JPS6339008B2 - - Google Patents
Info
- Publication number
- JPS6339008B2 JPS6339008B2 JP57502399A JP50239982A JPS6339008B2 JP S6339008 B2 JPS6339008 B2 JP S6339008B2 JP 57502399 A JP57502399 A JP 57502399A JP 50239982 A JP50239982 A JP 50239982A JP S6339008 B2 JPS6339008 B2 JP S6339008B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl ester
- resin
- viscosity
- isocyanate
- 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
Links
- 229920005989 resin Polymers 0.000 description 31
- 239000011347 resin Substances 0.000 description 31
- 229920001567 vinyl ester resin Polymers 0.000 description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000012948 isocyanate Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- -1 hydroxyalkyl acrylates Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001844 chromium Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- QSQUPRFDZUDLIA-UHFFFAOYSA-N 2-[[4-[bis[4-(oxiran-2-ylmethyl)phenyl]methyl]phenyl]methyl]oxirane Chemical compound C=1C=C(C(C=2C=CC(CC3OC3)=CC=2)C=2C=CC(CC3OC3)=CC=2)C=CC=1CC1CO1 QSQUPRFDZUDLIA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004412 Bulk moulding compound Substances 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000003677 Sheet moulding compound Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- HTAFVGKAHGNWQO-UHFFFAOYSA-N droprenilamine Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)CCNC(C)CC1CCCCC1 HTAFVGKAHGNWQO-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
- C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
請求の範囲
1 ビニルエステル樹脂の第二級ヒドロキシル基
と第二級ヒドロキシルに基き0.05〜1当量のイソ
シアナトエチルメタクリレートとを反応させるこ
とからなる減少した粘度を有するビニルエステル
樹脂を製造する方法。
2 ビニルエステル樹脂がポリグリシジルエーテ
ルと不飽和モノカルボン酸とのジエステルであ
る、特許請求の範囲第1項記載の方法。
3 ビニルエステル樹脂がビスフエノールAのジ
グリシジルエーテルとモノカルボン酸とのジエス
テルである、特許請求の範囲第1項記載の方法。
4 モノカルボン酸がメタクリル酸である、特許
請求の範囲第2項かあるいは第3項のいずれか記
載の方法。
5 錫塩が触媒として使用される特許請求の範囲
第1項記載の方法。
明細書
本発明は減少した粘度を有するビニルエステル
樹脂の製造方法に関する。
数多くの樹脂の応用分野において、最小の加熱
キユア後に、粘度が低いことおよび物性が良好で
あることが必要である。しかし、これらの目的と
するところは全く相反することがしばしばであ
る。ビニルエステル樹脂のようなポリグリシジル
エーテルベースのポリマー系は、その分子構造に
ヒドロキシル基を有している。これらのヒドロキ
シル基はそのビニルエステル樹脂の粘度を相当な
程度にまで増加させる。一般にそのような高粘度
を持つたビニルエステル樹脂組成物を使用して樹
脂加工を行なう場合、又その樹脂組成物を使用し
て成形を実施しようとする場合、50%以下のスチ
レン又は他のモノビニルモノマー等で稀釈を必要
とする。このような稀釈剤の使用は製造コストの
上昇につながる。ビニルエステル樹脂組成物の粘
度を減少させるか又は、所望の粘度を得るために
必要な稀釈剤の量を減らし、そして同時にビニル
エステル樹脂本来の性質を保持することが特に望
ましい。
このようなビニルエステル樹脂が粘度が高いと
いう欠点は、第二級ヒドロキシル基を有するビニ
ルエステル樹脂とその第二級ヒドロキシル基に基
づいて0.05〜1当量のイソシアナトエチルメタク
リレートとを反応させることによつて解決できる
ことを本発明は発見した。本発明はこれらの発見
に基づいてなされた。本発明で得られた反応生成
物(粘度の減少したビニルエステル樹脂)は未硬
化の場合、相当する未改質樹脂より粘度が低い
が、硬化した場合、架橋密度が大きくなることに
より加熱ひずみ温度および硬度が向上し、更に水
および溶剤の吸収性が低下する。
反応生成物をつくる上で有用なビニルエステル
樹脂は、ポリマー鎖に一つより多くのセカンダリ
ーヒドロキシル基を有することが必要である。
アメリカ特許No.3066112およびNo.3179623で、
Bowenは、アクリル酸あるいはメタクリル酸を
ポリエポキシドとのエステル化による、ビニルエ
ステル樹脂の製造法について記載している。又、
その特許においてグリシジルアクリレートあるい
はメタクリレートをビスフエノールのナトリウム
塩と反応させる別な方法について記載されてい
る。エポキシノボラツクによるビニルエステル樹
脂については、アメリカ特許No.3301743で開示さ
れている。
ここで使用されるビニルエステル樹脂はいかな
るグリシジルポリエーテルからもつくることがで
きる。有用なグリシジルエーテルは多価のアルコ
ールおよびフエノールのグリシジルエーテルであ
る。このようなグリシジルポリエーテルは市販さ
れているが、また少くとも2モルのエピハロヒド
リンあるいは、グリセロールジハロヒドリンと、
1モルの多価アルコールあるいはフエノールと
を、ハロヒドリン中のハロゲンと反応するために
充分な量の苛性ソーダを用いて、反応させること
により容易につくることができる。この生成物の
特徴は分子あたり一つより多くのグリシジルエー
テル基を有するところにある。
ビニルエステル樹脂をつくるための有用な酸は
エチレン性不飽和モノカルボン酸であり、アクリ
ル酸、メタクリル酸、ケイ皮酸およびそれらのハ
ロゲン化異性体などである。またアメリカ特許No.
