TWI242571B - Materials for production of stable polyoxymethylene copolymer and method for producing the same copolymer from the same materials - Google Patents

Abstract

A crude POM copolymer powder particle as a raw material for producing a stabilized POM copolymer for practical use is provided in an economically advantageous and simple process. A process for producing the stabilized POM copolymer employing the crude POM copolymer powder article is also disclosed. A crude polyoxymethylene copolymer powder particle is discharged from a polymerization reactor and has particle size distribution characteristics and surface pore characteristics in which (1) a component having a particle diameter of over 1.0 mm is present in an amount of up to 50% by weight, an average diameter of surface pores in the component is 4 mum or more, the total volume of the pores having a diameter of up to 4 mum is up to 50% of the total volume of the surface pores of the component; and (2) a component having a particle diameter of less than 0.18 mm is present in an amount of up to 30% by weight.

Description

1242571 Printed by A7 B7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of the invention () [Detailed description of the invention] [Technical field to which the invention belongs], The invention relates to stabilization, especially to thermal stability Raw POM copolymer powder and granules as raw materials of aldehyde copolymer (hereinafter referred to as POM copolymer), and an economical manufacturing method of the stabilized POM copolymer using the powder and granules. [Known Technology] POM copolymers are excellent in mechanical properties, heat resistance, chemical resistance, electrical characteristics, and bending properties, and they are also excellent in formability. Therefore, engineering plastics are used in mechanical components, automotive components, A wide range of uses for electrical and electronic machine components. Stabilizable POM copolymers which can be used practically are generally manufactured by the following process. First, a cyclic acetal such as irioxane is used as a main monomer, and a cyclic acetal or a cyclic ether containing a structure adjacent to a carbon atom is used as a copolymer, and a polymer is added for adjustment according to the purpose. The chain shifting agent used is copolymerized by using a cationic active catalyst to obtain an ancestral POM copolymer. Generally related crude POM copolymers have a considerable amount of stable end-use purpose. In addition, the polymerization catalyst remains in an active state, which can easily cause depolymerization of the copolymer and cause an increase in unstable terminal portions. Therefore, the crude POM copolymer of the polymerization product is catalyzed by organic or inorganic test compounds, such as alkyl amines, oxy amines, hindered amines or hydroxides of test metals, alkaline earth metals, etc. Neutralization or deactivation • After the treatment, the step of decomposing and removing the unstable terminal part is performed by heating the test compound in the presence of alcohol, such as the above-mentioned compound, and the combined use of water as expected To decompose and remove the unstable terminal part. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

