JPS63159463A - Method of stabilizing oxymethylene copolymer - Google Patents
Method of stabilizing oxymethylene copolymerInfo
- Publication number
- JPS63159463A JPS63159463A JP30522486A JP30522486A JPS63159463A JP S63159463 A JPS63159463 A JP S63159463A JP 30522486 A JP30522486 A JP 30522486A JP 30522486 A JP30522486 A JP 30522486A JP S63159463 A JPS63159463 A JP S63159463A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- oxymethylene copolymer
- oxymethylene
- unstable
- earth metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title description 19
- 230000000087 stabilizing effect Effects 0.000 title description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- -1 alkaline earth metal salt Chemical class 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims abstract 2
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 abstract description 2
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 abstract description 2
- 229960001484 edetic acid Drugs 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 7
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- AUAGGMPIKOZAJZ-UHFFFAOYSA-N 1,3,6-trioxocane Chemical compound C1COCOCCO1 AUAGGMPIKOZAJZ-UHFFFAOYSA-N 0.000 description 1
- KODJTPVSRWYRDF-UHFFFAOYSA-N 2-butyl-1,3-dioxolane Chemical compound CCCCC1OCCO1 KODJTPVSRWYRDF-UHFFFAOYSA-N 0.000 description 1
- HTWIZMNMTWYQRN-UHFFFAOYSA-N 2-methyl-1,3-dioxolane Chemical compound CC1OCCO1 HTWIZMNMTWYQRN-UHFFFAOYSA-N 0.000 description 1
- MRXPNWXSFCODDY-UHFFFAOYSA-N 2-methyl-2-phenyloxirane Chemical compound C=1C=CC=CC=1C1(C)CO1 MRXPNWXSFCODDY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- OVKDCYKVNYLEHK-UHFFFAOYSA-N 4-phenyl-1,3-dioxolane Chemical compound O1COCC1C1=CC=CC=C1 OVKDCYKVNYLEHK-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- NWNSUODQYUQWOK-UHFFFAOYSA-H C(C(=O)[O-])N(CC(=O)[O-])CC(=O)[O-].C(C(=O)[O-])N(CC(=O)[O-])CC(=O)[O-].[Ba+2].[Ba+2].[Ba+2] Chemical compound C(C(=O)[O-])N(CC(=O)[O-])CC(=O)[O-].C(C(=O)[O-])N(CC(=O)[O-])CC(=O)[O-].[Ba+2].[Ba+2].[Ba+2] NWNSUODQYUQWOK-UHFFFAOYSA-H 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- NVTRPRFAWJGJAJ-UHFFFAOYSA-L EDTA monocalcium salt Chemical compound [Ca+2].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O NVTRPRFAWJGJAJ-UHFFFAOYSA-L 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- VBDAYDRQBDDTBH-UHFFFAOYSA-N [(3,5-ditert-butyl-2,6-dioctadecylphenyl)-hydroxymethyl]phosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCC1=C(C(=C(C=C1C(C)(C)C)C(C)(C)C)CCCCCCCCCCCCCCCCCC)C(O)P(=O)(O)O VBDAYDRQBDDTBH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- WXMZPPIDLJRXNK-UHFFFAOYSA-N butyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCC)C1=CC=CC=C1 WXMZPPIDLJRXNK-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- ACYGYJFTZSAZKR-UHFFFAOYSA-J dicalcium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Ca+2].[Ca+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O ACYGYJFTZSAZKR-UHFFFAOYSA-J 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- IKPSWHSUPZNPTL-UHFFFAOYSA-J magnesium disodium tetraacetate Chemical compound [Na+].[Na+].C(C)(=O)[O-].[Mg+2].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] IKPSWHSUPZNPTL-UHFFFAOYSA-J 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JZBRFIUYUGTUGG-UHFFFAOYSA-J tetrapotassium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JZBRFIUYUGTUGG-UHFFFAOYSA-J 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- KKFOMYPMTJLQGA-UHFFFAOYSA-N tribenzyl phosphite Chemical compound C=1C=CC=CC=1COP(OCC=1C=CC=CC=1)OCC1=CC=CC=C1 KKFOMYPMTJLQGA-UHFFFAOYSA-N 0.000 description 1
