JP2997813B2 - Method for producing olefin-terminated polyoxytetramethylene - Google Patents
Method for producing olefin-terminated polyoxytetramethyleneInfo
- Publication number
- JP2997813B2 JP2997813B2 JP2144045A JP14404590A JP2997813B2 JP 2997813 B2 JP2997813 B2 JP 2997813B2 JP 2144045 A JP2144045 A JP 2144045A JP 14404590 A JP14404590 A JP 14404590A JP 2997813 B2 JP2997813 B2 JP 2997813B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- polyoxytetramethylene
- olefin
- amount
- terminal hydroxyl
- 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.)
- Expired - Fee Related
Links
- -1 polyoxytetramethylene Polymers 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 26
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 21
- 150000004703 alkoxides Chemical class 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 150000001336 alkenes Chemical group 0.000 claims description 9
- 150000004820 halides Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 15
- 238000006772 olefination reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
Landscapes
- Polyethers (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明はオレフィン末端ポリオキシテトラメチレンの
製造方法に関する。The present invention relates to a method for producing an olefin-terminated polyoxytetramethylene.
［従来の技術］ ポリオキシテトラメチレンは、耐熱性、耐候性及び機
械特性に優れているところから、熱可塑性エラストマ
ー、ポリウレタンエラストマー等の成分として利用され
ている。[Prior Art] Polyoxytetramethylene is used as a component of thermoplastic elastomers, polyurethane elastomers and the like because of its excellent heat resistance, weather resistance and mechanical properties.
通常、ポリオキシテトラメチレンは、その末端の水酸
基を利用してウレタン結合やエステル結合等を形成させ
ること等により利用されているが、この水酸基を他の官
能基に変性することによりポリオキシテトラメチレンの
利用範囲が広がり、各種用途への適用が考えられる。特
に、末端をオレフィンとしたものは反応性に富み、利用
範囲が広いところから、有用である。Usually, polyoxytetramethylene is used by forming a urethane bond or an ester bond by utilizing a hydroxyl group at the terminal, and the like, but by modifying this hydroxyl group to another functional group, polyoxytetramethylene is used. The range of use is expanded, and application to various applications is conceivable. In particular, those having an olefin at the terminal are useful because they have high reactivity and a wide range of use.
ポリオキシテトラメチレンの末端水酸基をオレフィン
とするには、ポリプロピレングリコールの場合と同様に
行なうことが考えられる。In order to make the terminal hydroxyl group of polyoxytetramethylene an olefin, it is conceivable to carry out in the same manner as in the case of polypropylene glycol.
ポリプロピレングリコールの末端水酸基をオレフィン
とするには、通常、ナトリウムメトキシドのような金属
アルコキシドを使用し、脱メタノールを行なう平衡反応
により末端の水酸基をナトリウムアルコキシドにした後
に、オレフィン基を有するハロゲン化物、例えば塩化ア
リル等を反応させてオレフィン基を導入する方法がとら
れている。In order to make the terminal hydroxyl group of the polypropylene glycol an olefin, usually, a metal alkoxide such as sodium methoxide is used. For example, a method of introducing an olefin group by reacting allyl chloride or the like is employed.
［発明が解決しようとする課題］ しかし、この方法をそのままポリオキシテトラメチレ
ン末端のオレフィン化に適用すると、アルコキシド化さ
れた中間生成物の粘度が高いため反応系内の粘度が上昇
し、脱メタノールが充分に行なえず、以後の反応を充分
に進行させることができないという問題があった。[Problems to be Solved by the Invention] However, when this method is applied to olefination of a polyoxytetramethylene terminal as it is, the viscosity of the reaction system increases due to the high viscosity of the alkoxided intermediate product, and the methanol removal occurs. However, there has been a problem that the reaction cannot be carried out sufficiently and the subsequent reaction cannot proceed sufficiently.