1242571 A7 B7 V. Description of the invention () POM copolymer which has been decomposed and removed in such unstable terminal part, it is considered to be imparted with stability, especially heat-resistant stability, and long-term stability. Furthermore, according to expectations, a stable POM copolymer can be obtained by blending various additives, reinforcing agents, etc. to give characteristics corresponding to the purpose, and melt-kneading. It is necessary to omit such complicated multi-step steps, and the viewpoint of cost reduction is strongly demanded. Therefore, for example, the improvement of the deactivation step and deactivation method of the residual catalyst deactivation step such as the polymerization machine of the polymerization step and the improvement of the polymerization catalyst, the decomposition accelerator and the decomposition removal device of the decomposition removal step of the unstable terminal The improvement of waiting is presented. However, regardless of which only focuses on a specific step, the improvement of the purpose of the present invention caused by its improvement is inherently limited. It will be a comprehensive step from the polymerization step to the final stabilization step of the POM copolymer. The manufacturing method of the stabilized POM copolymer is required. Especially in the foregoing steps, the step of decomposing and removing the unstable terminal part requires the most complicated processing operation, and the processing requires a large amount of energy. If the POM copolymer can be used in the last step without substantially going through this step, When the stabilization step (stabilizing agent compounding step) is performed, the economically advantageous production of the stabilized polyoxymethylene copolymer becomes possible. However, in the polymerization step and / or the residual catalyst deactivation step, quality needs to be obtained. Good crude POM copolymer. Among these, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, as for the improvement method of the residual catalyst deactivation, the efficiency of the residual catalyst deactivation efficiency and the decomposition and removal of the unstable terminal following the efficiency, etc. From the viewpoint of pulverizing the crude POM copolymer of the polymerization product and subjecting it to deactivation treatment, it is known that the smaller the particle size of the pulverized product, the better (Japanese Patent Application Laid-Open No. 57-80414, Kaizhao 58-34819). This paper is suitable for 0 0 homes (CNS) Al specifications (210 X 297 cm) 1242571 A7 B7 V. Description of the invention () However, if the particle size is too small, the subsequent steps such as kneading will be The problem of bad bite of the crushed material of the extrusion kneading machine is generated. Therefore, when the coarse POM copolymer with a regularly adjusted particle size distribution is produced, the unstable part can be substantially eliminated and removed. The substantial removal of the steps has proposed a method that enables the production of stable additive-added ingredients (Japanese Patent Application Laid-Open No. 10-101756). The present inventors have further reviewed this technology. For the average particle size or particle size distribution of the crude POM copolymer to be pulverized and fall within the specified range, there are technical limitations and it is easy to appear crude polyformaldehyde beyond this condition. For scales, if the particle size distribution is excessively shifted to the small particle diameter side, handling of the powder and granules becomes difficult, and if it is excessively shifted to the large particle diameter side, it is difficult to stabilize it. As mentioned, the simplified process, especially without the conventional step of decomposing and removing the unstable terminal part, is intended to make the polyacetal copolymer for the final stabilization step, and to provide economical manufacturing stability. The solution decision and expectation for the conversion of polymethyl methacrylate copolymer. ”[Problems to be Solved by the Invention] Therefore, the present invention provides a crude POM copolymer powder and granules that can be practically used as a raw material for stabilizing polyoxymethylene with an economically advantageous and simple process. The method of producing a stabilized POM copolymer is a subject. [Means to solve the problem j The inventors and others, in order to achieve the relevant purpose, comprehensively reviewed the results of all processes from the polymerization step of the POM copolymer to the stabilization step, and found that the crude POM from the polymerization product Copolymer powder and granularity The characteristics of the coarse POM copolymer powder and granularity are the key factors to master. By dividing the particle size into 4 'this paper & degree applies the Chinese National Standard (CNS) A4 specification ( 210 x 297 mm) (Please read the notes on the back before filling out this page)

Order --------- Line L Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1242571 A7 B7 V. Description of the invention () The state of the pores on the surface of the cloth and its particles is adjusted to an appropriate range. By using the powder and granules that have been prescribed, the particle size distribution proposed by Japanese Patent Application Laid-Open No. 10-101756 can maintain the above-mentioned quality target even if the component with a large particle size becomes large, and it can also produce squeeze The stabilized POM copolymer with excellent press operability has completed the present invention. The technical features of the present invention are as follows. The first aspect of the present invention relates to a coarse polymerization of a crude polyacetal copolymer discharged from a polymerizer and having a particle size distribution characteristic and a surface characteristic specified in the following (1) to (2), which are pulverized. Formaldehyde copolymer powder and granules; (1) The component exceeding the diameter of 1.0 leg is 50% by weight or less. (1-a) The average diameter of the surface pores of the above components is 4 / zm or more, (1 -b) Of the total volume of the surface pores of the above components, the total volume of the pores of diameters below 4 / zm is 50% the following. (2) A component having a particle diameter of less than 0.18 mm is 30% by weight or less. The second aspect of the present invention is a method for producing a stabilized polyacetal copolymer, and is characterized in that the crude polyoxymethylene copolymer powder and granules of the first aspect of the present invention are subjected to deactivation treatment of the residual polymerization catalyst, Melt and knead at the same time as the stabilizer. The third aspect of the present invention is a method for producing a stabilized polyacetal copolymer, which is characterized in that a residue is added to the crude polyacetal copolymer before it is discharged from the polymerizer to the end of the pulverization process > The deactivation treatment agent of the polymerization catalyst is pulverized to obtain the above-mentioned crude polyoxymethylene copolymer powder and particles of the first aspect of the present invention, and then melt-kneaded with the stabilizer at the same time. The fourth aspect of the present invention relates to a method for manufacturing the stabilized polyoxymethylene copolymer of the second or third aspect of the present invention, wherein the size of the crude polyformaldehyde paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page) Order --------- Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1242571 A7

