KR101522978B1 - Method for polymerizing polyoxymethylene polymer and polyoxymethylene polymer using thereof - Google Patents
Method for polymerizing polyoxymethylene polymer and polyoxymethylene polymer using thereof Download PDFInfo
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- 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
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- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/10—Polymerisation of cyclic oligomers of formaldehyde
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- C08G4/00—Condensation polymers of aldehydes or ketones with polyalcohols; Addition polymers of heterocyclic oxygen compounds containing in the ring at least once the grouping —O—C—O—
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Abstract
The present invention relates to a process for producing a polyoxymethylene polymer and a polyoxymethylene polymer produced by the process, and more particularly, to a process for producing a polyoxymethylene polymer by using a novel polymerization catalyst and a polymerization terminator, The present invention relates to a process for producing a polyoxymethylene polymer which can be omitted or simplified, has excellent thermal stability and can reduce formaldehyde released during the production process, and a polyoxymethylene polymer produced by the process.
Description
The present invention relates to a process for producing a polyoxymethylene polymer and a polyoxymethylene polymer produced by the process, and more particularly, to a process for producing a polyoxymethylene polymer by using a novel polymerization catalyst and a polymerization terminator, The present invention relates to a process for producing a polyoxymethylene polymer which can be omitted or simplified, has excellent thermal stability and can reduce formaldehyde released during the production process, and a polyoxymethylene polymer produced by the process.
Generally, the polyoxymethylene resin is prepared by bulk polymerization, solution polymerization or suspension of trioxane alone or trioxane and cyclic ether and / or cyclic acetal to prepare an oxymethylene homopolymer or copolymer. Such a method is disclosed in Korean Patent Laid-Open No. 10-2002-0074490 (Patent Document 1).
However, polymers obtained by such bulk polymerization, solution polymerization, or suspension polymerization are thermally unstable in themselves. Therefore, in the case of homopolymers, end groups are blocked by esterification or the like, and in the case of copolymers, unstable terminal groups are decomposed To stabilize the polymer, and it is necessary to stop the polymerization reaction by inactivating the catalyst prior to such stabilization step. That is, if the catalyst remaining in the reaction product in the oxime-methylene homopolymer and copolymer obtained by cation polymerization of trioxane or the like is not deactivated, the polymerization is gradually depolymerized, and the molecular weight of the polymer is remarkably lowered, resulting in a very unstable thermal state.
With respect to the deactivation of such a catalyst, JP-A-1994-211953 (Patent Document 2) proposes the use of an amine compound and a fluoride of an alkali metal as a BF 3 polymerization catalyst release agent, In the case of deactivation, the depolymerization can be prevented by removing the deflocculant through a separate washing step or the like, and the polymer is stabilized and the molecular weight is not lowered during long-term storage.
As described above, in order to solve the problems of the prior art, there has been developed a polymerization catalyst which can be completely deactivated and an activator capable of effectively completely deactivating such a polymerization catalyst, thereby eliminating the need for a cleaning process for removing the polymerization catalyst or deflocculant , A method for producing a polyoxymethylene polymer having excellent heat stability and few unstable portions is required.
In order to solve the above-mentioned problems, it is an object of the present invention to provide a process for producing a polyoxymethylene polymer which can eliminate or simplify the deactivation process by using a novel polymerization catalyst which can be completely deactivated.
Another object of the present invention is to provide a process for producing a polyoxymethylene polymer capable of completely deactivating a polymerization catalyst by using a polymerization terminator optimized for deactivation of a novel polymerization catalyst, minimizing an unstable part with excellent thermal stability .
In order to accomplish the above object, the present invention provides a process for producing an olefin polymer comprising the steps of: using an olefin polymer comprising repeating units represented by the following formula (2) And a repeating unit represented by the following formula (3) are randomly bonded to each other to produce a polyoxymethylene polymer.
[Chemical Formula 1]
(Wherein X is nitrogen or oxygen, Y is SiR 1 R 2 R 3 , and n is 1 or 2.)