本発明の課題は、アルコキシド化における反応系内の
粘度上昇を防ぐとともに、以後の反応を充分に進行さ
せ、オレフィン化率の高いオレフィン末端ポリオキシテ
トラメチレンの製造方法を提供する処にある。An object of the present invention is to provide a method for producing an olefin-terminated polyoxytetramethylene having a high olefination rate while preventing the viscosity in the reaction system from increasing in the alkoxide formation and allowing the subsequent reaction to proceed sufficiently.
［課題を解決するための手段及び作用］ 本発明の製造方法は、ポリオキシテトラメチレンの末
端の水酸基を金属アルコキシドによりアルコキシド化反
応した後に一般式（１）で示されるハロゲン化物を反応
させてオレフィン基を導入するにあたって、反応を２回
以上に分割して行なうことを特徴とする。[Means and Actions for Solving the Problems] In the production method of the present invention, the hydroxyl group at the terminal of polyoxytetramethylene is subjected to an alkoxide conversion reaction with a metal alkoxide, and then the olefin is reacted with a halide represented by the general formula (1). The introduction of the group is characterized in that the reaction is carried out two or more times.
ＸCH2 nCH＝CH2 ……（１） （式中、Ｘは塩素、臭素、沃素のいずれかを示す。ｎは
１〜８の整数を示す。） 本発明で用いる金属アルコキシドとしては特に限定は
ないが、アルコキシド化反応で生じるアルコールを減圧
系で系外へ取り除くことにより反応が進行するため、対
応するアルコールが低沸点であることが望ましく、メト
キシド系、エトキシド系が好ましい。また、金属として
は、反応性やコストの面からナトリウム、カリウムが好
ましい。とくに、実用上はナトリウムメトキシドが好ま
しく、通常はナトリウムメトキシドの28重量％程度のメ
タノール溶液が使用できる。 XCH 2 n CH = CH 2 ...... (1) ( wherein, X is chlorine, bromine, .n indicating one of iodine is an integer of 1-8.) Particularly limited metal alkoxide used in the present invention However, since the reaction proceeds by removing the alcohol generated in the alkoxidation reaction to the outside of the system by a reduced pressure system, the corresponding alcohol preferably has a low boiling point, and a methoxide system and an ethoxide system are preferable. As the metal, sodium and potassium are preferable from the viewpoint of reactivity and cost. In particular, sodium methoxide is preferred for practical use, and a methanol solution of about 28% by weight of sodium methoxide can be used.
一般式（１）で示されるハロゲン化物の具体例として
は、塩化アリル、臭化アリル、ヨウ化アリル、４−塩化
ブテン、４−臭化ブテン、４−ヨウ化ブテン、５−塩化
ペンテン、５−臭化ペンテン、５−ヨウ化ペンテン、６
−塩化ヘキセン、６−臭化ヘキセン、６−ヨウ化ヘキセ
ン、７−塩化ヘプテン、７−臭化ヘプテン、７−ヨウ化
ヘプテン、８−塩化オクテン、８−臭化オクテン、８−
ヨウ化オクテン、９−塩化ノネン、９−臭化ノネン、９
−ヨウ化ノネン、10−塩化デセン、10−臭化デセン、10
−ヨウ化デセン等があげられる。Specific examples of the halide represented by the general formula (1) include allyl chloride, allyl bromide, allyl iodide, 4-butene chloride, 4-bromide butene, 4-iodine butene, 5-pentene chloride, and -Bromide pentene, 5-iodide pentene, 6
-Hexene chloride, 6-hexene bromide, 6-hexene iodide, 7-heptene chloride, 7-heptene bromide, 7-heptene iodide, 8-octene chloride, 8-octene bromide, 8-
Octene iodide, 9-nonene chloride, 9-nonene bromide, 9
-Nonene iodide, 10-decene chloride, 10-decene bromide, 10
-Decene iodide and the like.