1242571 A7 V. Description of the invention (-Alcohol 1, 1,4-butanediol methyl jun. Is the amount used 0.1 to 20 mol% of the third of the main monomer, preferably 0.2 to 10 mol Ear%.… As for the polymerization catalysts used for the copolymerization of monomers and co-monomers, they are used as general cationic polymerization catalysts. Specific examples include ... Its derivatives are especially functional compounds such as copper, tin, titanium, saucer, arsenic, and antimony, such as trifluoride, tin tetrachloride, ammonium tetrachloride, saucer pentachloride, phosphorus pentafluoride, and pentafluoride. Cleavage and pentafluoride, these chlorine compounds and these wrong compounds, such as the coordination compounds of boron trifluoride and organic compounds are more suitable. In addition to the Lewis acid, there are examples The f-protonic acid and its derivatives can be more specifically exemplified by trifluoromethane acid, perchloric acid, etc., such as esters such as perchloric acid tertiary butyl vinegar, proton anhydride, such as acetic acid Polybasic acid, acid salts, etc. are more suitable. Polyacids such as heteropolyacids, isopolyacids, etc. may also be mentioned, and in particular, phosphomolybdic acid is more suitable. Other examples include ion-pair catalysts that are more suitable, and examples include triethylzinc hexaphosphate, triphenylmethylhexafluoroarsenate, etc. Printed by the Intellectual Property Office of the Ministry of Economic Affairs and the Consumers ’Cooperative System, China-Israel boron difluoride, or the compound compound of boron difluoride and organic compounds (eg =) Tongtong County. In addition, the material reading, μ yuan = two son I, is more active as a catalyst High, with a small amount of catalyst, it is easy to produce high-quality crude POM copolymer, and it is also easy to deactivate the catalyst. J The crude POM copolymer and copolymer of the present invention are selected from related compounds. It is advisable to polymerize one or more mixtures of two or more catalysts. Also, in the case where a Lewis acid such as boron trifluoride is used as a catalyst, it is appropriate to add an amount of 5% to the raw material monomer. In addition, in order to obtain a high-quality water-pumped copolymer, it is preferable to use a monomer having a water content of 10 ppm or less. 7