(2)
(3)
(Wherein, X 1 and X 2 are each independently hydrogen or (C 1 -C 6) alkyl, and are not hydrogen at the same time, x is an integer selected from 2 to 6, n in the formula (2) To 200.)
The carbodiimide type polymerization terminator may be a compound represented by the following formula (4).
[Chemical Formula 4]
Wherein R 1 and R 2 are each independently selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 3 -C 20) cycloalkyl, , (C3-C20) heterocycloalkyl, is selected from heteroaryl (C4-C20), wherein R 1, and alkyl of R 2, aryl, alkoxy, cycloalkyl, alkenyl, heterocycloalkyl, heteroaryl (C1 -C7) alkyl, halogen, nitro, cyano, and at least one selected from the amino may further be substituted, provided that R 1 and R 2 is at least one of (C3-C20) cycloalkyl, (C6-C20) Aryl, (C3-C20) heterocycloalkyl, (C4-C20) heteroaryl.
The polymerization catalyst of Formula 1 may be selected from the following formulas.
1-1 1-2 1-3 1-4
The carbodiimide type polymerization terminator may be one or more selected from the following formulas (4-1) and (4-2).
[Formula 4-1]
(In the formula 4-1, n is an integer selected from 50 to 200.)
[Formula 4-2]
The content of the polymerization catalyst is 0.03 to 200 ppm relative to the total monomer content, and the content of the polymerization terminator may be 10 to 5000 ppm based on the total monomer content.
The polymerization catalyst may be added by dissolving in an organic solvent. The organic solvent may be selected from the group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, di Ethylene glycol dimethyl ether, ethylene glycol methyl butyl ether, triethylene glycol methyl butyl ether, propylene glycol dimethyl ether, and dipropylene glycol dimethyl ether.
In order to accomplish the above object, the present invention also relates to a polyoxymethylene polymer produced by the above-mentioned production method.
The polyoxymethylene polymer may have a terminal Formate content of 3.0 to 8.0 μmol / g-POM and a formaldehyde emission amount of 50 to 200 ppm.
The present invention can omit or simplify the deactivation process by using a novel polymerization catalyst, effectively inactivate the polymerization catalyst by using a polymerization terminator optimized for a novel polymerization catalyst, and provide a poly There is an advantage that an oxymethylene polymer can be produced.
Hereinafter, the method for producing the polyoxymethylene polymer of the present invention and the polyoxymethylene polymer produced by the method will be described in detail. The present invention may be better understood by the following examples, which are for the purpose of illustrating the present invention and are not intended to limit the scope of protection defined by the appended claims.
Hereinafter, each configuration of the present invention will be described in more detail.
The polyoxymethylene polymer to be polymerized by the present invention is a homopolymer composed of an oxymethylene repeating unit represented by the following formula (2) or a homopolymer represented by the following formula (2) using a polymerization catalyst and a carbomide- And a repeating unit represented by the following formula (3) may be randomly bonded to each other.
[Chemical Formula 1]
(Wherein X is nitrogen or oxygen, Y is SiR 1 R 2 R 3 , and n is 1 or 2.)
Wherein R 1 , R 2 and R 3 are each independently selected from (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 4 -C 20) heteroaryl However,
The alkyl, aryl, alkoxy and heteroaryl of R 1 , R 2 and R 3 may be further substituted with one or more selected from (C 1 -C 5) alkyl, halogen, nitro, cyano and amino.
Specifically, X is oxygen in the formula (1), R 1, R 2 and R 3 are, each independently, preferably (C1-C20) alkyl, more preferably selected from the formula to the polymerized catalyst of formula (I) Is effective since the inactivating process of the polymerization catalyst can be omitted or simplified.
1-1 1-2 1-3 1-4
In the production of the polyoxymethylene polymer of the present invention, the addition of the polymerization catalyst dissolved in an organic solvent is effective since homogeneous polyoxymethylene polymer can be produced by uniformly inducing polymerization reaction.
