JPH0749471B2 - Method for producing polyester oligomer - Google Patents
Method for producing polyester oligomerInfo
- Publication number
- JPH0749471B2 JPH0749471B2 JP59246098A JP24609884A JPH0749471B2 JP H0749471 B2 JPH0749471 B2 JP H0749471B2 JP 59246098 A JP59246098 A JP 59246098A JP 24609884 A JP24609884 A JP 24609884A JP H0749471 B2 JPH0749471 B2 JP H0749471B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester oligomer
- molecular weight
- mol
- double bond
- molecule
- 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
- 229920000728 polyester Polymers 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- -1 cyclic acid anhydride Chemical class 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 description 10
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N cyclohexene-1,2-dicarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- PQANGXXSEABURG-UHFFFAOYSA-N cyclohex-2-en-1-ol Chemical compound OC1CCCC=C1 PQANGXXSEABURG-UHFFFAOYSA-N 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】 〔発明の目的〕 （産業上のの利用分野） 本発明は環状酸無水物とエポキシモノマーとから得られ
るポリエステルオリゴマーの製造法に関し，詳しくは１
分子中に水酸基１個とエチレン性二重結合１個とを有す
る有機化合物の存在下に上記環状酸無水物およびエポキ
シモノマーを反応せしめることによるエチレン性二重結
合を末端に有するポリエステルオリゴマーの製造法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a method for producing a polyester oligomer obtained from a cyclic acid anhydride and an epoxy monomer.
Process for producing polyester oligomer having terminal ethylenic double bond by reacting the above cyclic acid anhydride and epoxy monomer in the presence of an organic compound having one hydroxyl group and one ethylenic double bond in the molecule Regarding
（従来の技術） 従来，環状酸無水物とエポキシモノマーとは，塩基性触
媒下で交互共重合し，ポリエステルが得られることが知
られている。(Prior Art) It has been conventionally known that a cyclic acid anhydride and an epoxy monomer are alternately copolymerized under a basic catalyst to obtain a polyester.
このような手法を用いてポリエステルの側鎖にエチレン
性二重結合を導入するには，環状酸無水物，エチレン性
二重結合を有するエポキシモノマーおよびジオール類を
反応させて得られることがすでに特願昭59−167762に示
されている。In order to introduce an ethylenic double bond into the side chain of polyester using such a method, it has already been found that it can be obtained by reacting a cyclic acid anhydride, an epoxy monomer having an ethylenic double bond and a diol. It is shown in Japanese Patent Application No. 59-167762.
また，ポリエステルの末端にエチレン性二重結合を導入
するには，ポリエチレングリコール（またはポリプロピ
レングリコール）と過剰の（メタ）アクリル酸クロリド
とを反応させて得られることが知られているが，この方
法は未反応の（メタ）アクリル酸クロリドが多量に残存
し反応生成物の精製が困難で目的物の収率が低いという
欠点があった。It is known that in order to introduce an ethylenic double bond at the terminal of polyester, it can be obtained by reacting polyethylene glycol (or polypropylene glycol) with an excess of (meth) acrylic acid chloride. Had a drawback that a large amount of unreacted (meth) acrylic acid chloride remained, purification of the reaction product was difficult, and the yield of the target product was low.
（発明が解決しようとする問題点） 本発明の目的は，環状酸無水物とエポキシモノマーから
得られるポリエステルオリゴマーの末端にエチレン性二
重結合を導入したポリエステルオリゴマーを収率よく得
ることにある。この際,1分子中に水酸基１個とエチレン
性二重結合１個とを有する有機化合物の存在量を調整す
ることにより，分子量のコントロールされたポリエステ
ルオリゴマーを得るものである。(Problems to be Solved by the Invention) An object of the present invention is to obtain a polyester oligomer in which an ethylenic double bond is introduced at the terminal of a polyester oligomer obtained from a cyclic acid anhydride and an epoxy monomer in good yield. At this time, a polyester oligomer having a controlled molecular weight is obtained by adjusting the existing amount of an organic compound having one hydroxyl group and one ethylenic double bond in one molecule.
