 6-three (3; 5-two-tertiary butyl-4-hydroxy benzyl) benzene; Octadecane base-3-(4 '-hydroxyl-3 '; 5 '-two-tert-butyl phenol) propionic ester; 4; 4 '-methylene-bis (2; 6-two-tert-butyl phenol); 4; 4 '-butylidene-two-(the 6-tertiary butyl-3-sylvan); 2; 2 '-sulfo-diethyl-two-[3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester; two-stearyl--3,5-two-tertiary butyl-4-hydroxy benzylphosphonic acid ester; the 2-tertiary butyl-6-(the 3-tertiary butyl-5-methyl-2-hydroxybenzyl)-4-aminomethyl phenyl acrylate.The sterically hindered phenol that more than exemplifies can separately or be used in combination.The example is not limited thereto, and the sterically hindered phenol of same kind all can use.Wherein, hexylene glycol-two (3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate) " Irganox 259 " (trade(brand)name for example, Ciba Geigy product), four [methylene radical (3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate)] methane " Irganox 1010 " (trade(brand)name for example, Ciba Geigy product) and triethylene glycol-two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester for example " Irganox 245 " (trade(brand)name, Ciba Geigy product) is effective especially.On the other hand, when will be except sterically hindered phenol, any oxidation inhibitor have polyreaction to take place when for example amine, amidine and the material that generally is used for the stablizer of polyacetal add monomer.
The sterically hindered phenol that added in the past in the monomer in polymerization process is effectively, even also is like this under the situation of trace.Its consumption in the scope of monomeric 0.001-2.0% (weight) based on all, preferred especially 0.005-1.0% (weight).It is less that the consumption that is lower than above-mentioned scope causes being used for the effect of anti-oxidation and decomposition, and the consumption that exceeds above-mentioned scope trends towards reducing polymerization rate, thereby be uneconomic.Thereby the consumption beyond above-mentioned scope is unwanted.
With regard to this sterically hindered phenol being added the method in monomer, it is added in liquid monomer, be that solution form in the inert solvent adds it so that dissolve the former in the latter or to be dissolved on a small quantity to described polymerization process.Under the situation of successive polymerization, may provide a certain amount of sterically hindered phenol in the monomer line of polymeric kettle feed, with after its mixing and being dissolved in the described monomer, provide this solution in polymeric kettle; Or in advance with its adding and be dissolved in the described monomer layer under storing.
Then, institute's polymeric crude product POM multipolymer is ground into powder, they satisfy the requirement of the size distribution of following (1)-(a 4) regulation:
(1) median size is 0.3-0.7mm,
(2) having diameter is 3-20% (weight) greater than the content of the particle of 1.0mm,
(3) have content that diameter is not less than 0.18mm and is not more than the particle of 1.0mm be 50-97% (weight) and
(4) having diameter is 0-30% (weight) [the supposition total amount is 100% (weight)] less than the content of the particle of 0.18mm.
Above-mentioned size distribution is to be found through after the deep research by inventor of the present invention, purpose is in order to satisfy quality particularly by pulverizing and make the unstable endgroup content in the POM multipolymer that the catalyzer inerting obtains and satisfying the operability of described stabilization procedures, wherein, with POM multipolymer exhaust under the vacuum fusion state of described pulverizing, with rear stabilization with water and stablizer.
In the middle of above-mentioned requirements, the upper limit that has the ratio that exceeds 1.0mm diameter particle in (1) in the upper limit (0.7mm) of median size and (2) is to be mainly used in the essential condition of determining described POM copolymer quality.On the other hand, having the upper limit that has in the lower limit of the ratio that exceeds 1.0mm diameter particle and (4) less than the ratio of 0.18mm diameter particle in (1) in the lower limit (0.3mm) of median size and (2) is to be mainly used in the essential condition of determining operability in the usefulness stabilization procedures of stablizer.