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- MLNKCMDGRLCKRP-UHFFFAOYSA-H tricalcium 2-[bis(carboxylatomethyl)amino]acetate Chemical compound [Ca++].[Ca++].[Ca++].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O.[O-]C(=O)CN(CC([O-])=O)CC([O-])=O MLNKCMDGRLCKRP-UHFFFAOYSA-H 0.000 description 1
- JEVFKQIDHQGBFB-UHFFFAOYSA-K tripotassium;2-[bis(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O JEVFKQIDHQGBFB-UHFFFAOYSA-K 0.000 description 1
- JAYKPAAGOYELFD-UHFFFAOYSA-N tris(2,4-ditert-butylphenyl)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1P(C=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)C1=CC=C(C(C)(C)C)C=C1C(C)(C)C JAYKPAAGOYELFD-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- FEVFLQDDNUQKRY-UHFFFAOYSA-N tris(4-methylphenyl) phosphite Chemical compound C1=CC(C)=CC=C1OP(OC=1C=CC(C)=CC=1)OC1=CC=C(C)C=C1 FEVFLQDDNUQKRY-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はオキシメチレン共重合体の安定化法に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a method for stabilizing oxymethylene copolymers.
（従来の技術及びその問題点）
ホルムアルデヒド又はその環状オリゴマーと環状ホルマ
ールとの共重合によって、主鎖末端部にオキシメチレン
単位からなる熱不安定部を有する末端未安定化オキシメ
チレン共重合体が得られることは公知である。この末端
未安定化オキシメチレン共重合体の熱不安定部分は、使
用に先立って除去する必要がある。その除去方法として
は、例えば、水−アルコール混合溶媒中、エチレンジア
ミンテトラ酢酸金属塩の存在下に末端未安定化オキシメ
チレン共重合体を加熱する方法（特公昭５３−３６８７
６号公報）、三価の有機燐化合物、フェノール系抗酸化
剤及び金属水酸化物の存在下に、末端未安定化オキシメ
チレン共重合体を加熱する方法（特公昭５５−４５０８
７号公報）が提案されている。(Prior art and its problems) By copolymerizing formaldehyde or a cyclic oligomer thereof with a cyclic formal, an unstabilized terminal oxymethylene copolymer having a thermally unstable part consisting of oxymethylene units at the end of the main chain can be obtained. It is publicly known that The thermally unstable portions of this terminally unstabilized oxymethylene copolymer must be removed prior to use. As a method for removing it, for example, a method (Japanese Patent Publication No. 53-3687
6), a method of heating a terminally unstabilized oxymethylene copolymer in the presence of a trivalent organic phosphorus compound, a phenolic antioxidant, and a metal hydroxide (Japanese Patent Publication No. 55-4508
Publication No. 7) has been proposed.
前者の方法は大量の溶媒中でオキシメチレン共重合体の
安定化を行うため、工業的プロセスでは安定化後に溶媒
の回収及び精製を行う必要があり、そのための装置及び
経費を必要とする。In the former method, the oxymethylene copolymer is stabilized in a large amount of solvent, so in an industrial process, it is necessary to recover and purify the solvent after stabilization, which requires equipment and expense.
後者の方法においては、溶媒を使用しないため、前者の
方法におけるような不都合は生じないので工業的プロセ
スとしては適している。この方法においては、未安定化
共重合体をその融点近傍で加熱する必要があり、主鎖の
切断による分子量の低下を防止するために、加熱処理時
間をできるだけ短くすることが望まれる。加熱処理時間
を短くするという観点からすると提案の方法は未だ充分
なものであるとは言い難い。In the latter method, since no solvent is used, there are no inconveniences as in the former method, and therefore it is suitable as an industrial process. In this method, it is necessary to heat the unstabilized copolymer near its melting point, and it is desirable to shorten the heat treatment time as much as possible in order to prevent a decrease in molecular weight due to cleavage of the main chain. From the viewpoint of shortening the heat treatment time, it is difficult to say that the proposed method is still sufficient.