（問題点を解決するための手段） 本発明は，環状酸無水物（Ａ）と１分子中に１個のエポ
キシ基を有するモノマー（Ｂ）とを反応させて得られる
ポリエステルオリゴマーの製造方法において，実質的
に，ほぼ等モル量の上記（Ａ）および（Ｂ）を，（Ａ）
もしくは（Ｂ）１モルに対して0.1〜0.5モルの１分子中
に水酸基１個とエチレン性二重結合１個とを有する有機
化合物（Ｃ）の存在下にて反応させることを特徴とする
ポリエステルオリゴマーの製造方法である。(Means for Solving Problems) The present invention provides a method for producing a polyester oligomer obtained by reacting a cyclic acid anhydride (A) with a monomer (B) having one epoxy group in one molecule. , (A) and (A) in substantially equimolar amounts
Alternatively, the polyester is characterized by reacting in the presence of an organic compound (C) having one hydroxyl group and one ethylenic double bond in one molecule of 0.1 to 0.5 mol per 1 mol of (B). It is a method for producing an oligomer.
本発明にいう環状酸無水物（Ａ）は，下記一般式（Ｉ）
〜（Ｖ）で示される骨格を有するものである。The cyclic acid anhydride (A) referred to in the present invention has the following general formula (I):
To (V) have a skeleton.
ここで，上記式（Ｉ）中の芳香族炭化水素基中の水素原
子，式（II）ないし（Ｖ）中の飽和もしくは不飽和脂肪
族炭化水素基中の水素原子は，飽和もしくは不飽和アル
キル基，アリール基，ハロゲン原子，ヘテロ環基などと
置換されていてもよい。環状酸無水物（Ａ）としてより
具体的には，例えば，無水マレイン酸，無水フタル酸，
無水1,2−シクロヘキサンジカルボン酸，無水シス−４
−シクロヘキセン−1,2−ジカルボン酸，無水イタコン
酸，無水グルタル酸，無水シトラコン酸，無水コハク酸
などが例示できる。 Here, the hydrogen atom in the aromatic hydrocarbon group in the above formula (I) and the hydrogen atom in the saturated or unsaturated aliphatic hydrocarbon group in the formulas (II) to (V) are saturated or unsaturated alkyl groups. It may be substituted with a group, an aryl group, a halogen atom, a heterocyclic group or the like. More specifically as the cyclic acid anhydride (A), for example, maleic anhydride, phthalic anhydride,
Anhydrous 1,2-cyclohexanedicarboxylic acid, anhydrous cis-4
Examples thereof include cyclohexene-1,2-dicarboxylic acid, itaconic anhydride, glutaric anhydride, citraconic anhydride, and succinic anhydride.
本発明にいう,1分子中に１個のエポキシ基を有するモノ
マー（Ｂ）としては，下記一般式（VI）で示されるもの
である。The monomer (B) having one epoxy group in one molecule referred to in the present invention is represented by the following general formula (VI).
ここで,R1,R2は水素原子，ハロゲン原子，ハロゲン原子
により置換されていてもよい飽和もしくは不飽和アルキ
ル基，アリール基，へテロ環基，エーテル結合の酸素原
子に結ばれた飽和もしくは不飽和アルキル基（アルキル
基の水素原子はハロゲン原子と置換されていてもよ
い。）もしくはアリール基である。エポキシモノマー
（Ｂ）として，より具体的には，エチレンオキサイド，
プロピレンオキサイド，スチレンオキサイド，エピクロ
ルヒドリン，エピブロモヒドリン，フェニルグリシジル
エーテル，アリルグリシジルエーテル，シクロヘキセン
オキサイド，グリシジル（メタ）アクリレート，ブテン
オキサイドなどが例示できる。 Here, R 1 and R 2 are a hydrogen atom, a halogen atom, a saturated or unsaturated alkyl group optionally substituted by a halogen atom, an aryl group, a heterocyclic group, or a saturated or unsaturated group bonded to an oxygen atom of an ether bond. It is an unsaturated alkyl group (the hydrogen atom of the alkyl group may be substituted with a halogen atom) or an aryl group. As the epoxy monomer (B), more specifically, ethylene oxide,
Examples thereof include propylene oxide, styrene oxide, epichlorohydrin, epibromohydrin, phenylglycidyl ether, allyl glycidyl ether, cyclohexene oxide, glycidyl (meth) acrylate and butene oxide.