When particle diameter exceeds above-mentioned size distribution, for example, average particle size distribution exceeds its upper limit or has particle diameter and exceeds its upper limit greater than the ratio of the particle of 1mm, the quality of the POM multipolymer of formed pulverizing is reduced, the amount of especially unstable end group increases, and, without the stabilization treatment process of decomposing and removing the end group of unstable end group, and, be difficult to obtain enough stable to offer the POM multipolymer in market only by stabilization procedures with stablizer.On the other hand, when described particle diameter is lower than above-mentioned size distribution, for example described median size is lower than its lower limit, having particle diameter is lower than its lower limit or exceeds its upper limit less than the ratio of the particle of 0.18mm greater than the ratio of the particle of 1mm, the obvious variation of operability in passing through the stabilization procedures of mediating with stablizer, can not obtain the satisfied quality of POM multipolymer, so that be difficult to prepare economically stable POM multipolymer.
Generally speaking, can satisfy the preferable particle size that POM multipolymer preferable quality can satisfy the operability of described stabilization procedures again is distributed as:
(1) ' median size is 0.4-0.7mm,
(2) ' having diameter is 5-1 5% (weight) greater than the content of the particle of 1.0mm,
(3) ' have content that diameter is not less than 0.18mm and is not more than the particle of 1.0mm be 60-95% (weight) and
(4) ' having diameter is 0-25% (weight) [the supposition total amount is 100% (weight)] less than the content of the particle of 0.18mm.
In above-mentioned crushing process, to used pulverizer particular restriction not in addition.The example comprises the impact grinder of rotary shredder, hammer mill, jaw crusher, feather mill, rotary cut-out shredder, turbine mill and size classification type.Rotation frequency or gap by pulverizer or be installed in the sieve number on the pulverizer and/or the substitute of installing respectively as required can be controlled described size distribution.
In making the process that is included in the catalyzer inerting in the described crude product POM multipolymer, can use common known method.In the present invention, preferably use the inerting process of finishing as the aqueous solution of the organic or inorganic basic cpd of representative with triethylamine, trolamine, yellow soda ash or calcium hydroxide; Simultaneously, by the broken process of wet-milling described crude product POM multipolymer is crushed into the powder with above-mentioned size distribution.At first, preferably between the pulverizer inlet, adding inerting agent, thereby can obtain high-quality POM multipolymer near the position before the pulverizer outlet.After described catalyzer inerting and pulverizing, as required, make this POM multipolymer through processing such as washing, dryings.Crude product POM multipolymer through so handling can be as the raw material of stabilization procedures.
The invention provides the other method that is used to make the stable polyoxymethylene of the stable process of preparing of polyacetal copolymer with unstable end group, it is characterized in that using as the unstable endgroup content of having of raw material being 0.3-0.8% (weight) (based on described polymkeric substance) and POM multipolymer with specific size distribution; Stablizer is added in the POM multipolymer that is generated with water; Reach the mixture exhaust that makes molten state in a vacuum.
Refer to weight percentage at this used term POM multipolymer " unstable end group amount " with respect to the formaldehyde of described multipolymer, this Determination on content method is: the POM multipolymer of 1 gram is placed the pressure bottle of sealing with 100 milliliters of 50% methanol aqueous solutions that contain 0.5% ammonium hydroxide, heated formed mixtures 45 minutes in 180 ℃, described liquid is also taken out in cooling from this bottle, analyze the formaldehyde amount that decomposition and wash-out go out in described liquid then.
By following method the amount of described unstable end group is controlled in the scope of 0.3-0.8% (weight), described method is to comprise the polymerization process that adds the sterically hindered phenol process; Or by in the inerting process after polymerization, described polymerisate is dissolved in the methanol solution of organic or inorganic basic cpd (for example triethylamine, trolamine, yellow soda ash or calcium hydroxide), and then precipitate this POM multipolymer, do not add sterically hindered phenol in the case.With the crude product POM that so obtains.Multipolymer is made the powder that can satisfy the size distribution of regulation in the item of following (1)-(4), thereby provides as raw material.