（発明の目的）
この発明の目的は、熱分解安定化を短時間で完了するこ
とのできるオキシメチレン共重合体の安定化法を提供す
ることにある。(Objective of the Invention) An object of the present invention is to provide a method for stabilizing an oxymethylene copolymer that can complete thermal decomposition stabilization in a short time.
（発明の要旨）
本発明によれば、末端未安定化オキシメチレン共重合体
に、
（１） ニトリロトリ酢酸又はエチレンジアミンテト
ラ酢酸のアルカリ金属塩又はアルカリ土類金属塩（以下
化合物ｆｌ）という）、
（２） フェノール系抗酸化剤（以下化合物（２）と
いう）、
（３） アルカリ土類金属の水酸化物（以下化合物（
３）という）、及び
（４）三価の有機燐化合物（以下化合物（４）という）
が配合された配合物を、上記共重合体の融点以上の温度
に加熱することを特徴とするオキシメチレン共重合体の
安定化法が提供される。(Summary of the Invention) According to the present invention, the terminal-unstabilized oxymethylene copolymer contains (1) an alkali metal salt or alkaline earth metal salt of nitrilotriacetic acid or ethylenediaminetetraacetic acid (hereinafter referred to as compound fl); 2) Phenolic antioxidant (hereinafter referred to as compound (2)), (3) Alkaline earth metal hydroxide (hereinafter referred to as compound (2))
(3)), and (4) trivalent organic phosphorus compound (hereinafter referred to as compound (4))
Provided is a method for stabilizing an oxymethylene copolymer, which comprises heating a blend containing the above to a temperature equal to or higher than the melting point of the copolymer.
（発明の詳細な説明）
本発明における末端未安定化オキシメチレン共重合体は
、オキシメチレン繰り返し単位中に０．１〜１０モル％
、好ましくは１〜４モル％の環状ホルマールから誘導さ
れた単位を有し、かつその分子末端にオキシメチレンの
繰り返し単位からなる熱不安定部分を有する共重合体で
ある。(Detailed Description of the Invention) The terminally unstabilized oxymethylene copolymer in the present invention is contained in an oxymethylene repeating unit in an amount of 0.1 to 10 mol%.
It is a copolymer having preferably 1 to 4 mol % of units derived from cyclic formal, and having a thermally unstable portion consisting of a repeating unit of oxymethylene at the molecular end.
上記環状ホルマールの例としては、
で表される化合物、及び
で表される化合物が挙げられる。上記両式において、Ｒ
１、Ｒ２、Ｒ３及びＲ４は、それぞれ、水素原子、アル
キル基、アリル基及びシクロアルキル基を示し、ｍは１
〜３の整数、ｎは２〜６の整数である。Examples of the above-mentioned cyclic formals include compounds represented by and compounds represented by. In both the above formulas, R
1, R2, R3 and R4 each represent a hydrogen atom, an alkyl group, an allyl group, and a cycloalkyl group, and m is 1
an integer of ˜3, n is an integer of 2-6.
