JPH0321536B2 - - Google Patents
Info
- Publication number
- JPH0321536B2 JPH0321536B2 JP58175194A JP17519483A JPH0321536B2 JP H0321536 B2 JPH0321536 B2 JP H0321536B2 JP 58175194 A JP58175194 A JP 58175194A JP 17519483 A JP17519483 A JP 17519483A JP H0321536 B2 JPH0321536 B2 JP H0321536B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- caprolactone
- radically polymerizable
- unsaturated monomer
- 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 - Lifetime
Links
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 27
- 229920000728 polyester Polymers 0.000 claims description 26
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- -1 acryloyloxy group Chemical group 0.000 claims 2
- 229920000642 polymer Polymers 0.000 claims 1
- 238000007142 ring opening reaction Methods 0.000 claims 1
- 238000004458 analytical method Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 229940048053 acrylate Drugs 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- MMEJYPZZFYTVLJ-WAYWQWQTSA-N (z)-2-(2-prop-2-enoyloxyethyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\CCOC(=O)C=C MMEJYPZZFYTVLJ-WAYWQWQTSA-N 0.000 description 1
- JHVQWALHXJPODC-ALCCZGGFSA-N (z)-2-[2-(2-methylprop-2-enoyloxy)ethyl]but-2-enedioic acid Chemical compound CC(=C)C(=O)OCC\C(C(O)=O)=C\C(O)=O JHVQWALHXJPODC-ALCCZGGFSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LBNDGEZENJUBCO-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethyl]butanedioic acid Chemical compound CC(=C)C(=O)OCCC(C(O)=O)CC(O)=O LBNDGEZENJUBCO-UHFFFAOYSA-N 0.000 description 1
- OMPRMWFZHLNRQJ-UHFFFAOYSA-N 2-chlorohexanoic acid Chemical compound CCCCC(Cl)C(O)=O OMPRMWFZHLNRQJ-UHFFFAOYSA-N 0.000 description 1
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 1
- DWTKNKBWDQHROK-UHFFFAOYSA-N 3-[2-(2-methylprop-2-enoyloxy)ethyl]phthalic acid Chemical compound CC(=C)C(=O)OCCC1=CC=CC(C(O)=O)=C1C(O)=O DWTKNKBWDQHROK-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】
本発明はカプロラクトンポリエステル不飽和単
量体の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing caprolactone polyester unsaturated monomers.
従来、カルボキシル基を有するラジカル重合性
不飽和単量体としてアクリル酸、メタクリル酸、
イタコン酸、マレイン酸、β−メタクリロイルオ
キシエチルコハク酸、β−メタクリロイルオキシ
エチルマレイン酸、β−メタクリロイルオキシエ
チルフタル酸、β−アクリロイルオキシエチルコ
ハク酸、β−アクリロイルオキシエチルマレイン
酸、β−アクリロイルオキシエチルフタル酸など
が知られている。これらカルボキシル基を有する
ラジカル重合性不飽和単量体は、熱硬化性塗料、
接着剤、紙加工用コポリマーの改質剤、架橋剤、
繊維処理剤などの原料又は中間体として極めて広
範囲の用途に用いられているが、各々の用途に最
も適したカルボキシル基を有するラジカル重合性
単量体の種類を慎重に選択する必要がある。 Conventionally, acrylic acid, methacrylic acid,
Itaconic acid, maleic acid, β-methacryloyloxyethylsuccinic acid, β-methacryloyloxyethylmaleic acid, β-methacryloyloxyethyl phthalic acid, β-acryloyloxyethylsuccinic acid, β-acryloyloxyethylmaleic acid, β-acryloyloxy Ethyl phthalic acid is known. These radically polymerizable unsaturated monomers having a carboxyl group can be used for thermosetting coatings,
Adhesives, copolymer modifiers for paper processing, crosslinking agents,
Although it is used in a very wide range of applications as a raw material or intermediate for fiber treatment agents, it is necessary to carefully select the type of radically polymerizable monomer having a carboxyl group that is most suitable for each application.
