JPH03195728A - Method for purifying polyoxyalkylenepolyol - Google Patents
Method for purifying polyoxyalkylenepolyolInfo
- Publication number
- JPH03195728A JPH03195728A JP33280489A JP33280489A JPH03195728A JP H03195728 A JPH03195728 A JP H03195728A JP 33280489 A JP33280489 A JP 33280489A JP 33280489 A JP33280489 A JP 33280489A JP H03195728 A JPH03195728 A JP H03195728A
- Authority
- JP
- Japan
- Prior art keywords
- polyoxyalkylene polyol
- polyol
- content
- magnesium silicate
- crude
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 45
- 150000003077 polyols Chemical class 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 claims abstract description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 7
- 239000011707 mineral Substances 0.000 claims abstract description 7
- 239000003463 adsorbent Substances 0.000 claims description 14
- 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 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 6
- 238000006386 neutralization reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002745 absorbent Effects 0.000 abstract 2
- 239000002250 absorbent Substances 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- -1 hydrogen compound Chemical class 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002483 hydrogen compounds Chemical class 0.000 description 2
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、アルカリ性触媒の存在下で合成された粗製ポ
リオキシアルキレンポリオールより、アルカリ分が極め
て少ない高品質のポリオキシアルキレンポリオールを得
るための精製法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method for obtaining high-quality polyoxyalkylene polyols with extremely low alkali content than crude polyoxyalkylene polyols synthesized in the presence of alkaline catalysts. It concerns purification methods.
ポリオキシアルキレンリオールは、−最にアルカリ性触
媒存在下、活性水素化合物にアルキレンオキシドを付加
重合させて得られ、ポリウレタンの原料、界面活性剤、
化粧品原料等に広く使用されている。このような方法で
製造されたポリオキシアルキレンポリオールはアルカリ
性触媒を含有しているが、ポリウレタンとする場合のイ
ソシアネート化合物との反応に悪影響を及ぼすため出来
る限り除去することが望ましい。Polyoxyalkyleneliol is obtained by addition-polymerizing alkylene oxide to an active hydrogen compound in the presence of an alkaline catalyst, and is a raw material for polyurethane, a surfactant,
Widely used as a raw material for cosmetics, etc. Although the polyoxyalkylene polyol produced by such a method contains an alkaline catalyst, it is desirable to remove it as much as possible because it has an adverse effect on the reaction with an isocyanate compound when making polyurethane.
ポリオキシアルキレンポリオールからアルカリ性触媒を
除去する精製法として、（１）リン酸、塩酸、硫酸等の
無機酸、酢酸等の有機酸で中和する方法（特公昭３７−
５５９７号公報、特公昭４１−２１２３７号公報）、
（２）合成ケイ酸マグネシウム、合成ケイ酸アルミニウ
ム等で吸着処理する方法（特公昭４２−１３０２１号公
報、特公昭４５−４００６８号公報）、 （３）酸で中
和後、過剰の酸を合成ケイ酸マグネシウム、合成ケイ酸
アルミニウム等で吸着処理する方法（特公昭５７−２２
０５５号公報）等が知られている。As a purification method for removing alkaline catalysts from polyoxyalkylene polyols, (1) method of neutralization with inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid, and organic acids such as acetic acid (Japanese Patent Publication No. 1977-
5597, Special Publication No. 41-21237),
(2) A method of adsorption treatment with synthetic magnesium silicate, synthetic aluminum silicate, etc. (Japanese Patent Publication No. 13021/1972, Japanese Patent Publication No. 40068/1982), (3) Synthesis of excess acid after neutralization with acid. Method of adsorption treatment with magnesium silicate, synthetic aluminum silicate, etc.
No. 055) and the like are known.
しかしながら、（１）の方法では品質面での大幅なばら
つきや製品の濁りを生じやすい。However, method (1) tends to cause large variations in quality and cloudiness of the product.
また、近年はイソシアネート化合物との反応に悪影響を
及ぼすため、極力アルカリ分の少ないポリオキシアルキ
レンポリオールが望まれているが、（２）の方法では触
媒量に比較し多量の吸着剤が必要であり不経済であるだ
けでなく、アルカリ性触媒の除去が不十分であるという
欠点を有する。In addition, in recent years, polyoxyalkylene polyols with as low alkali content as possible have been desired because they have an adverse effect on the reaction with isocyanate compounds, but method (2) requires a large amount of adsorbent compared to the amount of catalyst. Not only is it uneconomical, but it also has the disadvantage of insufficient removal of the alkaline catalyst.