The organic solvent is selected from the group consisting of tylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol methyl butyl ether, Propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and the like.
The content of the polymerization catalyst according to the present invention is preferably 0.03 to 200 ppm, more preferably 0.1 to 100 ppm, based on the total amount of the monomers. If the content of the polymerization catalyst is less than 0.03 ppm, the polymerization reaction may not be sufficiently carried out, and the reaction rate may be significantly slowed and the production cost may increase. When the content exceeds 200 ppm, A methylene polymer may be formed, and the content of the polymerization catalyst to be inactivated may increase to increase the content of the polymerization terminator, thereby raising the manufacturing cost.
(2)
(3)
(Wherein X 1 and X 2 are each independently hydrogen or (C 1 -C 6) alkyl, not simultaneously hydrogen, x is an integer selected from 2 to 6,
N in Formula 2 and m in Formula 3 are integers selected from 1 to 200.)
The polyoxymethylene polymer is not particularly limited, but may preferably have a weight average molecular weight of 10,000 to 200,000 g / mol.
The oxymethylene homopolymer may be prepared by polymerizing formaldehyde or a cyclic oligomer thereof, that is, trioxane. The oxymethylene copolymer to which the unit of the formula (2) and the unit of the formula (3) are bonded may be formaldehyde or a cyclic oligomer thereof Can be obtained by random copolymerizing a cyclic ether represented by the following formula (5) or a cyclic formal represented by the following formula (6)
[Chemical Formula 5]
[Chemical Formula 6]
In the above formulas (5) and (6)
X 3, X 4, X 5 and X 6 are each independently hydrogen or (C1-C6) alkyl, a bond to the same carbon atom or may be bonded to other carbon atoms, and not simultaneously hydrogen, wherein n and m are Each is an integer selected from 2 to 6.
Of the comonomers used in the random copolymerization, examples of the cyclic ether include ethylene oxide, propylene oxide, butylene oxide, and phenylene oxide. The cyclic formate includes 1,3-dioxolane, diethylene glycol formal, , 3-propanediol formal, 1,4-butanediol formal, 1,3-dioxepanformal, 1,3,6-trioxocane, and the like. Preferably, one or more monomers selected from monomers such as ethylene oxide, 1,3-dioxolane and 1,4-butanediol formal can be used.
These monomers are added to the main monomer, trioxane or formaldehyde, and random copolymerization is carried out by using Lewis acid as a catalyst to obtain an oxymethylene copolymer. The copolymer thus obtained has a melting point of 150 ° C or higher and has two or more And has a bonding carbon atom.
In the above oxymethylene copolymer, the ratio of the oxymethylene bond structure to the oxymethylene repeat unit is in the range of 0.05 to 50 mole times, preferably 0.1 to 20 mole times.
The polymerization method for producing the polyoxymethylene polymer can be carried out in the form of bulk polymerization, suspension polymerization or solution polymerization, and is not limited as long as it is a polymerization method for producing the polyoxymethylene polymer which is well known in the art.
The temperature for the polymerization reaction is preferably 0 to 100 캜, more preferably 20 to 80 캜.
If the polymerization temperature is lower than 0 ° C, the polymerization reaction may not occur. If the polymerization temperature is higher than 100 ° C, the reaction rate becomes too fast, which may make it difficult to form a uniform polyoxymethylene polymer. , The reaction rate can be appropriately controlled, and the polymerization catalyst can be effectively deactivated.
In the polymerization of polyoxymethylene, an alkyl-substituted phenol or an ether may be used as a chain transferring agent, and alkyl ethers such as dimethoxymethane may be particularly preferably used.
In order to stop the polymerization reaction of the polyoxymethylene, a carbomide-based polymerization terminator represented by the following general formula (4) may be added.
