TW593399B - Method for producing polyacetal copolymer - Google Patents

Abstract

The present invention relates to a method for producing a polyacetal copolymer using trioxane as a main monomer and a cyclic ether and/or a cyclic formal having at least a carbon-carbon bond as a comonomer, and a cationic active catalyst, which comprises adding a compound containing a triazine ring replaced with an amino group to a polymerization-reaction product obtained, and conducting a melt-kneading treatment of the mixture obtained to deactivate the catalyst. According to the present invention, a polyacetal copolymer is produced which is featured by having an extremely little amount of unstable terminal part, being very stable to heat and being least in a releasing amount of formaldehyde therefrom, using a simple process in which deactivation of a catalyst can briefly be conducted, a washing operation is unnecessary and a high polymerization yield can be obtained.

Description

593399 V. Description of the Invention (1) Technical Field The present invention relates to a method for preparing a polyacetal composition, which is a method in which trioxane and a comonomer are copolymerized in the presence of a polymerization catalyst, and then the amine-substituted The method of adding the compound of the three farming rings to the copolymerization reaction product to passivate the catalyst. According to the present invention, the production process can be simplified, and a polyacetal copolymer having excellent quality such as thermal stability and low formaldehyde emission can be obtained. BACKGROUND ART Conventionally, a known method for producing a polyacetal copolymer is carried out by using trioxane as a main monomer and cyclic ether and / or cyclic methylal having at least one carbon-carbon bond as a comonomer. Cationic copolymerization. As a cationic active catalyst used in this copolymerization, boron trifluoride, or a complex compound of boron trifluoride and an organic compound, such as an ester, is proposed in the case of trioxane as a main monomer. It is most commonly used as a polymerization catalyst and is widely used in industry. However, when using boron trifluoride or the like as a general polymerization catalyst, the amount must be relatively large (for example, 40 ppm or more relative to all monomers), so the passivation treatment of the catalyst after polymerization is very difficult, even if it is performed. The passivation treatment will also have residual catalyst substances, which promotes decomposition, making the polymerization yield and degree of polymerization limited, and because a considerable amount of unstable end portions exist, it must have a complicated stabilization step and so on. question. Japanese Patent Application Laid-Open No. 1-1 706 1 0 discloses a production method using heteropolyacid as a catalyst. It is preferable to add mixed ammonia or