一般に末端にカルボキシル基を有するポリエス
テル不飽和単量体を合成する方法としては、ω−
ヒドロキシカルボン酸とカルボキシル基を有する
ラジカル重合性不飽和単量体を反応させる方法、
α，ω，−ポリエステルジカルボン酸とヒドロキ
シル基を有するラジカル重合性不飽和単量体を反
応させる方法、酸無水物、カルボキシル基を有す
るラジカル重合性不飽和単量体及びエポキシ化合
物を反応させる方法などが知られている。しか
し、これらの方法によると、ラジカル重合性官能
基が全くないもの、又は、２個入つたものなどが
副生成物として多量に生じる欠点を有している。
又、別の方法としてカルボキシル基を有するラジ
カル重合性不飽和単量体の金属塩例えばアクリル
酸ナトリウムとω−ハロゲノカルボン酸例えばω
−クロルカプロン酸を反応させる方法もあるが、
この方法は原料となるω−ハロゲノカルボン酸の
製造工程が多く、またラジカル重合性官能基を２
個以上導入するには複数の工程を必要とし、さら
に副生するハロゲン化金属塩との分離工程も必要
となり、工業的製造方法に至つていないのが現状
である。 In general, the method for synthesizing polyester unsaturated monomers having carboxyl groups at the terminals is ω-
A method of reacting a hydroxycarboxylic acid with a radically polymerizable unsaturated monomer having a carboxyl group,
A method of reacting an α,ω,-polyester dicarboxylic acid with a radically polymerizable unsaturated monomer having a hydroxyl group, a method of reacting an acid anhydride, a radically polymerizable unsaturated monomer having a carboxyl group, and an epoxy compound, etc. It has been known. However, these methods have the disadvantage that a large amount of by-products, such as those having no radically polymerizable functional groups or those containing two radically polymerizable functional groups, are disadvantageous.
Alternatively, a metal salt of a radically polymerizable unsaturated monomer having a carboxyl group, such as sodium acrylate, and an ω-halogenocarboxylic acid, such as ω
-There is also a method of reacting with chlorcaproic acid,
This method requires many steps to produce the raw material ω-halogenocarboxylic acid, and also has two radically polymerizable functional groups.
Introducing more than one metal salt requires multiple steps, and also requires a separation step from the by-produced metal halide salt, so at present no industrial production method has been developed.
本発明者らは従来のこれらの欠点に鑑み鋭意研
究した結果、アクリル酸及び／又はメタクリル酸
とω−カプロラクトンとを酸性触媒の存在下で反
応させることにより、カプロラクトンポリエステ
ル不飽和単量体が得られることを見出し本発明を
完成するに至つたものである。 As a result of intensive research in view of these conventional drawbacks, the present inventors have discovered that a caprolactone polyester unsaturated monomer can be obtained by reacting acrylic acid and/or methacrylic acid with ω-caprolactone in the presence of an acidic catalyst. This discovery led to the completion of the present invention.
本発明によれば、原料として用いるカルボキシ
ル基を有するラジカル重合体不飽和単量体として
アクリル酸、メタクリル酸を用いた場合には、ラ
ジカル重合性官能基を全く含まない化合物や２個
以上含む化合物を生成させることなく、ラジカル
重合性官能基を必ず１個含むカプロラクトンポリ
エステル不飽和単量体を製造することができる。
得られたカプロラクトンポリエステル不飽和単量
体は、反応性に富むカルボキシル基を片末端に有
し、さらに、このカルボキシル基から遠く離れた
ところにラジカル重合性不飽和基があるという特
長をもつている。 According to the present invention, when acrylic acid or methacrylic acid is used as a radical polymerizable unsaturated monomer having a carboxyl group as a raw material, a compound containing no radically polymerizable functional group or a compound containing two or more radically polymerizable functional groups can be used. Caprolactone polyester unsaturated monomers that always contain one radically polymerizable functional group can be produced without producing.
The obtained caprolactone polyester unsaturated monomer has a highly reactive carboxyl group at one end, and further has a radically polymerizable unsaturated group located far away from this carboxyl group. .
