CN1105127C - Process for producing stabilized oxymethylene copolymer - Google Patents
Process for producing stabilized oxymethylene copolymer Download PDFInfo
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- CN1105127C CN1105127C CN97121125A CN97121125A CN1105127C CN 1105127 C CN1105127 C CN 1105127C CN 97121125 A CN97121125 A CN 97121125A CN 97121125 A CN97121125 A CN 97121125A CN 1105127 C CN1105127 C CN 1105127C
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- oxymethylene copolymer
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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
- C08G2/18—Copolymerisation of aldehydes or ketones
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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
- C08G2/02—Polymerisation initiated by wave energy or by particle radiation
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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
- C08G2/06—Catalysts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- Polymers & Plastics (AREA)
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
To provide an economical process for producing an oxymethylene copolymer excellent in thermal stability. A crude oxymethylene copolymer discharged from a polymerizer is pulverized into a powder having a specified particle diameter distribution and simultaneously the polymerization catalyst is deactivated and then the pulverized oxymethylene copolymer is melt-kneaded together with a stabilizer to obtain a stabilized oxymethylene copolymer substantially without any treatment for stabilizing the ends by removing the unstable end parts by decomposition.
Description
The present invention relates to produce the method for the economy of copolyoxymethylenes with splendid thermostability.
Because polyacetal copolymer (hereinafter referred is " a POM multipolymer ") has splendid mechanical property, thermotolerance, chemical resistant properties, electric property and sliding capability, have splendid mouldability or workability simultaneously, it is used as engineering plastics, is widely used for machine part, trolley part or electrical/electronic components.
People know, for stable POM multipolymer that practical application provided normally according to following method preparation.
At first, be main monomer with ring-type acetal (for example trioxane), ring-type acetal or cyclic ether with adjoining carbons are comonomer, according to purpose to wherein adding chain-transfer agent to regulate the polymerization degree; Copolymerization in the presence of the cation activity catalyzer then obtains the POM multipolymer.Such POM polymkeric substance crude product generally contains a large amount of unstable end group parts.When heating kept active polymerizing catalyst, the depolymerization of multipolymer or the increase of unstable end group part can appear.
Therefore, after contained catalyzer is used organic or inorganic basic cpd (for example alkylamine, alkoxylamine or hindered amine or basic metal or alkaline earth metal hydroxides) neutralization or deactivation in multipolymer subsequently, will carry out the decomposition of unstable end group part as the rough POM multipolymer of polymerisate and remove step.Then, the multipolymer of so handling is heated in the presence of basic cpd (for example above-named compound), can also be used in combination water or ethanol in case of necessity, remove unstable end group part thereby decompose.
Then, to decompose the POM multipolymer of removing unstable end group part with this mode in, add suitable additive to give polymkeric substance with thermostability and permanent stability, in addition, according to application target, can add various additives or strengthening agent to give this multipolymer with required performance, follow melt kneading, thereby make the stable POM multipolymer that is suitable for actual use.
On the other hand, people have carried out many-sided research and have stablized the POM multipolymer in the hope of prepare more economically.The example of the production measure of known economy comprises the polymeric kettle that improves in the polymerization procedure, polymerizing catalyst etc., the deactivation device of improvement in catalyzer deactivation step, deactivation method etc. and improve in the decomposition of unstable end group part and remove decomposition accelerator, decomposition and removal equipment in the step.
Yet above-mentioned any measure only is the improvement of concrete steps, and is limited certainly by its improvement that brings.Therefore, people need provide a kind of and consider from the method for producing the POM multipolymer of the whole process of the stabilization that is aggregated to final POM multipolymer more economically.Particularly in above-mentioned steps, the decomposition of unstable end group part and removal need loaded down with trivial details operation to handle and this processing needs lot of energy.If can under the situation of the final stabilization step that need not to decompose and remove step basically, provide POM multipolymer, then can be extremely economical, produce easily.To decompose and the removal step in order saving, must in polymerization procedure and/or catalyzer deactivation step, to prepare high-quality (rough) POM multipolymer.From decomposition efficiency that improves catalyzer deactivation efficient and unstable end group subsequently and the viewpoint of removing efficient,, known by pulverizing the method for the rough POM multipolymer of deactivation polymerisate----as the method that promotes the catalyzer deactivation.According to these viewpoints, the less copolymer powder of granularity is considered to preferably (JP-A-57-80414 and JP-A-58-34819).