反応に使用される金属アルコキシドの量は、原料のポ
リオキシテトラメチレンの水酸基量に対して、トータル
として0.8〜2.0倍当量が好ましく、1.0〜1.5倍当量がさ
らに好ましい。反応は２回以上に分割して行なうが、好
ましくは３〜６回に分割して行なう。一回の反応には、
金属アルコキシドを0.1〜0.8倍当量使用するのが好まし
い。The total amount of the metal alkoxide used in the reaction is preferably 0.8 to 2.0 equivalents, more preferably 1.0 to 1.5 equivalents, based on the amount of hydroxyl groups of the raw material polyoxytetramethylene. The reaction is carried out in two or more portions, preferably in three to six portions. For one reaction,
It is preferable to use 0.1 to 0.8 equivalent of the metal alkoxide.
アルコキシド化反応は、ポリオキシテトラメチレンに
所定量の金属アルコキシドを投入して80〜150℃に加熱
し、生じるアルコールを減圧下で系外へ留出させること
により進行する。この時、ポリオキシテトラメチレンの
水酸基に対して金属アルコキシドの量が多いと、粘度の
高いアルコキシド化物が多量に生成して反応系内の粘度
が上昇し、生じるアルコールを充分に系外へ取り出すこ
とができなくなる。そこで、反応を２回以上に分割し
て、原料のポリオキシテトラメチレンの水酸基の一部を
まずアルコキシド化し、これに一般式（１）で示される
ハロゲン化物を投入した後に30分〜１時間程度撹拌する
ことによりアルコキシド化物をオレフィン化する。The alkoxide conversion reaction proceeds by charging a predetermined amount of metal alkoxide to polyoxytetramethylene, heating the mixture to 80 to 150 ° C., and distilling off the resulting alcohol under reduced pressure. At this time, if the amount of the metal alkoxide is large relative to the hydroxyl group of the polyoxytetramethylene, a large amount of a high-viscosity alkoxide is generated, the viscosity in the reaction system is increased, and the generated alcohol is sufficiently taken out of the system. Can not be done. Therefore, the reaction is divided into two or more times, a part of the hydroxyl group of the raw material polyoxytetramethylene is first alkoxide-converted, and the halide represented by the general formula (1) is added thereto, and after about 30 minutes to 1 hour The alkoxide is olefinated by stirring.
このオレフィン化が終了した後に、ふたたびアルコキ
シド化反応とオレフィン化反応を繰り返すことにより、
反応系内の粘度の上昇を防ぐことができ、オレフィン化
率の高いオレフィン末端ポリオキシテトラメチレンを得
ることができる。一般式（１）のハロゲン化物はアルコ
キシド化物に対して少し過剰に投入するのが好ましく、
未反応のハロゲン化物は、オレフィン化反応終了後、次
のアルコキシド化の前に、減圧により取り除いておく必
要がある。After this olefination is completed, by repeating the alkoxidation reaction and the olefination reaction again,
An increase in viscosity in the reaction system can be prevented, and an olefin-terminated polyoxytetramethylene having a high olefination rate can be obtained. The halide of the general formula (1) is preferably introduced in a slightly excessive amount relative to the alkoxide.
Unreacted halides must be removed by reduced pressure after the olefination reaction and before the next alkoxidation.
なお、本発明による方法は、分子量の大きいポリオキ
シテトラメチレンを原料とする場合において効果的であ
り、特に2,000以上の数平均分子量のものについて効果
的である。The method according to the present invention is effective when polyoxytetramethylene having a large molecular weight is used as a raw material, and is particularly effective for those having a number average molecular weight of 2,000 or more.
本発明によって得られたオレフィン末端ポリオキシテ
トラメチレンは、そのまま共重合成分として用いること
もできるし、各種ポリマーの可塑剤や変性剤として用い
ることができる。また、末端のオレフィンを他の官能基
に変性させて用いることもできる。例えば、加水分解性
基を有するシランをヒドロシリル化反応により付加させ
て室温硬化性樹脂を得ることもできる。The olefin-terminated polyoxytetramethylene obtained by the present invention can be used as it is as a copolymerization component, or can be used as a plasticizer or a modifier for various polymers. Further, the terminal olefin may be used after being modified to another functional group. For example, a room temperature curable resin can be obtained by adding a silane having a hydrolyzable group by a hydrosilylation reaction.