（３）の方法は比較的好ましいが吸着剤から溶出するア
ルカリ分のために未だ満足できる品質のものが得られて
いない。Although method (3) is relatively preferable, it has not yet been possible to obtain a product of satisfactory quality due to the alkali content eluted from the adsorbent.
本発明の目的は、酸で中和したポリオキシアルキレンポ
リオールに含まれる過剰の酸を吸着処理する際に、吸着
剤から溶出するアルカリ分を抑制することにより、アル
カリ分が極めて少なく、ウレタン化反応に悪影響をあた
えることがなく、ウレタン原料としてのすべての用途に
有用であるポリオキシアルキレンポリオールの精製法を
提供することにある。The purpose of the present invention is to suppress the alkaline content eluted from the adsorbent when adsorbing excess acid contained in polyoxyalkylene polyol neutralized with acid, thereby reducing the alkaline content to an extremely low level and facilitating the urethanization reaction. It is an object of the present invention to provide a method for purifying polyoxyalkylene polyol that does not adversely affect the polyoxyalkylene polyol and is useful for all uses as a urethane raw material.
本発明者らは、上記問題点を解決するため鋭意検討した
結果、本発明に到達した。The present inventors have made extensive studies to solve the above problems, and as a result, have arrived at the present invention.
即ち、本発明は、アルカリ性触媒の存在下で合成された
粗製ポリオキシアルキレンポリオールに、鉱酸を加えて
中和後、吸着剤を用いて吸着精製するに際して、吸着剤
としてナトリウム含量が０．５重量％以下の合成ケイ酸
マグネシウムを使用することを特徴とするポリオキシア
ルキレンポリオールの精製法である。That is, in the present invention, when a crude polyoxyalkylene polyol synthesized in the presence of an alkaline catalyst is neutralized by adding a mineral acid and then purified by adsorption using an adsorbent, the sodium content of the adsorbent is 0.5. This is a method for purifying a polyoxyalkylene polyol, characterized in that less than % by weight of synthetic magnesium silicate is used.
本発明により精製される粗製ポリオキシアルキレンポリ
オールは、アルカリ性触媒存在下、活性水素化合物にア
ルキレンオキシドを付加重合させて得られる通常のポリ
オキシアルキレンポリオールである。The crude polyoxyalkylene polyol purified by the present invention is a normal polyoxyalkylene polyol obtained by addition polymerizing an alkylene oxide to an active hydrogen compound in the presence of an alkaline catalyst.
本発明に用い得る活性水素化合物としては、メタノール
、エタノール、ブタノール、オクタツール、ラウリルア
ルコール、ステアリルアルコール等の１価アルコール、
エチレングリコール、ジエチレングリコール、プロピレ
ングリコール、ジプロピレングリコール、１．４−ブタ
ンジオール等の２価アルコール、グリセリン、トリメチ
ロールプロパン、ジグリセリン、ペンタエリスリトール
、ソルビトール、ショ糖等の多価アルコール、エチレン
ジアミン、ジエチレントリアミン等の脂肪族アミン、ア
ニリン、トルエンジアミン、４．４′−ジアミノジフェ
ニルメタン、ポリフェニルポリメチレンポリアミン等の
芳香族アミン、モノエタノールアミン、ジェタノールア
ミン、トリエタノールアミン等のアルカノールアミン、
フェノール、ビスフェノールＡ等のフェノール化合物、
ノボラック樹脂等が挙げられる。これら活性水素化合物
は１種類、または、２種類以上併用して用いることが出
来る。Active hydrogen compounds that can be used in the present invention include monohydric alcohols such as methanol, ethanol, butanol, octatool, lauryl alcohol, and stearyl alcohol;
Dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, polyhydric alcohols such as glycerin, trimethylolpropane, diglycerin, pentaerythritol, sorbitol, sucrose, ethylenediamine, diethylenetriamine, etc. aliphatic amines such as aniline, toluenediamine, 4,4'-diaminodiphenylmethane, polyphenylpolymethylene polyamines, alkanolamines such as monoethanolamine, jetanolamine, triethanolamine,
Phenol compounds such as phenol and bisphenol A,
Examples include novolak resin. These active hydrogen compounds can be used alone or in combination of two or more.