3367992に記載のようなジカルボン酸のヒドロキ
シアルキルアクリレートあるいはメタクリレート
のハーフエステルも含まれ、好ましくは、そのヒ
ドロキシアルキル基の炭素原子は2〜6である。
グリシジルエーテルと酸との反応は、一般に、
ほぼ化学量論当量で、例えば三塩化クロムのよう
な三価クロム塩あるいは、例えばトリス(N,N
−ジメチルアミノメチルフエノール)のようなタ
ーシヤリーアミンなどの、触媒の存在下、加熱す
ることによりおこなわれる。通常、急激な重合を
防止するためビニル重合禁止剤が添加されてい
る。
ビニルエステル樹脂を使用する場合、その液状
の未硬化樹脂の粘度を、反応性溶剤、通常は共重
合性モノマーで調整することは一般に行われてい
る。このために使用される適当なモノマーは、ス
チレンおよびビニルトルエンのようなビニル芳香
族モノマーおよび、低級アルカノールのアクリレ
ートあるいはメタクリレートエステルである。こ
の反応性溶剤の量は樹脂/モノマー全量につき60
重量%である。
イソシアネートエチルメタクリレートの使用量
は、ヒドロキシル当量あたり0.05〜1.00当量であ
る。0.05当量より少ない場合、硬化生成物にほと
んど変化が認められない。1.0当量より多い場合、
過剰のイソシアネートは反応せず、かえつてキユ
ア生成物の所望の性質を低下させる。
イソシアネートと第二級ヒドロキシルとの反応
は公知の方法により実施される。典型的な反応に
おいては、ポリマーあるいは、ポリマー先駆体、
反応性溶媒およびスズオクトエートのような触媒
を充分に混合した後、ゆつくりと、例えば50℃ま
で加温する。ついで撹拌しながらイソシアネート
を添加する。反応の完了を示す。すなわち赤外ス
ペクトールによりイソシアネートバンドがなくな
る迄、加熱しつづける。
イソシアネート生成物の架橋度は、いくつから
の方法により調整することができる。すなわちポ
リマーあるいは先駆体の不飽和度を変化させるこ
とができるし、また、原料のヒドロキシル数を変
えることもできる。不飽和イソシアネートの量を
所望の架橋度となるような量に調整することも可
能である。更にいくらかのヒドロキシル基を飽和
脂肪族イソシアネートと反応させることができ
る。
生成物は改良された特性、特に、加熱ひずみ温
度、硬度および低溶剤吸収性を有している。生成
物はストレート樹脂としての用途および強化プラ
スチツクとしての用途がある。特記すべき用途に
は、フアイバーグラス強化フイラメント曲げパイ
プ、電導性ラミネート、電気絶縁ワニスおよび被
覆物、バルクおよびシート状成形コンパウンド、
および耐食性の容器および容器用ラミネート等が
ある。
本発明の概念は以下の実施例により更に明確に
説明されるが文中のすべての部および%は重量に
よるものである。
実施例 1
トリス(4−グリシジルフエニル)メタンのト
リメタクリレート100部、スチレン25部およびス
ズオクトエートを混合し、50℃まで加熱した。つ
いで混合物へ撹拌しながらイソシアネートエチル
メタクリレート(IEM)47.02部をゆつくりと添
加した後、60℃まで加熱した。更に加熱、撹拌し
つづけIRスペクトルのイソシアネートバンド、
2280cm-1が消失することにより反応を終了した。
IEMの使用量はヒドロキシル当量あたり0.7当量
であつた。
この生成物へスチレン11.75gを添加した。この
樹脂を樹脂100部あたり1.5部のベンゾイルパーオ
キシドと共に、90℃×2時間、165℃×4時間、
200℃×16時間の温度スケジユールでキユアした。
比較のために、トリメタクリレートと20%のス
チレンとを同じ方法でキユアした。サンプルは標
準の方法によりテストした。その結果はつぎの通
りである。Claim 1. A method for producing a vinyl ester resin with reduced viscosity comprising reacting the secondary hydroxyl groups of the vinyl ester resin with 0.05 to 1 equivalent of isocyanatoethyl methacrylate based on the secondary hydroxyl. 2. The method according to claim 1, wherein the vinyl ester resin is a diester of a polyglycidyl ether and an unsaturated monocarboxylic acid. 3. The method according to claim 1, wherein the vinyl ester resin is a diester of diglycidyl ether of bisphenol A and a monocarboxylic acid. 4. The method according to claim 2 or 3, wherein the monocarboxylic acid is methacrylic acid. 5. Process according to claim 1, in which a tin salt is used as a catalyst. Description The present invention relates to a method for producing vinyl ester resins having reduced viscosity. In many resin applications, low viscosity and good physical properties are required after minimal heat curing. However, these objectives are often completely contradictory. Polyglycidyl ether-based polymer systems, such as vinyl ester resins, have hydroxyl groups in their molecular structure. These hydroxyl groups increase the viscosity of the vinyl ester resin to a considerable extent. Generally, when performing resin processing using such a high viscosity vinyl ester resin composition, or when attempting to perform molding using such a resin composition, 50% or less of styrene or other monovinyl Requires dilution with monomer etc. The use of such diluents leads to increased manufacturing