JPS6381124A - Production of lactone-modified diol - Google Patents
Production of lactone-modified diolInfo
- Publication number
- JPS6381124A JPS6381124A JP22552786A JP22552786A JPS6381124A JP S6381124 A JPS6381124 A JP S6381124A JP 22552786 A JP22552786 A JP 22552786A JP 22552786 A JP22552786 A JP 22552786A JP S6381124 A JPS6381124 A JP S6381124A
- Authority
- JP
- Japan
- Prior art keywords
- lactone
- lactones
- bromomethyl
- bis
- formula
- 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
- 150000002009 diols Chemical class 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000002596 lactones Chemical class 0.000 claims abstract description 22
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 abstract description 4
- 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 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 239000004814 polyurethane Substances 0.000 abstract description 4
- -1 gamma-butyrolactone Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 2
- WDNXKYRHRFUEKA-UHFFFAOYSA-N BrCC(C(O)O)(C)CBr Chemical compound BrCC(C(O)O)(C)CBr WDNXKYRHRFUEKA-UHFFFAOYSA-N 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 125000005997 bromomethyl group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920000728 polyester Polymers 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
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GSJBKPNSLRKRNR-UHFFFAOYSA-N $l^{2}-stannanylidenetin Chemical compound [Sn].[Sn] GSJBKPNSLRKRNR-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 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
- 229940035437 1,3-propanediol Drugs 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
- 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
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007788 liquid 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
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000000843 powder Substances 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
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002904 solvent Substances 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
- 239000007858 starting material Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
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の製造方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a novel lactone-modified diol.
さらに詳しくは、２．２−ビス（ブロムメチル）１．３
プロパンジオ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難燃性に優れた新規なラクト
ン重合体の製造方法に関するものである。More specifically, 2,2-bis(bromomethyl)1.3
The present invention relates to a method for producing a novel lactone polymer with excellent flame retardancy, which is characterized by carrying out ring-opening polymerization of lactones using propanediol 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、ポリカーボネート樹脂、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
の強靭性、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。It is also used as a modifier for imparting toughness, processability, etc. to polyester resins, polycarbonate resins, polyvinyl chloride resins, acrylonitrile-styrene resins, etc., and 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
、難燃性が不足しているという欠点がある。(Prior art) However, conventionally known ethylene glycol, diethylene glycol, neopentyl glycol, 1.4
Polyurethane polymers obtained by reacting lactone polymers obtained by ring-opening polymerization of lactones with initiators such as butanediol and diisocyanate compounds have a disadvantage of lacking flame retardancy. There is.
従って一般的には難燃性を付与する目的で難燃剤等を添
加して使用している。Therefore, flame retardants and the like are generally added for the purpose of imparting flame retardancy.
（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。(Problem to be solved by the invention) However, these are additives, and when added in large amounts,
The product has the disadvantage that it tends to cause a powder blowing phenomenon (blooming) on the surface.
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、分子内にハロゲン基を有するラクトン変性ジオール
を用いた場合、そのラクトン変性ジオール自身が難燃性
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 a lactone-modified diol having a halogen group in the molecule is used, the lactone-modified diol itself has flame retardancy, and as described above, The present invention was achieved based on the discovery that there is no need to add additives and other properties are not impaired.
（発明の構成）
すなわち９本発明は、
「下記式（Ｉ）で示される２、２−ビス（ブロムメチル
）１，３−プロパンジオールに炭素数４ないし８のラク
トン類を２〜１５モル添加して反応させることを特徴と
する式（ＩＩ）で示されるラクトン変性ジオールの製造
方法。(Structure of the Invention) That is, 9 the present invention is based on ``adding 2 to 15 moles of a lactone having 4 to 8 carbon atoms to 2,2-bis(bromomethyl)1,3-propanediol represented by the following formula (I). A method for producing a lactone-modified diol represented by formula (II), which comprises reacting with a lactone-modified diol.
Ｈ２８ｒ
）１０ＣＨ２−Ｃ−ＣＨ２０ト１
（■ ）Ｈ２８ｒ
）１ ＋ ０−Ｙ−Ｇｏ −＋−十−Ｈ２８ｒ
−〇−ＣＨ２−Ｃ−ＣＨ２０−
−＋Ｇ Ｏ−Ｙ −０→１ヒー Ｈ（Ｉ）（但し、Ｙは
炭素数４ないし８のラクトン類のモル数でｎ＋ｍ−２〜
１５である）」
である。H28r)10CH2-C-CH20to1
(■) H28r )1 + 0-Y-Go -+-10-H28r -〇-CH2-C-CH20- -+G O-Y -0→1He H(I) (However, Y has 4 or more carbon atoms. The number of moles of lactones in 8 is n + m-2 ~
15).