本発明に用い得るアルカリ性触媒としては、水酸化カリ
ウム、水酸化ナトリウム、カリウムアルコラード、ナト
リウムアルコラード、炭酸カリウム、炭酸ナトリウム、
金属カリウム、金属ナトリウム等が挙げられる。Examples of alkaline catalysts that can be used in the present invention include potassium hydroxide, sodium hydroxide, potassium alcolade, sodium alcolade, potassium carbonate, sodium carbonate,
Examples include metallic potassium and metallic sodium.
本発明に用い得るアルキレンオキシドとしては、エチレ
ンオキシド、プロピレンオキシド、１．２−ブチレンオ
キシド、スチレンオキシド、アリルグリシジルエーテル
等が挙げられ、これらは１１１！！、または、２種類以
上併用して用いることが出来る。Examples of alkylene oxides that can be used in the present invention include ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, allyl glycidyl ether, and the like. ! Alternatively, two or more types can be used in combination.
このようにして得られた粗製ポリオキシアルキレンポリ
オールは、添加した量に相当するアルカリ性触媒を含有
しているが、通常は目的とするポリオキシアルキレンポ
リオールに対し０．０５〜１．０重量％である。The crude polyoxyalkylene polyol obtained in this way contains an alkaline catalyst corresponding to the amount added, but usually it is 0.05 to 1.0% by weight based on the target polyoxyalkylene polyol. be.
本発明の好ましい精製法は、上記粗製ポリオキシアルキ
レンポリオールに鉱酸を加えてｐＨ４，５〜７．５にし
た後、吸着剤として市販の合成ケイ酸マグネシウムを、
必要によりあらかじめ水洗処理してナトリウム含量が０
．５重量％以下とし、粗製ポリオキシアルキレンポリオ
ールに対し０．０５〜５重量％使用し、５０〜１５０℃
で吸着処理を行う０次いで濾過することにより精製され
たポリオキシアルキレンポリオールが得られる。A preferred purification method of the present invention is to add a mineral acid to the crude polyoxyalkylene polyol to adjust the pH to 4.5 to 7.5, and then add commercially available synthetic magnesium silicate as an adsorbent.
If necessary, wash with water beforehand to reduce sodium content to 0.
．． 5% by weight or less, 0.05 to 5% by weight based on the crude polyoxyalkylene polyol, and 50 to 150°C.
A purified polyoxyalkylene polyol is obtained by performing an adsorption treatment at 0 and then filtration.
本発明で用いる鉱酸としては、リン酸、塩酸、硫酸、硝
酸、亜硫酸等が挙げられる。その添加量としては、系内
のｐＨが４．５〜７．５になるように添加するのが好ま
しい。Examples of the mineral acids used in the present invention include phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, and sulfurous acid. The amount added is preferably such that the pH within the system is 4.5 to 7.5.
系内のｐＨが７．５を超えたときは、中和が不十分とな
り、アルカリ性触媒が残存してしまう。If the pH in the system exceeds 7.5, neutralization will be insufficient and the alkaline catalyst will remain.
ｐＨ４，５未満のときは、多量の吸着剤が必要となり、
排出されるケーキも多量となり好ましくない。When the pH is less than 4.5, a large amount of adsorbent is required,
A large amount of cake is also discharged, which is not preferable.
本発明で用いる吸着剤としては、ナトリウム含量が０．
５重量％以下の合成ケイ酸マグネシウムである。ナトリ
ウム含量が０．５重量％を超えると、ポリウレタンとす
る場合のイソシアネート化合物との反応に悪影響を及ぼ
す、市販のケイ酸マグネシウムはナトリウム含量が高く
、このまま使用した場合、吸着処理中にナトリウムがポ
リオキシアルキレンポリオール中に溶出するために、ア
ルカリ分が残存してしまう、水洗してナトリウム含量が
０．５重量％以下とした合成ケイ酸マグネシウムを使用
することにより、ポリオキシアルキレンポリオールへの
ナトリウムの溶出はなくなり、アルカリ分の極めて少な
いポリオキシアルキレンポリオールが得られる。The adsorbent used in the present invention has a sodium content of 0.
