JPS63159418A - Production of modified epoxy resin - Google Patents
Production of modified epoxy resinInfo
- Publication number
- JPS63159418A JPS63159418A JP30708586A JP30708586A JPS63159418A JP S63159418 A JPS63159418 A JP S63159418A JP 30708586 A JP30708586 A JP 30708586A JP 30708586 A JP30708586 A JP 30708586A JP S63159418 A JPS63159418 A JP S63159418A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- formulas
- formula
- tables
- modified epoxy
- 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.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 41
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 3
- 239000000126 substance Substances 0.000 claims 11
- 239000001257 hydrogen Substances 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 11
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 abstract description 5
- -1 diphenol compound Chemical class 0.000 abstract description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- ANVPJIVTLVQUNV-UHFFFAOYSA-N 1-[butyl(chloro)phosphoryl]butane Chemical compound CCCCP(Cl)(=O)CCCC ANVPJIVTLVQUNV-UHFFFAOYSA-N 0.000 description 1
- MOBNLCPBAMKACS-UHFFFAOYSA-N 2-(1-chloroethyl)oxirane Chemical compound CC(Cl)C1CO1 MOBNLCPBAMKACS-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、変性エポキシ樹脂の製法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a modified epoxy resin.
一般にエポキシ樹脂は、接着性、被覆性、耐候性、耐溶
剤性、電気特性、透明性および機械的強度等の優れた特
性を有している。Generally, epoxy resins have excellent properties such as adhesiveness, coating properties, weather resistance, solvent resistance, electrical properties, transparency, and mechanical strength.
したがって、エポキシ樹脂は広範囲の用途に使用されて
いる。Therefore, epoxy resins are used in a wide range of applications.
本発明は、従来のエポキシ樹脂の特性を生かして接若剤
、４ａ！脂改良剤、繊維処理剤、被覆材料、充填材料お
よび電子部品材料等として有用かつ新規な変性エポキシ
樹脂を提供することにある。すなわち、
一般式（１）
で示されるエポキシ樹脂と、
一般式（２）
で示される化合物を、脱ハロゲン化水素剤の存在下で反
応させて
一般式（３）
で示されるエポキシ樹脂の製法である。The present invention utilizes the properties of conventional epoxy resins to create an adhesive, 4a! It is an object of the present invention to provide a novel modified epoxy resin that is useful as a fat improver, a fiber treatment agent, a coating material, a filling material, an electronic component material, and the like. That is, in the method for producing the epoxy resin represented by the general formula (3), the epoxy resin represented by the general formula (1) and the compound represented by the general formula (2) are reacted in the presence of a dehydrohalogenating agent. be.
木発ＩＪＩで使用する一般式（１）で示されるエポキシ
樹脂としては、一般式（４）で示される二官能フェノー
ル化合物、例えば
とエピハロゲンヒドリンもしくはメチルエピハロゲンヒ
ドリンを反応させて得られる化合物が挙げられる。The epoxy resin represented by the general formula (1) used in Kibatsu IJI is a compound obtained by reacting a bifunctional phenol compound represented by the general formula (4), for example, with epihalogenhydrin or methyl epihalogenhydrin. Can be mentioned.
エビハロゲンヒドリンおよびメチルエピハロゲンヒドリ
ンとしては、例えばエピクロルヒドリン、エピブロムヒ
ドリン、メチルエピハロクロルヒドリン、メチルエピク
ロルヒドリンおよびメチルエピブロムヒドリン等が挙げ
られる。Examples of the shrimp halogenhydrin and methylepihalogenhydrin include epichlorohydrin, epibromohydrin, methylepihalochlorohydrin, methylepichlorohydrin, and methylepibromhydrin.
一般式（２）で示される化合物としては１例えば、
脱ハロゲン化水素剤としては、例えばトリメチルアミン
、トリエチルアミン、トリアクリルアミン、トリブチル
アミン等のアミン類、ビリンン、ピコリン、ジエチルア
ニリン、苛性アルカリおよび炭酸アルカリ等が挙げられ
る。Examples of the compound represented by the general formula (2) include 1. Examples of the dehydrohalogenation agent include amines such as trimethylamine, triethylamine, triacrylamine, and tributylamine, biline, picoline, diethylaniline, caustic alkali, and alkali carbonate. etc.