本発明で使用されるカルボキシル基を有するラ
ジカル重合性不飽和単量体は、アクリル酸及び／
又はカルボキシル基を有するラジカル重合性不飽
和単量体に対するω−カプロラクトンの使用量
は、目的物の分子量に応じて決まる量であり、ま
た特に触媒量、溶媒の種類、溶媒量によつて影響
を受けるが、カルボキシル基を有するラジカル重
合性不飽和単量体100重量部（以下単に部と称す
る）に対して50〜2000部が好ましい。 The radically polymerizable unsaturated monomer having a carboxyl group used in the present invention includes acrylic acid and/or
The amount of ω-caprolactone used relative to the radically polymerizable unsaturated monomer having a carboxyl group is determined depending on the molecular weight of the target product, and is particularly influenced by the amount of catalyst, type of solvent, and amount of solvent. However, it is preferably 50 to 2000 parts per 100 parts by weight (hereinafter simply referred to as parts) of the radically polymerizable unsaturated monomer having a carboxyl group.
本発明で使用しうる酸性触媒としては、塩化ア
ルミニウム、塩化第二スズなどのルイス酸及び硫
酸、Ｐ−トルエンスルホン酸、ベンゼンスルホン
酸、スルホン酸型イオン交換樹脂などのブレンス
テツド酸が挙げられるが、反応液に溶解する触媒
がよく、硫酸、Ｐ−トルエンスルホン酸、ベンゼ
ンスルホン酸が好ましい。酸性触媒の使用量はカ
ルボキシル基を有するラジカル重合性不飽和単量
体100部に対して0.1〜50部が好ましく、１〜20部
がさらに好ましいが、スルホン酸型イオン交換樹
脂を用いる場合には硫酸、Ｐ−トルエンスルホン
酸等に比べ多量必要とする。 Acidic catalysts that can be used in the present invention include Lewis acids such as aluminum chloride and stannic chloride, and Brønsted acids such as sulfuric acid, P-toluenesulfonic acid, benzenesulfonic acid, and sulfonic acid type ion exchange resins. A catalyst that dissolves in the reaction solution is preferred, and sulfuric acid, P-toluenesulfonic acid, and benzenesulfonic acid are preferred. The amount of the acidic catalyst used is preferably 0.1 to 50 parts, more preferably 1 to 20 parts, per 100 parts of the radically polymerizable unsaturated monomer having a carboxyl group. However, when using a sulfonic acid type ion exchange resin, A large amount is required compared to sulfuric acid, P-toluenesulfonic acid, etc.
本発明において使用しうる溶媒としては、酸性
触媒、ε−カプロラクトン及びカルボキシル基を
有するラジカル重合性不飽和単量体と反応しない
ものであり、具体的にはベンゼン、トルエン、キ
シレン等の芳香族炭化水素が挙げられる。また無
溶媒でも製造することができる。 Solvents that can be used in the present invention include those that do not react with the acidic catalyst, ε-caprolactone, and radically polymerizable unsaturated monomers having carboxyl groups. Examples include hydrogen. It can also be produced without a solvent.
本発明のカプロラクトンポリエステル不飽和単
量体の製造方法を具体的に述べると、カルボキシ
ル基を有するラジカル重合性不飽和単量体100部
に対し酸性触媒0.1〜50部及び必要に応じて重合
防止剤として例えばハイドロキノン、ハイドロキ
ノンモノメチルエーテル、BHTなどを0.01〜0.5
部加え、反応温度40〜150℃好ましくは60〜130℃
でε−カプロラクトンを一括又は連続的に加えて
反応させる。溶媒の量としては反応液中０〜95重
量％の濃度で使用できる。カプロラクトンポリエ
ステル不飽和単量体を含む反応液から中和、吸着
等の処理により酸性触媒を除去し、又必要に応じ
て水洗、蒸留等の操作によりカプロラクトンポリ
エステル不飽和単量体の単一品又はε−カプロラ
クトンの付加モル数の異なる混合物が得られる。
得られたカプロラクトンポリエステル不飽和単量
体の構造は、NMR、元素分析、GPC、酸価、二
重結合の測定などにより同定確認することができ
る。 To specifically describe the method for producing the caprolactone polyester unsaturated monomer of the present invention, 0.1 to 50 parts of an acidic catalyst and a polymerization inhibitor as necessary are added to 100 parts of a radically polymerizable unsaturated monomer having a carboxyl group. For example hydroquinone, hydroquinone monomethyl ether, BHT etc. 0.01~0.5
reaction temperature 40~150℃, preferably 60~130℃
ε-caprolactone is added all at once or continuously and reacted. The amount of the solvent used may range from 0 to 95% by weight in the reaction solution. The acidic catalyst is removed from the reaction solution containing the caprolactone polyester unsaturated monomer by treatments such as neutralization and adsorption, and if necessary, a single product of caprolactone polyester unsaturated monomer or ε - Mixtures with different numbers of added moles of caprolactone are obtained.