The result, though the inventor still finds by pulverizing rough POM multipolymer have been carried out the quality that such deactivation processing has improved gained POM multipolymer, if but gained POM multipolymer is used in the stabilization step, this gained multipolymer and stablizer together add, melt kneading then, and do not carry out the removal step of unstable end group, then gained POM multipolymer shows relatively poor operability inevitably.
As mentioned above, also be not found to be up to now final stabilization step the POM multipolymer is provided and need not the decomposition of unstable end group and remove step produce the effective and simple method of stablizing the POM multipolymer economically.
The purpose of this invention is to provide extremely economical, easily and simple method of producing the stable POM multipolymer that is suitable for actual use, thereby solved the problems referred to above.
In order to achieve the above object, the inventor studies to the whole process of stabilization step the polymerization procedure from the POM multipolymer.Found that, be an important factor as the pulverizing of the rough POM multipolymer of polymerisate, and above-mentioned purpose can reach by the size-grade distribution of suitable control multipolymer.Thereby caused of the present invention finishing.
That is to say, the present invention is a kind of method of producing stabilized oxymethylene copolymer, it is characterized in that the rough copolyoxymethylenes that will discharge is ground into the powder that satisfies following size-grade distribution requirement (1) to (4) from polymeric kettle, simultaneously with the polymerizing catalyst deactivation, then with the copolyoxymethylenes pulverized with the stablizer melt kneading, need not to remove unstable end group part basically and handled with stable end groups by decomposition:
(1) mean particle size is 0.3-0.7mm,
(2) the particulate diameter of 3-20% (weight) is greater than 1.0mm,
(3) the particulate diameter of 50-97% (weight) be 0.18-1.0mm and
(4) the particulate diameter of 0-30% (weight) is less than 0.18mm (total amount is 100% (weight)).
In other words, the present invention relates to produce the method for copolyoxymethylenes, this method comprises the steps: that polymerization obtains yuban, rough copolymer products is ground into size-grade distribution meet the demands (1), (2), the powder of (3) and (4) is with the catalyzer deactivation that remains in the powder, then with this powder with the stablizer melt kneading, just this powder needn't be through disaggregating treatment to remove the unstable end group in the molecule.The present invention also provides by above-mentioned steps and makes the yuban method of stabilizing.
Below the present invention will be described more specifically.
At first, used (rough) copolyoxymethylenes (POM multipolymer) can obtain by make ring-type acetal (for example trioxane) main monomer and cyclic ether or the copolymerization of cyclic formal comonomer in the presence of the cation activity catalyzer among the present invention.
Cyclic formal as comonomer is the ring compound that contains at least one pair of coupling carbon atom and Sauerstoffatom herein.The example comprises oxyethane, 1,3-dioxolane, 1,3,5-three butyl oxide links, Diethylene Glycol formal, 1,4-butyleneglycol formal, 1,3-dioxane and propylene oxide.Wherein, preferred comonomer is an oxyethane, 1,3-dioxolane, Diethylene Glycol formal and 1,4-butyleneglycol formal.With respect to main monomer trioxane meter, the consumption of comonomer is 0.1-20% (mole), preferred 0.2-10% (mole).
By this class monomer and comonomer preparation (rough) POM multipolymer the time, be polymerizing catalyst with conventional cationic catalyst.The example of cationic catalyst comprises for example muriate of boron, tin, titanium, phosphorus, arsenic and antimony of Lewis acid, more specifically, boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentachloride, phosphorus pentafluoride, arsenic pentafluoride and antimony pentafluoride, compound be title complex or its salt for example; Protonic acid is ester for example mixed acid anhydride and lower alphatic carboxylic acid (for example acetylperchlorate), different polyacid, heteropolyacid (for example phospho-molybdic acid), phosphofluoric acid triethyl oxygen, hexafluoroarsenate triphenyl methyl esters and the hexafluoro boric acid acetonyl ester of acid anhydrides, the particularly perchloric acid of ester (for example tert-butyl ester of perchloric acid), the protonic acid of the ester of perchloric acid and lower aliphatic alcohols of trifluoromethanesulfonic acid and perchloric acid, protonic acid for example.
Wherein the coordination compound of boron trifluoride and boron trifluoride and organic compound (for example ether) is the most frequently used catalyzer.In addition, owing to have high catalytic activity, high-quality rough POM multipolymer can easily be provided in the presence of little amount of catalyst and be easy to deactivation such as heteropolyacid or different polyacid.Therefore preferably by polymerization prepares rough POM multipolymer in the presence of two or more the catalyzer of mixture of this compounds or its being selected from.When using Lewis acid for example boron trifluoride is made catalyzer, its add-on is preferably the monomeric 15-25ppm of starting material.Preferably use water content to be no more than the monomer of 10ppm to obtain high-quality rough POM multipolymer.