5. Description of the invention (2) or amines such as triethylamine, tri-n-butylamine, hindered amine, etc., or alkali metal, alkaline earth metal hydroxides, organic acid salts (such as fatty acid salts) and other known catalysts Passivating agents, which reveal that the solution containing these passivating agents is added for processing, so that the polymerization catalyst is neutralized and deactivated. However, in this method, a solution of a passivating agent containing 0.1% tributylamine in water is added to stop the reaction, and at the same time, it is crushed to less than 200 meshes, washed with acetone, and dried. That is, it is important that the above-mentioned copolymerization method using a catalyst is to deactivate the catalyst after polymerization. If the catalyst is not sufficiently deactivated, it will promote the decomposition of the resulting copolymer, thereby hindering the subsequent copolymer. The big reason for its stability. Among them, in order to fully perform the passivation treatment of the catalyst, a large amount of a passivator solution is added to the polymerized product, and the product is sufficiently washed to remove the residue from the residual monomer or catalyst, and then the copolymer is separated from the treatment solution. Drying, or the recovery of monomers from washing liquids, etc., require extremely complicated steps and are economically unsatisfactory. In order to avoid the trouble associated with the passivation treatment of the catalyst, a method of adding a trivalent phosphorus compound to the resulting copolymer (Japanese Patent Publication No. 55-42085) or a method of adding a hindered amine compound (Japanese Patent Application Laid-Open No. 62 -Publication No. 257922, etc.) As a result of a review by the inventor of the present case, the passivation cannot be sufficiently performed, and it is very difficult to obtain a copolymer having good thermal stability. In particular, if the polymerization yield at the time of polymerization is increased, the resulting polymer system is more unstable, and complicated stabilization processes are required in the subsequent steps. Therefore, the final step cannot be simplified, and its stability is limited. , So the quality is not desirable. 593399 5. Description of the invention (3) The purpose of the present invention is to provide a method for preparing a polyacetal copolymer, which can simply passivate the catalyst, and is a simple method that does not require a washing step, and has a high polymerization yield. There are very few unstable ends, extremely stable heat, and very little formaldehyde emission. Summary of the Invention In order to achieve the above-mentioned problem, the inventor of this case conducted a careful and intensive review of the passivation method. As a result, it was found that the compound containing the amine group-substituted triphen ring was only added to the reaction product as it is in a non-solution state (also known as In the crude copolymer), the melt-kneading process can be extremely simple, and the passivation of the catalyst can be surely performed, which can achieve the above purpose. That is, the first aspect of the present invention is to provide a method for producing a polyacetal copolymer, which is characterized in that trioxane is used as a main monomer (a), and a cyclic ether and / or a cyclic methyl ester having at least one carbon-carbon bond is used. Acetal is used as a comonomer (b). When a cationic active catalyst (c) is used to produce a polyacetal copolymer, the compound (d) containing an amine-substituted triphen ring is added to the reaction product and melted. The catalyst (c) is passivated by a kneading process. The second aspect of the present invention is to provide a method for producing the polyacetal copolymer according to the first aspect of the present invention, wherein the comonomer (b) is at least one selected from the group consisting of 1,3-D-Doxoin, and ethylene. Alcohol methylation, 1,2,4-butanediol methylal, 1,3-dioxane and ethylene oxide. The third aspect of the present invention is to provide a method for producing the polyacetal copolymer according to the first or second aspect of the present invention, wherein the compound (d) containing the amine group-substituted three plough ring is melamine, a melamine resin, and / Or the spiral shape of the three-cooked ring containing an amine group substitution 593399 5. Description of the invention (0 compound. The fourth aspect of the present invention is to provide a method for manufacturing the polycondensation copolymer of the third aspect of the present invention, wherein the amine-containing copolymer The spiro compound of the three-substituted tricyclic ring is a compound represented by the following formula (1),