The structure of the obtained caprolactone polyester unsaturated monomer can be identified and confirmed by NMR, elemental analysis, GPC, acid value, double bond measurement, etc.
本発明によれば、カルボキシル基を有するラジ
カル重合性不飽和単量体に含まれるラジカル重合
性官能基と同一のラジカル重合性官能基を有する
カプロラクトンポリエステル不飽和単量体か短か
い工程で工業的に容易に製造することができ、得
られたカプロラクトンポリエステル不飽和単量体
は、ラジカル重合性不飽和基を１個有し、また末
端にカルボキシル基を有しているので、これを利
用して熱硬化性塗料、接着剤、架橋剤、エマルジ
ヨン安定剤、分散剤、乳化剤などの原料、中間体
として広範囲な応用が期待される。 According to the present invention, the caprolactone polyester unsaturated monomer having the same radically polymerizable functional group as the radically polymerizable functional group contained in the radically polymerizable unsaturated monomer having a carboxyl group can be produced industrially in a short process. The caprolactone polyester unsaturated monomer obtained has one radically polymerizable unsaturated group and a carboxyl group at the terminal, so it can be easily produced by using this. It is expected to have a wide range of applications as a raw material and intermediate for thermosetting paints, adhesives, crosslinking agents, emulsion stabilizers, dispersants, emulsifiers, etc.
以下に実施例をあげて本発明をさらに具体的に
説明する。なお各例における部は重量部を意味す
る。 The present invention will be explained in more detail with reference to Examples below. Note that parts in each example mean parts by weight.
実施例 １
撹拌機、還流冷却器、滴下ロート、温度計を備
えたガラスフラスコにアクリル酸144部、Ｐ−ト
ルエンスルホン酸１水塩８部及び重合防止剤とし
てハイドロキノンモノメチルエーテル0.08部を仕
込み、液温を80℃に保ちつつ、滴下ロートよりε
−カプロラクトン114部を４時間かかつて滴下反
応させた。滴下終了後さらに２時間同温度で反応
させ反応を完結させた。反応液をガスクロ分析し
たところε−カプロラクトンの転化率は99.3％で
あつた。Example 1 A glass flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer was charged with 144 parts of acrylic acid, 8 parts of P-toluenesulfonic acid monohydrate, and 0.08 parts of hydroquinone monomethyl ether as a polymerization inhibitor. ε from the dropping funnel while keeping the temperature at 80℃.
- 114 parts of caprolactone was added dropwise for 4 hours. After the dropwise addition was completed, the reaction was continued at the same temperature for another 2 hours to complete the reaction. Gas chromatography analysis of the reaction solution revealed that the conversion rate of ε-caprolactone was 99.3%.
得られたカプロラクトンポリエステルアクリレ
ートの構造を確認するため、反応液中のＰ−トル
エンスルホン酸を1.05倍当量の10％NaOHメタノ
ール液で中和を行ないロータリーエバポレーター
にて過剰のアクリル酸を減圧下100℃で除去を行
なつた。得られた反応液を過してカプロラクト
ンポリエステルアクリレート118.7部を得た。得
られたカプロラクトンポリエステルアクリレート
について物性を測定した。 In order to confirm the structure of the obtained caprolactone polyester acrylate, P-toluenesulfonic acid in the reaction solution was neutralized with 1.05 times equivalent of 10% NaOH methanol solution, and excess acrylic acid was removed using a rotary evaporator at 100°C under reduced pressure. I did the removal. The resulting reaction solution was filtered to obtain 118.7 parts of caprolactone polyester acrylate. Physical properties of the obtained caprolactone polyester acrylate were measured.