環状ホルマールの具体例としては、エチレンオキサイド
、プロピレンオキサイド、ブテン−１−オキサイド、１
，３−ブタジェン−１−オキサイド、スチレンオキサイ
ド、α−メチルスチレンオキサイド、オキセタン、テト
ラヒドロフラン、１゜３−ジオキソラン、４−フェニル
−１，３−ジオキソラン、２−メチル−１，３−ジオキ
ソラン、１．３−ジオキソラン、２−ブチル−１，３−
ジオキソラン、１，３．６−トリオキソカン、１゜３、
５−）ジオキソラン及びポリエチレングリコールホル
マールが挙げられる。Specific examples of cyclic formals include ethylene oxide, propylene oxide, butene-1-oxide,
, 3-butadiene-1-oxide, styrene oxide, α-methylstyrene oxide, oxetane, tetrahydrofuran, 1°3-dioxolane, 4-phenyl-1,3-dioxolane, 2-methyl-1,3-dioxolane, 1. 3-dioxolane, 2-butyl-1,3-
Dioxolane, 1,3.6-trioxocane, 1°3,
5-) Dioxolane and polyethylene glycol formal.
末端未安定化オキシメチレン共重合体は、公知の方法、
例えば、ホルムアルデヒド又はトリオキサンと環状ホル
マールとを三弗化ホウ素、そのエーテル錯体のようなル
イス酸の存在下に共重合させる方法、オキシメチレン単
独重合体と環状ホルマールとをルイス酸の存在下に反応
させる方法で調製することができる。The terminal-unstabilized oxymethylene copolymer can be prepared by a known method,
For example, a method in which formaldehyde or trioxane and a cyclic formal are copolymerized in the presence of a Lewis acid such as boron trifluoride or its ether complex, or a method in which an oxymethylene homopolymer and a cyclic formal are reacted in the presence of a Lewis acid. It can be prepared by a method.
化合物（１）におけるアルカリ金属又はアルカリ土類金
属の例としては、ナトリウム、カリウム、マグネシウム
、カルシウム及びバリウムが挙げられる。化合物＋１１
の具体例としては、ニトリロトリ酢酸三ナトリウム、ニ
トリロトリ酢酸三カリウム、ニトリロトリ酢酸ナトリウ
ム・カルシウム、ニトリロトリ酢酸カリウム・バリウム
、エチレンジアミンテトラ酢酸四ナトリウム、エチレン
ジアミンテトラ酢酸四カリウム、エチレンジアミンテト
ラ酢酸二ナトリウム・カルシウム、エチレンジアミンテ
トラ酢酸二ナトリウム・マグネシウム、エチレンジアミ
ンテトラ酢酸二カルシウム、エチレンジアミンテトラ酢
酸ニバリウムが挙げられる。Examples of alkali metals or alkaline earth metals in compound (1) include sodium, potassium, magnesium, calcium and barium. compound +11
Specific examples include trisodium nitrilotriacetate, tripotassium nitrilotriacetate, sodium and calcium nitrilotriacetate, potassium and barium nitrilotriacetate, tetrasodium ethylenediaminetetraacetate, tetrapotassium ethylenediaminetetraacetate, disodium and calcium ethylenediaminetetraacetate, and ethylenediaminetetraacetate. Examples include disodium magnesium acetate, dicalcium ethylenediaminetetraacetate, and nivalium ethylenediaminetetraacetate.