Specifications (210x297 2 > iT 1242571 Printed by A7 B7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs, V. Description of the invention () In addition, in order to adjust the molecular weight of the crude POM copolymer obtained by copolymerization, an appropriate amount can be added as necessary For example, an appropriate amount of a chain moving agent such as acetal or dioxomethylene difluorenyl ether is added to the polymer to polymerize it. In addition, the production of a crude POM copolymer obtained by related copolymerization may also be used. It will be performed in the presence of an anti-oxidant of hindered antioxidants to inhibit the oxidative decomposition of the POM copolymer formed during polymerization or the oxidative decomposition of the POM copolymer at a high temperature connected to the subsequent steps, etc. The POM copolymer is effective for the final stabilization step, so it is more suitable for use as the crude polyacetal copolymer related to the present invention. The production of the copolymerized crude POM copolymer can be performed using conventionally known equipment. And methods. That is, any type such as batch type and continuous type is possible, and any method such as melt polymerization and melt block polymerization is acceptable, but liquid monomers are used simultaneously with the polymerization. A continuous block polymerization method for obtaining a solid scale-like polymer is more common on an industrial scale, and is particularly suitable. In this case, an inert liquid medium can coexist if necessary. In addition, a co-kneader can be used as a polymerization device. , Biaxial screw type continuous extrusion mixer, biaxial paddle type continuous mixer, etc., the crude polyoxymethylene copolymer powder and granules related to the present invention are the crude POM copolymer obtained above, and are assigned to a specific For particle size distribution and surface structure, it is necessary to perform the deactivation treatment of the polymerization catalyst included here before, during, or after the pulverization. Inactivation of the catalyst is not an immediate reaction. After the chemical treatment is started, sufficient effect can be obtained even if it is crushed. The inactivation of the catalyst is to store the slurry containing the crushed coarse POM copolymer powder and catalyst inactivator in the storage tank. Available. Secondly, the POM copolymer powder and stabilizer are melt-kneaded and stabilized at the same time. ^ 8 This paper size is applicable to the four national standards (CNS) Al specifications (210 X 297 cm) (Please Read the notes on the back first Page) ------- Order --------- 1242571 A7 V. Description of the invention () Here, the pre-pulverized crude POM copolymer needs to satisfy the following (丨) ~ (2 ) Predetermined particle size distribution characteristics and surface pore characteristics. (1) The component exceeding the particle diameter of 1.0% is 50% by weight or less. (1-a) The average diameter of the surface pores of the above components is m or more, ( 1-b) Of the total volume of surface pores of the above components, the total volume of pores with a diameter of 4 # m or less is 50% or less. (2) Components with a particle size of less than 18 mm are 30% by weight or less. The particle size distribution characteristics and the pore characteristics of the surface of the powder and granules are preferably 50% by weight or less if the component exceeds 1.0mmi in particle size, and 10% by weight is preferred. The component having a particle size of less than 18mm is 30% % Or less, the average diameter of the surface pores is 4 / zm or more, and in the total volume of the surface pores, if the total volume of the pores below the diameter does not satisfy the condition of 50% or less, the catalyst is not deactivated. It can be fully carried out, and the amount of the unstable portion in the polymer increases, and the thermal stability decreases. In addition, even if the above-mentioned surface porosity is satisfied, the component having a particle diameter exceeding 1.0 mm is more than 50% by weight, and the quality of the lead is lowered. On the other hand, even if the above-mentioned requirements for surface pore characteristics are met, if the particle size is less than full (in the case where the component amount of U8mm exceeds 30% by weight), the characteristics of the feed into the extruder will be reduced and stable Monographs, problems that reduce workability. ~ The recording of the cloth has good surface area characteristics, and it is used for crushing and carrying out the bonding process or relying on a piece of work =:; pom copolymer and stability At the same time, the agent blends and blends and stabilizes = the view that both of the operability are satisfied, which is the essence of the inventors :: This paper size is based on the standard of the family (CNSM4 specification x 297 public ^ " Item page 5. Description of the invention ( ), That is, if the particle size of the crude POM copolymer powder is too large: the phenomenon that the efficiency of the chemical reaction will significantly decrease is so far: the limitation of the particle size is necessary, but by simultaneously satisfying ( 1 2 makes the particle size dependency of = small, even if the presence of large particles is possible, activation of 2 ^ is possible, so the secrecy in the crushing step can be reduced, which can be related to the improvement of the operability. Also, large particle sizes The restriction of relaxation is also related to the suppression of the overall small particle size. It is related to the force. In the pulverization step, as the pores of the polymer sheet (scales) are broken, it can be known from this that the pores on the surface of the original 4 sheets become smaller. In more extreme cases, the fine The pores are divided into two peaks. Therefore, when the above pulverization is performed, the selection of the pulverization device or the adjustment of the operating conditions almost eliminates the wear and occlusion of the pores on the surface. For the pulverizer, there are no special restrictions. For example, needle milling, rotary milling, hammer milling, jaw crusher, feather paddle milling: rotary cutting milling, turbine milling, or step impact crusher, etc., particle size distribution. The characteristics and surface pore characteristics can be controlled by the number of revolutions, clearance of the grinder, the screen installed in the grinder and / or another screen as required. When using pin milling as an example, the particle size distribution characteristics and pore characteristics on the surface of the present invention can be obtained by, for example, the following pulverization methods. In the case of a plurality of disks fixed to a rotating shaft, Many pins are attached around High-speed rotary pulverizing chamber, to combat scales, so that scales and by impingement plate disposed around and strong forces to instantaneously feed 10

Printed by Consumers Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs

1242571 = 接 = The size that can be wiped to the screen on the wall is destroyed by the scales. The surface of the powder and granular material is hardly ground by the pin pins. Adjust the shape of the door gap ten locks, the disk rotation speed, the screen size, the pin lock and the sieve pin 22, which can have powder and granules with the desired shape. In particular, the adjustment of the screen size and division gap is important. ^ ^ ^ ^ ^ ^ ^ ^, The same, but the main size of the screen will affect the particle size range, can control the size distribution, and mainly lock and screen △ s "《spore characteristics of the shirt, if it becomes small, then The average diameter of the surface pores will be larger. If the diameter becomes larger, the average diameter of the pores on the surface will increase. Therefore, the characteristics of (1-b) on the surface of the large particle size component of ^ :: 丄 〇 are determined by the appropriate relationship between the size of the screen and the gap between the screens. I, depending on the type of crusher, (b) the characteristics and screen size and lock system will change, so you can set the value of the target by trial. When deactivating the residual catalyst contained in the coarse POM copolymer or the coarse mound polymer powder discharged from the polymerizer, a known method can be used as the deactivation method. For example, a method of using a large amount or a small amount of an aqueous solution or a solvent / valley solution containing a basic compound, and a method of bringing this into contact with an alkaline gas may be used. As the inactivating agent that can be used as an aqueous solution or a solvent solution, any known alkaline substance is effective, and examples thereof include ammonia, various amine compounds, or oxides, hydroxides, and organic compounds of alkali or alkaline earth metals. Acid salt or inorganic acid salt, trivalent phosphide, etc.