[Chemical Formula 4]
Wherein R 1 and R 2 are each independently selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 3 -C 20) cycloalkyl, , (C3-C20) heterocycloalkyl, (C4-C20) heteroaryl,
The alkyl, aryl, alkoxy, cycloalkyl, alkenyl, heterocycloalkyl, heteroaryl of R 1 and R 2 may be further substituted with one or more selected from (C 1 -C 7) alkyl, halogen, nitro, cyano and amino However,
Provided that at least one of R 1 and R 2 is a cyclic substituent selected from (C 3 -C 20) cycloalkyl, (C 6 -C 20) aryl, (C 3 -C 20) heterocycloalkyl and (C 4 -C 20) .
The formula (4) may be selected from one or more of the following formulas (4-1) and (4-2).
[Formula 4-1]
(In the formula 4-1, n is an integer selected from 50 to 200.)
[Formula 4-2]
The content of the polymerization terminator according to the present invention is preferably 10 to 5000 ppm, more preferably 50 to 1000 ppm, based on the total monomer content. If the content of the polymerization terminator is less than 10 ppm, the deactivation effect on the polymerization catalyst may be decreased to deteriorate the heat stability. If the content of the polymerization terminator is higher than 5000 ppm, the content of the low molecular weight polymer may be increased to increase the physical properties of the polyoxymethylene polymer Or may cause discoloration of the polymer. Therefore, it is effective to use it in the above-mentioned range.
The carbostyril-based polymerization terminator according to the present invention may be added in the form as it is or dissolved in an organic solvent.
Examples of the organic solvent capable of dissolving the carboymide polymerization terminator include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as n-hexane, n-heptane and cyclohexane, alcohols such as methanol and the like, , 1,2-dichloroethane and the like, ketones such as acetone, methyl ethyl ketone and the like, and any organic solvents capable of dissolving the carboymide-based polymerization terminator.
&Quot; Alkyl " &Quot; Alkoxy " and other " alkyl " include both straight and branched forms, and " alkenyl " includes both straight chain or branched forms containing from two to eight carbon atoms and containing one or more double bonds do.
The "(C3-C20) cycloalkyl" described in the present invention includes both saturated monocyclic or saturated bicyclic ring structure forms having 3 to 20 carbon atoms.
&Quot; Aryl " as used in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination, a single or fused ring system containing, suitably, 4 to 7, preferably 5 to 6 ring atoms in each ring . Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, tolyl, and the like.
&Quot; Heterocycloalkyl " as used herein refers to a saturated cyclic hydrocarbon skeletal atom containing 1 to 3 heteroatoms selected from N, O, S and the remaining saturated monocyclic or bicyclic ring skeletal atom carbon Alkyl group which may be substituted with at least one substituent selected from the group consisting of pyrrolidinyl, azetidinyl, pyrazolidinyl, oxazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, Wherein the substituent is selected from the group consisting of alkyl, alkoxy, alkylthio, alkylthio, alkylthio, alkylthio, alkylthio, alkylthio, alkylthio, alkylthio, alkylthio, Tetrahydropyrimidinyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, diazepanyl, and azepanyl.
&Quot; Heteroaryl " as used in the present invention means an aryl group having 1 to 3 hetero atoms selected from N, O, S as an aromatic ring skeletal atom and the remaining aromatic ring skeletal atoms carbon, Include heteroaryl groups in the ring which are oxidized or tanned to form, for example, N-oxides or quaternary salts. Specific examples include furyl, thiophenyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isosazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, tri Pyrimidinyl, pyridazinyl, and the like, including, but not limited to, pyrimidinyl, pyrimidinyl, pyridazinyl, pyridazinyl,
By preparing the polyoxymethylene polymer by adding the polymerization catalyst and the polymerization terminator of the present invention, it is possible to form a polyoxymethylene polymer which has a uniform molecular weight distribution and other physical properties and can omit or simplify the deactivation process, The polymerization catalyst can be effectively deactivated to inhibit occurrence of depolymerization, and a polyoxymethylene polymer having a low molecular weight content and excellent thermal stability can be produced.