本発明にいう,1分子中に水酸基１個とエチレン性二重結
合１個とをする有機化合物（Ｃ）は開始触媒としての機
能を有するものである。すなわち，上記有機化合物
（Ｃ）は始めに環状酸無水物（Ａ）と反応することによ
り環状酸無水物（Ａ）は開環し，エステル化合物を生成
し，ついでこのエステル化合物のカルボン酸基にエポキ
シモノマー（Ｂ）のエポキシ基が反応していくことによ
りポリエステルオリゴマーが生成していくものと考えら
れる。The organic compound (C) having one hydroxyl group and one ethylenic double bond in one molecule according to the present invention has a function as an initiation catalyst. That is, the organic compound (C) first reacts with the cyclic acid anhydride (A) to open the cyclic acid anhydride (A) to form an ester compound, which is then converted into a carboxylic acid group of the ester compound. It is considered that the polyester oligomer is produced by the reaction of the epoxy groups of the epoxy monomer (B).
１分子中に水酸基１個とエチレン性二重結合１個とを有
する有機化合物（Ｃ）としては,2−ヒドロキシエチル
（メタ）アクリレート，ヒドロキシプロピル（メタ）ア
クリレート，アリルアルコール,p−ヒドロキシスチレ
ン,2−シクロヘキセン−１−オールなどがある。As the organic compound (C) having one hydroxyl group and one ethylenic double bond in one molecule, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, allyl alcohol, p-hydroxystyrene, 2-cyclohexen-1-ol and the like.
環状酸無水物（Ａ）とエポキシモノマー（Ｂ）はほぼ等
モル量使用する。１分子中に水酸基１個とエチレン性二
重結合１個とを有する有機化合物（Ｃ）の使用割合は，
環状酸無水物（Ａ）もしくはエポキシモノマー（Ｂ）１
モルに対して,0.1〜0.5モルである。上記有機化合物
（Ｃ）の存在量が0.10モルより少ないと，ポリエステル
の分子量が急速に増大し，反応のコントロールが難し
く，逆に,0.5モルより多くなると必要とする分子量が得
られない。反応温度は60〜150℃，反応時間は30分間〜1
0時間の範囲から選ぶことができる。環状酸無水物
（Ａ）とエポキシモノマー（Ｂ）との交互共重合反応に
使用される従来の公知の触媒，例えば，水酸化ナトリウ
ム，水酸化カリウム，リチウムクロライド，ジエチル亜
鉛，テトラ（ｎ−ブトキシ）チタン，トリエチルアミ
ン,N,N−ジメチルベンジルアミンなどを必要に応じて反
応時に使用することができる。また，反応に際して，ハ
イドロキノン，モノメトキシハイドロキノンなどの重合
禁止剤を添加することが好ましい。The cyclic acid anhydride (A) and the epoxy monomer (B) are used in approximately equimolar amounts. The usage ratio of the organic compound (C) having one hydroxyl group and one ethylenic double bond in one molecule is:
Cyclic acid anhydride (A) or epoxy monomer (B) 1
It is 0.1 to 0.5 mol per mol. If the amount of the organic compound (C) present is less than 0.10 mol, the molecular weight of the polyester increases rapidly, making it difficult to control the reaction. Conversely, if it exceeds 0.5 mol, the required molecular weight cannot be obtained. Reaction temperature is 60 to 150 ℃, reaction time is 30 minutes to 1
You can choose from a range of 0 hours. Conventional known catalysts used in the alternating copolymerization reaction of cyclic acid anhydride (A) and epoxy monomer (B), for example, sodium hydroxide, potassium hydroxide, lithium chloride, diethyl zinc, tetra (n-butoxy) ) Titanium, triethylamine, N, N-dimethylbenzylamine and the like can be used during the reaction, if necessary. In addition, it is preferable to add a polymerization inhibitor such as hydroquinone or monomethoxyhydroquinone during the reaction.