［発明の効果］ 本発明の製造方法によれば、オレフィン化率の高いオ
レフィン末端ポリオキシテトラメチレンを容易に得るこ
とができる。[Effect of the Invention] According to the production method of the present invention, an olefin-terminated polyoxytetramethylene having a high olefination rate can be easily obtained.
［実施例］ 本発明をより一層明らかにするために以下に実施例を
掲げる。[Examples] In order to further clarify the present invention, examples will be given below.
実施例１ 数平均分子量4,000のポリオキシテトラメチレン500g
を１オートクレーブに計りとり、トルエン500mlを加
え共沸脱水によりポリマー中の水分を取り除いた。これ
を原料として、以下に示すようにアルコキシド化反応と
オレフィン化反応をそれぞれ３回繰り返した。Example 1 500 g of polyoxytetramethylene having a number average molecular weight of 4,000
Was weighed into one autoclave, 500 ml of toluene was added, and water in the polymer was removed by azeotropic dehydration. Using this as a raw material, an alkoxidation reaction and an olefination reaction were repeated three times as shown below.
第一回目の反応： ナトリウムメトキシドの28重量％メタノール溶液29g
（原料のポリオキシテトラメチレンの末端水酸基量に対
して0.6倍当量）を加え、120℃で４時間、減圧下（0.1
〜1.0mmHg）で撹拌しながら脱メタノールを行なった。
次に、温度を100℃まで下げた後に塩化アリル15ml（原
料のポリオキシテトラメチレンの末端水酸基量に対して
0.74倍当量）を加え、１時間撹拌反応した。反応終了
後、減圧にして未反応の塩化アリルを取り除いた。First reaction: 29 g of a 28% by weight methanol solution of sodium methoxide
(0.6 equivalents to the amount of terminal hydroxyl groups of the raw material polyoxytetramethylene) and added under reduced pressure (0.1
メ タ ノ ー ル 1.0 mmHg) while stirring to remove methanol.
Next, after lowering the temperature to 100 ° C., 15 ml of allyl chloride (based on the amount of terminal hydroxyl groups of the raw material polyoxytetramethylene)
(0.74 equivalent) was added and the mixture was stirred and reacted for 1 hour. After completion of the reaction, the pressure was reduced to remove unreacted allyl chloride.
第二回目の反応： ナトリウムメトキシドの28重量％メタノール溶液14.5
g（当初の末端水酸基量に対して0.3倍当量）を加え、12
0℃で４時間、減圧下（0.1〜1.0mmHg）で撹拌しながら
脱メタノールを行なった。次に、温度を100℃まで下げ
た後に塩化アリル8ml（当初の末端水酸基量に対して0.3
9倍当量）を加え、１時間撹拌反応した。反応終了後、
減圧にして未反応の塩化アリルを取り除いた。Second reaction: 14.5% by weight of sodium methoxide in 28% methanol solution
g (0.3 equivalents to the initial amount of terminal hydroxyl groups) and add 12
The methanol was removed at 0 ° C. for 4 hours while stirring under reduced pressure (0.1 to 1.0 mmHg). Next, after lowering the temperature to 100 ° C., 8 ml of allyl chloride (0.3 ml based on the initial amount of terminal hydroxyl groups).
(9 equivalents), and the mixture was stirred and reacted for 1 hour. After the reaction,
The pressure was reduced to remove unreacted allyl chloride.
第三回目の反応： ナトリウムメトキシドの28重量％メタノール溶液14.5
g（当初の末端水酸基量に対して0.3倍当量）を加え、12
0℃で４時間、減圧下（0.1〜1.0mmHg）で撹拌しながら
脱メタノールを行なった。次に、温度を100℃まで下げ
た後に塩化アリル10ml（当初の末端水酸基量に対して0.