(1) median size is 0.3-0.7mm,
(2) having diameter is 3-20% (weight) greater than the content of the particle of 1.0mm,
(3) have content that diameter is not less than 0.18mm and is not more than the particle of 1.0mm be 50-97% (weight) and
(4) having diameter is 0-30% (weight) [the supposition total amount is 100% (weight)] less than the content of the particle of 0.18mm.
Stablizer and water are added in the prepared raw material crude product POM multipolymer, and make the exhaust under molten state of formed mixture in a vacuum, thereby obtain stable POM multipolymer.
Of the present invention being characterized as uses prepared crude product POM multipolymer as raw material; In its stabilization procedures, add water in this raw material, in formed mixture, sneak into stablizer etc. then, remove for example degradation production of POM multipolymer (formaldehyde gas) of volatile composition simultaneously, they are former to be present in the described raw material or to be produced in stabilization procedures.
The add-on of water is the 0.05-5.0% (weight) based on described raw material weight, preferred 0.5-3.0% (weight).The consumption that is lower than above-mentioned scope does not produce the effect of removing volatile component, and does not preferably exceed the consumption of above-mentioned scope, because the described water yield still is retained in the described kneading mixture.Can with the raw material pre-mixing after or make raw material melt plasticizing after add entry.In last method, in advance with water-dispersion, this makes it possible in melt plasticizing back fully disperse water.Preferably during the melt plasticizing of described raw material, do not add entry,, thereby suppress the plasticizing process of described raw material or worry that plastifying is not partly sneaked in the raw material because the part of big water gaging exists.
At this used stablizer is not proposed special restriction, can use any known stablizer.Yet, generally be used in combination oxidation inhibitor and thermo-stabilizer.The example of oxidation inhibitor comprises 1,6-hexylene glycol-two-[3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester], [3-(3 for tetramethylolmethane four, 5-two-tert-butyl-hydroxy phenyl) propionic ester], triglycol-two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester] and N, N '-hexa-methylene-two (3,5-di-t-butyl-4-hydroxyl-cyanamide).
The example of thermo-stabilizer comprises triaizine compounds for example trimeric cyanamide and carbamide condenses, and polymeric amide is nylon 12 and nylon 6.10 for example; The oxyhydroxide of basic metal or alkaline-earth metal, carbonate, phosphonate, acetate and oxalate; Reach for example stearic acid of higher fatty acid or have for example metal-salt of the higher fatty acid of hydroxyl of substituting group.
Can different additives be added in the POM multipolymer of the present invention according to purpose.The example comprises weather (light) stablizer, lubricant, nucleator, releasing agent, static inhibitor, dyestuff, pigment, other organic polymer material and inorganic or organic fibre, sheet or pulverulent filler.
The device instance that is used for stabilization procedures of the present invention comprises that continuous extruder for example has the Bitruder and the single shaft multiple screw extruder that has ventilating pit of ventilating pit.Under reduced pressure, by described ventilating pit described volatile component is removed.
Hereinafter, will introduce the present invention by embodiment and comparing embodiment, yet, should remember to be not limited to the following example or be not limited.
[evaluation method]
. extrudable property (the infiltration power character of raw material)
In stablizer being mixed described Powdered POM multipolymer and with the mixture that is generated, in extruding machine, in the melt-kneaded, observe described raw material and enter infiltration power (biting) condition of extruding machine and the condition that stable POM discharges in described extruding machine.According to following Three Estate A-C, it is made evaluation:
A: infiltrate the power condition and all stablize with discharge line material.
B: occur the infiltration power condition of difference and the denseness of described line material sometimes and fluctuation occurs.
C: the fluctuation of described infiltration power condition aspect is bigger, and fracture appears in the fluctuation of the denseness of line material greatly and sometimes line material.
.POM the content of the unstable end group of multipolymer
The POM multipolymer of 1 gram is placed the pressure bottle of sealing with 100 milliliters of 50% methanol aqueous solutions that contain 0.5% ammonium hydroxide, then in 180 ℃ of heating 45 minutes.Then, the cooling and from this bottle the taking-up described reaction mixture.In described liquid, decompose and the amount of dissolved formaldehyde and represent by assay determination with weight percent based on described multipolymer.