In order to regulate the molecular weight of the rough POM multipolymer that can obtain by copolymerization, also can be where necessary by add an amount of suitable chain-transfer agent for example acetal compound for example methylal or dioxy methylene radical dimethyl ether carry out polymerization.
Perhaps, can in the presence of the hindered phenol compound oxygenant, produce so rough POM multipolymer.The oxidation destruction that this method can be controlled at the oxidation destruction of gained POM multipolymer between polymerization period effectively or suppress the caused POM multipolymer of heat treatment step subsequently, this just can provide the final stabilization step that keeps high-quality POM multipolymer.Therefore, so just obtain preferred rough POM multipolymer of the present invention.
Can come the rough POM multipolymer of copolymerization by using conventional known equipment and method (for example batch process and continuous processing, melt polymerization or fusion mass polymerization).From the viewpoint of industry, preferred method commonly used is the continuous bulk polymerization method, wherein uses liquid monomer and obtains the polymkeric substance of pressed powder form along with polymeric.In this case, polymerization in case of necessity can be carried out in the presence of inert liquid medium.The example of available polymerization unit of the present invention comprises that Ko-Kneader kneader, twin screw extrude mixing machine and two ponds types (twin-puddletype) continuous mixer continuously.
Method of the present invention is characterised in that the rough POM multipolymer that will obtain as stated above is ground into the powder with certain particle size distribution, simultaneously with polymerizing catalyst deactivation contained in the powder, with POM multipolymer and the stablizer melt kneading pulverized, needn't remove the processing partly of unstable end group by decomposition and come stable end groups then.
Need make the POM multipolymer of pulverizing like this satisfy the described size-grade distribution in following (1) to (4) herein:
(1) mean particle size is 0.3-0.7mm,
(2) the particulate diameter of 3-20% (weight) is greater than 1.0mm,
(3) the particulate diameter of 50-97% (weight) be 0.18-1.0mm and
(4) the particulate diameter of 0-30% (weight) is less than 0.18mm (total amount is 100% (weight)).
Above-mentioned size-grade distribution is that the inventor finds through broad research, with the deactivation of the amount of the unstable end group of the POM multipolymer that satisfies quality, particularly pulverize to obtain and catalyzer with the POM multipolymer pulverized operability with this stabilization step of stablizer melt kneading.
In above-mentioned requirement, diameter is the essential condition of major decision POM copolymer quality above the upper limit of the particulate ratio of 1.0mm in the upper limit of the mean diameter in (1) (0.7mm) and (2).On the other hand, in (1) in the minimum (0.3mm) of median size, (2) diameter to surpass particle diameter in the minimum of particulate ratio of 1.0mm and (4) be the essential condition of major decision with operability in the stablizer stabilization step less than the upper limit of the particulate ratio of 0.18mm.
When granularity surpasses above-mentioned size-grade distribution, for example mean particle size surpasses its upper limit or granularity and surpasses it greater than the particulate ratio of 1.0mm and go up and prescribe a time limit, the degradation of the POM multipolymer that gained is pulverized, particularly the amount of unstable end group increases, only do not adopt and decompose the stable end groups processing of removing unstable end group part, can not obtain commercially available stable POM multipolymer with the stablizer stabilization.On the other hand, when granularity is lower than above-mentioned size-grade distribution, when for example mean particle size is lower than its minimum, when granularity is lower than its minimum greater than the particulate ratio of 1.0mm, perhaps granularity surpasses it less than the ratio of 0.18mm and goes up and prescribe a time limit, the obvious variation of operability of the stabilization step of mediating with stablizer, and can not produce the POM multipolymer of satisfactory quality, thus being difficult to produce economically stablizes the POM multipolymer.
Consider above situation, can satisfy POM copolymer quality and stabilization step preferably operability, preferred size-grade distribution is as follows:
(1) ' mean particle size is 0.4-0.7mm,
(2) ' the particulate diameter of 5-15% (weight) is greater than 1.0mm,
(3) ' the particulate diameter of 60-95% (weight) be 0.18-1.0mm and
(4) ' the particulate diameter of 0-25% (weight) is less than 0.18mm (total amount is 100% (weight)).
