JP2733328B2 - Esterification reaction method - Google Patents
Esterification reaction methodInfo
- Publication number
- JP2733328B2 JP2733328B2 JP1217723A JP21772389A JP2733328B2 JP 2733328 B2 JP2733328 B2 JP 2733328B2 JP 1217723 A JP1217723 A JP 1217723A JP 21772389 A JP21772389 A JP 21772389A JP 2733328 B2 JP2733328 B2 JP 2733328B2
- Authority
- JP
- Japan
- Prior art keywords
- esterification reaction
- crown
- carboxyl group
- reaction
- containing compound
- 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
- 238000005886 esterification reaction Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000003700 epoxy group Chemical group 0.000 claims description 12
- 150000003983 crown ethers Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 description 13
- 229920000728 polyester Polymers 0.000 description 10
- -1 quaternary ammonium halide Chemical class 0.000 description 9
- 239000002739 cryptand Substances 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008096 xylene Substances 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は，カルボキシル基含有化合物とエポキシ基含
有化合物とから目的とするエステルを効率良く得ること
のできるエステル化反応方法に関するものである。Description: TECHNICAL FIELD The present invention relates to an esterification reaction method capable of efficiently obtaining a target ester from a carboxyl group-containing compound and an epoxy group-containing compound.
（従来の技術） カルボキシル基含有化合物とエポキシ基含有化合物と
のエステル化反応は，頻繁に行われる反応の一つであ
り，種々の触媒系で行われ，代表例としては，アルカ
リ例えば水酸化ナトリウムを用いて行う方法，アニオ
ン交換樹脂を用いて行う方法，第４級アンモニウムハ
ライドの存在下で行う方法等がある。(Prior Art) The esterification reaction between a carboxyl group-containing compound and an epoxy group-containing compound is one of the frequently performed reactions, and is carried out with various catalyst systems. A typical example is an alkali such as sodium hydroxide. , A method using an anion exchange resin, a method in the presence of a quaternary ammonium halide, and the like.
これらの方法の得失は様々であるが，例えば，末端に
カルボキシル基を有するポリエステルと，エポキシ基を
有し反応性に富む不飽和基も有するグリシジルアクリレ
ートやグリシジルメタクリレートのようなエポキシドと
の反応の場合には，前記，，の方法では次のよう
な問題がある。The advantages and disadvantages of these methods are various. For example, in the case of a reaction between a polyester having a carboxyl group at a terminal and an epoxide such as glycidyl acrylate or glycidyl methacrylate having an epoxy group and also having a reactive unsaturated group. However, the above methods have the following problems.
まずではアルカリ存在下で反応が行われるので，け
ん化反応により主鎖の切断が起こり，目的とするポリエ
ステルを得るためのコントロールが非常に難しい。で
は触媒活性が低いのに加え，反応後樹脂を分離する操作
が必要である。またにおいては触媒活性は高いが，生
成物中にハロゲンが残留したり，あるいはアンモニア臭
がする等の問題がある。また，二重結合にミカエル型の
付加が起こりエステル化物自体が重合開始剤となってし
まう。First, since the reaction is carried out in the presence of an alkali, the main chain is cut by the saponification reaction, and it is very difficult to control to obtain the desired polyester. However, in addition to the low catalytic activity, an operation of separating the resin after the reaction is required. In addition, although the catalyst activity is high, there are problems such as halogen remaining in the product or smell of ammonia. Further, Michael-type addition occurs to the double bond, and the esterified product itself becomes a polymerization initiator.
（発明が解決しようとする課題） このような状況に鑑み，本発明の課題は，カルボキシ
ル基含有化合物とエポキシ基含有化合物の反応におい
て，カルボキシル基とエポキシ基が選択的に反応して目
的とするエステル化合物が得られると共に，反応が効率
良く進行するようなエステル化反応方法の提供にある。(Problems to be Solved by the Invention) In view of such a situation, an object of the present invention is to selectively react a carboxyl group and an epoxy group in a reaction between a carboxyl group-containing compound and an epoxy group-containing compound. An object of the present invention is to provide an esterification reaction method in which an ester compound is obtained and the reaction proceeds efficiently.
（課題を解決するための手段） 本発明者等は前記課題について鋭意検討した結果，カ
ルボキシル基含有化合物とエポキシ基含有化合物をエス
テル化する際，触媒としてクラウンエーテル類を用いる
と，これが良好な選択的触媒活性を示し目的とするエス
テル化合物が得られ，また，反応が効率良く進行するこ
とを知り，本発明に到達した。(Means for Solving the Problems) As a result of intensive studies on the above problems, the present inventors have found that when a crown ether is used as a catalyst when esterifying a carboxyl group-containing compound and an epoxy group-containing compound, this is a good choice. It was found that the desired ester compound was obtained which showed a catalytic activity and that the reaction proceeded efficiently, and the present invention was reached.
すなわち，本発明の要旨は次に述べる通りである。 That is, the gist of the present invention is as described below.