化合物（２）の具体例としては、２，２−メチレンビス
（４−メチル−６−ｔ−ブチルフェノール）、４．４−
メチレンビス（２，６−ジーｔ−ブチルフェノール）、
２．６−ジーｔ−ブチル−４−ヒドロキシメチルフェノ
ール、トリエチレングリコール−ビス−３−（３−ｔ−
ブチル−４−ヒドロキシ−５−メチルフェニル）プロピ
オネート、１゜６−ヘキサンジオール−ビスー３− （
３，５−ジ−ｔ−７’チル−４−ヒドロキシフェニル）
プロピオネート、ペンタエリスリチル−テトラキス−３
−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル
）プロピオネート、１．３．５−トリメチル−２，４，
６−）リス（３，５−ジ−ｔ−ブチル−４−ヒドロキシ
ベンジル）ベンゼン、ジステアリル−３，５−ジ−ｔ−
ブチル−ヒドロキシベンジルホスホネート、２，６．７
−１−ジオキサ−ｌ−ホスファ−ビシクロ［２，２，２
］−オクト−４−イル−メチル−３，５−ジ−ｔ−ブチ
ル−４−ヒドロキシフェニルプロピオネート、３．５−
ジ−ｔ−ブチル−４−ヒドロキシベンジルジメチルアミ
ン、３．５−ジ−ｔ−ブチル−４−ヒドロキシフェニル
−３，５−ジステアリル−チオトリアジルアミン等が挙
げられる。Specific examples of compound (2) include 2,2-methylenebis(4-methyl-6-t-butylphenol), 4.4-
methylenebis(2,6-di-t-butylphenol),
2.6-di-t-butyl-4-hydroxymethylphenol, triethylene glycol-bis-3-(3-t-
Butyl-4-hydroxy-5-methylphenyl)propionate, 1゜6-hexanediol-bis-3-(
3,5-di-t-7'thyl-4-hydroxyphenyl)
Propionate, pentaerythrityl-tetrakis-3
-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1.3.5-trimethyl-2,4,
6-) Lis(3,5-di-t-butyl-4-hydroxybenzyl)benzene, distearyl-3,5-di-t-
Butyl-hydroxybenzylphosphonate, 2,6.7
-1-dioxa-l-phospha-bicyclo[2,2,2
]-Oct-4-yl-methyl-3,5-di-t-butyl-4-hydroxyphenylpropionate, 3.5-
Di-t-butyl-4-hydroxybenzyldimethylamine, 3.5-di-t-butyl-4-hydroxyphenyl-3,5-distearyl-thiotriazylamine, and the like.
化合物（３）の具体例としては、水酸化マグネシウム、
水酸化カルシウム及び水酸化バリウムが挙げられる。Specific examples of compound (3) include magnesium hydroxide,
Mention may be made of calcium hydroxide and barium hydroxide.
化合物（４）の具体例としては、トリーｎ−ブチルホス
ファイト、トリフェニルホスファイト、トリベンジルホ
スファイト、トリトリルホスファイト、トリス（２，４
−ジ−ｔ−ブチルフェニル）ホスファイト、トリーｎ−
ブチルホスフィン、ｎ−ブチルジフェニルホスフィン、
ジ−ｎ−ブチルヘンシルホスフィン、トリフェニルホス
フィン、トリベンジルホスフィン、トリトリルホスフィ
ン、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスフ
ィン等が挙げられる。Specific examples of compound (4) include tri-n-butyl phosphite, triphenyl phosphite, tribenzyl phosphite, tritolyl phosphite, tris(2,4
-di-t-butylphenyl) phosphite, tri-n-
Butylphosphine, n-butyldiphenylphosphine,
Examples include di-n-butylhensylphosphine, triphenylphosphine, tribenzylphosphine, tritolylphosphine, tris(2,4-di-t-butylphenyl)phosphine, and the like.
化合物（１）ないしく４）の使用量は、末端未安定化オ
キシメチレン共重合体１００重１部当たり、それぞれ、
０．００１〜２重量部、特に０．１〜１重量部であるこ
とが好ましい。The amount of compound (1) to 4) used per 100 parts by weight of the terminally unstabilized oxymethylene copolymer is as follows:
It is preferably 0.001 to 2 parts by weight, particularly 0.1 to 1 part by weight.
化合物（１１の使用量が過度に小さいと、末端未安定化
オキシメチレン共重合体の末端熱不安定部分の分解に長
い時間を要し、その結果主鎖の切断が生ずるようになる
。化合物（２）及び（３）の使用量が過度に少ないと、
安定化処理後のオキシメチレン共重合体の熱安定性が不
充分なものとなる。さらに、化合物（４）の使用量が少
なすぎると安定化処理後のオキシメチレン共重合体を高
い温度で長時間加熱したときに、この共重合体が着色す
るようになる。If the amount of compound (11) used is too small, it will take a long time to decompose the terminal thermally unstable moieties of the terminally unstabilized oxymethylene copolymer, resulting in cleavage of the main chain.Compound (11) If the usage amount of 2) and (3) is too small,
The thermal stability of the oxymethylene copolymer after the stabilization treatment becomes insufficient. Furthermore, if the amount of compound (4) used is too small, the oxymethylene copolymer after the stabilization treatment will become colored when it is heated at high temperature for a long time.