When having carried out pulverizing as above, have no particular limits for used pulverizer.Its example comprises grindstone, hammer mill, jaw crusher, feather shredder, rotation cutting grinding machine, steamer formula shredder and branch type impact grinder.Can be controlled by the variator of the rotation frequency of pulverizer, the space that is connected the screen cloth on the pulverizer and/or connection respectively in case of necessity.
When contained catalyzer carries out deactivation in to rough POM multipolymer, can use conventional currently known methods.In the present invention, the aqueous solution of the most handy organic or inorganic basic cpd of deactivation (for example triethylamine, trolamine, yellow soda ash or calcium hydroxide) carries out deactivation as deactivator, simultaneously the powder that rough POM multipolymer wet pulverization is become to have above-mentioned size-grade distribution.At first, be preferably in the pulverizer ingress that exports to that is right after polymeric kettle and add deactivator, thereby can obtain high-quality POM multipolymer.
After the deactivation and pulverizing of catalyzer, in case of necessity with the washing of POM multipolymer, drying etc.
In the present invention, can obtain to have the high quality P OM multipolymer of less unstable end group like this: will be as the catalyzer deactivation as described above of the rough POM multipolymer of polymerisate, it is ground into has the powder that certain particle size distributes simultaneously.Especially preferably the gained multipolymer that is 0.3-0.8 with unstable end group amount carries out stabilization step subsequently.
By the way, " the unstable end group amount " of the said POM multipolymer of this paper is meant the amount (weight percentage) with respect to multipolymer meter formaldehyde, this amount is by in the pressure bottle that 1 gram POM multipolymer and the 100 milliliter of 50% methanol aqueous solution input that contains 0.5% ammonium hydroxide are sealed, the gained mixture was heated 45 minutes in 180 ℃, cooling, from bottle, take out, analyze the amount of decomposing and being dissolved in the formaldehyde in the liquid then.
To be ground into then and have above-mentioned certain particle size and distribute, subsequently contained catalyzer carried out pulverizing POM multipolymer that deactivation handles with the stablizer melt kneading, basically the conventional processing of removing unstable end group needn't be decomposed, thereby the POM multipolymer can be obtained to stablize.
Herein, have no particular limits for the available stablizer.Any known stablizer can be used, but in general, antioxidant and thermo-stabilizer be used in combination.
Examples of antioxidants comprises 1, [3-(3 for 6-hexylene glycol-two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], [3-(3 for tetramethylolmethane four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], triethylene glycol 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 NYLON610 for example; The oxyhydroxide of basic metal or alkaline-earth metal, carbonate, phosphoric acid salt, acetate and oxalate; With higher fatty acid stearic acid or have the metal-salt of the higher fatty acid of substituting group (for example hydroxyl) for example.
According to different purposes, can in POM multipolymer of the present invention, add various additives.The example of additive comprises weathering resistance stablizer (perhaps photostabilizer), lubricant, nucleator, releasing agent, static inhibitor, dyestuff, pigment, other organic polymer material, inorganic or organic fibre shape, tabular or fleut.
Generally in forcing machine, carry out with the melt kneading of stablizer etc.
Embodiment and comparative example are described now.Obviously, the present invention is not subjected to their restriction.Embodiment 1-5 and comparative example 1-4
Is Jiang 1 of trioxane (water that contains 15ppm or 8ppm) and 2.5% (weight) (based on whole monomer meter) in each embodiment, the 3-dioxolane is sent in two pond type successive polymerization stills continuously, carries out polymerization in the presence of boron trifluoride or phospho-molybdic acid (providing with the form with the monomeric mixture of copolymerization) catalyzer., carry out the deactivation of catalyzer simultaneously and handle rough POM multipolymer wet pulverization or dry ground that polymeric kettle end outlet place discharges with following method, follow dehydration, drying, thus the Powdered POM multipolymer that acquisition has the size-grade distribution shown in the table 1.Come control size to distribute by the rotation frequency or the sieve aperture shape that change pulverizer.Wet pulverization
The aqueous solution that will contain the 500ppm triethylamine is delivered to the exit of polymer reactor as catalyzer.Contact with the rough POM multipolymer of just discharging at it and to make and introduce the gained mixture in the ball mill that screen cloth is housed the inside and pulverizing therein in the catalyzer deactivation from outlet.From pulverizer, discharge the slurries that contain Powdered POM multipolymer and catalyzer deactivator, introduce then in the basin, carry out further deactivation therein, then dehydration, drying.Dry ground:
The rough POM multipolymer that to discharge from the polymeric kettle exit is introduced the pulverizer by the pipeline of sealing (in order to avoid contacting with water and air), then pulverizes.Then, will introduce from the Powdered POM multipolymer that pulverizer is discharged and be equipped with the basin of 500ppm triethylamine aqueous solution, and carry out deactivation and handle, then dehydration, drying.