This paper size applies to China 0 National Coal Standard (CNSM.) Specifications (2 丨 〇 X 297

1242571 A7 B7 V. Description of the invention (-Among them, especially suitable deactivation treatment agents, such as diethanolamine, sodium carbonate, hydrolyzation: aqueous solution of two dimers, and also tested by wet powder It is better to have the characteristics of the North North cloth. It is more appropriate to deactivate the related ": ;; can = before the coarse mi copolymer of the diameter extension machine is discharged to the crushing treatment '== = to be added and crushed in the presence of a deactivator '' ', ^ 2 quality coarse POM copolymer powder and granules.' · ', So that high-quality products can be obtained by pre-catalyst deactivation treatment and pulverized or crushed by pre-loss and coarse POM copolymer powder. Granules, if necessary, washing, drying, etc. ^ In the present invention, if the crude copolymer is touched as described above = processing, and at the same time by pulverization to have a specific: = order i =; The stable granules with fewer stable terminals are more suitable, but the unstable terminal quantity is preferably 0. 8% can be used for the next feminization step. In addition, the instability line end of the crude POM copolymer powder and granules specified herein contains 1 g of H-based powder and granules, and at the same time, it contains 0.5% by weight of hydroxide solution containing methanol and water. mi was placed in a pressure-resistant closed container at 180. After adding for 45 minutes, cooling and taking out, the amount of formaldehyde that has been decomposed and dissolved in the liquid is determined by S analysis, and it is expressed as the weight% of the powder and granules. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ As mentioned above, the coarse pom copolymer powders and granules with pre-deactivation treatment of the residual catalyst have been pulverized into specific particle size distribution characteristics and surface pore characteristics. The stabilization polyacetal copolymer can be obtained immediately after the melt-kneading treatment is simultaneously performed with the stabilizer without substantially undergoing the step of destabilizing the terminal portion of the unstable stabilizer.

This paper is suitable for medium size X X 295 1242571

V. Description of the invention (The stabilizers used by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs for printing are not particularly limited. Any of the well-known stabilizers can also be used, but it is usually a combination of antioxidants and heat-resistant stabilizers. As for the antioxidant, there can be listed: i, 6-hexanediol-bis [3- (3,5-1,2-second butyl-4-hydroxyphenyl) propionate], pentaerythritol group [3 — (3, buthi-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [3- (3-second-butyl-5-methyl-4-hydroxyphenyl) Propionate], N, N, _hexamethylenebis (3,5-di-tertiary-butyl-4-hydroxycinnamate), etc. As for hot female tinctures, melamine, melamine— Jiajun condensate and other coax compounds, polyamide 12, nylon 6,10 and other polyamides, hydroxides of alkali metals or alkaline earth metals, carbonates, phosphates, acetates, oxalates, etc. , Stearic acid-based higher fatty acids or metal salts of higher fatty acids with substituents such as hydroxyl groups etc. In addition, it is related to the stabilized polyoxymethylene copolymers related to the present invention. In addition, depending on the purpose, various other additives can be added, such as weathering (light) stabilizers, lubricants, lubricants, nucleating agents, release agents, antistatic agents, dyes, pigments, other organic polymer materials, Inorganic and organic fibrous, plate-like, powdery fillers, etc. Melting and kneading with stabilizers are generally performed using an extruder. [Examples] Examples and comparative examples are shown below. The invention is of course not limited by these. FjyM Comparative Examples 1 to 3 Continuous polymerizers using a twin-shaft paddle type to continuously supply the trioxane comonomer and 1,3-dioxolane 2, 5% by weight (in the whole monomer), will be composed of boron trifluoride, (please read the phonetic note on the back ΗΦ before filling this page}