5% by weight or less of synthetic magnesium silicate. If the sodium content exceeds 0.5% by weight, it will have a negative effect on the reaction with isocyanate compounds when making polyurethane.Commercially available magnesium silicate has a high sodium content, and if used as is, sodium will be absorbed into the polyurethane during the adsorption process. By using synthetic magnesium silicate, which has a residual alkali content due to its elution into the oxyalkylene polyol, the sodium content can be reduced to 0.5% by weight or less by washing with water. Elution is eliminated and a polyoxyalkylene polyol with extremely low alkali content is obtained.
本発明において、合成ケイ酸マグネシウムは、ポリオキ
シアルキレンポリオールに対し０．０５〜５重量％使用
するのが好ましい、さらに好ましくは、０．１〜３重量
％である。 ０．０５重量％未満では、ケーキ量が多く
なるため好ましくない。５重量％を超えると、ポリオキ
シアルキレンボリオールヘナトリウムが溶出する。In the present invention, the synthetic magnesium silicate is preferably used in an amount of 0.05 to 5% by weight, more preferably 0.1 to 3% by weight based on the polyoxyalkylene polyol. If it is less than 0.05% by weight, the amount of cake increases, which is not preferable. If it exceeds 5% by weight, polyoxyalkylene polyol hesodium will be eluted.
吸着処理は５０〜１５０°Ｃで行うのが好ましく、さら
に好ましくは７０〜１２０℃である。５０℃未満では吸
着剤の吸着能が低下し、１５０℃を超えるとポリオキシ
アルキレンポリオールに変性をきたす。The adsorption treatment is preferably carried out at a temperature of 50 to 150°C, more preferably 70 to 120°C. If the temperature is below 50°C, the adsorption capacity of the adsorbent decreases, and if it exceeds 150°C, the polyoxyalkylene polyol will be denatured.
中和により精製した塩、及び吸着剤は、濾過によりポリ
オキシアルキレンポリオールより除去す〔実施例〕
以下、実施例及び比較例を挙げて、本発明について説明
する。The salt purified by neutralization and the adsorbent are removed from the polyoxyalkylene polyol by filtration [Example] The present invention will be described below with reference to Examples and Comparative Examples.
粗製ポリオキシアルキレンポリオールの製造製造例１
２１のオートクレーブにグリセリン３７ｇ、水酸化カリ
ウム３．６ｇを仕込み、窒素置換した後１２０℃に加熱
し、減圧下（５ｓｕ＋Ｈｇ）で２時間脱水を行った。次
に、プロピレンオキシド１１７０ｇを温度１２０°Ｃ１
反応圧力４ ｋｇ／ｃｊＧ以下で徐々に装入し、４時間
反応を行った。得られた粗製ポリオキシアルキレンポリ
オールをポリオールＡとする。Production of Crude Polyoxyalkylene Polyol Production Example 1 37 g of glycerin and 3.6 g of potassium hydroxide were placed in a 21 autoclave, the autoclave was purged with nitrogen, heated to 120°C, and dehydrated under reduced pressure (5su+Hg) for 2 hours. Next, 1170g of propylene oxide was added at a temperature of 120°C1.
The reactor was gradually charged at a reaction pressure of 4 kg/cjG or less, and the reaction was carried out for 4 hours. The obtained crude polyoxyalkylene polyol is referred to as polyol A.
製造例２
２１のオートクレーブにジプロピレングリコール８０ｇ
、水酸化カリウム３．６ｇを仕込み、窒素置換した後、
１２０℃に加熱し、減圧下（５＋ｕ＋Ｈｇ）で２時間脱
水を行ワた０次にプロピレンオキシド１０３０ｇを温度
１２０°Ｃ１反応圧力４ｋｇ／ｄＧ以下で徐々に装入し
、４時間反応を行った後、さらに１２０℃でエチレンオ
キシド１００ｇを装入し１時間反応を行った。得られた
粗製ポリオキシアルキレンポリオールをポリオールＢと
する。Production example 2 80g of dipropylene glycol in 21 autoclave
After charging 3.6 g of potassium hydroxide and purging with nitrogen,
After heating to 120°C and dehydrating for 2 hours under reduced pressure (5+U+Hg), 1030 g of propylene oxide was gradually charged at a temperature of 120°C and a reaction pressure of 4 kg/dG or less, and the reaction was carried out for 4 hours. Then, 100 g of ethylene oxide was charged at 120° C. and the reaction was carried out for 1 hour. The obtained crude polyoxyalkylene polyol is referred to as polyol B.