(Wherein R1 and R2 represent an alkylene group having 1 to 10 carbon atoms, an alkylene group having 6 to 10 carbon atoms, or an alkylene group formed by combining the alkylene group and an alkylene group, and R1 and R2 Can be the same or different). The fifth aspect of the present invention is to provide a method for producing a polycondensation copolymer according to the fourth aspect of the present invention, wherein in the formula (1), R 2 is a linear or branched chain having a carbon number of 1 to 6 alkyl. The sixth aspect of the present invention provides a method for producing the polycondensation copolymer according to the fourth aspect of the present invention, wherein the amine group-containing three-coil spiral compound is at least one selected from the group consisting of (11 guanamine, 〇 & 17'11 guanamine and 3,9-bis [1- (3,5-diamino-2,4,6-triazaphenyl) -1,1_dimethylethyl] _ 2,4,8,10-tetraoxaspiro [5,5] undecane. The seventh aspect of the present invention is to provide a method for producing the polyacetal copolymer according to any one of the first to sixth aspects of the present invention. Wherein, the melt-kneading process causes the catalyst (c) passivation to be performed in the presence of an antioxidant. V. Description of the invention (5) Detailed discussion of the dry and good embodiments The following describes the present invention in detail. The main monomer of the present invention ( a) It is a cyclic trimer using formaldehyde, that is, trioxane. The comonomer (b) of the present invention is a cyclic ether and / or cyclic methylal having at least one carbon-carbon bond. Any known comonomer used for copolymerization with trioxane was used. Representative examples of the cyclic ether and cyclic methylal are 1,3 · dioxane, diethylene glycol methylal, 1,4-butanediol methylal, 1,3-dioxane, ethylene oxide, propylene oxide, epichlorohydrin, etc. Among them, 1,3 · dioxane, diethylene glycol methylal, 1,4-butanediol methyl Acetal, 1,3-dioxane, ethylene oxide and the like are preferred. In addition, cyclic ethers such as β-propiolactone and vinyl compounds such as styrene can also be used. In addition, copolymers are also used. Comonomers capable of forming branched or cross-linked molecular structures, such as those having two or more polymerizable cyclic ether groups or cyclic methylal groups such as alkylene-diglycidyl ether or dimethyl acetal, can be used. Compounds, for example, butanediol dimethylene glyceryl ether, butanediol diglycidyl ether, etc. The amount of comonomer (b) used in the present invention is from 0.1 to 2 for trioxane Molar%, preferably 0.2 to 10 Molar%. If it is less than 0.1 Molar%, the unstable end portion will increase, resulting in poor stability, and if too large, the resulting copolymerization If the substance becomes soft and the melting point is lowered, it is not good. Furthermore, in the polymerization method of the present invention, when the degree of polymerization is to be adjusted according to the purpose, a known chain transfer agent such as formazan can be added. Low molecular weight of acetal dimethanol, etc. 5. Description of the invention (6) Linear acetal, etc. In addition, there are substantially no impurities having active hydrogen in the polymerization reaction system, such as water, methanol, formic acid, etc., for example, they are each 10 ppm The following are preferred. Cationic active catalysts, known catalysts can be used. That is, Lewis acids, especially halides of boron, tin, titanium, phosphorus, arsenic, and antimony, such as boron trifluoride, tetrachloride Compounds such as tin, titanium tetrachloride, phosphorus pentachloride, phosphorus pentafluoride, arsenic pentafluoride, and antimony pentafluoride, and complexes or salts thereof; proton acids such as trifluoromethanesulfonic acid or Chloric acid; isopolyacid; protonic acid esters, especially esters of perchloric acid and lower aliphatic alcohols, such as perchloric acid-third butyl ester; protic anhydrides, especially mixed anhydrides of protonic acid and lower aliphatic carboxylic acids, For example, ethyl perchlorate; or ion-pair catalysts, such as triethyloxohexafluorophosphide, triethyloxohexafluoroboride, triphenylmethylhexafluorophosphide, and the like. The amount of the catalyst varies depending on the type, and can be appropriately changed to adjust the polymerization reaction, but it is generally 0.05 to 500 ppm relative to the total amount of monomers suitable for polymerization (hereinafter expressed by weight / weight ppm) ), Preferably 0.5 to 30 ppm. It is also a better method to add a solution prepared by dissolving the catalyst in part or all of the main monomer (a), comonomer (b), molecular weight regulator, etc. in a desired amount to the polymerization system. method. The polymerization method of the present invention can be carried out using the same equipment as the conventional copolymerization of trioxane. That is, any of a batch type, a continuous type, and a semi-continuous type can be used. Generally, a liquid monomer is used, and a solid powder block polymer is simultaneously obtained during the polymerization.

593399 5. Description of the invention (7) The polymerization device used in the present invention can be used in a batch type, generally a reaction tank with a stirrer, and in a continuous type, a co-kneader biaxial spiral type continuous can be used. Extruder mixers, twin-shaft paddle continuous mixers, and continuous mixing devices such as trioxane, which have been proposed so far, can be combined with two or more types of polymerizers. Although the polymerization method is not particularly limited, if the trioxane% comonomer and polymerization catalyst are kept in a liquid phase state in advance while being sufficiently mixed, and the obtained reaction raw material mixed solution is supplied to a polymerization device to perform a copolymerization reaction, Since the amount of formaldehyde released is small, and a polyacetal copolymer can be obtained favorably, it is a preferred polymerization method. The polymerization temperature can be in the range of 60 ~ 120 ° C. In the present invention, when the catalyst is passivated after polymerization, the less unreacted monomer is, the better, the unreacted monomer in the crude copolymer (The total amount of the main monomer am (a) and the comonomer (b)) is preferably 10 weight% or less, more preferably 5 weight% or less, and particularly preferably 3 weight% or less. In order that the main copolymer of the present invention does not need to clean the crude copolymer, if there are too many residual monomers, it is not appropriate. If the amount of unreacted monomers is reduced, the polymerization rate can usually be increased above- In the case of the present invention, it can be easily achieved by appropriately adjusting the amount of catalyst used and the polymerization time (retention time in a continuous system), and after the copolymerization reaction, a part of the remaining monomers can be removed. Evaporation and gasification removal to achieve the specified residual monomer amount. Furthermore, during or after copolymerization, the recovered gaseous unreacted triπoxane and comonomer can be liquefied and reused as part of the raw monomer as it is, which is more economical. -9- 〇