49倍当量）を加え、１時間撹拌反応した。反応終了後、
減圧にして未反応の塩化アリルを取り除いた。Third reaction: 14.5% by weight of sodium methoxide in 28% methanol solution
g (0.3 equivalent of the initial amount of terminal hydroxyl groups) and add 12
The methanol was removed at 0 ° C. for 4 hours while stirring under reduced pressure (0.1 to 1.0 mmHg). Next, after lowering the temperature to 100 ° C., 10 ml of allyl chloride (0.1 ml based on the initial amount of terminal hydroxyl groups).
(49 equivalents) was added thereto, and the mixture was stirred and reacted for 1 hour. After the reaction,
The pressure was reduced to remove unreacted allyl chloride.
次に、トルエン300mlとケイ酸アルミニウム50gを加
え、30分撹拌して塩を吸着させた後に濾過助材を使用し
て濾過精製し、トルエンを減圧系で取り除いてオレフィ
ン末端ポリオキシテトラメチレンを得た。Next, 300 ml of toluene and 50 g of aluminum silicate were added, and the mixture was stirred for 30 minutes to adsorb the salt, followed by filtration and purification using a filter aid, and toluene was removed under reduced pressure to obtain an olefin-terminated polyoxytetramethylene. Was.
実施例２ 数平均分子量4,000のポリオキシテトラメチレン500g
を１オートクレーブに計りとり、トルエン50mlを加え
共沸脱水によりポリマー中の水分を取り除いた。これを
原料として、以下に示すようにアルコキシド化反応とオ
レフィン化反応をそれぞれ３回繰り返した。Example 2 500 g of polyoxytetramethylene having a number average molecular weight of 4,000
Was weighed in one autoclave, 50 ml of toluene was added, and water in the polymer was removed by azeotropic dehydration. Using this as a raw material, an alkoxidation reaction and an olefination reaction were repeated three times as shown below.
第一回目の反応： ナトリウムメトキシドの28重量％メタノール溶液29g
（原料のポリオキシテトラメチレンの末端水酸基量に対
して0.6倍当量）を加え、120℃で４時間、減圧下（0.1
〜1.0mmHg）で撹拌しながら脱メタノールを行なった。
次に、温度を100℃まで下げた後に塩化アリル15ml（原
料のポリオキシテトラメチレンの末端水酸基量に対して
0.74倍当量）を加え、１時間撹拌反応した。反応終了
後、減圧にして未反応の塩化アリルを取り除いた。First reaction: 29 g of a 28% by weight methanol solution of sodium methoxide
(0.6 equivalents to the amount of terminal hydroxyl groups of the raw material polyoxytetramethylene) and added under reduced pressure (0.1
メ タ ノ ー ル 1.0 mmHg) while stirring to remove methanol.
Next, after lowering the temperature to 100 ° C., 15 ml of allyl chloride (based on the amount of terminal hydroxyl groups of the raw material polyoxytetramethylene)
(0.74 equivalent) was added and the mixture was stirred and reacted for 1 hour. After completion of the reaction, the pressure was reduced to remove unreacted allyl chloride.
第二回目の反応： ナトリウムメトキシドの28重量％メタノール溶液14.5
g（当初の末端水酸基量に対して0.3倍当量）を加え、12
0℃で４時間、減圧下（0.1〜1.0mmHg）で撹拌しながら
脱メタノールを行なった。次に、温度を100℃まで下げ
た後に塩化アリル8ml（当初の末端水酸基量に対して0.3
9倍当量）を加え、１時間撹拌反応した。反応終了後、
減圧にして未反応の塩化アリルを取り除いた。Second reaction: 14.5% by weight of sodium methoxide in 28% methanol solution
g (0.3 equivalent of the initial amount of terminal hydroxyl groups) and add 12
The methanol was removed at 0 ° C. for 4 hours while stirring under reduced pressure (0.1 to 1.0 mmHg). Next, after lowering the temperature to 100 ° C., 8 ml of allyl chloride (0.3 ml with respect to the initial amount of terminal hydroxyl groups).
(9 equivalents), and the mixture was stirred and reacted for 1 hour. After the reaction,
The pressure was reduced to remove unreacted allyl chloride.