化合物（１）ないしく４）の使用量を過度に多くしても
、特に効果はなく経済的でない。Even if the amount of compound (1) to 4) used is excessively increased, there is no particular effect and it is not economical.
これらの化合物は粉末のまま、又はＧ ’／ｆｉｔとし
て、末端未安定化オキシメチレン共重合体に配合するこ
とができる。These compounds can be blended into the terminally unstabilized oxymethylene copolymer as a powder or as G'/fit.
本発明においては、化合物（１）ないしく４）が配合さ
れた末端未安定化オキシメチレン共重合体を、その融点
以上の温度に加熱し、分解によって発生するホルムアル
デヒドガスを系外に排出させながら、安定化オキシメチ
レン共重合体を製造する。In the present invention, an unstabilized terminal oxymethylene copolymer containing compound (1) or 4) is heated to a temperature higher than its melting point, and formaldehyde gas generated by decomposition is discharged from the system. , producing a stabilized oxymethylene copolymer.
加熱温度が下圃より低いと、充分に安定化されたオキシ
メチレン共重合体を得ることができない。If the heating temperature is lower than that of the lower field, a sufficiently stabilized oxymethylene copolymer cannot be obtained.
加熱温度の上累は通常２４５℃である。加熱温度が過度
に高いとオキシメチレン共重合体の主鎖の切断が起こる
よ、うになる。好ましい加熱温度は融点〜融点より８０
℃高い温度の範囲である。The maximum heating temperature is usually 245°C. If the heating temperature is too high, scission of the main chain of the oxymethylene copolymer will occur. The preferred heating temperature is from the melting point to 80°C from the melting point.
℃ higher temperature range.
加熱時間は加熱温度によって種々異なるが、通常１〜６
０分である。The heating time varies depending on the heating temperature, but is usually 1 to 6
It is 0 minutes.
化合物（１）ないしく４）が配合された末端未安定化オ
キシメチレン共重合体を加熱する方法については特に制
限はなく、例えば、所定温度に加熱したヘンシェルミキ
サー、二軸混練機中で不活性ガスを流通させながら攪拌
する方法を採用することができる。There are no particular restrictions on the method of heating the terminal-unstabilized oxymethylene copolymer blended with compound (1) or 4). A method of stirring while flowing gas can be adopted.
（実施例） 以下に実施例を示す。(Example) Examples are shown below.
オキシメチレン共重合体の極限粘度は、２％のα−ピネ
ンを含有するｐ−クロルフェノールを溶媒として６０℃
で測定した。Ａ ｚ２ｚは２２２°Ｃの空気雰囲気中で
の安定化オキシメチレン共重合体の重量減少率（％／分
）である。以下において部はすべて重量部を示す。The intrinsic viscosity of the oxymethylene copolymer is 60°C using p-chlorophenol containing 2% α-pinene as a solvent.
It was measured with A z2z is the weight loss rate (%/min) of the stabilized oxymethylene copolymer in an air atmosphere at 222°C. In the following, all parts indicate parts by weight.
