JPH04183713A - High-molecular weight unsaturated polyester - Google Patents
High-molecular weight unsaturated polyesterInfo
- Publication number
- JPH04183713A JPH04183713A JP30881090A JP30881090A JPH04183713A JP H04183713 A JPH04183713 A JP H04183713A JP 30881090 A JP30881090 A JP 30881090A JP 30881090 A JP30881090 A JP 30881090A JP H04183713 A JPH04183713 A JP H04183713A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- unsaturated polyester
- polyester
- glycol
- average molecular
- 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
- 229920006305 unsaturated polyester Polymers 0.000 title claims abstract description 29
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000002253 acid Substances 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 4
- 229920002430 Fibre-reinforced plastic Polymers 0.000 abstract description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011151 fibre-reinforced plastic Substances 0.000 abstract description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract 4
- 239000011261 inert gas Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- -1 sialyl ester Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕 □
本発明は、繊維強化プラスチックス、ライニング、注型
の各分野に有用な高分子量を有する不飽和ポリエステル
、およびこの不飽和ポリエステルにこれと共重合するモ
ノマーを配合した高分子量不飽和ポリエステル樹脂に関
するものである。Detailed Description of the Invention [Field of Industrial Application] □ The present invention is directed to an unsaturated polyester having a high molecular weight useful in the fields of fiber reinforced plastics, linings, and casting, and to this unsaturated polyester. It relates to a high molecular weight unsaturated polyester resin blended with a copolymerizable monomer.
し従来の技術および課題〕
不飽和ポリエステル樹脂（ポリエステル樹脂と同意語）
は、ラジカル硬化型樹脂の代表として、繊維強化プラス
チックス（以下ＦＲＰと略記）、塗料、ライニング材料
、注型材料なととして広く用いられていることは良く知
られている。[Conventional technology and issues] Unsaturated polyester resin (synonymous with polyester resin)
It is well known that as a representative radical curable resin, it is widely used in fiber reinforced plastics (hereinafter abbreviated as FRP), paints, lining materials, casting materials, etc.
不飽和ポリエステル樹脂の用途の拡大につれて、樹脂に
要求される物性も高度なものとなるのは当然であり、例
えばジイソシアナートを反応させて、高分子量化による
機械的性質の向上、あるいはエポキシ樹脂を反応させて
塗膜性能をレベルアップする例、さらにはゴム状ポリマ
ーを併用して靭性を付与するといった諸方法が実用化さ
れている。As the uses of unsaturated polyester resins expand, it is natural that the physical properties required of the resins will also become more sophisticated. Various methods have been put into practical use, such as increasing the performance of the coating film by reacting with the rubber-like polymer, and adding toughness by using a rubber-like polymer in combination.
しかし、不飽和ポリエステル樹脂を構成する不飽和ポリ
エステル（不飽和アルキッドと同意語）の分子量を高め
て問題点解決に対処しようとする動きは、少なくとも公
表された段階で見ることができない。However, there are no efforts to solve the problem by increasing the molecular weight of the unsaturated polyester (synonymous with unsaturated alkyd) that makes up the unsaturated polyester resin, at least not yet.
理由は、不飽和ポリエステルの分子量（数平均、以下同
じ）が、たかだか２０００〜２５００位で、島って、反
応中のゲル化のために、３０００を超二るこ′二は頗る
困難と見られていたことにあるものビ考２らｔしる。The reason is that the molecular weight (number average, the same applies hereinafter) of unsaturated polyester is at most 2,000 to 2,500, and it is considered extremely difficult to exceed 3,000 because of gelation during the reaction. I think about what happened to me.
事天、現在−・殻に不飽和ポリエステル樹脂製造５ご用
いられているエステル化反応のみでは、分子量３０００
の壁を破ることは、少なくとも安定的にＶ遣でき、且つ
使用樹脂が粘度、硬化性、成形性等の取扱性の面で実用
性のあるものを前提とする限り、難しい、
しかし、本発明者らは、次の条件を用いれば従来不可能
視されていた、高分子量不飽和ポリエステルの分子量を
５０００以上とすることができることを見いだした。Currently, the esterification reaction used in the production of unsaturated polyester resin for the shell is sufficient to achieve a molecular weight of 3000.