第三回目の反応： ナトリウムメトキシドの28重量％メタノール溶液29g
（当初の末端水酸基量に対して0.6倍当量）を加え、120
℃で４時間、減圧下（0.1〜1.0mmHg）で撹拌しながら脱
メタノールを行なった。次に、温度を100℃まで下げた
後に塩化アリル20ml（当初の末端水酸基量に対して0.99
倍当量）を加え、１時間撹拌反応した。反応終了後、減
圧にして未反応の塩化アリルを取り除いた。Third reaction: 29 g of a 28% by weight methanol solution of sodium methoxide
(0.6 equivalents to the initial amount of terminal hydroxyl groups) and add 120
De-methanol was performed while stirring under reduced pressure (0.1 to 1.0 mmHg) at 4 ° C for 4 hours. Next, after lowering the temperature to 100 ° C., 20 ml of allyl chloride (0.99 parts with respect to the initial amount of terminal hydroxyl groups).
(Equivalent to twice the equivalent) was added and the mixture was stirred and reacted for 1 hour. After completion of the reaction, the pressure was reduced to remove unreacted allyl chloride.
次に、トルエン300mlとケイ酸アルミニウム50gを加
え、30分撹拌して塩を吸着させた後に濾過助材を使用し
て濾過精製し、トルエンを減圧系で取り除いてオレフィ
ン末端ポリオキシテトラメチレンを得た。Next, 300 ml of toluene and 50 g of aluminum silicate were added, and the mixture was stirred for 30 minutes to adsorb the salt, followed by filtration and purification using a filter aid, and toluene was removed under reduced pressure to obtain an olefin-terminated polyoxytetramethylene. Was.
実施例３ 数平均分子量4,000のポリオキシテトラメチレン500g
を１オートクレーブに計りとり、トルエン50mlを加え
共沸脱水によりポリマー中の水分を取り除いた。これを
原料として、以下に示すようにアルコキシド化反応とオ
レフィン化反応をそれぞれ２回繰り返した。Example 3 500 g of polyoxytetramethylene having a number average molecular weight of 4,000
Was weighed in one autoclave, 50 ml of toluene was added, and water in the polymer was removed by azeotropic dehydration. Using this as a raw material, an alkoxidation reaction and an olefination reaction were each repeated twice as shown below.
第一回目の反応： ナトリウムメトキシドの28重量％メタノール溶液29g
（原料のポリオキシテトラメチレンの末端水酸基量に対
して0.6倍当量）を加え、120℃で４時間、減圧下（0.1
〜1.0mmHg）で撹拌しながら脱メタノールを行なった。
次に、温度を100℃まで下げた後に塩化アリル15ml（原
料のポリオキシテトラメチレンの末端水酸基量に対して
0.74倍当量）を加え、１時間撹拌反応した。反応終了
後、減圧にして未反応の塩化アリルを取り除いた。First reaction: 29 g of a 28% by weight methanol solution of sodium methoxide
(0.6 equivalents to the amount of terminal hydroxyl groups of the raw material polyoxytetramethylene) and added under reduced pressure (0.1
メ タ ノ ー ル 1.0 mmHg) while stirring to remove methanol.
Next, after lowering the temperature to 100 ° C., 15 ml of allyl chloride (based on the amount of terminal hydroxyl groups of the raw material polyoxytetramethylene)
(0.74 equivalent) was added and the mixture was stirred and reacted for 1 hour. After completion of the reaction, the pressure was reduced to remove unreacted allyl chloride.
第二回目の反応： ナトリウムメトキシドの28重量％メタノール溶液29g
（当初の末端水酸基量に対して0.6倍当量）を加え、120
℃で４時間、減圧下（0.1〜1.0mmHg）で撹拌しながら脱
メタノールを行なった。次に、温度を100℃まで下げた
後に塩化アリル20ml（当初の末端水酸基量に対して0.99
倍当量）を加え、１時間撹拌反応した。反応終了後、減
圧にして未反応の塩化アリルを取り除いた。2nd reaction: 29 g of a 28% by weight methanol solution of sodium methoxide
(0.6 equivalents to the initial amount of terminal hydroxyl groups) and add 120
De-methanol was performed while stirring under reduced pressure (0.1 to 1.0 mmHg) at 4 ° C for 4 hours. Next, after lowering the temperature to 100 ° C., 20 ml of allyl chloride (0.99 parts with respect to the initial amount of terminal hydroxyl groups).