本発明にかかる一般式（３）で示される変性エポキシ樹
脂の製法は、前記一般式（１）で示されるエポキシ樹脂
と前記一般式（２）で示される化合物を前記脱ハロゲン
化剤の存在下で反応させるものであり、具体的に詳述す
れば、
一般式（１）で示されるエポキシ樹脂を溶媒、例えば塩
化メチレン、トリクロロエタン等の塩素化炭化水素、ジ
メチルホルムアミドもしくはジメチルスルホキサイド等
に溶解させ、
次に脱ハロゲン化水素剤を添加し溶解させ、反応系内の
温度を ０〜４０°Ｃに保ち、次に一般式（２）で示さ
れる化合物をそのままもしくは溶媒に溶解させて滴下す
る。The method for producing the modified epoxy resin represented by the general formula (3) according to the present invention includes combining the epoxy resin represented by the general formula (1) and the compound represented by the general formula (2) in the presence of the dehalogenating agent. Specifically, the epoxy resin represented by the general formula (1) is dissolved in a solvent, such as a chlorinated hydrocarbon such as methylene chloride or trichloroethane, dimethylformamide or dimethyl sulfoxide. Next, a dehydrohalogenating agent is added and dissolved, the temperature in the reaction system is maintained at 0 to 40°C, and then the compound represented by general formula (2) is added dropwise as it is or dissolved in a solvent. .
滴下終了後、さらに前記温度で攪拌を続け、反応を終了
させる。After completion of the dropwise addition, stirring is further continued at the above temperature to complete the reaction.
反応終了後、濾別し副生塩を除去するか、または反応系
内に水を添加し、副生塩を溶解した後水洗し、必要に応
じて任意の濃度のＮａ２ＣＯ３もしくはＮａＨＣＯｓ水
溶液で洗浄した後、さらに水洗し、結晶を濾別し乾燥す
るか、または溶媒を留去することによって得る。After the reaction was completed, the by-product salts were removed by filtration, or water was added to the reaction system to dissolve the by-product salts, and then washed with water, and if necessary, with an aqueous solution of Na2CO3 or NaHCOs at an arbitrary concentration. After that, the crystals are further washed with water, and the crystals are filtered and dried, or the solvent is distilled off.
一般式（２）で示される化合物の使用量は、一般式（１
）で示されるエポキシ樹脂中に含有されるＯＨ基 １個
に対し、一般式（２）で示される化合物１〜１．３モル
が好ましい。The amount of the compound represented by the general formula (2) to be used is the amount of the compound represented by the general formula (1
) The compound represented by the general formula (2) is preferably used in an amount of 1 to 1.3 moles per 1 OH group contained in the epoxy resin represented by the formula (2).
脱ハロゲン化水素剤の使用量は、一般式（２）で示され
る化合物１モルに対し、１〜１．１モルが好ましい。The amount of the dehydrohalogenating agent used is preferably 1 to 1.1 mol per 1 mol of the compound represented by general formula (2).
本発明の変性エポキシ樹脂の製法に従って得られる一般
式（３）で示される変性エポキシ樹脂は、耐水性の向上
、可塑性の付与、電気特性の改善、架橋による物性の向
上、＃候性の向上等の優れた特性を有するものであり、
接若剤、樹脂改質剤、繊維処理剤、被覆材料。The modified epoxy resin represented by the general formula (3) obtained according to the method for producing a modified epoxy resin of the present invention has improved water resistance, imparted plasticity, improved electrical properties, improved physical properties through crosslinking, improved weatherability, etc. It has excellent properties, and is suitable for use as an attractive agent, resin modifier, fiber treatment agent, and coating material.
充填材料、電子部品材料、顔料、無機材料の分散剤、架
橋剤、塗料、エマルジョン改質剤として最適である。Ideal as filler materials, electronic component materials, pigments, dispersants for inorganic materials, crosslinking agents, paints, and emulsion modifiers.
次に本発明の実施例を記載する。実施例中、「％」はｆ
ｆｉ＋ｊ！、基準である。Next, examples of the present invention will be described. In the examples, "%" is f
fi+j! , is the standard.