593399 V. Description of the invention (8) Secondly, the crude copolymer obtained after the copolymerization reaction is not washed, and (d) as a passivating agent is added to it as it is, usually subjected to a melt-kneading treatment, And complete the passivation of the catalyst. As the compound containing a sham ring which is substituted with an amine group, although there are examples of melamine, a melamine resin, and / or a spiral compound with a sham ring which is substituted with an amine group, the number of the sham ring is not particularly limited. It is preferably 1-4, more preferably 1-2, and even more preferably 2. In particular, a compound having a structure in which three sloping rings are connected to a spiral compound (i.e., a compound having a three sloping ring at both ends of the spiral compound) is preferable. The three-coupling ring includes 1,2,3-coupling, 1,2,4-copper and 1,3,5-copper. Among them, 1, 3, 5-three-tillage system is better. Moreover, the three plough ring may have a substituent such as a G-C4 alkyl group, a C6-C1 () aryl group, an amine group, or a substituted amine group. The three plough ring is preferably a 1,3,5-triplet having an amine group or a substituted amine group, especially a guanamine ring. The spiral ring portion may be a spiral ring made of carbon only, but a spiral ring having a hetero atom (especially an oxygen atom) as a constituent atom of the ring is preferable. The spiral compound is, for example, a spiral compound having a guanamine ring at both ends represented by the formula (1). In the formula (1), the alkylene group represented by R1 and R2 may be, for example, a straight or branched chain of methylene, ethylene, propyl, isopropyl, butyl, or isobutyl. For example, the arylene group may be a phenylene group, a naphthyl group, or the like; and the aralkylene group is, for example, a group in which the above arylene group and an arylene group are connected. Preferably, R1 and R2 are alkylene groups having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms,

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V. Description of the invention (9)

The spiral compound (d) may be, for example, 3,9-bis [2_ (3 5

[1-(3,5-diamino-2,4 2,4,8, 10-tetraoxaspiro [5, 5] Eleven, 3,9-bis [3- (3,5-bis Amino-2,4,6-diazaphenyl) -1,1-dimethylpropyl] _2,4,8,10-tetraoxaspiro [5,5] undecane etc. 3 , 9-bis [(3,5-diamino-2,4,6-triazaphenyl) (: 1-(: 6 alkyl) -2,4,8,10-tetraoxa Spiro [5,5] undecane, etc. The spiro compound may be a crystal-containing compound, an anhydrous compound. 1- (3,5-diamino-2,4,6-triazaphenyl) methyl 4 heterospiro [5,5] undecane (CMTU guanamine), 3,9-bis-2,4,6-diazaphenylphenyl, ^^ dimethylethyl] _ The spiro compound ( The production of d) can be carried out, for example, by reacting a dinitrile having a tetraazaspiro ring with dicyandiamine in an alcoholic organic solvent under the presence of a basic catalyst (Japanese Patent Application Laid-Open No. 5-32664 ), A method for reacting in an ether-based organic solvent in the presence of a basic catalyst (Japanese Patent Publication No. 44-8676), etc. In the case of adding a compound (d) containing a shamura ring containing an amine group The coarse copolymer is preferably fine powder and granules, so the reactor is preferably sufficiently pulverized. The function of the block polymer, and it is also possible to contact the compound (d) containing the amine group-substituted Sanka ring after pulverizing the polymerized reactant with a pulverizer. The particle size of the passivated coarse copolymer is at least 90 weight % Or more is 10 mm or less, preferably 4 mm or less, and more preferably 2 mm or less. -11- 593399 5. Description of the invention (10) The crude copolymer added with the amine-substituted tricyclic compound (d) is not washed. The melt-kneading treatment is carried out as it is, so that the catalyst is completely passivated. The melt-kneading treatment is preferably in a temperature range above the melting point of the copolymer and up to 260 ° C. Above 260 ° C will cause the polymer to occur. Decomposition and deterioration are not suitable. The melt-kneading device is not particularly limited as long as it has the function of melt-kneading the copolymer, and preferably has a vent function, for example, uniaxial or multiaxial continuous with at least one vent hole Extruder a kneader, co-kneader, etc. The melt-kneading treatment is preferably performed in the presence of an antioxidant. The antioxidant may be a conventional stabilizer used as a stabilizer for polyacetal, such as various hindered phenols. Antioxidants, etc. For example, 2,6-di-tert-butyl-4-methylphenol, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) ) Propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], [3- (3,5 · di Tertiary butyl-4-hydroxyphenyl) propionate] methane, N, N, -hexamethylenebis (3, 5-di-tertiary butyl-4-hydroxyhydrocinnamate, 2-tertiary Butyl-6- (3-third butyl-5'-methyl-2'-hydroxypentyl) -4-methylphenylacrylate, 3,9-bis [2-{(3-third butyl Methyl-4-hydroxy-5-methylphenyl) propanyloxydimethylethyl] -2,4,8,10 "tetraoxaspiro [5,5] -Eleven and so on. Furthermore, a part or all of the hindered phenol-based antioxidant may be added to the main monomer (a) or comonomer ib) before polymerization, and the polymerization is performed as long as the amount of the hindered phenol-based antioxidant is not particularly excessive, It will not adversely affect the activity of the polymerization catalyst, which is a preferred embodiment.