（実施例） 実施例 １ 無水1,2−シクロヘキサンジカルボン酸からのポリエス
テルオリゴマー フェニルグリシジルエーテルの0.04モルと無水1,2−シ
クロヘキサンジカルボン酸0.04モルと２−ヒドロキシメ
タアクリレートの0.012モルを反応容器に入れ100℃に加
熱し９時間撹拌した。反応生成物の分子量はGPCにより
測定し，この際,2−ヒドロキシメタアクリレート，フェ
ニルグリシジルエーテルおよび無水1,2−シクロヘキサ
ンジカルボン酸の各ピークが完全に消失していることを
確認した。また，反応の終了はIRスペクトルで酸無水物
の吸収1850cm-1とエポキシ基の吸収920cm-1が消失して
いることでも確認できた。EXAMPLES Example 1 Polyester oligomer from anhydrous 1,2-cyclohexanedicarboxylic acid 0.04 mol of phenylglycidyl ether, 0.04 mol of anhydrous 1,2-cyclohexanedicarboxylic acid and 0.012 mol of 2-hydroxymethacrylate were placed in a reaction vessel. The mixture was heated to 100 ° C. and stirred for 9 hours. The molecular weight of the reaction product was measured by GPC, and it was confirmed that the peaks of 2-hydroxymethacrylate, phenylglycidyl ether and anhydrous 1,2-cyclohexanedicarboxylic acid were completely eliminated. Also, termination of the reaction was confirmed also by absorption 920 cm -1 absorption 1850 cm -1 and an epoxy group of the acid anhydride by IR spectrum disappeared.
フェニルグリシジルエーテルの代りに，グリシジルメタ
アクリレート，アリルグリシジルエーテル，スチレンオ
キサイド，エピクロルヒドリンを用いて同様の条件下で
反応させた。Instead of phenyl glycidyl ether, glycidyl methacrylate, allyl glycidyl ether, styrene oxide, and epichlorohydrin were used and reacted under the same conditions.
さらに，無触媒で反応性の低かったアリルグリシジルエ
ーテル，フェニルグリシジルエーテル，スチレンオキサ
イド，エピクロルヒドリンについては触媒N,N−ジメチ
ルベンジルアミンを１モル％添加して反応させた。Further, for allyl glycidyl ether, phenyl glycidyl ether, styrene oxide, and epichlorohydrin, which had no catalyst and had low reactivity, 1 mol% of catalyst N, N-dimethylbenzylamine was added and reacted.
結果を表−１に示す。The results are shown in Table-1.
実施例 ２ （分子量の異なるポリエステルオリゴマー） 無水1,2−シクロヘキサンジカルボン酸の0.04モルとグ
リシジルメタアクリレートの0.04モルを加えその中に種
々のモル比の２−ヒドロキシメタアクリレートを添加し
100℃に加熱し所定の時間撹拌し，ポリエステルオリゴ
マーを得た。反応の終了は実施例１と同じようにIRスペ
クトルにて酸無水物およびエポキシ基の特性吸収が消失
していることにより確認した。結果を表−２に示す。 Example 2 (Polyester Oligomers with Different Molecular Weights) 0.04 mol of anhydrous 1,2-cyclohexanedicarboxylic acid and 0.04 mol of glycidyl methacrylate were added, and 2-hydroxymethacrylate of various molar ratios were added thereto.
The mixture was heated to 100 ° C and stirred for a predetermined time to obtain a polyester oligomer. The end of the reaction was confirmed by the IR spectrum as in Example 1 by the disappearance of the characteristic absorption of the acid anhydride and the epoxy group. The results are shown in Table-2.