実施例１
で示され、かつエポキシ当量が約１４００であるエポキ
シ樹脂２００ｇを、塩化メチレン５８０ｇに溶解し１反
応系内を１０℃以下に保ち、さらにトリエチルアミン９
９．９ｇを添加し、攪拌する。200 g of the epoxy resin shown in Example 1 and having an epoxy equivalent of about 1400 was dissolved in 580 g of methylene chloride, the inside of the reaction system was kept at 10°C or less, and triethylamine 9.
Add 9.9g and stir.
次に反応系内を１０〜２０℃に保ち、ジフェニルホスフ
ィン酸クロライド
る。Next, the inside of the reaction system is maintained at 10 to 20°C and diphenylphosphinic acid chloride is added.
滴下終了後、３０°Ｃで３時間、さらに４０℃で３時間
攪拌する。After the addition was completed, the mixture was stirred at 30°C for 3 hours and then at 40°C for 3 hours.
次に水６００ｇ、 １％Ｎａ２Ｃ’Ｏｓ水溶液８００
ｇおよび水６００ｇを順次加えて洗浄し、下層の塩化メ
チレン層を取り出し、脱水乾燥後溶媒を留去し、下記の
式で示される変性エポキシ樹脂３０８ ｇ（収率８５％
）を得た。Next, 600 g of water, 800 g of 1% Na2C'Os aqueous solution
The lower methylene chloride layer was taken out, and after dehydration and drying, the solvent was distilled off to obtain 308 g of a modified epoxy resin represented by the following formula (yield: 85%).
) was obtained.
この変性エポキシ樹脂は、
エポキシ醜素が０．６６％（計算値０．６８％）、りん
含量が５．９６％（計算値５．９４％）であった。This modified epoxy resin had an epoxy ugliness of 0.66% (calculated value 0.68%) and a phosphorus content of 5.96% (calculated value 5.94%).
実施例２
で示され、かつエポキシ出量が約５００であるエポキシ
樹脂９０．８ｇを、塩化メチレン２００ｇに溶解し、反
応系内を１０℃以下に保ち、さらにトリエチルアミン２
２ｇを添加し、攪拌する。90.8 g of the epoxy resin shown in Example 2 and having an epoxy output of about 500 was dissolved in 200 g of methylene chloride, the reaction system was kept at 10°C or less, and triethylamine 2
Add 2g and stir.
次に反応系内を１０〜２０℃に保ち、
ジブチルホスフィン酸クロライド
（ＣａＨｑ ） ２ＰＣＩ ３９．３ｇを滴下し反
応させる。Next, the inside of the reaction system was maintained at 10 to 20°C, and 39.3 g of dibutylphosphinic acid chloride (CaHq) 2PCI was added dropwise to react.
滴下終了後、２０°Ｃで２時間、さらに３０℃で５時間
攪拌する。After the addition was completed, the mixture was stirred at 20°C for 2 hours and then at 30°C for 5 hours.
次に水１００ｇ、 １％Ｎａ２ＧＯ，水溶液１００ｇお
よび水１００ｇを順次加えて洗浄し、下層の塩化メチレ
ン層を取り出し、脱水乾燥後溶媒を留去し、下記の式で
示される変性エポキシ樹脂１１６．３ｇ （収率９６％
）を得た。Next, 100 g of water, 1% Na2GO, 100 g of an aqueous solution, and 100 g of water were sequentially added for washing, the lower methylene chloride layer was taken out, and after dehydration and drying, the solvent was distilled off to obtain 116.3 g of a modified epoxy resin represented by the following formula. (Yield 96%
) was obtained.
この変性エポキシ樹脂はエポキシ醜素が２．８３％（計
算値２．６１％）、りん含量が５．１０％（計算値５．
０６％）であった。This modified epoxy resin has an epoxy ugliness of 2.83% (calculated value 2.61%) and a phosphorus content of 5.10% (calculated value 5.
06%).