-12- 593399 V. Description of the invention (11) It depends on the stage. If necessary, it can add known substances as stabilizers for various polyacetal resins. In addition, for example, a filler such as glass fiber, a crystallization accelerator (nucleating agent), and a release agent can be added. As described above, "the compound (d) containing an amine group-containing sanka ring is added to a crude copolymer" and melt-kneaded, it is usually formed into a resin processing product such as nine pellets. Nine capsules can be dried as needed. When drying, for example at 140 ° C: 3 hours. EXAMPLES The present invention will be described in detail by the following examples, but the present invention is not limited thereto. The terms and measurement methods in the examples and comparative examples are as follows. Both% and ppm are% by weight or ppm by weight. Melt index (MI): The melt index (unit: g / 1.0 minute) measured at 190 ° C. This was evaluated as a characteristic corresponding to molecular weight. That is, the lower the MI, the higher the molecular weight. Alkali decomposition rate (existing amount of unstable parts): Nine pellets of the copolymer were pulverized, and 1 g thereof was placed in a 100% 50% methanol aqueous solution containing 0.5% ammonium hydroxide in a closed container at 180 ° C. After heating for 45 minutes, the amount of formaldehyde dissolved in the liquid was quantitatively analyzed, and expressed as% relative to the polymer. Heating weight reduction rate: It means the weight reduction rate of 5 grams of nine copolymers when heated in air at 230 ° C for 45 minutes. (Referred to as weight reduction rate in Table 1) Formaldehyde emission: Fill the sample in a cylinder maintained at 200 ° C.