製造例３
２２のオートクレーブにペンタエリスリトール３２ｇと
水酸化カリウム３ｇを仕込み、窒素置換を行った０次に
、プロピレンオキシド１０００ ｇを温度１２０℃、反
応圧力４ｋｇ／ｃｊＧ以下で徐々に装入し、４時間反応
を行った後、さらに同温度でエチレンオキシド１６８ｇ
を装入し、１時間反応を行った。Production Example 3 32 g of pentaerythritol and 3 g of potassium hydroxide were charged into an autoclave of 22, and the autoclave was replaced with nitrogen. Next, 1000 g of propylene oxide was gradually charged at a temperature of 120°C and a reaction pressure of 4 kg/cjG or less. After carrying out the reaction for an hour, 168 g of ethylene oxide was added at the same temperature.
was charged and the reaction was carried out for 1 hour.
得られた粗製ポリオキシアルキレンポリオールをポリオ
゛−ルＣとする。The obtained crude polyoxyalkylene polyol is referred to as polyol C.
製造例４
２１のオートクレーブにショ糖１９６ ｇ 、グリセリ
ン１３２ｇ、水酸化ナトリウム１．５ｇを仕込み、窒素
置換を行った０次にプロピレンオキシド６７２ｇを温度
１２０℃、反応圧力４ｋｇ／ｃｊＧ以下で徐々に装入し
、５時間反応を行った。得られた粗製ポリオキシアルキ
レンポリオールをポリオールＤとする。Production Example 4 196 g of sucrose, 132 g of glycerin, and 1.5 g of sodium hydroxide were placed in a No. 21 autoclave, and then 672 g of propylene oxide was gradually charged at a temperature of 120°C and a reaction pressure of 4 kg/cjG or less. The reaction was carried out for 5 hours. The obtained crude polyoxyalkylene polyol is referred to as Polyol D.
実施例１〜１２、比較例１〜８
製造例１〜４で得られたポリオールＡ−Ｄを攪拌機、温
度計、窒素導入管を有した２１の四つロフラスコに１０
００ ｇ仕込み、窒素を吹き込みながら攪拌し、８０℃
まで昇温した。同温度で第１表に示す鉱酸を添加し、３
０分攪拌を続けた後、ｐＨを確認した。次に、あらかじ
め水洗処理を行った市販の合成ケイ酸マグネシウム（ナ
トリウム含有量を第１表に示す）を添加し、第１表に示
す温度の減圧下で吸着、及び脱水を４時間行った。生成
した塩、及び吸着剤を濾過により除去し精製ポリオキシ
アルキレンポリオールを得た。結果を第１表に示す。Examples 1 to 12, Comparative Examples 1 to 8 Polyols A-D obtained in Production Examples 1 to 4 were placed in 21 four-bottle flasks equipped with a stirrer, a thermometer, and a nitrogen inlet tube.
00 g, stirred while blowing nitrogen, and heated to 80℃.
The temperature rose to . At the same temperature, add the mineral acids shown in Table 1,
After continuing stirring for 0 minutes, the pH was checked. Next, commercially available synthetic magnesium silicate (sodium content shown in Table 1) which had been previously washed with water was added, and adsorption and dehydration were performed under reduced pressure at the temperatures shown in Table 1 for 4 hours. The generated salt and adsorbent were removed by filtration to obtain a purified polyoxyalkylene polyol. The results are shown in Table 1.
第１表に示す実施例の結果のように、本発明の精製によ
り得られたポリオキシアルキレンポリオールは、アルカ
リ分が非常に少ないが、比較例のように本発明の条件を
はずれた場合、残存アルカリ分は多くなる。As shown in the results of the Examples shown in Table 1, the polyoxyalkylene polyol obtained by the purification of the present invention has a very low alkaline content, but when the conditions of the present invention are deviated as in the comparative example, residual Alkaline content increases.
本発明の方法により精製されたポリオキシアルキレンポ
リオールは、極めてアルカリ分が少ないため、ポリウレ
タンとする場合のイソシアネート化合物との反応に悪影
響を与えることがなく、ウレタン原料としてのすべての
用途に有用である。Since the polyoxyalkylene polyol purified by the method of the present invention has an extremely low alkaline content, it does not adversely affect the reaction with isocyanate compounds when making polyurethane, and is useful for all uses as a urethane raw material. .