実施例３
ＣＦ ｓ ＯＨＣＨｘ
で示されるエポキシ樹脂１０１１３ｇを、塩化メチレン
５０００ｇに溶解し、反応系内を１０℃以下に保ち、こ
れにトリエチルアミン２０５ｇを添加し、攪拌する。Example 3 10,113 g of an epoxy resin represented by CF s OHCHx is dissolved in 5,000 g of methylene chloride, and while the inside of the reaction system is maintained at 10° C. or lower, 205 g of triethylamine is added thereto and stirred.
次に反応系内を１０〜２０℃に保ち、ジフェニルホスフ
ィン酸クロライド
る。Next, the inside of the reaction system is maintained at 10 to 20°C and diphenylphosphinic acid chloride is added.
滴下終了後、２０℃で１時間、さらに３０℃で３時間攪
拌する。After completion of the dropwise addition, the mixture was stirred at 20°C for 1 hour and then at 30°C for 3 hours.
次に反応系内に水５０００ｇを加え洗浄後、 １％Ｎａ
２ＣＯ３水溶液５００ｇおよび水５０００ｇを加え２回
洗浄後、下層の塩化メチレン層を取り、脱水乾燥後溶媒
を留去し、下式で示す変性エポキシ樹脂１４２７ｇ
（収率８８．８％）を得た。Next, 5000 g of water was added to the reaction system, and after washing, 1% Na
After adding 500 g of 2CO3 aqueous solution and 5000 g of water and washing twice, the lower methylene chloride layer was removed, dehydrated and dried, and the solvent was distilled off to obtain 1427 g of a modified epoxy resin represented by the following formula.
(yield: 88.8%).
この変性エポキシ樹脂はエポキシ酸素含量が２゜１％（
計算値２．３％）、りん含量が４．３１％（計算値４．
２９％）であった・
実施例４
で示されるＢｒ、 Ｆ原子含有エポキシ樹脂２５７ｇを
、塩化メチレン１０００．に溶解し、反応系内を１０℃
に保ち、さらにトリエチルアミン４１．０ｇを添加し、
攪拌する。This modified epoxy resin has an epoxy oxygen content of 2.1% (
Calculated value 2.3%), phosphorus content 4.31% (calculated value 4.
29%). 257 g of the Br, F atom-containing epoxy resin shown in Example 4 was mixed with 1000.0 g of methylene chloride. The inside of the reaction system was heated to 10°C.
and further added 41.0 g of triethylamine.
Stir.
次に反応系内を１０〜２０℃に保ち、 させる。Next, maintain the inside of the reaction system at 10 to 20°C, let
滴下終了後、２０℃で１時間、さらに３０’０で３時間
攪拌する。After the addition was completed, the mixture was stirred at 20°C for 1 hour and then at 30'0 for 3 hours.
次に反応系内に水３０００ｇを加え洗浄後、 １％Ｎａ
２ＣＯａ水溶液５００ｇオよび水３００Ｇｇを加え２回
洗浄後、下層の塩化メチレン層を取り、脱水乾燥後溶媒
を留去し、変性エポキシ樹脂３３４ｇ （収率３７％）
を得た。Next, 3000 g of water was added to the reaction system, and after washing, 1% Na
After washing twice by adding 500 g of 2COa aqueous solution and 300 Gg of water, the lower methylene chloride layer was removed, dehydrated and dried, and the solvent was distilled off to give 334 g of modified epoxy resin (yield 37%).
I got it.
この変性エポキシ樹脂は、エポキシ酸素含量が０．８０
％（計算値０．８３％）、りん含量が３．８５％（計算
値３．６１％）であった。This modified epoxy resin has an epoxy oxygen content of 0.80
% (calculated value 0.83%), and the phosphorus content was 3.85% (calculated value 3.61%).
実施例５
で示され、かつエポキシ当量が６３３であるエポキシ樹
脂１２８ｇを、トリクロロエタン３００８に溶解し１反
応系内を１０℃以下に保ち、さらにピリジン２９．５ｇ
を添加し、攪拌する。128 g of the epoxy resin shown in Example 5 and having an epoxy equivalent of 633 was dissolved in trichloroethane 3008, the inside of the reaction system was kept at 10°C or less, and 29.5 g of pyridine was dissolved.
Add and stir.