-13- 593399 V. Description of the invention (12) After melting in 12 minutes, press the molten material out of the cylinder into a closed container. Nitrogen was allowed to flow into the closed container, and the formaldehyde contained in the nitrogen gas trapped was dissolved with water. The formaldehyde concentration in the water was measured to determine the weight of formaldehyde released from the melt. The weight of formaldehyde was divided by the weight of the melt to determine the amount of formaldehyde emission (unit P P m). [Examples 1 to 11 and Comparative Examples 1 to 2] The polymerization reaction device uses a continuous mixing reactor, which has a cross section in which two circles are partially overlapped, and the barrel is provided with a jacket for passing heat (cold) media on the outside. The barrel There are many propellers for propulsion inside to stir, and there are two rotary shafts in the longitudinal direction. The jacket of the reactor was passed with warm water at 80 ° C, and two rotary shafts were rotated at a certain speed, and one end was continuously fed with a formazan containing 3.5% comonomer shown in Table 1 and 700ppm as a chain transfer agent. A mixed solution of acetal dimethanol and trioxane. At the same time, 0.5% cyclohexane solution of boron trifluoride dibutyl etherate (BF, Bu20) in the amount shown in Table 1 relative to all the monomers was continuously added at the same place. 0.2% diethylene glycol diglyme solution of trifluoromethanesulfonic acid (CF3S03H), 0.2% diethylene glycol dimethyl ether solution of acetamyl perchlorate (CH3C0C104), or triethyl Oxyhexafluorophosphide (Et3OPF6: ^ 3 0.5% dichloromethane solution for copolymerization. However, in Table 1, the addition amount of the polymerization catalyst is a weight ratio (ppm) relative to the total of all monomers. The case of boron trifluoride dibutyl etherate is that of boron trifluoride (BF3). Secondly, to the reaction product discharged from the reactor outlet, add the tri-containing catalyst shown in Table 1 as a catalyst passivating agent. Spiral compound, melamine or -14-593399 5. Description of the invention (13) Melamine resin, added 0 as an antioxidant . 3% triethylene glycol-bis [3-(3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionate], using a twin shaft extruder with exhaust port, at 220 When the vacuum degree of the exhaust part is ° C and the vacuum degree is 5mmHg, it is melt-kneaded and extruded into nine pellets. However, in Table 1, the amount of the passivating agent is the weight ratio (ppm) to the crude copolymer. At 1 40 ° C After drying these nine tablets for 3 hours, MI measurement, thermal decomposition ratio measurement, heating weight reduction ratio measurement, and formaldehyde emission measurement were performed. The results are shown in Table 1. Also, for comparison, 0.5 as a catalyst was used. % Boron trifluoride butyl etherate in cyclohexane solution, known triphenylphosphine as passivator, bis (2,2,6,6, -tetramethyl-4-piperidinyl) decane as hindered amine [Comparative Example 3] Polymerization was performed in the same manner as in Example 1 using a cyclohexane solution containing boron trifluoride butyl etherate containing 0. The reaction product discharged from the discharge port was prepared into a 20% by weight slurry in an aqueous triethylamine solution, and was passivated at 80 ° C for 1 hour. After the processed tablets were filtered, they were dried at 10 (rc dry). 1 hour. Secondly, 0.3% triethylene glycol-bis [3- (3-second butyl-5-methyl-1_hydroxyphenyl) propionate] was added as an antioxidant, as in Example 1. Extrusion and evaluation. -15- 593399 V. Description of the invention (14) Table 1 Nine grains extruded by the polymerization catalyst copolymerization single passivation agent Characteristic Type Species Type JS- MI MI Weight loss HCH0 (ppm) ( ppm) (g / 10 minutes) Low solution rate Release rate (%) (%) (ppm) Example 1 BF3 * Bu20 40 DOXO A 2000 10.7 0.62 0.53 47 Example 2 BF3 * Bu20 40 DOXO B 2000 10.3 0.65 0.54 45 Example 3 BF3 * Bu20 40 BDFM C 2000 10.5 0.67 0.55 43 Example 4 BF3 * Bu20 40 DEGFM A 2000 10.3 0.66 0.52 42 Example 5 BF3 * Bu20 40 EO B 2000 10.8 0.69 0.54 43 Example 6 CF3SO3H 1.0 DOXO C 1000 9.9 0.58 0.49 38 Example 7 CF3SO3H 1.0 DXN A 1000 9.7 0.55 0.48 37 Example 8 CH3COCIO4 1.0 DOXO A 1000 9.8 0.61 0.49 42 Example 9 Et3OPF6 150 DOXO B 3000 11.1 0.72 0.52 57 Example 10 BF3.Bu20 40 DOXO D 2000 10.5 0.61 0.51 45 Example 11 BF3.Bu20 40 DOXO E 2000 11.0 0.69 0.53 47 Comparative Example 1 BF3 # Bu2〇40 DOXO F 500 14.5 1.49 0.66 109 Comparative Example 2 BF3.Bu20 40 DOXO G 2000 15.5 1.55 0.69 118 Comparative Example 3 BF3 * Bu20 40 DOXO H 14.7 1.42 0.64 103 In Table 1, copolymerization The symbol of the monomer indicates the following. DOXO ·· 1,3-dioxane BDFM · 1,4-butanediol methylal DEGFM: Diethylene glycol methylal DXN: 1,3-Dioxane-16-593399 5. Description of the invention (15) E0: Ethylene oxide uses the following compounds as passivation agents or methods. A: CTU guanamine B: CMTU guanamine C: 3,9-bis [1- (3,5-diamino · 2,4,6- ^ azaphenylphenyl, fluorene-dimethylethyl ] -2,4,8,1 0 -tetraoxaspiro [5,5] Union D: melamine E: melamine resin_F: triphenylphosphine G: bis (2,2,6,6, -Tetramethyl-4-erimyl) sebacic acid acetoacetate: The crude copolymer sheet was slurried in a 0.1% aqueous solution of triethylamine by a wet quenching method compared with the conventional wet method Next, the present invention can simplify the passivation step of the catalyst by the dry method, and omit the washing step. It is a very reasonable method, which can completely passivate the polymerization catalyst without obstacles such as deterioration, and has less unstable parts. It is thermally stable and the amount of formaldehyde released is very small, so it can economically produce a polyacetal copolymer with excellent quality ...