-------- Order ----- I .---- Line J

1242571 A7 B7 V. Description of the invention (a kind of toilet selected by phosphomolybdic acid and perchloric acid and then V is inserted into a pin mill with a division net and pulverized. The coarse p 0M copolymer powder particles discharged from the pulverizer are: :： Guide: In the storage tank, after the deactivation treatment is fully performed, the surface pores are two thick: 1 == 1: powder diameter distribution characteristics and surface right pull W /, support particles, particle size distribution. Characteristics, fine pore adjustment. The mesh size of the sieve and the gap between the lock and the sieve are described in general: the crude polyformic acid copolymer powder and granules obtained by the method are mixed and stabilized without undergoing the step of silking Agent = di-based [3- (3,5-di-third butyl. Mesitylphenyl) propanyl 1 stearic acid @ 〇 · 1% by weight, dazzled by using a dust squeezer: Guangde Granule-shaped stable fluorene copolymer. Evaluation results are shown below: And the evaluation method and reference system are as follows: [Powder characteristics] • The particle size distribution characteristics use a plurality of metal meshes with different openings. The knife and pores are measured by a specific mercury indentation method for measuring the volume of pores and the heart cloth of pores. The diameter of the pores is 0.bw. Can cause the sample 14 X 297 mm)

When ordering 4 sheets of paper, the specifications for the paper (210.5, the description of the invention), when compressed and pulverized, it becomes a measurable sample void at 100 // m, so it can be used in the range of 0.4 / zm and 20em The obtained fine pores were straightly distributed for evaluation. '[Thermal stability of the stabilized polyoxymethylene copolymer]

5 g of stabilized polyoxymethylene copolymer was measured in the air at 22 (rCM for 45 minutes when the weight was reduced, and expressed as a weight reduction rate per minute (%). 0 [Squeezability] • Feedability of raw materials was less than Coarse + Jiajun co-t powder and granules are mixed with stabilizers in the body. Observe the state of the raw materials feeding into the extruder and the discharge of the stabilized polyoxymethylene copolymer from the extruder when melted and kneaded with the extruder. A to D are evaluated in four stages. A: The feeding and discharging yarn bundles are stable. B · Frequent feeding failures are often found, but the thickness of the yarn bundles is changed, but the stable operation is still sufficient. C · Feed changes Slightly large, the change in the thickness of the yarn bundle is also large, and often the yarn bundle is cut off. Second, D: The feeding changes drastically, the feeding amount is also low as a whole, and the yarn bundle cannot be pulled normally. • Motor Load amplitude and the difference between the maximum value and the minimum value of the motor current during extrusion (in amps). • The maximum and minimum values of the resin pressure gauge indicated by the resin pressure gauge set directly behind the screw tip of the extruder The difference between the minimum values (in kg / cm2). 1242571 A? B 7 V. Description of the invention (Table 1) Example Comparative Example 1 2 3 4 1 2 3 Catalyst—-BF3 bf3 HPA HC104 bf3 bf3 bf3 Concentration (rora) 10 3 2 20 20 20 Powder mill crusher screen ~~ 2.0 1.8 2.0 2.0 2.0 2.0 1.5 Clearance between pin and screen (mm) 4.0 4.0 4.0 4.0 3.0 5.0 5.0 Powder characteristics Weight fraction of large particle size w 45 18 40 43 35 55 5 Weight fraction of small particle size c) 4 25 5 10 8 2 45 Average diameter of fine pores on the surface of large particle size (/ zm) --------- 4.5 4.6 5.0 5.3 2.8 5.2 4.8 Fine pore fraction of the surface of large particle size (%) e) 28 22 15 35 55 40 20 Instability terminal amount after inactivation% 0. 70 0.49 0. 65 0. 66 1.10 0.65 0. 65 Thermal stability% of stabilization POM 6X 1 (Γ3 2X 10'3 2X ΙΟ-3 7X ΙΟ'3 33 x ΙΟ-3 40 x 10_3 6x i〇 · 3 Extruded material feedability ABAAAAD Motor load amplitude (A) 2 2 2 2 5 7 19 Resin pressure fluctuation width (kg / cm2) 2 3 2 2 4 4 18 (Please read the notes on the back before writing this page)% Order --------- The Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is printed in Table 1, * a) ·· · Indicates the POM polymerization catalyst Class, Table 3 shows the volumes boron trifluoride, ΗΡΑ represents phosphomolybdic acid, acid gas HCl〇4 expressed. b)... represents the weight ratio of the component having a particle size exceeding 1.0 ⑻. c)... indicates the weight ratio (%) of components with a particle size of less than 0.18 legs. d) ··· represents the average diameter (#m) of surface pores of components having a particle size exceeding 1.0. e) ························································· represents the volume ratio (%) of pores with a diameter of 4am or less in the entire surface pores of the component having a particle diameter exceeding 1.0. —_______ 16 _; _ This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 1242571 A7 B7 V. Description of the invention () [Effect of the invention] In the crude POM of the polymer discharged from the polymerization machine If given the specified particle size distribution characteristics and surface pore characteristics, it can be known that it has nothing to do with the average particle diameter, and does not need a terminal, so that a stable POM copolymer can be efficiently produced. [Reference] Main monomer: Acura co-monomer: 13-two gas miscellaneous catalyst: bf3 Antioxidant catalyst deactivation treatment agent just before discharge +: Polymerization of aqueous amine solution / / crushing / / storage sludge \ 1 Unstable terminal treatment \ / Dewatering and drying grinder: pin-milling condition with screen and (2) 1 Assign (I-a) and (1-b) to (1-a) and (17) Deactivation treatment is easy to perform. Unusual unstable terminal processing steps are not required. Polymerization machine: Double-shaft paddle type. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Stabilizers: Antioxidants and heat-resistant stabilizers.