得られた分析結果は次のとおりである。 The analysis results obtained are as follows.
酸価分析値 ；4.01mg 当量／ｇ 二重結合の分析値 ；4.11mg 当量／ｇ ポリスチレン換算数平均分子量 ；376 GPC分析 ；第１図 なおGPC分析の分析条件は次のとおりである。Acid value analysis value: 4.01mg equivalent/g Analysis value of double bond: 4.11mg equivalent/g Polystyrene equivalent number average molecular weight: 376 GPC analysis; Figure 1 The analysis conditions for GPC analysis are as follows.
カラム ；G3000H8＋G4000H8
溶 媒 ；THF
温 度 ；40℃
さらに各付加体の真の分子量（Mw）とポリスチ
レンの分子量（Ms）との間の相関をみたところ、
Mw＝27＋0.58Ms
となりこれにより数平均分子量245となる。Column: G3000H8 + G4000H8 Solvent: THF Temperature: 40°C Furthermore, when we looked at the correlation between the true molecular weight (Mw) of each adduct and the molecular weight (Ms) of polystyrene, we found that Mw = 27 + 0.58Ms, which leads to the number average molecular weight It becomes 245.
元素分析 ；C59.2％
H7.8％
NMR分析；第２図
また得られたカプロラクトンポリエステルアク
リレートの示性式は次のようである。 Elemental analysis; C59.2% H7.8% NMR analysis; Figure 2 The specific formula of the obtained caprolactone polyester acrylate is as follows.
実施例 ２
酸性触媒として98％硫酸８部使用した以外は実
施例１と同様にしてカプロラクトンポリエステル
アクリレートを製造した。得られた反応液をガス
クロ分析したところε−カプロラクトンの転化率
は99.1％であつた。 Example 2 Caprolactone polyester acrylate was produced in the same manner as in Example 1 except that 8 parts of 98% sulfuric acid was used as the acidic catalyst. Gas chromatography analysis of the resulting reaction solution revealed that the conversion rate of ε-caprolactone was 99.1%.
さらに実施例１と同様の操作により硫酸の中和
後アクリル酸を除去して、過することによりカ
プロラクトンポリエステルアクリレート120部を
得た。得られたカプロラクトンポリエステルアク
リレートについて実施例１と同様の分析を行なつ
た。その結果は次のとおりである。 Furthermore, acrylic acid was removed after neutralization of sulfuric acid by the same operation as in Example 1, and 120 parts of caprolactone polyester acrylate was obtained by filtering. The obtained caprolactone polyester acrylate was analyzed in the same manner as in Example 1. The results are as follows.
酸価分析値 ；3.91mg当量／ｇ
二重結合分析値；3.85mg／当量／ｇ
GPCによるポリスチレン換算数平均分子量
；405
実施例 ３
カルボキシル基を有するラジカル重合性不飽和
単量体としてメタクリル酸172部使用した以外は
実施例１と同様にしてカプロラクトンポリエステ
ルアクリレートを製造した。得られた反応液をガ
スクロ分析したところε−カプロラクトンの転化
率は99.2％であつた。Acid value analysis value: 3.91 mg equivalent/g Double bond analysis value: 3.85 mg/equivalent/g Polystyrene equivalent number average molecular weight by GPC: 405 Example 3 Methacrylic acid 172 as a radically polymerizable unsaturated monomer having a carboxyl group Caprolactone polyester acrylate was produced in the same manner as in Example 1, except that 50% of the caprolactone polyester acrylate was used. Gas chromatography analysis of the resulting reaction solution revealed that the conversion rate of ε-caprolactone was 99.2%.
さらに実施例１と同様に精製したところカプロ
ラクトンポリエステルメタクリレート95部を得
た。得られたカプロラクトンポリエステルアクリ
レートについて実施例１と同様の分析を行なつ
た。その結果は次のとおりである。 Further purification was performed in the same manner as in Example 1 to obtain 95 parts of caprolactone polyester methacrylate. The obtained caprolactone polyester acrylate was analyzed in the same manner as in Example 1. The results are as follows.