The polyoxymethylene polymer produced by the process of the present invention has a terminal formate content of 3.0 to 8.0 μmol / g-POM, and a formaldehyde emission amount of 50 to 200 ppm is remarkably decreased.
Hereinafter, the process for producing the polyoxymethylene polymer of the present invention and the polyoxymethylene polymer produced by the process will be described in detail with reference to Examples and Comparative Examples.
Property measurement
1. Melt Index (MI)
The weight of the polyoxymethylene polymer sample extruded at a temperature of 190 ° C. under a load of 2.16 kg for 10 minutes was measured in an orifice having a constant inner diameter. This value was a measure for evaluating the depolymerization rate of the polymer, The higher the value, the higher the depolarization rate.
2. Determination of terminal formate content
The polyoxymethylene polymer of the present invention is prepared in the form of a film, immersed in a chloroform solution at 100 ° C for 6 hours, and then the area of 1778 to 1697 cm -1 is measured using FT-IR (Perkin Elmer Spectrum 2000). The formate group is a typical unstable terminal of a polyoxymethylene polymer. The higher the value, the more easily depolymerization occurs and the thermal stability is poor.
3. Formaldehyde emission measurement (HS-GC method)
3 g of the polyoxymethylene polymer sample pellet of the present invention is subjected to quantitative analysis by using Headspace GC (Agilent 7890A) at a temperature of 185 ° C for 1 hour and then the generated formaldehyde gas is quantitatively analyzed. The higher the value, the worse the thermal stability.
4. Measurement of Acetic Acid Property
The polyoxymethylene polymer of the present invention was prepared by making a test piece having a surface area of 100 cm 2 and immersing it in a 3 wt% acetic acid solution at 40 ° C for 10 days. The extract solution was applied to UV-VIS (Perkin-Elmer) . This value represents the degree of depolymerization of the polyoxymethylene polymer by acetic acid, and the higher the value, the higher the depolymerization rate.
[Example 1]
500cc of trioxane and 20g of 1,3-dioxolane were injected as a comonomer using a metering device, and then 0.0015g of trimethylsilyl trifluoromethanesulfonate (TMST) (ethylene glycol dimethyl ether , 3 ppm relative to trioxane). After 10 minutes from the addition of the polymerization catalyst, PCDI (1,3,5-triisopropyl-phenylene-2,4-carbodiimide, Mw: 20,000) as a polymerization terminator was added to the polyoxymethylene copolymer at 100 ppm The melt index, the amount of terminal formate, the amount of formaldehyde generated and the acidity of acetic acid were measured for the resulting polyoxymethylene polymer, and the result was shown in Table 2 shows the results.
[Examples 2 to 11]
As shown in the following Table 1, a polyoxymethylene polymer was obtained in the same manner as in Example 1, except that the solvent and content of the polymerization catalyst, the kind and content of the polymerization terminator were changed. The melt index, terminal formate content, formaldehyde generation amount and acetic acid acidity of the resulting polyoxymethylene polymer were measured, and the results are shown in Table 2.
[Comparative Example 1]
As shown in the following Table 1, except that boron trifluoride diethyl etherate was dissolved in benzene as a polymerization catalyst and 70 ppm of trioxane was added thereto, and TPP (Triphenylphosphine) as a polymerization terminator was added in an amount of 500 ppm relative to the polyoxymethylene copolymer Was carried out in the same manner as in Example 1 to obtain a polyoxymethylene polymer. The melt index, terminal formate content, formaldehyde generation amount and acetic acid acidity of the resulting polyoxymethylene polymer were measured, and the results are shown in Table 2.
[Comparative Example 2]
As shown in the following Table 1, TIN 765 (Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate + methyl 1,2,2,6,6-pentamethyl- sebacate), to obtain a polyoxymethylene polymer. < tb >< TABLE > The melt index, terminal formate content, formaldehyde generation amount and acetic acid acidity of the resulting polyoxymethylene polymer were measured, and the results are shown in Table 2.