As above the Powdered POM multipolymer of Huo Deing is without the decomposition of routine with remove the processing of unstable end group part, but in that [3-(3 with 0.5% (weight) tetramethylolmethane four as stablizer, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] and after 0.1% (weight) calcium stearate mixes, melt kneading in forcing machine, thus granular stable POM multipolymer obtained.Evaluation result is shown in Table 1.
By the way, assessment method and standard are as follows: [stablizing the thermostability of POM]
Mensuration will stablize POM multipolymer (5 gram) in air in 45 minutes weight loss of 220 ℃ of heating, the weight that is expressed as per minute reduces ratio (%) [extrudable property]
Raw-material interlock (biting)
Observe when stablizer is sneaked into Powdered POM multipolymer and gained compound when mediating in forcing machine, starting material enter the interlocking pattern of forcing machine and the stable POM multipolymer state from the forcing machine discharge.According to following A to four rankings of D.
A: the line material of interlocking pattern and discharge all is stable.
B: occur relatively poor interlocking pattern sometimes, the fluctuation of line material thickness occurs.
C: the fluctuation of interlocking pattern is big slightly, and the fluctuation of line material thickness is big, occurs the fracture of line material sometimes.
D: the interlocking pattern surging, the interlock amount is very low, can not form the line material.
Motor load amplification
When extrusion molding, the poor (unit: ampere) of the lowest high-current value of motor and minimum current value
The resin pressure fluctuation is poor
Be installed in maximum value shown in the resin pressure meter that is right after behind the extruder screw top and the poor (unit: kg/cm between the minimum value
2).
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Monomeric water ratio (ppm) | 15 | 8 | 8 | 8 | 8 | 15 | 8 | 8 | 8 |
| Catalyst type concentration (ppm) | BF 3 30 | BF 3 20 | BF 3 20 | BF 3 20 | HPA 5 | BF 3 30 | BF 3 20 | BF 3 20 | BF 3 20 |
| Breaking method | Wet | Wet | Wet | Do | Wet | Wet | Wet | Wet | Do |
| Size-grade distribution mean particle size D＞1.0mm (%) 1.0mm 〉=D 〉=0.18mm (%) 0.18mm＞D (%) | 0.45 8 71 21 | 0.46 7 70 23 | 0.59 18 77 5 | 0.47 10 72 18 | 0.46 8 69 23 | 0.72 38 57 5 | 0.72 37 58 5 | 0.17 2 43 55 | 0.74 42 55 3 |
| The amount of unstable end group (%) after the deactivation | 0.78 | 0.68 | 0.70 | 0.85 | 0.68 | 1.10 | 1.07 | 0.68 | 1.10 |
| Stablize the thermostability of POM | 0.013 | 0.005 | 0.006 | 0.011 | 0.005 | 0.040 | 0.032 | 0.005 | 0.037 |
| The fluctuation of the raw-material interlocking pattern motor load of extrudable property amplification resin pressure is poor | A 2 3 | A 2 3 | A 2 2 | A 2 2 | A 2 3 | A 4 5 | A 5 4 | D 18 17 | A 4 5 |
BF
3: boron trifluoride HPA: phospho-molybdic acid
Claims (8)
1. produce the method for stabilized oxymethylene copolymer, it is characterized in that the rough copolyoxymethylenes that will discharge is ground into the powder that satisfies following size-grade distribution requirement (1) to (4) from polymeric kettle, simultaneously with the polymerizing catalyst deactivation, then with the copolyoxymethylenes pulverized with the stablizer melt kneading, the processing that need not basically to remove unstable end group part by decomposition is with stable end groups:
(1) mean particle size is 0.3-0.7mm,
(2) the particulate diameter of 3-20% weight is greater than 1.0mm,
(3) the particulate diameter of 50-97% weight be 0.18-1.0mm and
The particulate diameter of (4) 0.30% weight is less than 0.18mm,
Total amount is 100% weight.
2. according to the method for the production stabilized oxymethylene copolymer of claim 1, wherein the copolyoxymethylenes of Fen Suiing has the unstable end group that accounts for multipolymer 0.3-0.8% weight.
3. according to the method for the production stabilized oxymethylene copolymer of claim 1, wherein rough copolyoxymethylenes is to obtain by carry out polymerization in the presence of bronsted acid catalyst.