costs. It is particularly desirable to reduce the viscosity of vinyl ester resin compositions, or to reduce the amount of diluent needed to obtain a desired viscosity, while at the same time preserving the original properties of the vinyl ester resin. The drawback of high viscosity of such vinyl ester resins can be solved by reacting a vinyl ester resin with secondary hydroxyl groups with 0.05 to 1 equivalent of isocyanatoethyl methacrylate based on the secondary hydroxyl groups. The present invention has discovered that this problem can be solved. The present invention was made based on these discoveries. The reaction product (vinyl ester resin with reduced viscosity) obtained in the present invention has a lower viscosity than the corresponding unmodified resin when uncured, but when cured, the crosslinking density increases and the heat strain temperature increases. and hardness, as well as reduced water and solvent absorption. Vinyl ester resins useful in making reaction products need to have more than one secondary hydroxyl group on the polymer chain. In US Patent No.3066112 and No.3179623,
Bowen describes the production of vinyl ester resins by esterification of acrylic or methacrylic acid with polyepoxides. or,
In that patent, another method is described in which glycidyl acrylate or methacrylate is reacted with the sodium salt of bisphenol. Vinyl ester resins based on epoxy novolacs are disclosed in US Pat. No. 3,301,743. The vinyl ester resin used herein can be made from any glycidyl polyether. Useful glycidyl ethers are those of polyhydric alcohols and phenols. Such glycidyl polyethers are commercially available and may also contain at least 2 moles of epihalohydrin or glycerol dihalohydrin;
It can be easily prepared by reacting 1 mole of polyhydric alcohol or phenol with a sufficient amount of caustic soda to react with the halogen in the halohydrin. This product is characterized by more than one glycidyl ether group per molecule. Useful acids for making vinyl ester resins are ethylenically unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, cinnamic acid and their halogenated isomers. Also, US Patent No.
Also included are half esters of hydroxyalkyl acrylates or methacrylates of dicarboxylic acids such as those described in US Pat. The reaction between glycidyl ether and acid is generally
Trivalent chromium salts, such as chromium trichloride, or trivalent chromium salts, such as trichloride, or trivalent chromium salts, such as tris(N,N
-dimethylaminomethylphenol) by heating in the presence of a catalyst, such as a tertiary amine such as -dimethylaminomethylphenol). Usually, a vinyl polymerization inhibitor is added to prevent rapid polymerization. When using vinyl ester resins, it is common practice to adjust the viscosity of the liquid uncured resin with a reactive solvent, usually a copolymerizable monomer. Suitable monomers used for this purpose are vinyl aromatic monomers, such as styrene and vinyltoluene, and acrylate or methacrylate esters of lower alkanols. The amount of this reactive solvent is 60% of the total amount of resin/monomer.