[Comparative Examples 3 to 4]
A polyoxymethylene polymer was obtained in the same manner as in Example 1, except that the content of the polymerization catalyst was changed as shown in Table 1 below. The melt index, terminal formate content, formaldehyde generation amount and acetic acid acidity of the resulting polyoxymethylene polymer were measured, and the results are shown in Table 2.
[Table 1]
[Table 2]
As shown in Table 2, the melt index, terminal formate content, formaldehyde release amount and acetic acid acidity of Comparative Examples 1 to 4 were significantly lower than those of Examples 1 to 10.
Therefore, the polyoxymethylene polymer of Examples 1 to 10 of the present invention can polymerize a polyoxymethylene polymer having sufficient physical properties even if only a small amount of a novel polymerization catalyst is used, and a polymerization terminator suitable for such a polymerization catalyst is used It is possible to inactivate the polymerization catalyst effectively, and the unstable part can be remarkably reduced to remarkably improve the durability and the heat resistance.
While the present invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Accordingly, the above description should not be construed as limiting the scope of the present invention defined by the limits of the following claims.
Claims (9)
Wherein the carbodiimide type polymerization terminator is at least one selected from the following formulas (4-1) and (4-2).
[Chemical Formula 1]
(In the formula 1,
X is nitrogen or oxygen, Y is SiR 1 R 2 R 3 , n is 1 or 2,
Wherein R 1 , R 2 and R 3 are each independently selected from (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy, (C 4 -C 20)
The alkyl, aryl, alkoxy and heteroaryl of R 1 , R 2 and R 3 may be further substituted with one or more selected from (C 1 -C 5) alkyl, halogen, nitro, cyano and amino.
(2)
(3)
(Wherein X 1 and X 2 are each independently hydrogen or (C 1 -C 6) alkyl, not simultaneously hydrogen, x is an integer selected from 2 to 6,
N in Formula 2 and m in Formula 3 are integers selected from 1 to 200.)
[Formula 4-1]
(In the formula 4-1, n is an integer selected from 50 to 200)
[Formula 4-2]
A process for producing a polyoxymethylene polymer wherein the polymerization catalyst of the formula (1) is selected from the following formulas
1-1 1-2 1-3 1-4
The content of the polymerization catalyst is 0.03 to 200 ppm based on the total monomer content,
Wherein the content of the polymerization terminator is in the range of 10 to 5000 ppm based on the total monomer content.
Wherein the polymerization catalyst is dissolved and added as an organic solvent.
The organic solvent may be selected from the group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol methyl butyl ether, Propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and mixtures thereof. 2. A process for producing a polyoxymethylene polymer, comprising:
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| DE1128139B (en) * | 1959-02-14 | 1962-04-19 | Bayer Ag | Process for the catalytic polymerization of anhydrous formaldehyde |
| EP2546272A1 (en) * | 2011-07-15 | 2013-01-16 | Ticona GmbH | Process for producing oxymethylene polymers |
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| KR960010248B1 (en) * | 1990-10-05 | 1996-07-26 | 아사히가세이고오교 가부시끼가이샤 | Polyoxymethylene copolymer and production thereof |
| KR100574164B1 (en) * | 2003-04-09 | 2006-04-27 | 한국엔지니어링플라스틱 주식회사 | Polyoxymethylene Resin Composition Having an Excellent Heat Stability |
| KR100574165B1 (en) * | 2004-10-08 | 2006-04-27 | 한국엔지니어링플라스틱 주식회사 | Polyoxymethylene Resin Composition Having an Excellent Heat Stability |
| KR20130005695A (en) * | 2011-07-07 | 2013-01-16 | 한국엔지니어링플라스틱 주식회사 | Method for polymerizing polyoxymethylene polymer |
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| KR20140108878A (en) | 2014-09-15 |
| WO2014137126A1 (en) | 2014-09-12 |
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