次に反応系内を１０〜２０℃に保ち、ジフェニルホスフ
ィン酸クロライド
タン１００ｇに溶解したものを滴下し反応させる。Next, the inside of the reaction system is maintained at 10 to 20°C, and a solution of 100 g of diphenylphosphinic acid chloride tane is added dropwise to react.
滴下終了後、２０℃で１時間、さらに４０℃で３時間攪
拌する。After the addition was completed, the mixture was stirred at 20°C for 1 hour and then at 40°C for 3 hours.
次に濾別し、濾液に水５００ｇ、 １％Ｎａ２ＣＯ３水
溶液３００８および水５００ｇを順次加えて洗節し、下
層のトリクロロエタン層を取り出し、脱水乾燥後溶媒を
留去し、下記の式で示される変性エポキシ樹脂１９０ｇ
（収率８５％）を得た。Next, it was separated by filtration, 500 g of water, 300 g of 1% Na2CO3 aqueous solution, and 500 g of water were successively added to the filtrate for washing. The lower trichloroethane layer was taken out, and after dehydration and drying, the solvent was distilled off to obtain a modified product represented by the following formula. 190g of epoxy resin
(yield 85%).
変性エポキシ樹脂はエポキシ酸素含量が１．５１％（計
算値１．６０％）、りん含量が８．１０％（計算値８．
１８％）であった。The modified epoxy resin has an epoxy oxygen content of 1.51% (calculated value 1.60%) and a phosphorus content of 8.10% (calculated value 8.
18%).
応用例１
市販エポキシ樹脂（エビコー） ８２Ｂ） １００部に
硬化剤ジアミノジフェニルメタン２７部、シリカ５部、
実施例４の変性エポキシ樹脂２０部を加え、十分混合し
た後、注型し、８０℃で２時間加温後、さらに １８０
℃で３時間硬化せしめて得た成形体について、衝撃強度
、抗張力、抗折力。Application example 1 Commercially available epoxy resin (Ebicor 82B) 100 parts, hardening agent diaminodiphenylmethane 27 parts, silica 5 parts,
Add 20 parts of the modified epoxy resin of Example 4, mix well, cast, heat at 80°C for 2 hours, and then add 180 parts of the modified epoxy resin.
Impact strength, tensile strength, and transverse rupture strength of the molded product obtained by curing at °C for 3 hours.
吸水試験（１００℃、 １時間）、固有抵抗を測定し、
同様に変性エポキシ樹脂を添加しないものと比較した。Water absorption test (100℃, 1 hour), measuring specific resistance,
Similarly, a comparison was made with one in which no modified epoxy resin was added.
結果を第１表に示す。The results are shown in Table 1.
第１表
応用例２
市１阪エポキシ樹脂（エピ：１− ） ８２８） １０
０ｍ ニ１７１化剤ジアミノジフェニルメタン２７部、
シリカ５部、実施例３の変性エポキシ樹脂２５部を加え
、応用例１と同様、硬化せしめて得た成形体について、
同様の評価を行なった。Table 1 Application example 2 Ichiichisaka epoxy resin (Epi: 1-) 828) 10
0m 27 parts of di-171-forming agent diaminodiphenylmethane,
Regarding the molded product obtained by adding 5 parts of silica and 25 parts of the modified epoxy resin of Example 3 and curing it in the same manner as in Application Example 1,
A similar evaluation was conducted.
結果を第２表に示した。The results are shown in Table 2.