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Claims (1)

593399 one * tTr: ... + ― factory ... —---------------------- one one —... one, 4 .like. / 3 year month a 1-6. Application for Patent No. 9 1 1 1 4856 "Method for the Preparation of Polyacetal Copolymer" (as amended on April 1993) Six. Scope of Application for Patent: 1. Method for making a polyacetal copolymer 'It is characterized in that trioxane is used as the main monomer (a), a cyclic ether having at least one carbon-carbon bond and / or a cyclic methylal is used as a comonomer (b), and a cationic active catalyst ( c) When manufacturing a polyacetal copolymer, the compound (d) containing an amine-substituted succinyl ring is added to the reaction product, and melt-kneading is performed to passivate the catalyst (c). 02. For example, when applying for a patent The method for preparing a polyacetal copolymer according to item 1, wherein the comonomer (b) is at least one selected from the group consisting of 1,3-dioxane, diethylene glycol acetal, and 1,4-butanediol Methyl acetal, 1,3-dioxane and ethylene oxide. The method for preparing a polyacetal copolymer according to item 1 of the patent application, wherein the compound containing the amine-substituted succinyl ring (d ) Department of melamine, melamine Spiral compound of resin and / or succinyl ring containing amine substitution. 4. The method for preparing a polyacetal copolymer according to item 3 of the scope of patent application, wherein the spiral compound containing the amine-substituted triple well ring is a compound represented by the following formula (丨), H2N V = N /, • HsN (1) -1- 593399 6. Application scope (where R1 and R2 represent an alkylene group having 1 to 10 carbon atoms, an alkylene group having 6 to 10 carbon atoms, or the same For the Shenfang Academy, which is a combination of Yuanfang and Shenfang, R1 and R2 may be the same or different). 5. The method for preparing a polyacetal copolymer according to item 4 of the scope of patent application, wherein in formula (1), R1 and R2 are linear or branched linear alkylene groups having a carbon number of 1 to 6. A method for preparing a polyacetal copolymer according to item 4 of the patent application, wherein the spiro compound containing the amine-substituted succinyl ring is at least one kind selected from CTU guanamine (ie, 3,9-bis [2-(3 , 5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane), 01 ^ 11 guanamine (Ie 3,9-bis [1- (3,5-diamino-2,4,6-triazaphenyl) methyl] -2,4,8,1 0 -tetraoxaspiro [5 , 5] undecane) and 3,9-bis [1- (3,5-diamino-2,4,6-triazaphenyldimethylethyl) -2,4,8,10 -Tetraoxaspiro [5,5] undecane. 7. The method for preparing a polyacetal copolymer according to any one of claims 1 to 6, wherein the melt-kneading treatment deactivates the catalyst (c) Performed in the presence of antioxidants -2-