〔発明の効果〕 本発明においては重量平均分子量（Mw）が400〜3000の
末端にエチレン性二重結合を有するポリエステルオリゴ
マーが一段の反応で容易に高収率で得られ，その分子量
は,1分子中に水酸基１個とエチレン性二重結合１個とを
有する有機化合物の使用量を変えることにより容易にコ
ントロールすることができる。 EFFECT OF THE INVENTION In the present invention, a polyester oligomer having an ethylenic double bond at the terminal with a weight average molecular weight (Mw) of 400 to 3000 can be easily obtained in a high yield in a single step, and its molecular weight is 1 It can be easily controlled by changing the amount of the organic compound having one hydroxyl group and one ethylenic double bond in the molecule.
また，得られるポリエステルオリゴマーの分子量分布
（Mw/Mn）は1.0〜2.0という単分散に近いものである。The molecular weight distribution (Mw / Mn) of the obtained polyester oligomer is 1.0 to 2.0, which is close to monodisperse.
得られたポリエステルオリゴマーは放射線硬化樹脂とし
て用いることができる。また，得られたポリエステルオ
リゴマーは，さらにスチレン，（メタ）アクリル酸エス
テルなどのラジカル重合性モノマーと共重合させること
によって，所定の鎖長を有するグラフトポリマーを合成
することができ，得られたポリマーは塗料，接着剤など
の原料として用いることができる。The obtained polyester oligomer can be used as a radiation curable resin. Further, the obtained polyester oligomer can be further copolymerized with a radical-polymerizable monomer such as styrene or (meth) acrylic acid ester to synthesize a graft polymer having a predetermined chain length. Can be used as a raw material for paints and adhesives.
Claims (1)
ポキシ基を有するモノマー（Ｂ）とを反応させて得られ
るポリエステルオリゴマーの製造方法において，実質的
に，ほぼ等モル量の上記（Ａ）および（Ｂ）を，（Ａ）
もしくは（Ｂ）１モルに対して0.1〜0.5モルの１分子中
に水酸基１個とエチレン性二重結合１個とを有する有機
化合物（Ｃ）の存在下にて反応させることを特徴とする
重量平均分子量（Mw）が400〜3000、分子量分布Mw/Mn
（ただし,Mnは数平均分子量を示す。）が1.0〜2.0であ
るポリエステルオリゴマーの製造方法。1. A method for producing a polyester oligomer obtained by reacting a cyclic acid anhydride (A) with a monomer (B) having one epoxy group in one molecule, which is substantially equimolar. The above (A) and (B) of (A)
Alternatively, the reaction is carried out in the presence of an organic compound (C) having 1 hydroxyl group and 1 ethylenic double bond in 1 molecule of 0.1 to 0.5 mol per 1 mol of (B). Average molecular weight (Mw) is 400-3000, molecular weight distribution Mw / Mn
(However, Mn shows a number average molecular weight.) The manufacturing method of the polyester oligomer which is 1.0-2.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59246098A JPH0749471B2 (en) | 1984-11-22 | 1984-11-22 | Method for producing polyester oligomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59246098A JPH0749471B2 (en) | 1984-11-22 | 1984-11-22 | Method for producing polyester oligomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61126128A JPS61126128A (en) | 1986-06-13 |
| JPH0749471B2 true JPH0749471B2 (en) | 1995-05-31 |
Family
ID=17143456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59246098A Expired - Fee Related JPH0749471B2 (en) | 1984-11-22 | 1984-11-22 | Method for producing polyester oligomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0749471B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9033494B2 (en) | 2007-03-29 | 2015-05-19 | Mitsui Chemicals, Inc. | Multifocal lens having a progressive optical power region and a discontinuity |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838486B (en) * | 2012-09-25 | 2016-08-10 | 上海展辰涂料有限公司 | ultraviolet curing polyester acrylic ester and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA796170B (en) * | 1978-12-07 | 1981-03-25 | Ici Ltd | Macromonomers |
| PL127634B1 (en) * | 1979-05-23 | 1983-11-30 | Inst Chemii Przemyslowej | Continuous process for manufacturing polyesters and apparatus therefor |
-
1984
- 1984-11-22 JP JP59246098A patent/JPH0749471B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9033494B2 (en) | 2007-03-29 | 2015-05-19 | Mitsui Chemicals, Inc. | Multifocal lens having a progressive optical power region and a discontinuity |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61126128A (en) | 1986-06-13 |
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