. at monomer described in the described polymkeric substance (formaldehyde) content (formaldehyde extracted amount)
2 gram POM multipolymers are added in 40 ml distilled waters, then, under boiling, refluxed 1.5 hours.Then, by analyzing, measure the amount of the formaldehyde that extracts in the water and represent by parts by weight with respect to described polymerisate.
Embodiment 1-5, comparing embodiment 1-5
[preparation crude product POM multipolymer raw material (POM multipolymer)] with unstable end group
In each embodiment, continuously Jiang 1 of trioxane and 2.5% (weight) (based on whole monomers), the 3-dioxolane is supplied with two stirring-type successive polymerization stills, and in the presence of as the boron trifluoride of catalyzer or phospho-molybdic acid, finishes described polymerization process.In certain embodiments, four [methylene radical (3,5-di-t-butyl-4-hydroxyl cortex cinnamomi acid ester)] methane (" Irganox 1010 ", the trade(brand)name that adds 0.05% consumption (based on all monomers), Ciba Geigy product) and do not add in further embodiments, be listed in table 1 and 2.After inerting broken at wet-milling and described catalyzer is handled, will be also dry by the crude product POM multipolymer dehydration that the polymeric kettle end outlet is discharged, obtain having Powdered POM multipolymer thus in size distribution shown in table 1 or 2.Control particle diameter by the rotation frequency of pulverizer shown in the change or the order number or the shape of screen cloth.
[stabilization treatment]
With the pulverous POM multipolymer that so obtains and the four [methylene radical (3 of 0.45% (weight), 5-di-t-butyl-4-hydroxyl cortex cinnamomi acid ester)] methane (" Irganox 1010 ", trade(brand)name, the CibaGeigy product) and the calcium stearate of 0.1% (weight) mix, then, melt-kneaded in single shaft that has ventilating pit or twin shaft extruding machine.At this moment, with water (1) with described raw material pre-mixing after add, (2) add in the melt of described raw material plasticizing back and (3) do not add water.
It the results are shown in table 1 and 2.
In following table, abbreviation has following meaning.
Size distribution:
In the scope: in the particle size distribution range that satisfies following (1)-(4) item, (1) median size is 0.3-0.7mm, (2) having diameter is 3-20% (weight) greater than the content of the particle of 1.0mm, (3) having content that diameter is not less than 0.18mm and is not more than the particle of 1.0mm is that to have diameter be 0-30% (weight) [the supposition total amount is 100% (weight)] less than the content of the particle of 0.18mm for 50-97% (weight) and (4).
Go beyond the scope 1: exceed above-mentioned particle size distribution range and have particle diameter and exceed 30% (weight) less than the content of the particle of 0.18mm.
Go beyond the scope 2: exceed above-mentioned particle size distribution range and have particle diameter at least the content of the particle of 1.00mm exceed 20% (weight).
The method that adds:
Inject: after described raw material melt plasticizing, water is added in the extruding machine.
Pre-mixing: after with water and described raw material pre-mixing, add entry.
