JPH0562891B2 - - Google Patents
Info
- Publication number
- JPH0562891B2 JPH0562891B2 JP60283980A JP28398085A JPH0562891B2 JP H0562891 B2 JPH0562891 B2 JP H0562891B2 JP 60283980 A JP60283980 A JP 60283980A JP 28398085 A JP28398085 A JP 28398085A JP H0562891 B2 JPH0562891 B2 JP H0562891B2
- Authority
- JP
- Japan
- Prior art keywords
- lactone
- lactones
- hydroxypiperidine
- tetramethyl
- hydroxyethyl
- 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 - Lifetime
Links
- 150000002596 lactones Chemical class 0.000 claims description 20
- 150000002009 diols Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KKZZSTCINUMTGD-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidin-4-ol Chemical compound CC1C(O)CCN(C)C1(C)C KKZZSTCINUMTGD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001412 amines Chemical group 0.000 description 3
- 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 3
- 238000000034 method Methods 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000000126 substance 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 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
- 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
- DXTCRSXRMZSEQP-UHFFFAOYSA-N 2-benzofuran-1,3-dione;pyridine Chemical compound C1=CC=NC=C1.C1=CC=C2C(=O)OC(=O)C2=C1 DXTCRSXRMZSEQP-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- -1 alkylene glycol Chemical compound 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 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
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000728 polyester Polymers 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
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229940108184 stannous iodide Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規なラクトン変性ジオールに関する
ものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel lactone-modified diol.
さらに詳しくは、１−（2′−ヒドロキシエチル）
−２，２，６，６，テトラメチル−４−ヒドロキ
シピペリジン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耐候性に優れた新規
なラクトン重合体に関するものである。 More specifically, 1-(2'-hydroxyethyl)
The present invention relates to a novel lactone polymer having excellent weather resistance, which is characterized by ring-opening polymerization of lactones using -2,2,6,6,tetramethyl-4-hydroxypiperidine as an initiator.
ラクトン重合体はエラストマー、接着剤、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。 Lactone polymers are very useful as raw materials for elastomers, adhesives, polyurethane polymers such as synthetic leather, and paints.
又、ポリエステル樹脂、ポリカーポネート樹
脂、ポリ塩化ビニール樹脂、アクリロニトリル−
スチレン系樹脂等の強靱性、加工性等を付与する
ための改質剤及びウレタンアクリル樹脂原料等に
利用されている。 Also, polyester resin, polycarbonate resin, polyvinyl chloride resin, acrylonitrile
It is used as a modifier for imparting toughness and processability to styrene resins, etc., and as raw materials for urethane acrylic resins.
（従来技術）
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、１，４ブタンジオール、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
ン重合体とジイソシアネート化合物を反応させて
得られたポリウレタン重合体の場合、耐候性が不
足しているという欠点がある。(Prior art) However, lactone polymers and diisocyanates obtained by ring-opening polymerization of lactones using conventionally known initiators such as ethylene glycol, diethylene glycol, neopentyl glycol, 1,4 butanediol, etc. Polyurethane polymers obtained by reacting compounds have a drawback of lacking weather resistance.
従つて一般的には耐候性を付与する目的で紫外
線吸収剤、酸化防止剤等を添加して使用してい
る。 Therefore, in general, ultraviolet absorbers, antioxidants, etc. are added for the purpose of imparting weather resistance.
（発明が解決しようとする問題点）
しかし、これらは添加剤であり、多量に添加し
た場合、製品の表面に粉吹き現象（ブルーミン
グ）が起きやすい欠点がある。(Problems to be Solved by the Invention) However, these are additives, and when they are added in large amounts, they have the disadvantage that they tend to cause a powdering phenomenon (blooming) on the surface of the product.
本発明者らはこれらの欠点を改良すべく鋭意検
討した結果、分子内にヒンダードアミン構造を有
するラクトン変性ジオールを用いてウレタン化し
た場合、そのウレタン樹脂自身が耐候性を有して
おり、前記のような添加剤を添加する必要がな
く、他の特性を損なうことがないことを見出し、
本発明に到達した。 The inventors of the present invention conducted intensive studies to improve these drawbacks, and found that when urethane is formed using a lactone-modified diol having a hindered amine structure in the molecule, the urethane resin itself has weather resistance, and the above-mentioned We discovered that there is no need to add such additives and that other properties are not impaired.
We have arrived at the present invention.