カルボキシル基含有化合物とエポキシ基含有化合物
を，クラウンエーテル類の存在下で反応させることを特
徴とするエステル化反応方法。An esterification reaction method comprising reacting a carboxyl group-containing compound with an epoxy group-containing compound in the presence of a crown ether.
次に本発明について詳述する。 Next, the present invention will be described in detail.
本発明において，カルボキシル基含有化合物としては
カルボキシル基を有するものであれば特に限定されず，
酢酸を初めとする脂肪族カルボン酸や安息香酸を初めと
する芳香族カルボン酸等の炭素数２〜20の低分子量のカ
ルボン酸から中・高分子量のカルボキシル基を有するポ
リエステル等が挙げられる。In the present invention, the carboxyl group-containing compound is not particularly limited as long as it has a carboxyl group.
Examples thereof include low molecular weight carboxylic acids having 2 to 20 carbon atoms, such as aliphatic carboxylic acids such as acetic acid and aromatic carboxylic acids such as benzoic acid, and polyesters having a medium to high molecular weight carboxyl group.
また，エポキシ基含有化合物もエポキシ基を有するも
のであれば特に限定されず，エチレンオキサイド，グリ
シジルアクリレート，グリシジルメタクリレート，グリ
シジルエタクリレート等が挙げられる。The epoxy group-containing compound is not particularly limited as long as it has an epoxy group, and examples thereof include ethylene oxide, glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate.
クラウンエーテル類とはヘテロ大環状化合物の総称で
あり，好ましく用いられる代表例としてはジシクロヘキ
シル−18−クラウン−6,ジシクロヘキシル−24−クラウ
ン−8,15−クラウン−5,18−クラウン−6,ジベンゾ−18
−クラウン−6,ジベンゾ−24−クラウン−8,〔2,2,2〕
−クリプタンド，〔2,2,1〕−クリプタンド，〔2,1,1〕
−クリプタンド，〔2,2,2〕−デシルクリプタンド，
〔2,2,2〕−ベンゾクリプタンド等が挙げられ，特に，
ジシクロヘキシル−18−クラウン−6,18−クラウン−6,
ジベンゾ−18−クラウン−６が使用効果の点で好まし
い。Crown ethers are a general term for heteromacrocyclic compounds, and preferred examples thereof are dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8,15-crown-5,18-crown-6, dibenzo. −18
-Crown-6, dibenzo-24-crown-8, [2,2,2]
−cryptand, [2,2,1] −cryptand, [2,1,1]
-Cryptand, [2,2,2]-decyl cryptand,
[2,2,2] -benzocryptand and the like.
Dicyclohexyl-18-crown-6,18-crown-6,
Dibenzo-18-crown-6 is preferred in terms of use effect.
本発明におけるエステル化反応は下記反応式 で表され，該反応はいわゆるバルクの状態や，有機溶媒
中で実施することが可能である。The esterification reaction in the present invention is represented by the following reaction formula. The reaction can be carried out in a so-called bulk state or in an organic solvent.
使用溶媒としては非極性溶媒であることが好ましく，
ベンゼン，トルエン，キシレン，メチルエチルケトン等
の汎用のものを使うことができる。The solvent used is preferably a non-polar solvent,
General-purpose products such as benzene, toluene, xylene, and methyl ethyl ketone can be used.
エステル化反応系へのクラウンエーテル類の添加量は
0.0001〜1.0重量％，好ましくは0.003〜0.8重量％であ
ることが良い。反応温度は50〜250℃，好ましくは70〜2
00℃であることが良い。また，場合によってはさらに反
応を促進する目的でリチウム，ナトリウム，カリウム、
マグネシウム，カルシウム等のアルカリ金属やアルカリ
土類金属を含む化合物を少量添加してクラウンエーテル
に該金属を配位させた形で行ってもよい。The amount of crown ethers added to the esterification reaction system is
The content is 0.0001 to 1.0% by weight, preferably 0.003 to 0.8% by weight. The reaction temperature is 50 to 250 ° C, preferably 70 to 2
It is good to be 00 ° C. In some cases, lithium, sodium, potassium,
It may be carried out in a form in which a small amount of a compound containing an alkali metal or an alkaline earth metal such as magnesium or calcium is added and the metal is coordinated with crown ether.
クラウンエーテル類のエステル化反応における選択性
及び促進効果については明らかでないが，クラウンエー
テルの存在によってカルボキシル基の水素原子が活性化
されるためではないかと考えられ，前述のように本発明
はエステル化以外の副反応が起こりやすい系で特に好ま
しく採用され，本発明を採用することによって目的とす
るエステルが効率良く得られ，反応性モノマー，反応性
オリゴマー，光硬化性ポリエステル等の合成に好適に利
用できる。Although the selectivity and promoting effect in the esterification reaction of crown ethers are not clear, it is thought that the presence of the crown ether may activate the hydrogen atom of the carboxyl group. It is particularly preferably used in a system in which side reactions other than the above tend to occur. By adopting the present invention, the desired ester can be obtained efficiently and is suitably used for the synthesis of reactive monomers, reactive oligomers, photocurable polyesters, and the like. it can.