The type of catalyzer:
BF
3: boron trifluoride
HPA: phospho-molybdic acid
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| The preparation of raw material. add " Irganox 1010 ". the kind add-on (ppm) of catalyzer. size distribution | Be BF 3In 20 scopes | Be BF 3In 20 scopes | Be BF 3In 20 scopes | Be BF 3In 20 scopes | Be in HPA 5 scopes |
| Stabilization procedures. extruding machine adds the water yield (%). the adding method. extrudable property | Single shaft 2 injects A | Single shaft 2 pre-mixing A | Twin shaft 2 injects A | Twin shaft 2 pre-mixing A | Twin shaft 2 injects A |
| Estimate (behind the extrusion molding). the amount of unstable end group (%). extract the amount (ppm) of formaldehyde | 0.41 65 | 0.49 78 | 0.40 63 | 0.45 70 | 0.50 80 |
Table 2
| Comparing embodiment 1 | Comparing embodiment 2 | Comparing embodiment 3 | Comparing embodiment 4 | Comparing embodiment 5 | |
| The preparation of raw material. add " Irganox 1010 ". the kind add-on (ppm) of catalyzer. size distribution | Deny BF 3In 20 scopes | Be BF 320 go beyond the scope 1 | Be BF 320 go beyond the scope 2 | Be BF 3In 20 scopes | Be BF 3In 20 scopes |
| Stabilization procedures. extruding machine adds the water yield (%). the adding method. extrudable property | Single shaft 2 injects A | Single shaft 2 pre-mixing C | Single shaft 2 injects A | Single shaft--A | Single shaft 5.5 injects B |
| Estimate (behind the extrusion molding). the amount of unstable end group (%). extract the amount (ppm) of formaldehyde | 0.59 152 | 0.50 96 | 0.92 182 | 0.61 253 | 0.83 70 |
Embodiment 6-8, comparing embodiment 6-9
[preparation crude product POM multipolymer raw material (POM multipolymer)] with unstable end group
In each embodiment, continuously Jiang 1 of trioxane and 2.5% (weight) (based on whole monomers), the 3-dioxolane is supplied with two stirring-type successive polymerization stills, and in the presence of as the boron trifluoride of the 20ppm of catalyzer, finishes described polymerization process.To under 180 ℃ of heating, be dissolved in the methanol solution that contains 0.25% (weight) triethylamine by the crude product POM multipolymer that the polymeric kettle end outlet is discharged, cooling then, thus make POM multipolymer precipitation.Formed precipitation is removed desolvated and drying, dry grinding then obtains having the Powdered POM multipolymer that predetermined particle diameter distributes thus.Control the amount of the unstable end group of described raw material POM multipolymer by the retention time of change in 180 ℃ of methanol solutions.
[stabilization treatment]
With the pulverous POM multipolymer that so obtains and the four [methylene radical (3 of 0.5% (weight), 5-di-t-butyl-4-hydroxyl cortex cinnamomi acid ester)] methane (" Irganox 1010 ", trade(brand)name, the CibaGeigy product) and the calcium stearate of 0.1% (weight) mix, then, melt-kneaded in single shaft that has ventilating pit or twin shaft extruding machine.At this moment, with water (1) with described raw material pre-mixing after add, (2) add in the melt of described raw material plasticizing back and (3) do not add water.
It the results are shown in table 3 and 4.
In following table, abbreviation has following meaning.
Size distribution:
In the scope: in the particle size distribution range that satisfies following (1)-(4) item, (1) median size is 0.3-0.7mm, (2) having diameter is 3-20% (weight) greater than the content of the particle of 1.0mm, (3) having content that diameter is not less than 0.18mm and is not more than the particle of 1.0mm is that to have diameter be 0-30% (weight) [the supposition total amount is 100% (weight)] less than the content of the particle of 0.18mm for 50-97% (weight) and (4).
Go beyond the scope 1: exceed above-mentioned particle size distribution range and have particle diameter and exceed 30% (weight) less than the content of the particle of 0.18mm.
Go beyond the scope 2: exceed above-mentioned particle size distribution range and have particle diameter at least the content of the particle of 1.00mm exceed 20% (weight).
The method that adds:
Inject: after described raw material melt plasticizing, water is added in the extruding machine.
Pre-mixing: after with water and described raw material pre-mixing, add entry.