実施例１〜３及び比較例１及び２
１．３．６４リオキソカンから誘導された単位を２．０
５モル％含有する末端未安定化オキシメチレン共重合体
（極限粘度： １．５１ｄｌ／ｇ） １００部に、第
１表に記載の添加剤を配合し、配合物をブラヘンダーに
投入し、２１０°Ｃで窒素流通下に所定時間加熱処理し
た。安定化共重合体の色調はいずれも白色であった。末
端熱不安定部分の分解率及び得られた安定化オキシメチ
レン共重合体の物性を第１表に示す。Examples 1 to 3 and Comparative Examples 1 and 2 1.3.64 units derived from rioxocane to 2.0
Additives listed in Table 1 were blended with 100 parts of an unstabilized terminal oxymethylene copolymer (intrinsic viscosity: 1.51 dl/g) containing 5 mol%, and the blend was placed in a brahender and heated at 210°. C. for a predetermined period of time under nitrogen flow. The stabilized copolymers were all white in color. Table 1 shows the decomposition rate of the terminal thermally unstable moiety and the physical properties of the stabilized oxymethylene copolymer obtained.
（発明の効果）
第１表から明らかなように、本発明によれば短い時間で
未安定化オキシメチレン共重合体の末端熱不安定部分が
、分子量の低下をもたらすことなく、分解除去される。(Effects of the Invention) As is clear from Table 1, according to the present invention, the terminal thermally unstable portion of the unstabilized oxymethylene copolymer can be decomposed and removed in a short period of time without causing a decrease in molecular weight. .
これに対して、公知の方法によると、上記熱不安定部分
の分解除去に長時間を要し、分解率を本発明のそれと同
じレベルにまで高めると安定化オキシメチレン共重合体
の分子量が低下する。In contrast, according to known methods, it takes a long time to decompose and remove the thermally unstable moieties, and when the decomposition rate is increased to the same level as that of the present invention, the molecular weight of the stabilized oxymethylene copolymer decreases. do.
Claims (1)
酸のアルカリ金属塩又はアルカリ土類金属塩、（２）フ
ェノール系抗酸化剤、 （３）アルカリ土類金属の水酸化物、及び （４）三価の有機燐化合物 が配合された配合物を、上記共重合体の融点以上の温度
に加熱することを特徴とするオキシメチレン共重合体の
安定化法。[Scope of Claims] The terminally unstabilized oxymethylene copolymer contains (1) an alkali metal salt or alkaline earth metal salt of nitrilotriacetic acid or ethylenediaminetetraacetic acid, (2) a phenolic antioxidant, and (3) an alkali. Stabilization of an oxymethylene copolymer characterized by heating a mixture containing an earth metal hydroxide and (4) a trivalent organic phosphorus compound to a temperature equal to or higher than the melting point of the copolymer. cation law.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61305224A JPH072893B2 (en) | 1986-12-23 | 1986-12-23 | Method for stabilizing oxymethylene copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61305224A JPH072893B2 (en) | 1986-12-23 | 1986-12-23 | Method for stabilizing oxymethylene copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63159463A true JPS63159463A (en) | 1988-07-02 |
| JPH072893B2 JPH072893B2 (en) | 1995-01-18 |
Family
ID=17942532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61305224A Expired - Lifetime JPH072893B2 (en) | 1986-12-23 | 1986-12-23 | Method for stabilizing oxymethylene copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH072893B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010013519A (en) * | 2008-07-02 | 2010-01-21 | Mitsubishi Gas Chemical Co Inc | Method for producing low-fisheye polyacetal resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5545087A (en) * | 1978-09-27 | 1980-03-29 | Sumitomo Electric Ind Ltd | Optical cable |
| JPS61151220A (en) * | 1984-12-25 | 1986-07-09 | Ube Ind Ltd | Stabilization of oxymethylene copolymer |
-
1986
- 1986-12-23 JP JP61305224A patent/JPH072893B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5545087A (en) * | 1978-09-27 | 1980-03-29 | Sumitomo Electric Ind Ltd | Optical cable |
| JPS61151220A (en) * | 1984-12-25 | 1986-07-09 | Ube Ind Ltd | Stabilization of oxymethylene copolymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010013519A (en) * | 2008-07-02 | 2010-01-21 | Mitsubishi Gas Chemical Co Inc | Method for producing low-fisheye polyacetal resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH072893B2 (en) | 1995-01-18 |
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