Weight%. The amount of isocyanate ethyl methacrylate used is 0.05 to 1.00 equivalents per hydroxyl equivalent. When the amount is less than 0.05 equivalent, almost no change is observed in the cured product. If it is more than 1.0 equivalent,
Excess isocyanate does not react and instead reduces the desired properties of the cured product. The reaction between isocyanate and secondary hydroxyl is carried out by known methods. In a typical reaction, a polymer or polymer precursor,
After the reactive solvent and catalyst such as tin octoate are thoroughly mixed, the mixture is slowly warmed to, for example, 50°C. The isocyanate is then added while stirring. Indicates completion of the reaction. That is, heating is continued until the isocyanate band disappears from the infrared spectrum. The degree of crosslinking of the isocyanate product can be adjusted in several ways. That is, the degree of unsaturation of the polymer or precursor can be varied, and the number of hydroxyls in the raw material can also be varied. It is also possible to adjust the amount of unsaturated isocyanate to provide the desired degree of crosslinking. Additionally, some of the hydroxyl groups can be reacted with saturated aliphatic isocyanates. The products have improved properties, in particular heat strain temperature, hardness and low solvent absorption. The products have applications as straight resins and as reinforced plastics. Notable applications include fiberglass reinforced filament bent pipes, electrically conductive laminates, electrically insulating varnishes and coatings, bulk and sheet molding compounds,
and corrosion-resistant containers and container laminates. The concept of the invention is more clearly illustrated by the following examples, in which all parts and percentages are by weight. Example 1 100 parts of trimethacrylate of tris(4-glycidylphenyl)methane, 25 parts of styrene and tin octoate were mixed and heated to 50°C. Then, 47.02 parts of isocyanate ethyl methacrylate (IEM) was slowly added to the mixture while stirring, and the mixture was heated to 60°C. Further heating and stirring continue to detect the isocyanate band in the IR spectrum.
The reaction was terminated when 2280 cm -1 disappeared.
The amount of IEM used was 0.7 equivalents per hydroxyl equivalent. To this product was added 11.75 g of styrene. This resin was mixed with 1.5 parts of benzoyl peroxide per 100 parts of resin at 90°C for 2 hours and at 165°C for 4 hours.
Curing was carried out using a temperature schedule of 200°C for 16 hours. For comparison, trimethacrylate and 20% styrene were cured in the same manner. Samples were tested using standard methods. The results are as follows.
【表】
上述の樹脂の他のサンプルをベンゾイルパーオ
キシド1.5部と、90℃×2時間、165℃×4時間で
キユアした。未改質樹脂の加熱ひずみ温度は203
℃であり、IEM改質樹脂のそれは230℃より高か
つた。バルコール硬度は、前者が42、後者が50で
あつた。
実施例 2
ポリマーとしてビスフエノールAのジグリシジ
ルエーテルのジメタクリレート、および反応性溶
剤として、ビニルトルエンを用いて、実施例1と
同じ方法および化学量論量により、樹脂をつくつ
た。
樹脂をその樹脂100部あたり1.5部のベンゾイル
パーオキシドと150℃×30分間キユアした。サン
プルを標準方法によりテストした結果をつぎに示
す。[Table] Other samples of the above resins were cured with 1.5 parts of benzoyl peroxide at 90°C for 2 hours and 165°C for 4 hours. The heating strain temperature of unmodified resin is 203
℃, and that of the IEM modified resin was higher than 230℃. The Valcor hardness was 42 for the former and 50 for the latter. Example 2 A resin was prepared by the same method and stoichiometry as in Example 1 using dimethacrylate of the diglycidyl ether of bisphenol A as the polymer and vinyltoluene as the reactive solvent. The resin was cured with 1.5 parts of benzoyl peroxide per 100 parts of resin at 150°C for 30 minutes. The samples were tested using standard methods and the results are shown below.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1982/000895 WO1984000173A1 (en) | 1982-07-02 | 1982-07-02 | Urethane modified vinyl ester resins having secondary hydroxyl groups |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59500969A JPS59500969A (en) | 1984-05-31 |
JPS6339008B2 true JPS6339008B2 (en) | 1988-08-03 |
Family
ID=22168074
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57502399A Granted JPS59500969A (en) | 1982-07-02 | 1982-07-02 | Method for producing vinyl ester resin with reduced viscosity |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0112824A4 (en) |