Claims (1)
シアルキレンポリオールに、鉱酸を加えて中和後、吸着
剤を用いて吸着精製するに際して、吸着剤としてナトリ
ウム含量が０．５重量％以下の合成ケイ酸マグネシウム
を使用することを特徴とするポリオキシアルキレンポリ
オールの精製法。 ２、粗製ポリオキシアルキレンポリオールの鉱酸による
中和時のｐＨが、４．５〜７．５であることを特徴とす
る請求項１記載のポリオキシアルキレンポリオールの精
製法。 ３、吸着剤として用いる合成ケイ酸マグネシウムの使用
量が、ポリオキシアルキレンポリオールの０．０５〜５
重量％であることを特徴とする請求項１記載のポリオキ
シアルキレンポリオールの精製法。[Claims] 1. When crude polyoxyalkylene polyol synthesized in the presence of an alkaline catalyst is neutralized by adding a mineral acid and then purified by adsorption using an adsorbent, the adsorbent has a sodium content of 0. A method for purifying a polyoxyalkylene polyol, characterized in that .5% by weight or less of synthetic magnesium silicate is used. 2. The method for purifying a polyoxyalkylene polyol according to claim 1, wherein the pH of the crude polyoxyalkylene polyol when neutralized with a mineral acid is 4.5 to 7.5. 3. The amount of synthetic magnesium silicate used as an adsorbent is 0.05 to 5% of the polyoxyalkylene polyol.
The method for purifying polyoxyalkylene polyol according to claim 1, characterized in that the amount is % by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33280489A JPH03195728A (en) | 1989-12-25 | 1989-12-25 | Method for purifying polyoxyalkylenepolyol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33280489A JPH03195728A (en) | 1989-12-25 | 1989-12-25 | Method for purifying polyoxyalkylenepolyol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03195728A true JPH03195728A (en) | 1991-08-27 |
Family
ID=18258988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33280489A Pending JPH03195728A (en) | 1989-12-25 | 1989-12-25 | Method for purifying polyoxyalkylenepolyol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03195728A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06157744A (en) * | 1992-11-18 | 1994-06-07 | Sanyo Chem Ind Ltd | Purification of crude polyoxyalkylene compound |
| US6274777B1 (en) | 1999-12-30 | 2001-08-14 | Chevron Chemical Company Llc | Method for removing boron from polyalkyl hydroxyaromatics |
| US6531571B1 (en) | 2000-09-29 | 2003-03-11 | Chevron Oronite Company Llc | Method for the removal of excess amounts of water-soluble amines from mannich condensation products |
| WO2003051952A1 (en) * | 2001-12-18 | 2003-06-26 | Sanyo Chemical Industries, Ltd. | Polymer and process for producing polymer |
| JP2012131897A (en) * | 2010-12-21 | 2012-07-12 | Tosoh Corp | Method for producing polyalkylene glycol |
| JP2017171708A (en) * | 2016-03-18 | 2017-09-28 | 東ソー株式会社 | Manufacturing method of polyoxyalkylene polyol |
-
1989
- 1989-12-25 JP JP33280489A patent/JPH03195728A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06157744A (en) * | 1992-11-18 | 1994-06-07 | Sanyo Chem Ind Ltd | Purification of crude polyoxyalkylene compound |
| US6274777B1 (en) | 1999-12-30 | 2001-08-14 | Chevron Chemical Company Llc | Method for removing boron from polyalkyl hydroxyaromatics |
| US6531571B1 (en) | 2000-09-29 | 2003-03-11 | Chevron Oronite Company Llc | Method for the removal of excess amounts of water-soluble amines from mannich condensation products |
| WO2003051952A1 (en) * | 2001-12-18 | 2003-06-26 | Sanyo Chemical Industries, Ltd. | Polymer and process for producing polymer |
| GB2399345A (en) * | 2001-12-18 | 2004-09-15 | Sanyo Chemical Ind Ltd | Polymer and process for producing polyer |
| GB2399345B (en) * | 2001-12-18 | 2006-02-01 | Sanyo Chemical Ind Ltd | Polymer and process for producing polymer |
| JP2012131897A (en) * | 2010-12-21 | 2012-07-12 | Tosoh Corp | Method for producing polyalkylene glycol |
| JP2017171708A (en) * | 2016-03-18 | 2017-09-28 | 東ソー株式会社 | Manufacturing method of polyoxyalkylene polyol |
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