(Equivalent to twice the equivalent) was added and the mixture was stirred and reacted for 1 hour. After completion of the reaction, the pressure was reduced to remove unreacted allyl chloride.
次に、トルエン300mlとケイ酸アルミニウム50gを加
え、30分撹拌して塩を吸着させた後に濾過助材を使用し
て濾過精製し、トルエンを減圧系で取り除いてオレフィ
ン末端ポリオキシテトラメチレンを得た。Next, 300 ml of toluene and 50 g of aluminum silicate were added, and the mixture was stirred for 30 minutes to adsorb the salt, followed by filtration and purification using a filter aid, and toluene was removed under reduced pressure to obtain an olefin-terminated polyoxytetramethylene. Was.
比較例１ 数平均分子量4,000のポリオキシテトラメチレン500g
を１オートクレーブに計りとり、トルエン50mlを加え
共沸脱水によりポリマー中の水分を取り除いた。Comparative Example 1 500 g of polyoxytetramethylene having a number average molecular weight of 4,000
Was weighed in one autoclave, 50 ml of toluene was added, and water in the polymer was removed by azeotropic dehydration.
これに、ナトリウムメトキシドの28重量％メタノール
溶液72.5g（原料のポリオキシテトラメチレンの末端水
酸基量に対して1.5倍当量）を加え、120℃で６時間、減
圧下（0.1〜1.0mmHg）で撹拌しながら脱メタノールを行
なった。次に、温度を100℃まで下げた後に塩化アリル3
8ml（原料のポリオキシテトラメチレンの末端水酸基量
に対して1.87倍当量）を加え、１時間撹拌反応した。反
応終了後、減圧にして未反応の塩化アリルを取り除い
た。To this, 72.5 g of a 28% by weight methanol solution of sodium methoxide (1.5 times equivalent to the amount of terminal hydroxyl groups of the raw material polyoxytetramethylene) was added, and the mixture was heated at 120 ° C. for 6 hours under reduced pressure (0.1 to 1.0 mmHg). The methanol was removed while stirring. Next, after lowering the temperature to 100 ° C., allyl chloride 3
8 ml (1.87 equivalents to the amount of terminal hydroxyl groups of the raw material polyoxytetramethylene) was added, and the mixture was stirred and reacted for 1 hour. After completion of the reaction, the pressure was reduced to remove unreacted allyl chloride.
次に、トルエン300mlとケイ酸アルミニウム50gを加
え、30分撹拌して塩を吸着させた後に濾過助材を使用し
て濾過精製し、トルエンを減圧系で取り除いてオレフィ
ン末端ポリオキシテトラメチレンを得た。Next, 300 ml of toluene and 50 g of aluminum silicate were added, and the mixture was stirred for 30 minutes to adsorb the salt, followed by filtration and purification using a filter aid, and toluene was removed under reduced pressure to obtain an olefin-terminated polyoxytetramethylene. Was.
以上の実施例１〜３および比較例１において、それぞ
れのアルコキシド化反応の終了時にサンプリングを行な
い、Ｅ型粘度計により50℃における粘度を測定した。表
−１にその結果を示す。In Examples 1 to 3 and Comparative Example 1, sampling was performed at the end of each alkoxidation reaction, and the viscosity at 50 ° C. was measured with an E-type viscometer. Table 1 shows the results.
