JPH04991B2 - - Google Patents
Info
- Publication number
- JPH04991B2 JPH04991B2 JP58008251A JP825183A JPH04991B2 JP H04991 B2 JPH04991 B2 JP H04991B2 JP 58008251 A JP58008251 A JP 58008251A JP 825183 A JP825183 A JP 825183A JP H04991 B2 JPH04991 B2 JP H04991B2
- Authority
- JP
- Japan
- Prior art keywords
- spiroglycol
- present
- lactones
- lactone
- parts
- 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
Links
- 150000002596 lactones Chemical class 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 17
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- -1 ε-caprolactone Chemical class 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 229940108184 stannous iodide Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】
本発明は新規なラクトン重合体の製造方法に関
する。さらに詳しくはスピロ環より構成されたス
ピログリコールを開始剤に用いてラクトン類を開
環重合させることを特徴とする新規なラクトン重
合体の製造方法に関する。
ラクトン重合体はエラストマー、合成皮革等の
ポリウレタン重合体及び塗料等の原料として非常
に有用なものである。しかし、従来から知られて
いるエチレングリコール、ジエチレングリコー
ル、ネオペンチルグリコール等の開始剤を用いて
ラクトン類を開環重合させて得られたラクトン重
合体はいずれも軟かい骨格を有しており、ジイソ
シアネート化合物を反応させてポリウレタン重合
体にした場合、初期モジユラスが低く、弾性はあ
るものの強靭性が不足している欠点がある。
一方、スピログリコールは融点が204℃で、通
常用いられるジオールに比べ非常に融解しにく
い、かつ溶剤に溶けにくい。従つて、スピログリ
コールをポリエステル樹脂、アルキツド樹脂等の
ポリエステル系可塑剤の原料、さらにはポリウレ
タンの鎖延長剤として用いる場合、問題が多い。
本発明者は、これらの欠点を改良すべく鋭意検
討した結果、本発明に到つた。
すなわち、本発明はスピロ環より構成されたス
ピログリコールを開始剤に用いてラクトン類を開
環重合したものである。
本発明は、各種用途分野において強靭性のある
硬い骨格を有するラクトン重合体を提供するもの
である。
すなわち、本発明の新規ラクトン重合体はスピ
ログリコールにラクトン類を開環重合することに
よりスピログリコールの融点を著るしく低下さ
せ、作業性を大きく改良したのみならず、これを
原料にして塗料、ポリウレタン等を合成した場
合、その可撓性、強靭性を著るしく向上させるも
のである。
以下本発明をさらに詳細に説明する。
本発明に使用するラクトン類は環の中に４以
上、好ましくは６またはそれ以上の炭素原子を持
つ。好ましいラクトンは５員環ないし８員環のラ
クトンであり、例えばε−カプロラクトン、８−
バレロラクトン、γ−ブチロラクトン等がある。
又、本発明に用いるスピログリコールは次の式
で示されるものである。
化学名 ３，９ビス（１，１ビスメチル−２−オ
キシメチル）２，４，８，10，テトラサキ
サスピロ〔５，５〕ウンデカン
そして、ラクトン類としてはε−カプロラクト
ンを用いて製造した新規なラクトン重合体は次の
式を示すものである。
（但し、45ｍ＋ｎ≧１）
ラクトン類の重合を開始し、かつ連続的に行な
わせるにはラクトン類と開始剤とを約100〜220
℃、好ましくは160〜180℃に加熱する。あまり高
温にすると熱分解が起り好ましくない。
なお、開環重合にあたつては好ましくは反応促
進の触媒を存在させる。触媒としてはテトラブチ
ルチタネート、テトラプロピルチタネート、テト
ラエチルチタネート等の有機チタン系化合物、オ
クチル酸スズ、ジブチルスズオキサイド、ジブチ
ルスズラウレート等の有機スズ化合物、塩化第１
スズ、臭化第１スズ、ヨウ化第１スズ等のハロゲ
ン化第１スズ等を0.05〜1000ppm、好ましくは、
0.1〜100ppm用いる。
本発明方法により得られるラクトン重合体は両
末端が水酸基である線状重合体であり、分子量は
通常500〜5000程度である。分子量の調節は重合
開始剤と原料ラクトンのモル比を定めることによ
り行なうことができる。
新規なラクトン重合体はポリウレタンの用途と
して熱可塑性ウレタンエラストマー、熱硬化性ウ
レタンエラストマー、ウレタンフオーム、接着
剤、人工皮革、合成皮革塗料等に極めて有利に利
用され得る。
次に実施例を挙げて本発明の説明を行なうが、
これらによつて本発明を限定するものではない。
なお、例中、部はいずれも重量部を示す。
実施例 １
撹拌機、温度計、窒素ガス導入管、コンデンサ
ーのついた四ツ口フラスコ、スピログリコール
（三菱瓦斯化学(株)品）304部、ε−カプロラクトン
696部、テトラブチルチタネート0.02部を仕込み、
170℃で５時間反応させ水酸基価（KOHmg／ｇ）
110.4、酸価（KOHmg／ｇ）0.64、融点37〜40℃
のラクトン重合体を得た。これらのｍ＋ｎは6.2
である。
実施例 ２
実施例１と同様の装置にスピログリコール（三
菱瓦斯化学(株)品）304部、ε−カプロラクトン
1696部、テトラブチルチタネート0.04部を仕込
み、170℃で７時間反応させ水酸基価55.3、酸価
0.66、融点41〜44℃のラクトン重合体を得た。こ
れらのｍ＋ｎは15.1である。
実施例 ３
実施例１と同様の装置にスピログリコール（三
菱瓦斯化学(株)品）304部、ε−カプロラクトン246
部、テトラブチルチタネート0.011部を仕込み、
170℃で４時間反応させ、水酸基価206.7、酸価
0.62、融点87〜90℃のラクトン重合体を得た。こ
れらのｍ＋ｎは2.1である。得られたラクトン重
合体のジメチルホルムアミド溶媒への溶解性は次