V-> Unstable terminal content rate 0.1 to 0.8% Extruder Feed well at (2) Stabilized POM copolymer 17

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

^ 42571 ΊCheli range Λ 8 Β8 C8 D8 As in the manufacture of the stabilized poly (methacrylic acid) · copolymer of item 2 of the patent application scope, in which the crude polyoxymethylene copolymer is made of a raw material monomer containing a water knife below 1 ppm. Converged. (Please read the notes on the back before filling this page) Order ^ t, w, spend the national standard of China (CNS 丨 ΛShige (2ι〇χ297 mm) 7 5 42 2 6. Scope of patent application [Scope of patent application] (Please read the precautions on the back before filling in this page) 1. A kind of coarse polyoxymethylene copolymer powder and granules, which is a crude polyfluoric acid copolymer discharged from a polymerization machine. Pre-pulverized, coarse polyoxymethylene copolymer powder having the following particle size distribution characteristics and surface pore characteristics specified by ⑴ ~ ⑴: (1) 50% by weight or less of the component exceeding the particle diameter of 1.0 leg; Π- a) The average diameter of the surface pores of the above components is 4 μηι or more; (1 -b) Of the total volume of the surface pores of the above components, the total volume of the pores below the diameter is 50% or less; The content of less than 0.18% is 30% by weight or less. 2. A method for producing a stabilizing polyoxymethylene copolymer, characterized in that the crude polyformic acid copolymer powder and granules of the first patent claim are subjected to inactivation treatment of the residual polymerization catalyst, and then melt-kneaded with the stabilizer at the same time deal with. 3. A method for producing a stabilized polyoxymethylene copolymer, characterized in that a deactivation treatment agent for a residual polymerization catalyst is added to the crude polyacetal copolymer before discharging from the polymerization machine to the end of the pulverization process. The pulverization treatment is performed to obtain the crude polyoxymethylene copolymer powder and granules in the scope of the patent application, and then melt-kneaded with the stabilizer at the same time. Printed by the Intellectual Property Department of the Ministry of Economic Affairs / I Bureau Consumer Cooperatives 4. If the application method for the stabilization of polyoxymethylene copolymer 1 in the scope of patent application item 2 or 3, the residual polymerization of crude polyoxymethylene copolymer powder The content of the unstable terminal of the medium after the inactivation treatment is in the range of 0.001 to 〇8%. 5. The method for manufacturing a stabilized polyoxymethylene copolymer according to item 2 of the scope of patent application, wherein the crude polyoxymethylene copolymer is obtained by using an acid catalyst as a polymerization catalyst. 6. The method for manufacturing a stabilized polyoxymethylene copolymer according to item 2 of the scope of patent application, wherein the crude polyoxymethylene copolymer is obtained by polymerizing a hindered phenolic compound. Applicable paper size for China National Standard (CNS) A4 (21〇χ 297mm)