次に本発明の詳細な説明する。Next, the present invention will be explained in detail.
先ずハロゲン基を有する式（１）で示される２゜２−ビ
ス（ブロムメチル）１，３１０パンジオールは公知の物
質であり、ポリエステルの改質剤として工業的に生産さ
れており、入手可能な物質である。First, 2゜2-bis(bromomethyl)1,310panediol represented by formula (1) having a halogen group is a known substance, industrially produced as a modifier for polyester, and an available substance. It is.
（Ｉ）式で表わされる化合物とラクトン類との反応モル
比は（Ｉ）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 formula (I) and lactones is 2 to 15 lactones per mole of compound (I).
Moles are appropriate.
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
鎮の有する可どう性が充分付与されない。If the amount is less than 2 moles, the lactone adduct produced will not have sufficient flexibility.
逆に１５モルを越えると分子量が大きくなり過ぎ、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 becomes high, making it difficult to handle.
また、１分子中に占める物質（Ｉ）の割合が低下するの
で目的とする難燃性が付与されない。Furthermore, since the proportion of substance (I) in one molecule decreases, the desired flame retardancy cannot be imparted.
本発明に用いる化合物（１）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 (1) used in the present invention is a crystalline solid, when it is used for an addition reaction with a lactone, it is dissolved in a liquid lactone 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−ブチロラクトン
、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。Examples of the lactones used in the present invention include γ-butyrolactone, ε-caprolactone, and δ-valerolactone.
中でもε−カプロラクトンが種々の点から好ましい。Among them, ε-caprolactone is preferred from various points of view.
２．２−ビス（ブロムメチル）１．３プロパンジオール
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１
３０℃ないし２２０℃に加熱する。To perform ring-opening polymerization of lactones using 2.2-bis(bromomethyl)1.3propanediol as an initiator, the reaction temperature is 50°C to 230°C in a nitrogen atmosphere at normal pressure, preferably 1
Heat to 30°C to 220°C.
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遅く、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。Below 50°C, the reaction rate is extremely slow, and above 230°C, oxycaproic acid is produced by thermal decomposition, resulting in a high acid value, which is not preferred.
本発明に用いられる化合物（１）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 (1) 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、開環重合にあたっ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 polymerization.
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, and stannous iodide. 1 halogenated material such as tin
Tin etc. are used.
触媒の添加量は出発原料に対して０．０５〜１０００１
）ｌ）ｌ １好ましくは、０，１〜１００ｐｐｌである
。The amount of catalyst added is 0.05 to 10,001 based on the starting material.
)l)l 1 Preferably, it is 0.1 to 100 ppl.
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
よって行なう。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ックス状の固体物質
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）
本発明方法のハロゲンを分子内に有するラクトン変性ジ
オールは、難燃性を有する添加剤を添加する方式のもの
とは異なり、難燃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 containing a halogen in the molecule produced by the method of the present invention differs from the method in which flame-retardant additives are added, since the flame-retardant component is bonded within the molecule. No blooming phenomenon occurs, and other properties are not impaired.
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.
The molecular weight can be set within a wide range by adjusting the amount of lactone 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、数平均分子計とし
ては少なくとも１０００以上、好ましくは５０００ない
しｓｏ、 ｏｏ。For example, when used as a diol component in polyurethane polymers, polyesters, urethane acrylic resins, etc., the
10,000 is appropriate, but when used as a modification modifier for polyester resins, polycarbonate resins, polyvinyl chloride, acrylonitrile-styrene resins, etc., it is preferable to have a somewhat higher molecular weight, and at least 1,000 or more as a number average molecular weight. , preferably 5000 to so, oo.
である。It is.
次に実施例を挙げて、本発明の内容を具体的に説明する
。Next, the content of the present invention will be specifically explained with reference to Examples.