の通りである。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing lactone polymers. More specifically, the present invention relates to a novel method for producing a lactone polymer, which is characterized by ring-opening polymerization of lactones using spiroglycol composed of spiro rings as an initiator. Lactone polymers are very useful as raw materials for elastomers, polyurethane polymers such as synthetic leather, and paints. However, all lactone polymers obtained by ring-opening polymerization of lactones using conventionally known initiators such as ethylene glycol, diethylene glycol, and neopentyl glycol have soft skeletons, and diisocyanate When compounds are reacted to form a polyurethane polymer, it has the disadvantage of a low initial modulus and, although it has elasticity, it lacks toughness. On the other hand, spiroglycol has a melting point of 204°C, which makes it much more difficult to melt than commonly used diols, and is also difficult to dissolve in solvents. Therefore, there are many problems when spiroglycol is used as a raw material for polyester plasticizers such as polyester resins and alkyd resins, or as a chain extender for polyurethane. The present inventor has conducted intensive studies to improve these drawbacks, and as a result, has arrived at the present invention. That is, the present invention involves ring-opening polymerization of lactones using spiroglycol composed of spiro rings as an initiator. The present invention provides a lactone polymer having a tough and hard skeleton for various fields of application. That is, the novel lactone polymer of the present invention not only significantly lowers the melting point of spiroglycol by ring-opening polymerization of lactones to spiroglycol and greatly improves workability, but also can be used as a raw material for paints, When polyurethane or the like is synthesized, its flexibility and toughness are significantly improved. The present invention will be explained in more detail below. The lactones used in the invention have 4 or more carbon atoms in the ring, preferably 6 or more. Preferred lactones are 5- to 8-membered ring lactones, such as ε-caprolactone, 8-
Examples include valerolactone and γ-butyrolactone. Further, the spiroglycol used in the present invention is represented by the following formula. Chemical name: 3,9bis(1,1bismethyl-2-oxymethyl)2,4,8,10,tetraxaxaspiro[5,5]undecane And, as a lactone, a new product produced using ε-caprolactone The lactone polymer has the following formula. (However, 45m+n≧1) In order to start and continuously polymerize lactones, the lactones and initiator should be mixed at about 100 to 220
℃, preferably 160-180℃. If the temperature is too high, thermal decomposition will occur, which is not desirable. In the ring-opening polymerization, a catalyst for promoting the reaction is preferably present. Examples of catalysts include organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, organic tin compounds such as tin octylate, dibutyltin oxide, and dibutyltin laurate, and stannous chloride.