Table 3
| Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| The preparation of raw material. the content of unstable end group (%). size distribution | 0.45 in the scope | 0.45 in the scope | 0.45 in the scope |
| Stabilization procedures. extruding machine adds the water yield (%). the adding method. extrudable property | Single shaft 2 injects A | Single shaft 2 pre-mixing A | Twin shaft 2 injects A |
| Estimate (behind the extrusion molding). the amount of unstable end group (%). extract the amount (ppm) of formaldehyde | 0.25 63 | 0.31 75 | 0.20 50 |
Table 4
| Comparing embodiment 6 | Comparing embodiment 7 | Comparing embodiment 8 | Comparing embodiment 9 | |
| The preparation of raw material. the content of unstable end group (%). size distribution | 0.45 in the scope | 0.44 go beyond the scope 1 | 0.46 go beyond the scope 2 | 0.70 in the scope |
| Stabilization procedures. extruding machine adds the water yield (%). the adding method. extrudable property | Single shaft--A | Single shaft 2 injects C | Single shaft 2 injects A | Single shaft 2 injects A |
| Estimate (behind the extrusion molding). the amount of unstable end group (%). extract the amount (ppm) of formaldehyde | 0.38 110 | 0.35 76 | 0.50 110 | 0.61 300 |
Claims (7)
1. by the copolymerized methanal with unstable end group being stablized prepare the method for stable copolymerized methanal, it is characterized in that
(A) as copolymerized methanal with unstable end group, use is by adding the multipolymer that obtains in the monomer mixture with sterically hindered phenol with the amount based on all monomeric 0.001-2.0% weight, make described monomer mixture polymerization, to be ground into powder by the crude product polyoxymethylene that this polymerization process produces with the size distribution that satisfies following (1)-(4) item, and make the polymerizing catalyst inerting that is included in this crude product multipolymer and
(B) stablizer is added in the copolymerized methanal as raw material with water, and in a vacuum with the mixture exhaust of molten state:
(1) median size is 0.3-0.7mm,
(2) having diameter is 3-20% weight greater than the content of the particle of 1.0mm,
(3) have content that diameter is not less than 0.18mm and is not more than the particle of 1.0mm be 50-97% weight and
(4) having diameter is 0-30% weight less than the content of the particle of 0.18mm,
Condition is that total amount is 100% weight.
2. by the copolymerized methanal with unstable end group being stablized prepare the method for stable copolymerized methanal, it is characterized in that:
(A) use the powdery copolymer contain based on the unstable end group of the 0.3-0.8% weight of described multipolymer and to have a size distribution that satisfies following (1)-(4) as the multipolymer formaldehyde with unstable end group and
(B) stablizer is added in the copolymerized methanal as raw material with water, and in a vacuum with the mixture exhaust of molten state:
(1) median size is 0.3-0.7mm,
(2) having diameter is 3-20% weight greater than the content of the particle of 1.0mm,
(3) have content that diameter is not less than 0.18mm and is not more than the particle of 1.0mm be 50-97% weight and
(4) having diameter is 0.30% weight less than the content of the particle of 0.18mm,
Condition is that total amount is 100% weight.
3. according to the method for the stable copolymerized methanal of the preparation of claim 1 or 2, wherein with described water and described copolymerized methanal raw material pre-mixing with unstable end group.
4. according to the method for the stable copolymerized methanal of the preparation of claim 1 or 2, wherein the copolymerized methanal raw material melt plasticizing back with unstable end group is added described water.
5. according to the method for the stable copolymerized methanal of the preparation of claim 1 or 2, wherein with described water and stablizer and have the copolymerized methanal raw material pre-mixing of unstable end group.
6. according to the method for the stable copolymerized methanal of the preparation of claim 1 or 2,, and after being plastified, described copolymerized methanal raw material melt with unstable end group adds entry wherein with described stablizer and described copolymerized methanal raw material pre-mixing with unstable end group.