第２表Table 2
Claims (1)
ＢｒまたはＦ、ｍおよびｎは１〜４の整数、Ａは−Ｏ−
、−ＳＯ＿２−、−Ｓ−、−ＣＨ＿２−、−、▲数式、
化学式、表等があります▼、▲数式、化学式、表等があ
ります▼、▲数式、化学式、表等があります▼または▲
数式、化学式、表等があります▼、 ｑは１〜１００の数を、それぞれ示す。〕 で示されるエポキシ樹脂と、 一般式（２） ▲数式、化学式、表等があります▼・・・・・・・・・
・・（２） 〔式中、Ｒａ、ＲｂはＣ＿１〜Ｃ＿２＿２のアルキル基
、▲数式、化学式、表等があります▼、▲数式、化学式
、表等があります▼、▲数式、化学式、表等があります
▼、または▲数式、化学式、表等があります▼、 ＲｃはＣ＿１〜Ｃ＿２＿２のアルキル基、 Ｘ′はＣｌまたはＢｒを、それぞれ示す。〕で示される
化合物を、脱ハロゲン化水素剤の存在下で反応させて 一般式（３） ▲数式、化学式、表等があります▼・・・・・・・・・
・・・・（３） 〔式中、Ｒ＿１、Ｘ、Ａ、ｍ、ｎ、ｑおよびＲａ、Ｒｂ
は前記と同じ。〕 で示されるエポキシ樹脂を得ることを特徴とする変性エ
ポキシ樹脂の製法。[Claims] General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(1) [In the formula, R_1 is hydrogen or CH_2, X is hydrogen, Cl,
Br or F, m and n are integers of 1 to 4, A is -O-
, -SO_2-, -S-, -CH_2-, -, ▲formula,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, q indicates a number from 1 to 100, respectively. ] Epoxy resin shown by General formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...(2) [In the formula, Ra and Rb are C_1 to C_2_2 alkyl groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, tables, etc. Yes▼, or▲There are mathematical formulas, chemical formulas, tables, etc.▼, Rc represents an alkyl group of C_1 to C_2_2, and X' represents Cl or Br, respectively. ] is reacted in the presence of a dehydrohalogenating agent to form the general formula (3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...(3) [In the formula, R_1, X, A, m, n, q and Ra, Rb
is the same as above. ] A method for producing a modified epoxy resin, which is characterized by obtaining an epoxy resin shown in the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30708586A JPH0621151B2 (en) | 1986-12-23 | 1986-12-23 | Modified epoxy resin manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30708586A JPH0621151B2 (en) | 1986-12-23 | 1986-12-23 | Modified epoxy resin manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63159418A true JPS63159418A (en) | 1988-07-02 |
| JPH0621151B2 JPH0621151B2 (en) | 1994-03-23 |
Family
ID=17964849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30708586A Expired - Lifetime JPH0621151B2 (en) | 1986-12-23 | 1986-12-23 | Modified epoxy resin manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0621151B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08134173A (en) * | 1994-11-10 | 1996-05-28 | Nippon Kayaku Co Ltd | Epoxy resin, epoxy resin composition and cured product thereof |
| JP2018044069A (en) * | 2016-09-14 | 2018-03-22 | 株式会社Adeka | Flame-retardant epoxy resin composition, and prepreg and laminate prepared therewith |
| CN113789002A (en) * | 2021-10-26 | 2021-12-14 | 北京普利宏斌化工材料有限责任公司 | High-flame-retardant antimony trioxide master batch |
| WO2022144881A1 (en) * | 2020-12-30 | 2022-07-07 | Bromine Compounds Ltd. | Polymeric flame retardants |
| CN116179082A (en) * | 2022-12-29 | 2023-05-30 | 四川卡柏莱尼科技有限公司 | Graphene solvent-free static conductive anticorrosive paint |
-
1986
- 1986-12-23 JP JP30708586A patent/JPH0621151B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08134173A (en) * | 1994-11-10 | 1996-05-28 | Nippon Kayaku Co Ltd | Epoxy resin, epoxy resin composition and cured product thereof |
| JP2018044069A (en) * | 2016-09-14 | 2018-03-22 | 株式会社Adeka | Flame-retardant epoxy resin composition, and prepreg and laminate prepared therewith |
| WO2022144881A1 (en) * | 2020-12-30 | 2022-07-07 | Bromine Compounds Ltd. | Polymeric flame retardants |
| CN113789002A (en) * | 2021-10-26 | 2021-12-14 | 北京普利宏斌化工材料有限责任公司 | High-flame-retardant antimony trioxide master batch |
| CN113789002B (en) * | 2021-10-26 | 2023-02-21 | 北京普利宏斌化工材料有限责任公司 | High-flame-retardant antimony trioxide master batch |
| CN116179082A (en) * | 2022-12-29 | 2023-05-30 | 四川卡柏莱尼科技有限公司 | Graphene solvent-free static conductive anticorrosive paint |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0621151B2 (en) | 1994-03-23 |
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