0.05 to 1000 ppm of tin, stannous halides such as stannous bromide, stannous iodide, etc., preferably,
Use 0.1-100ppm. The lactone polymer obtained by the method of the present invention is a linear polymer having hydroxyl groups at both ends, and its molecular weight is usually about 500 to 5,000. The molecular weight can be adjusted by determining the molar ratio of the polymerization initiator and the raw material lactone. The new lactone polymer can be extremely advantageously used in polyurethane applications such as thermoplastic urethane elastomers, thermosetting urethane elastomers, urethane foams, adhesives, artificial leathers, and synthetic leather coatings. Next, the present invention will be explained with reference to Examples.
The present invention is not limited to these.
In addition, in the examples, all parts indicate parts by weight. Example 1 Stirrer, thermometer, nitrogen gas inlet tube, four-necked flask with condenser, 304 parts of spiroglycol (Mitsubishi Gas Chemical Co., Ltd.), ε-caprolactone
696 parts, 0.02 parts of tetrabutyl titanate,
React at 170℃ for 5 hours to increase hydroxyl value (KOHmg/g)
110.4, acid value (KOHmg/g) 0.64, melting point 37-40℃
A lactone polymer was obtained. These m+n are 6.2
It is. Example 2 304 parts of spiroglycol (Mitsubishi Gas Chemical Co., Ltd. product) and ε-caprolactone were placed in the same apparatus as in Example 1.
1696 parts and 0.04 parts of tetrabutyl titanate were charged and reacted at 170℃ for 7 hours to obtain a hydroxyl value of 55.3 and an acid value.
A lactone polymer with a melting point of 0.66 and a melting point of 41-44°C was obtained. These m+n is 15.1. Example 3 Into the same apparatus as in Example 1, 304 parts of spiroglycol (Mitsubishi Gas Chemical Co., Ltd.) and 246 parts of ε-caprolactone were added.
and 0.011 parts of tetrabutyl titanate.
Reacted at 170℃ for 4 hours, hydroxyl value 206.7, acid value
A lactone polymer with a melting point of 0.62 and a melting point of 87-90°C was obtained. These m+n is 2.1. The solubility of the obtained lactone polymer in dimethylformamide solvent is as follows. 【table】
Claims (1)
てラクトン類を開環重合させることを特徴とする
新規なラクトン重合体の製造方法。 [Scope of Claims] 1. A novel method for producing a lactone polymer, which comprises carrying out ring-opening polymerization of lactones using spiroglycol shown in the following formula as an initiator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58008251A JPS59135218A (en) | 1983-01-21 | 1983-01-21 | Production of novel lactone polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58008251A JPS59135218A (en) | 1983-01-21 | 1983-01-21 | Production of novel lactone polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59135218A JPS59135218A (en) | 1984-08-03 |
| JPH04991B2 true JPH04991B2 (en) | 1992-01-09 |
Family
ID=11687911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58008251A Granted JPS59135218A (en) | 1983-01-21 | 1983-01-21 | Production of novel lactone polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59135218A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11225573B2 (en) * | 2018-02-26 | 2022-01-18 | Lubrizol Advanced Materials, Inc. | Thermoplastic polyurethane composition |
-
1983
- 1983-01-21 JP JP58008251A patent/JPS59135218A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59135218A (en) | 1984-08-03 |
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