JP (1) | JPS59500969A (en) |
BR (1) | BR8208087A (en) |
WO (1) | WO1984000173A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0459405A (en) * | 1990-06-29 | 1992-02-26 | Nissan Motor Co Ltd | Suspension device for vehicle |
WO2017195607A1 (en) * | 2016-05-13 | 2017-11-16 | 三菱ケミカル株式会社 | Molding material, sheet molding compound and fiber-reinforced composite material |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7872705B2 (en) * | 2007-07-29 | 2011-01-18 | Cree, Inc. | LED backlight system for LCD displays |
EP3441409B1 (en) * | 2016-04-06 | 2020-06-03 | Mitsubishi Chemical Corporation | Thermosetting resin composition, sheet-molding compound and production method therefor, and fiber-reinforced composite material |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2503209A (en) * | 1948-01-30 | 1950-04-04 | American Cyanamid Co | Unsaturated alkyd reacted with unsaturated isocyanate |
US2958704A (en) * | 1958-09-02 | 1960-11-01 | Goodrich Co B F | Alkenyl isocyanate-substituted carbamates |
US3118922A (en) * | 1959-03-03 | 1964-01-21 | Bayer Ag | Method of preparing organic isocyanates |
US3373221A (en) * | 1964-11-04 | 1968-03-12 | Shell Oil Co | Reaction products of unsaturated esters of polyepoxides and unsaturated carboxylic acids, and polyisocyanates |
US3509234A (en) * | 1965-08-13 | 1970-04-28 | Ford Motor Co | Radiation curable paint binders containing vinyl monomers and a hydroxylated polymer reacted with a polyisocyanate and an hydroxyl alkyl acrylate |
GB1143754A (en) * | 1965-11-19 | |||
US3478126A (en) * | 1967-05-26 | 1969-11-11 | Scm Corp | Urethane modified epoxy ester resin compositions and products |
JPS4831742B1 (en) * | 1968-03-01 | 1973-10-01 | ||
NL7117831A (en) * | 1970-12-31 | 1972-07-04 | Basf Ag | |
AU451354B2 (en) * | 1971-01-06 | 1974-08-08 | Inmont Corp. | "actinic radiation curing compositions and method of coating and printing using same" |
US3776889A (en) * | 1971-01-07 | 1973-12-04 | Powers Chemco Inc | Allyl carbamate esters of hydroxy-containing polymers |
US4004997A (en) * | 1972-01-30 | 1977-01-25 | Seiko Shimada | Process of curing a polymerizable composition containing a magnetized powered ferromagnetic material with radioactive rays |
JPS5422124B2 (en) * | 1975-01-22 | 1979-08-04 | ||
AT336148B (en) * | 1975-05-07 | 1977-04-25 | Vianova Kunstharz Ag | PROCESS FOR THE PRODUCTION OF IMPROVED ELECTRON RADIATION HARDENABLE COATING COMPOUNDS |
DE2557408C2 (en) * | 1975-12-19 | 1983-08-25 | Bayer Ag, 5090 Leverkusen | Process for the production of a crosslinkable urethane resin containing acryloyl and / or methacryloyl groups and carboxyl groups which is soluble in organic solvents and its use |
FR2361450A1 (en) * | 1976-08-13 | 1978-03-10 | Basf Ag | HARDENABLE COATING MATERIAL |
US4233425A (en) * | 1978-11-15 | 1980-11-11 | The Dow Chemical Company | Addition polymerizable polyethers having pendant ethylenically unsaturated urethane groups |
US4320221A (en) * | 1980-12-12 | 1982-03-16 | The Dow Chemical Company | Addition polymerizable isocyanate-polyol anaerobic adhesives |
-
1982
- 1982-07-02 JP JP57502399A patent/JPS59500969A/en active Granted
- 1982-07-02 BR BR8208087A patent/BR8208087A/en unknown
- 1982-07-02 EP EP19820902423 patent/EP0112824A4/en not_active Withdrawn
- 1982-07-02 WO PCT/US1982/000895 patent/WO1984000173A1/en not_active Application Discontinuation
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0459405A (en) * | 1990-06-29 | 1992-02-26 | Nissan Motor Co Ltd | Suspension device for vehicle |
WO2017195607A1 (en) * | 2016-05-13 | 2017-11-16 | 三菱ケミカル株式会社 | Molding material, sheet molding compound and fiber-reinforced composite material |
JPWO2017195607A1 (en) * | 2016-05-13 | 2018-06-21 | 三菱ケミカル株式会社 | Molding materials, sheet molding compounds and fiber reinforced composite materials |
Also Published As
Publication number | Publication date |
---|---|
WO1984000173A1 (en) | 1984-01-19 |
EP0112824A4 (en) | 1984-11-05 |
JPS59500969A (en) | 1984-05-31 |
BR8208087A (en) | 1984-07-17 |
EP0112824A1 (en) | 1984-07-11 |
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