（実施例） 以下，本発明の特徴を特に発揮するカルボキシル基を
有するポリエステルとグリシジルメタクリレートとの反
応について述べる。(Examples) Hereinafter, the reaction between glycidyl methacrylate and a polyester having a carboxyl group that particularly exhibits the features of the present invention will be described.
（１） 末端にカルボキシル基を有するポリエステルの
製造 テレフタル酸成分30モル％，イソフタル酸成分５モル
％，セバシン酸成分15モル％，エチレングリコール成分
20モル％及びネオペンチルグリコール成分30モル％よ
り，通常の溶融重縮合法で製造した数平均分子量20,000
のランダム共重合ポリエステル1.00kgに対してセバシン
酸3.0gを加えて,250℃で２時間アシドリシス反応を行い
末端カルボキシルの量が380g当量／トンのポリエステル
を得た。(1) Production of polyester having a carboxyl group at the end 30 mol% of terephthalic acid component, 5 mol% of isophthalic acid component, 15 mol% of sebacic acid component, ethylene glycol component
A number average molecular weight of 20,000 produced by a normal melt polycondensation method from 20 mol% and 30 mol% of neopentyl glycol component
3.0 g of sebacic acid was added to 1.00 kg of the random copolymerized polyester, and an acidolysis reaction was carried out at 250 ° C. for 2 hours to obtain a polyester having a terminal carboxyl amount of 380 g equivalent / ton.
（２） カルボキシル基とエポキシ基の反応 前記（１）で得た末端にカルボキシル基を有するポリ
エステル100重量部，グリシジルメタクリレート10重量
部，ハイドロキノンモノメチルエーテル0.003重量及び
0.1重量部のジベンゾ−18−クラウン−６をトルエン−1
00重量部に溶解し、100℃で30時間エステル化反応さ
せ，得られた溶液について，カルボキシル基を測定した
ところ5g当量／トンであった。また核磁気共鳴分析法に
よってメタクリロイル基を測定したところほとんど消失
していないことが分かった。(2) Reaction between carboxyl group and epoxy group 100 parts by weight of the polyester having a terminal carboxyl group obtained in the above (1), 10 parts by weight of glycidyl methacrylate, 0.003 parts by weight of hydroquinone monomethyl ether,
0.1 parts by weight of dibenzo-18-crown-6 is dissolved in toluene-1
The resulting solution was dissolved in 00 parts by weight, and subjected to an esterification reaction at 100 ° C. for 30 hours. The obtained solution was measured for carboxyl groups, and found to be 5 g equivalent / ton. The measurement of the methacryloyl group by nuclear magnetic resonance analysis showed that the methacryloyl group had hardly disappeared.
前記エステル化反応においてジベンゾ−18−クラウン
−６を使用しなかった以外は，同条件でエステル化反応
させたところ，得られた溶液におけるカルボキシル基は
64g当量／トンであった。When the esterification reaction was carried out under the same conditions except that dibenzo-18-crown-6 was not used in the esterification reaction, the carboxyl group in the resulting solution was
It was 64 g equivalent / ton.
（発明の効果） 本発明によれば，カルボキシル基含有化合物とエポキ
シ基含有化合物とのエステル化反応を選択的にしかも効
率良く行うことができる。したがって，目的とするエス
テル化合物を選択的に製造することができ本発明方法
は，反応性モノマー，反応性オリゴマー、光硬化性ポリ
エステル等の合成に好適に利用できる。(Effect of the Invention) According to the present invention, an esterification reaction between a carboxyl group-containing compound and an epoxy group-containing compound can be selectively and efficiently performed. Therefore, the desired ester compound can be selectively produced, and the method of the present invention can be suitably used for the synthesis of a reactive monomer, a reactive oligomer, a photocurable polyester and the like.
Claims (1)
有化合物を，クラウンエーテル類の存在下で反応させる
ことを特徴とするエステル化反応方法。An esterification reaction method comprising reacting a carboxyl group-containing compound with an epoxy group-containing compound in the presence of a crown ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1217723A JP2733328B2 (en) | 1989-08-24 | 1989-08-24 | Esterification reaction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1217723A JP2733328B2 (en) | 1989-08-24 | 1989-08-24 | Esterification reaction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0381250A JPH0381250A (en) | 1991-04-05 |
| JP2733328B2 true JP2733328B2 (en) | 1998-03-30 |
Family
ID=16708730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1217723A Expired - Fee Related JP2733328B2 (en) | 1989-08-24 | 1989-08-24 | Esterification reaction method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2733328B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016009392A1 (en) * | 2014-07-18 | 2016-01-21 | Sabic Global Technologies B.V. | Methods of forming dynamic cross-linked polymer compositions |
-
1989
- 1989-08-24 JP JP1217723A patent/JP2733328B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0381250A (en) | 1991-04-05 |
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Legal Events
| Date | Code | Title | Description |
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| LAPS | Cancellation because of no payment of annual fees |