7. according to the method for the stable copolymerized methanal of the preparation of claim 1 or 2, wherein described copolymerized methanal raw material melt plasticizing back with unstable end group is added described water and stablizer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP333737/1996 | 1996-12-13 | ||
| JP333737/96 | 1996-12-13 | ||
| JP33373796A JP3210872B2 (en) | 1996-12-13 | 1996-12-13 | Method for producing stabilized oxymethylene copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1191226A CN1191226A (en) | 1998-08-26 |
| CN1105126C true CN1105126C (en) | 2003-04-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97125490A Expired - Lifetime CN1105126C (en) | 1996-12-13 | 1997-12-12 | Process for producing stabilized oxymethylene copolymer |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JP3210872B2 (en) |
| KR (1) | KR100542901B1 (en) |
| CN (1) | CN1105126C (en) |
| AU (1) | AU738001B2 (en) |
| MY (1) | MY116970A (en) |
| SG (1) | SG67417A1 (en) |
| TH (1) | TH29900A (en) |
| TW (1) | TW438841B (en) |
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| DE102008018966A1 (en) | 2008-04-16 | 2009-10-22 | Ticona Gmbh | Process for the preparation of oxymethylene polymers and apparatus suitable therefor |
| CN104302683B (en) | 2012-05-14 | 2017-07-28 | 三菱瓦斯化学株式会社 | Aoxidize the manufacture method of methylene base co-polymer |
| CN103063665B (en) * | 2012-12-26 | 2015-04-29 | 中国海洋石油总公司 | Determination method for content of boron trifluoride in formaldehyde copolymerization catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51125A (en) * | 1974-06-19 | 1976-01-05 | Meisei Kogyo Kk | Kenchikuyohekitaino kyojiunpantachiokoshiki |
| JPS517547A (en) * | 1974-07-09 | 1976-01-21 | Mitsubishi Electric Corp | KOSHUHAKANETSUSOCHI |
| JPS57537A (en) * | 1980-06-02 | 1982-01-05 | Toshiba Corp | Balance working method for rotatable body |
| JPS59249A (en) * | 1982-06-25 | 1984-01-05 | Nec Corp | Fault detecting system of looped communication network |
| JPH1031028A (en) * | 1996-07-15 | 1998-02-03 | Mitsubishi Electric Corp | Airtight assembly of electronic part, and its manufacture |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4692290A (en) * | 1985-11-12 | 1987-09-08 | Celanese Corporation | Process for devolatilizing molten oxymethylene polymer |
| JPH0772220B2 (en) * | 1986-11-17 | 1995-08-02 | 三菱瓦斯化学株式会社 | Method for stabilizing oxymethylene copolymer |
| JP3230554B2 (en) * | 1994-02-23 | 2001-11-19 | 旭化成株式会社 | Production method of polyoxymethylene with excellent color tone and thermal stability |
-
1996
- 1996-12-13 JP JP33373796A patent/JP3210872B2/en not_active Expired - Lifetime
-
1997
- 1997-09-08 SG SG1997003336A patent/SG67417A1/en unknown
- 1997-09-10 AU AU37450/97A patent/AU738001B2/en not_active Ceased
- 1997-09-11 MY MYPI97004205A patent/MY116970A/en unknown
- 1997-10-02 TW TW086114359A patent/TW438841B/en not_active IP Right Cessation
- 1997-12-11 TH TH041208A patent/TH29900A/en unknown
- 1997-12-12 KR KR1019970068174A patent/KR100542901B1/en not_active IP Right Cessation
- 1997-12-12 CN CN97125490A patent/CN1105126C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51125A (en) * | 1974-06-19 | 1976-01-05 | Meisei Kogyo Kk | Kenchikuyohekitaino kyojiunpantachiokoshiki |
| JPS517547A (en) * | 1974-07-09 | 1976-01-21 | Mitsubishi Electric Corp | KOSHUHAKANETSUSOCHI |
| JPS57537A (en) * | 1980-06-02 | 1982-01-05 | Toshiba Corp | Balance working method for rotatable body |
| JPS59249A (en) * | 1982-06-25 | 1984-01-05 | Nec Corp | Fault detecting system of looped communication network |
| JPH1031028A (en) * | 1996-07-15 | 1998-02-03 | Mitsubishi Electric Corp | Airtight assembly of electronic part, and its manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100542901B1 (en) | 2006-08-30 |
| SG67417A1 (en) | 1999-09-21 |
| CN1191226A (en) | 1998-08-26 |
| AU3745097A (en) | 1998-06-18 |
| JP3210872B2 (en) | 2001-09-25 |
| AU738001B2 (en) | 2001-09-06 |
| JPH10168144A (en) | 1998-06-23 |
| MY116970A (en) | 2004-04-30 |
| KR19980064083A (en) | 1998-10-07 |
| TW438841B (en) | 2001-06-07 |
| TH29900A (en) | 1998-09-04 |
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