酸価分析値 ；2.94mg当量／ｇ 二重結合分析値；2.88mg当量／ｇ GPCによるポリスチレン換算数平均分子量 ；544Acid value analysis value: 2.94mg equivalent/g Double bond analysis value: 2.88 mg equivalent/g Polystyrene equivalent number average molecular weight by GPC ;544
第１図は実施例１において得られたカプロラク
トンポリエステルアクリレートのゲルパーミエー
シヨン（GPC）分析のチヤートであり、第２図
は同じく実施例１において得られたカプロラクト
ンポリエステルアクリレートのNMR分析のチヤ
ートである。
Figure 1 is a chart of gel permeation (GPC) analysis of caprolactone polyester acrylate obtained in Example 1, and Figure 2 is a chart of NMR analysis of caprolactone polyester acrylate obtained in Example 1. .
Claims (1)
プロラクトンを、酸性触媒の存在下で反応させる
ことを特徴とする、分子末端の一方にアクリロイ
ルオキシ基又はメタクリロイルオキシ基を有し、
他方にカルボキシル基を有する、ε−カプロラク
トンの開環重合体である、カプロラクトンポリエ
ステル不飽和単量体の製造方法。1. Acrylic acid and/or methacrylic acid and ε-caprolactone are reacted in the presence of an acidic catalyst, and have an acryloyloxy group or a methacryloyloxy group at one end of the molecule,
A method for producing a caprolactone polyester unsaturated monomer, which is a ring-opening polymer of ε-caprolactone having a carboxyl group on the other hand.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58175194A JPS6067446A (en) | 1983-09-24 | 1983-09-24 | Production of caprolactone polyester unsaturated monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58175194A JPS6067446A (en) | 1983-09-24 | 1983-09-24 | Production of caprolactone polyester unsaturated monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6067446A JPS6067446A (en) | 1985-04-17 |
| JPH0321536B2 true JPH0321536B2 (en) | 1991-03-22 |
Family
ID=15991933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58175194A Granted JPS6067446A (en) | 1983-09-24 | 1983-09-24 | Production of caprolactone polyester unsaturated monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6067446A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1978736A2 (en) | 2007-04-02 | 2008-10-08 | Funai Electric Co., Ltd. | Assembling structure for flat-panel display unit, and flat-panel television |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4732943A (en) * | 1985-04-24 | 1988-03-22 | Commonwealth Scientific And Industrial Research Organization | Dental restorative material |
| JPH0491104A (en) * | 1990-08-06 | 1992-03-24 | Ootex Kk | Photopolymerization reaction initiator |
| JP3601125B2 (en) * | 1995-08-31 | 2004-12-15 | ユニマテック株式会社 | Novel acrylic copolymer elastomer, its blended rubber and blended rubber composition |
| JP2004359656A (en) * | 2003-06-06 | 2004-12-24 | Daicel Chem Ind Ltd | Method for producing unsaturated monomer bearing carboxy terminal group for lactonic polyester |
| JP2007063460A (en) * | 2005-09-01 | 2007-03-15 | Daicel Chem Ind Ltd | Manufacturing method of carboxy group-containing lactone polyester unsaturated monomer |
| FR2912751B1 (en) * | 2007-02-16 | 2012-07-13 | Arkema France | PROCESS FOR THE PREPARATION OF POLYLACTONES AND POLYLACTAMES |
| EP3670569A1 (en) * | 2018-12-21 | 2020-06-24 | Covestro Deutschland AG | Method for producing a polyester |
| EP3670568A1 (en) * | 2018-12-21 | 2020-06-24 | Covestro Deutschland AG | Method for producing a polyester |
-
1983
- 1983-09-24 JP JP58175194A patent/JPS6067446A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1978736A2 (en) | 2007-04-02 | 2008-10-08 | Funai Electric Co., Ltd. | Assembling structure for flat-panel display unit, and flat-panel television |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6067446A (en) | 1985-04-17 |
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