4. according to the method for the production stabilized oxymethylene copolymer of claim 1, wherein rough copolyoxymethylenes is to obtain by carrying out polymerization in the presence of based on the lewis acid catalyst of the 15-25ppm of starting monomer meter.
5. according to the method for the production stabilized oxymethylene copolymer of claim 1, wherein rough copolyoxymethylenes obtains by carry out polymerization in the presence of hindered phenol compound.
6. according to the method for the production stabilized oxymethylene copolymer of claim 1, wherein rough copolyoxymethylenes is to obtain by the monomer polymerization that water content is no more than 10ppm.
7. according to the method for the production stabilized oxymethylene copolymer of claim 1-6, wherein pulverize and carry out with wet comminuting method, the deactivation processing is that the aqueous solution with basic cpd is that the activator of polymerizing catalyst carries out.
8. according to the method for the production stabilized oxymethylene copolymer of claim 7, wherein deactivation handle be by with the deactivator of polymerizing catalyst before the polymkeric substance outlet that is right after polymeric kettle and between the pulverizer inlet adding carry out.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP258983/96 | 1996-09-30 | ||
| JP258983/1996 | 1996-09-30 | ||
| JP8258983A JPH10101756A (en) | 1996-09-30 | 1996-09-30 | Production of stabilized oxymethylene copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1180713A CN1180713A (en) | 1998-05-06 |
| CN1105127C true CN1105127C (en) | 2003-04-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97121125A Expired - Lifetime CN1105127C (en) | 1996-09-30 | 1997-09-30 | Process for producing stabilized oxymethylene copolymer |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPH10101756A (en) |
| KR (1) | KR100521732B1 (en) |
| CN (1) | CN1105127C (en) |
| AU (1) | AU720117B2 (en) |
| MY (1) | MY119909A (en) |
| SG (1) | SG65677A1 (en) |
| TW (1) | TW422859B (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 |
| JP5829718B2 (en) | 2014-03-31 | 2015-12-09 | ポリプラスチックス株式会社 | Process for producing polyacetal copolymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5780414A (en) * | 1980-11-10 | 1982-05-20 | Mitsubishi Gas Chem Co Inc | Shortstopping of polymerization reaction |
| US4412067A (en) * | 1981-12-12 | 1983-10-25 | Degussa Aktiengesellschaft | Process for the continuous polymerization or copolymerization of trioxane |
| JPH04266917A (en) * | 1991-02-22 | 1992-09-22 | Toray Ind Inc | Oxymethylene multicomponent copolymer |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0235772B2 (en) * | 1981-08-25 | 1990-08-13 | Asahi Chemical Ind | HORIOKISHIMECHIRENKYOJUGOBUTSUNOSHITSUKATSUKAHOHO |
| JPH075695B2 (en) * | 1989-04-04 | 1995-01-25 | 宇部興産株式会社 | Method for producing oxymethylene copolymer |
-
1996
- 1996-09-30 JP JP8258983A patent/JPH10101756A/en active Pending
-
1997
- 1997-09-03 SG SG1997003221A patent/SG65677A1/en unknown
- 1997-09-04 MY MYPI97004084A patent/MY119909A/en unknown
- 1997-09-08 AU AU36855/97A patent/AU720117B2/en not_active Ceased
- 1997-09-12 TW TW086113262A patent/TW422859B/en not_active IP Right Cessation
- 1997-09-22 KR KR1019970047987A patent/KR100521732B1/en not_active IP Right Cessation
- 1997-09-30 CN CN97121125A patent/CN1105127C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5780414A (en) * | 1980-11-10 | 1982-05-20 | Mitsubishi Gas Chem Co Inc | Shortstopping of polymerization reaction |
| US4412067A (en) * | 1981-12-12 | 1983-10-25 | Degussa Aktiengesellschaft | Process for the continuous polymerization or copolymerization of trioxane |
| JPH04266917A (en) * | 1991-02-22 | 1992-09-22 | Toray Ind Inc | Oxymethylene multicomponent copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| MY119909A (en) | 2005-08-30 |
| KR100521732B1 (en) | 2006-02-28 |
| CN1180713A (en) | 1998-05-06 |
| AU3685597A (en) | 1998-04-02 |
| JPH10101756A (en) | 1998-04-21 |
| KR19980024838A (en) | 1998-07-06 |
| AU720117B2 (en) | 2000-05-25 |
| TW422859B (en) | 2001-02-21 |
| SG65677A1 (en) | 1999-06-22 |
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