実施例に示す水′ＦＩｉ基価はＪ ｌ５Ｋ−１５５７に
基づき、無水フタール酸−ビ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。The water'FIi value shown in the examples is the value measured by the phthalic anhydride-pyridine method based on J15K-1557, 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、コンデンサーをセッ
トした四ツロフラスコに２，２−ビス（ブロムメチル）
１，３プロパンジオ一ル２６０部、ε−カプロラクトン
９９０部、［２，２−ビス（ブロムメチル）１，３プロ
パンジオールとε−カプロラクトンのモル比＝１：８．
７］、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（ｉＩＩｉ（ＫＯＨｊ
ｙ／グ＞８９．８、酸価（ＫＯＧｑ／ｇ）０．３３ 、
融点４７℃を有する常温で固体のラクトン変性ジオール
を得た。Example-1゜2,2-bis(bromomethyl) was placed in a four-way flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, and condenser.
260 parts of 1,3-propanediol, 990 parts of ε-caprolactone, [molar ratio of 2,2-bis(bromomethyl)1,3-propanediol and ε-caprolactone=1:8.
7], 0.002 part of tetrabutyl titanate was added,
The reaction was carried out at 170°C for 6 hours to form hydroxyl groups (IIIi(KOHj
y/g>89.8, acid value (KOGq/g) 0.33,
A lactone-modified diol was obtained which was solid at room temperature and had a melting point of 47°C.
このものの分子量は１２４３であった。The molecular weight of this product was 1243.
実施例−２゜
実施例−１と同様の装置に２．２−ビス（ブロムメチル
）１，３プロパンジオ一ル２６０部、ε−カプロラクト
ン１７４０部、［２，２−ビス（ブロムメチル）１．３
プロパンジオールとε−カプロラクトンのモル比−１：
１５．３］、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Ｗ！鵡価ＣＫＯＨ
ＩＩＩ／９ ） ５６．１、酸価０．２５、融点４１〜
４８℃を有する常温で固体のワックス状ラクトン変性ジ
オールを得た。Example-2゜Into the same apparatus as in Example-1, 260 parts of 2,2-bis(bromomethyl)1,3propanediol, 1740 parts of ε-caprolactone, and 1.3 parts of [2,2-bis(bromomethyl)] were added.
Molar ratio of propanediol and ε-caprolactone -1:
15.3], 0.003 part of tetrabutyl titanate was added, reacted at 170°C for 8 hours, and water W! Price CKOH
III/9) 56.1, acid value 0.25, melting point 41~
A waxy lactone-modified diol was obtained which was solid at room temperature of 48°C.
このものの分子量は１９８８であった。The molecular weight of this product was 1,988.
Claims (1)
）１，３プロパンジオールに炭素数４ないし８のラクト
ン類を２〜１５モル添加して反応させることを特徴とす
る式（II）で示されるラクトン変性ジオールの製造方法
。 ▲数式、化学式、表等があります▼（ I ） ▲数式、化学式、表等があります▼（II） （但し、Ｙは炭素数４ないし８のラクトン類のモル数で
ｎ＋ｍ＝２〜１５である）[Claims] A method characterized by adding 2 to 15 moles of a lactone having 4 to 8 carbon atoms to 2,2-bis(bromomethyl)1,3propanediol represented by the following formula (I) and causing the reaction. A method for producing a lactone-modified diol represented by formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (However, Y is the number of moles of lactones having 4 to 8 carbon atoms, and n+m=2 to 15. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22552786A JPS6381124A (en) | 1986-09-24 | 1986-09-24 | Production of lactone-modified diol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22552786A JPS6381124A (en) | 1986-09-24 | 1986-09-24 | Production of lactone-modified diol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6381124A true JPS6381124A (en) | 1988-04-12 |
Family
ID=16830700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22552786A Pending JPS6381124A (en) | 1986-09-24 | 1986-09-24 | Production of lactone-modified diol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6381124A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002077061A1 (en) * | 2001-03-27 | 2002-10-03 | Southwest Distributing Co. | Preparation of browmine-containing hydroxy-functional copolymers |
| EP1462503A4 (en) * | 2001-12-06 | 2005-12-28 | Daicel Chem | Flame retardant composition, process for producing the same, flame-retardant resin composition, and molded object thereof |
-
1986
- 1986-09-24 JP JP22552786A patent/JPS6381124A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002077061A1 (en) * | 2001-03-27 | 2002-10-03 | Southwest Distributing Co. | Preparation of browmine-containing hydroxy-functional copolymers |
| US6600007B2 (en) | 2001-03-27 | 2003-07-29 | Southwest Distributing Co. | Preparation of bromine-containing hydroxy-functional copolymers |
| EP1462503A4 (en) * | 2001-12-06 | 2005-12-28 | Daicel Chem | Flame retardant composition, process for producing the same, flame-retardant resin composition, and molded object thereof |
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