（発明の構成）
すなわち、本発明は
「式（）
で示される１−（2′−ヒドロキシエチル）−２，
２，６，６，テトラメチル−４−ヒドロキシピペ
リジンに炭素数４ないし８のラクトン類を２〜15
モル添加して反応して得られる式（）
［だたし、式（）および（）において、Ｙ
は炭素数４ないし８のラクトン類が開環した分子
構造、
ｎおよびｍはそれぞれ０〜15の整数、
ｎ＋ｍは２〜15の整数を表わす］で示されるラ
クトン変性ジオール」
である。(Structure of the invention) In other words, the present invention is based on “Formula () 1-(2'-hydroxyethyl)-2,
2 to 15 lactones having 4 to 8 carbon atoms to 2,6,6,tetramethyl-4-hydroxypiperidine
Formula obtained by adding moles and reacting () [However, in formulas () and (), Y
is a lactone-modified diol having a ring-opened molecular structure of lactones having 4 to 8 carbon atoms, n and m each an integer of 0 to 15, and n+m an integer of 2 to 15.
次に本発明を詳細に説明する。 Next, the present invention will be explained in detail.
先ずヒンダードアミン構造を有する式（）で
示される１−（2′−ヒドロキシエチル）−２，２，
６，６，テトラメチル−４−ヒドロキシピペリジ
ンは公知の物質であり、たとえば特開昭57−
21368号公報に開示されているように以下の方法
で合成される。 First, 1-(2'-hydroxyethyl)-2,2, represented by the formula () having a hindered amine structure.
6,6,Tetramethyl-4-hydroxypiperidine is a known substance, for example, disclosed in JP-A-57-
It is synthesized by the following method as disclosed in Japanese Patent No. 21368.
１−（2′−ヒドロキシエチル）−２，２，６，
６，テトラメチル−４−ヒドロキシピペリジンを
水に溶解し、25〜30℃でエチレンオキサイドを吹
き込み溶解させる。 1-(2'-hydroxyethyl)-2,2,6,
6, Tetramethyl-4-hydroxypiperidine is dissolved in water, and ethylene oxide is blown into the solution at 25-30°C to dissolve it.
その後、反応器を加熱し、還流下１時間攪拌し
た後、60℃まで冷却し、さらにエチレンオキサイ
ドを吹き込んだ後、還流下２時間さらに攪拌す
る。 Thereafter, the reactor was heated and stirred under reflux for 1 hour, then cooled to 60°C, ethylene oxide was further blown into the reactor, and the mixture was further stirred under reflux for 2 hours.
次に室温まで冷却後析出した結晶を濾別、乾燥
後、トルエンより再結晶させて融点180〜182℃の
自然結晶を75％以上の収率で得ることができる。 Next, after cooling to room temperature, the precipitated crystals are separated by filtration, dried, and recrystallized from toluene to obtain natural crystals with a melting point of 180 to 182°C in a yield of 75% or more.
（）式で表わされる化合物とラクトン類との
反応モル比は（）の化合物１モルに対してラク
トン類２〜15モルが適切である。 The reaction molar ratio of the compound represented by the formula () and the lactones is suitably 2 to 15 moles of the lactone per 1 mole of the compound ().
２モル以下では生成されたラクトン付加物中の
ラクトン鎖の有する可とう性が充分付与されな
い。 If the amount is less than 2 moles, the flexibility of the lactone chains in the produced lactone adduct will not be imparted sufficiently.
逆に15モルを越えると分子量が大きくなり過
ぎ、ウレタン化の際、粘度が高くなり、取り扱い
にくくなる。 On the other hand, if it exceeds 15 moles, the molecular weight becomes too large and the viscosity increases during urethane formation, making it difficult to handle.
また、１分子中に占める物質（）の割合が低
下するので目的とする耐候性が付与されない。 Moreover, since the proportion of the substance () in one molecule decreases, the desired weather resistance cannot be imparted.
本発明に用いる化合物（）は結晶性の固体で
あるのでラクトンとの付加反応に用いる場合、液
体であるラクトンに溶解して所定の触媒を添加し
て反応させる。 Since the compound () used in the present invention is a crystalline solid, when it is used for an addition reaction with lactone, it is dissolved in lactone, which is a liquid, and a predetermined catalyst is added to cause the reaction.
本発明に用いるラクトン類としてはγ−プチロ
ラクトン、ε−カプロラクトン、δ−バレロラク
トン等をあげることが出来る。中でもε−カプロ
ラクトンが種々の点から好ましい。 Examples of the lactones used in the present invention include γ-butyrolactone, ε-caprolactone, and δ-valerolactone. Among them, ε-caprolactone is preferred from various points of view.
１−（2′−ヒドロキシエチル）−２，２，６，
６，テトラメチル−４−ヒドロキシピペリジンを
開始剤としてラクトン類の開環重合を行なうには
常圧の窒素雰囲気中で50℃ないし230℃、好まし
くは130℃ないし220℃に加熱する。 1-(2'-hydroxyethyl)-2,2,6,
To carry out ring-opening polymerization of lactones using 6,tetramethyl-4-hydroxypiperidine as an initiator, the polymer is heated to 50 DEG C. to 230 DEG C., preferably 130 DEG C. to 220 DEG C., in a nitrogen atmosphere at normal pressure.