また、実施例１〜３および比較例１において得られた
オレフィン末端ポリオキシテトラメチレンにおける末端
のオレフィン化率を300MHzのNMRを用いて、主鎖部分の
メチレン水素と末端オレフィン水素との積分値より算出
した。表−２にその結果を示す。Further, the olefination rate of the terminal in the olefin-terminated polyoxytetramethylene obtained in Examples 1 to 3 and Comparative Example 1 was determined by using the NMR of 300 MHz from the integrated value of the methylene hydrogen in the main chain portion and the terminal olefin hydrogen. Calculated. Table 2 shows the results.
表−１および表−２より明らかなように、反応を分割
して行なうことにより、反応系内の粘度の上昇を防ぐこ
とができ、オレフィン化率の高いオレフィン末端ポリオ
キシテトラメチレンを得ることができた。 As is clear from Tables 1 and 2, by performing the reaction in a divided manner, an increase in viscosity in the reaction system can be prevented, and an olefin-terminated polyoxytetramethylene having a high olefin conversion can be obtained. did it.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−218632（ＪＰ，Ａ) 特開 昭61−215623（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 65/00 - 65/48 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-61-218632 (JP, A) JP-A-61-215623 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08G 65/00-65/48
Claims (4)
を金属アルコキシドによりアルコキシド化反応した後に
下記一般式（１）で示されるハロゲン化物を反応させて
オレフィン基を導入するにあたって、反応を２回以上に
分割して行なうことを特徴とするオレフィン末端ポリオ
キシテトラメチレンの製造方法。 ＸCH2 nCH＝CH2 ……（１） （式中、Ｘは塩素、臭素、沃素のいずれかを示す。ｎは
１〜８の整数を示す。）1. An alkoxide conversion reaction of a terminal hydroxyl group of polyoxytetramethylene with a metal alkoxide, followed by reacting a halide represented by the following general formula (1) to introduce an olefin group, the reaction is performed twice or more. A process for producing an olefin-terminated polyoxytetramethylene, which is carried out in a divided manner. XCH 2 n CH = CH 2 ...... (1) ( wherein, X represents chlorine, bromine, an integer of .n 1-8 indicating either iodine.)
ルコキシドの量が、原料のポリオキシテトラメチレンの
水酸基量に対して0.1〜0.8倍当量であることを特徴とす
る請求項１記載の製造方法。2. The method according to claim 1, wherein the amount of the metal alkoxide used in one alkoxidation reaction is 0.1 to 0.8 times equivalent to the amount of hydroxyl group of the raw material polyoxytetramethylene. .
であることを特徴とする請求項１又は２に記載の製造方
法。3. The method according to claim 1, wherein the metal alkoxide is sodium methoxide.
化アリル又は臭化アリルであることを特徴とする請求項
１〜３のいずれか１項に記載の製造方法。4. The method according to claim 1, wherein the halide represented by the general formula (1) is allyl chloride or allyl bromide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2144045A JP2997813B2 (en) | 1990-05-31 | 1990-05-31 | Method for producing olefin-terminated polyoxytetramethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2144045A JP2997813B2 (en) | 1990-05-31 | 1990-05-31 | Method for producing olefin-terminated polyoxytetramethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0436312A JPH0436312A (en) | 1992-02-06 |
| JP2997813B2 true JP2997813B2 (en) | 2000-01-11 |
Family
ID=15353043
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2144045A Expired - Fee Related JP2997813B2 (en) | 1990-05-31 | 1990-05-31 | Method for producing olefin-terminated polyoxytetramethylene |
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| Country | Link |
|---|---|
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|---|---|---|---|---|
| JP4910249B2 (en) * | 2001-06-22 | 2012-04-04 | 株式会社カネカ | Method for alkoxideizing polyether polyols |
| JP7285248B2 (en) * | 2018-04-16 | 2023-06-01 | 株式会社カネカ | Method for producing polyether |
| WO2019203234A1 (en) * | 2018-04-18 | 2019-10-24 | 株式会社カネカ | Method for producing polyether |
| CN114656629A (en) * | 2022-04-13 | 2022-06-24 | 江苏瑞洋安泰新材料科技有限公司 | Preparation method of diallyl-terminated polyether |
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1990
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| Publication number | Publication date |
|---|---|
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