雰囲気を窒素ガスにする理由は生成物が著しく
着色するのを防止するためである。 The reason why the atmosphere is nitrogen gas is to prevent the product from being significantly colored.
50℃以下では反応速度が著しくおそく、230℃
を越えると熱分解によりオキシカプロン酸が生成
し、酸価が高くなるので好ましくない。 The reaction rate is extremely slow below 50℃, and at 230℃
Exceeding this is not preferable because oxycaproic acid is produced by thermal decomposition and the acid value becomes high.
本発明に用いられる化合物（）は一般的なラ
クトンの開環反応の開始剤であるアルキレングリ
コールなどと比較しても反応性において劣ること
はない。 Compound (2) used in the present invention is not inferior in reactivity to alkylene glycol, which is a general initiator for the ring-opening reaction of lactone.
なお、開環反重合にあたつて反応を促進させる
ため触媒を存在させることが好ましい。 In addition, it is preferable to have a catalyst present in order to promote the reaction during ring-opening antipolymerization.
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スズ等が用い
られる。 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, stannous chloride, stannous bromide,
A stannous halide such as stannous iodide is used.
触媒の添加量は出発原料に対して0.05〜1000
ppm、好ましくは、0.1〜100ppmである。 The amount of catalyst added is 0.05 to 1000 relative to the starting material
ppm, preferably 0.1 to 100 ppm.
反応は約６時間で終了し、
未反応のラクトンがガスクロマトグラフなどで
１％以下であることを確認することによつて行な
う。 The reaction is completed in about 6 hours, and the amount of unreacted lactone is confirmed by gas chromatography or the like to be 1% or less.
得られた反応生成物は常温で白色ワツクス状の
固体物質であり、これをウレタン化する場合には
加熱して融解して使用する。 The obtained reaction product is a white wax-like solid substance at room temperature, and when it is to be converted into urethane, it is heated and melted before use.
（発明の効果）
本発明のヒンダードアミン構造を有するラクト
ン変性ジオールは、耐候性を有する添加剤を添加
する方式のものとは異なり、耐候性成分が分子内
に結合しているのでブルーミング現象も起こさ
ず、また他の特性を損なうこともない。(Effect of the invention) The lactone-modified diol having a hindered amine structure of the present invention does not cause blooming because the weather-resistant component is bonded within the molecule, unlike diols that add weather-resistant additives. , and does not impair other properties.
そして構造は両末端が水酸基である線状重合体
であり、分子量は目的・用途に応じてラクトン類
の量を加減することにより広範囲に設定すること
ができる。 The structure is a linear polymer with hydroxyl groups at both ends, and the molecular weight can be set within a wide range by adjusting the amount of lactones depending on the purpose and use.
たとえば、ポリウレタン重合体、ポリエステル
及びウレタンアクリル樹脂等のジオール成分とし
て用いる場合はウレタン化やエステル化のプロセ
スから考えて500〜10000が適切であるが、ポリエ
ステル樹脂、ポリカーボネート樹脂、ポリ塩化ビ
ニール、アクリロニトリル−スチレン系樹脂等の
変性改質剤として使用する場合はある程度分子量
が高い方が好ましく、数平均分子量としては少な
くとも1000以上、好ましくは5000ないし50000で
ある。 For example, when used as a diol component in polyurethane polymers, polyesters, urethane acrylic resins, etc., 500 to 10,000 is appropriate considering the urethanization and esterification processes, but polyester resins, polycarbonate resins, polyvinyl chloride, acrylonitrile When used as a modification modifier for styrene resins, etc., it is preferable that the molecular weight is high to some extent, and the number average molecular weight is at least 1,000 or more, preferably 5,000 to 50,000.
次に実施例を挙げて、本発明の内容を具体的に
説明するが、実施例に示す水酸基価はJISK−
1557に基づき、無水フタール酸−ピリジン法で測
定した値であり、酸価はアセトン溶剤を使用し中
和適定して得られた値である。 Next, the contents of the present invention will be specifically explained with reference to Examples. The hydroxyl values shown in the Examples are JISK-
1557, measured by the phthalic anhydride-pyridine method, and the acid value is the value obtained by neutralization using an acetone solvent.
融点は柳本製作所製の微量融点測定器を用い測
定した値である。なお、例中の部はいずれも重量
部を示す。 The melting point is a value measured using a micro melting point meter manufactured by Yanagimoto Seisakusho. Note that all parts in the examples indicate parts by weight.
実施例 １
攪拌機、温度計、窒素ガス導入管、コンデンサ
ーをセツトした四ツ口フラスコに１−（2′−ヒド
ロキシエチル）−２，２，６，６，テトラメチル
−４−ヒドロキシピペリジン［三共株式会社（品
名C10−2625）］201部、ε−カプロラクトン1799
部、［１−（2′−ヒドロキシエチル）−２，２，６，
６，テトラメチル−４−ヒドロキシピペリジンと
ε−カプロラクトンのモル比１：15］テトラブチ
ルチタネート0.002部を仕込み、170℃で６時間反
応させ水酸基価（KOHmg／ｇ）56.3、酸価
（KOGmg／ｇ）1.25、融点43℃を有する常温で固
体のラクトン変性ジオールを得た。このものの分
子量は1990であつた。Example 1 1-(2'-hydroxyethyl)-2,2,6,6,tetramethyl-4-hydroxypiperidine [Sankyo Co., Ltd. Company (product name C10-2625)] 201 copies, ε-caprolactone 1799
part, [1-(2'-hydroxyethyl)-2,2,6,
6, Tetramethyl-4-hydroxypiperidine and ε-caprolactone molar ratio 1:15] 0.002 part of tetrabutyl titanate was charged and reacted at 170°C for 6 hours to obtain a hydroxyl value (KOHmg/g) of 56.3 and an acid value (KOGmg/g). ) 1.25, a lactone-modified diol which was solid at room temperature and had a melting point of 43°C was obtained. The molecular weight of this product was 1990.
実施例 ２
実施例−１と同様の装置に１−（2′−ヒドロキ
シエチル）−２，２，６，６，テトラメチル−４
−ヒドロキシピペリジン［三共株式会社（品名
C10−2625）］201部、ε−カプロラクトン1049
部、［１−（2′−ヒドロキシエチル）−２，２，６，
６，テトラメチル−４−ヒドロキシピペリジンと
ε−カプロラクトンのモル比１：９］、テトラブ
チルチタネート0.003部を仕込み、170℃で８時間
反応させ、水酸基価（KOHmg／ｇ）90.2、酸価
1.05、融点42〜46℃を有する常温で固体のラクト
ン変性ジオールを得た。Example 2 1-(2'-hydroxyethyl)-2,2,6,6,tetramethyl-4 was added to the same apparatus as in Example-1.
-Hydroxypiperidine [Sankyo Co., Ltd. (product name)
C10-2625)] 201 parts, ε-caprolactone 1049
part, [1-(2'-hydroxyethyl)-2,2,6,
6, tetramethyl-4-hydroxypiperidine and ε-caprolactone in a molar ratio of 1:9] and 0.003 part of tetrabutyl titanate, and reacted at 170°C for 8 hours to obtain a hydroxyl value (KOHmg/g) of 90.2 and an acid value.
1.05, a lactone-modified diol which was solid at room temperature and had a melting point of 42-46°C was obtained.
Claims (1)
２，６，６，テトラメチル−４−ヒドロキシピペ
リジンに炭素数４ないし８のラクトン類を２〜15
モル添加して反応して得られる下記式（） ［だたし、式（）および（）において、Ｙ
は炭素数４ないし８のラクトン類が開環した分子
構造、ｎおよびｍはそれぞれ０〜15の整数、ｎ＋
ｍは２〜15の整数を表わす］ で示されるラクトン変性ジオール。[Claims] 1 The following formula () 1-(2'-hydroxyethyl)-2,
2 to 15 lactones having 4 to 8 carbon atoms to 2,6,6,tetramethyl-4-hydroxypiperidine
The following formula () obtained by adding moles and reacting [However, in formulas () and (), Y
is a ring-opened molecular structure of lactones having 4 to 8 carbon atoms, n and m are each integers of 0 to 15, and n+
m represents an integer of 2 to 15] A lactone-modified diol represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60283980A JPS62143926A (en) | 1985-12-17 | 1985-12-17 | Lactone-modified diol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60283980A JPS62143926A (en) | 1985-12-17 | 1985-12-17 | Lactone-modified diol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62143926A JPS62143926A (en) | 1987-06-27 |
| JPH0562891B2 true JPH0562891B2 (en) | 1993-09-09 |
Family
ID=17672724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60283980A Granted JPS62143926A (en) | 1985-12-17 | 1985-12-17 | Lactone-modified diol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62143926A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4868267A (en) * | 1988-01-11 | 1989-09-19 | Owens-Corning Fiberglas Corporation | Aminated hydroxylated polyester polyol resin and molding compositions comprised thereof |
| WO2004106303A1 (en) * | 2003-05-28 | 2004-12-09 | Daicel Chemical Industries, Ltd. | Lactone-added hindered amine compound |
-
1985
- 1985-12-17 JP JP60283980A patent/JPS62143926A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62143926A (en) | 1987-06-27 |
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