Breaking the wall is difficult, at least as long as V can be used stably and the resin used is practical in terms of handling such as viscosity, curing properties, moldability, etc. However, the present invention The authors discovered that the molecular weight of a high molecular weight unsaturated polyester, which had previously been considered impossible, could be increased to 5000 or more by using the following conditions.
イ）不飽和ポリエステルの酸価を１５以下となるまで、
エステル化し、この段階で
口）脱グリコール反応の触媒を加え、
ハ）’５丁ｏｒｒ以下、盟ましくはＩ Ｔｏｒｒ以下の
減圧として脱グリコール反応を促進する。b) Until the acid value of the unsaturated polyester becomes 15 or less,
esterification, and at this stage a) a catalyst for the deglycol reaction is added; and c) the deglycol reaction is promoted by reducing the pressure to less than 1 Torr, preferably less than 1 Torr.
本発明は、特に低反応性領域（α、β−不飽和多塩基酸
の使用割合のすくないタイプ、すなわち前記−最大でｍ
の大きい場合）で、このようにして得られる不飽和ポリ
エステルの構造、なちびに分子量が以下の如くである種
類のものは、低分子量不飽和ポリエステル樹脂と同一組
成であっても、分子量３０００以下の低分子量不飽和ポ
リエステル樹脂に比較し、著しく優れた物性を備えてい
ることを見いだした点に基づいている。The present invention is particularly suitable for low-reactivity regions (types with a low proportion of α,β-unsaturated polybasic acids, i.e.,
The unsaturated polyester obtained in this way has a structure and a molecular weight as shown below, even if it has the same composition as a low molecular weight unsaturated polyester resin, it has a molecular weight of 3000 or less. This is based on the discovery that it has significantly superior physical properties compared to low molecular weight unsaturated polyester resins.
すなわち本発明は、次の一般式
くただし、Ｇはα−グリコールの残基、ｍ＝３を超え５
未満、ｎ＝１．Ｍ＝数平均分子量が５０００以上に対応
する数）
で示される、数平均分子量が５０００以上の高分子量不
飽和ポリエステルを提供するものである。That is, the present invention provides the following general formula, where G is a residue of α-glycol, and m is greater than 3 and 5
Less than, n=1. M=number corresponding to number average molecular weight of 5,000 or more) A high molecular weight unsaturated polyester having a number average molecular weight of 5,000 or more is provided.
さらに本発明は、上記不飽和ポリエステルにこれと共重
合するモノマーを配合した不飽和ポリエステル樹脂を提
供するものである。Furthermore, the present invention provides an unsaturated polyester resin obtained by blending the above-mentioned unsaturated polyester with a monomer that copolymerizes with the unsaturated polyester.
本発明による高分子量不飽和ポリエステルを合成する原
料は、従来の不飽和ポリエステル樹脂製ｉ貴ご〕そｔし
と異なる所はなく、例えば次のようにあけられる。The raw materials for synthesizing the high molecular weight unsaturated polyester according to the present invention are the same as those for conventional unsaturated polyester resin products, and are prepared, for example, as follows.
（伺 α、β−不飽和多塩基酸およびその酸無水物と１
．では、実用的には無水マレイン酸、フマル酸等がある
。(See α, β-unsaturated polybasic acids and their acid anhydrides and 1
．． Practical examples include maleic anhydride and fumaric acid.
（１７）飽和多塩基酸類としては、ベンゼン核を有する
ものとして、無水フタル酸、イソフタル酸、テレフタル
酸、ならびにテレフタル酸ジメチルエステル等があげち
れる。(17) Examples of saturated polybasic acids having a benzene nucleus include phthalic anhydride, isophthalic acid, terephthalic acid, and dimethyl terephthalate.
前述し；ｌ’：： Ｚ塩基酸顕と併用する多価アルコー
ル類の中のα−グリコールとしては、エチトングリコー
ル、プロビレ〉′グリコール等があげられる。As mentioned above, examples of the α-glycol among the polyhydric alcohols used in combination with the Z base acid concentration include ethitone glycol, probilene glycol, and the like.
また、ジエチレングリコール、ジプロピレングリコール
、ブタンジオール１，３、ブタンジオール１．４、ネオ
ペンチルグリコール、ベンタンジオール１，５、ヘキサ
ンジオール１．６や、高沸点でグリコール交換し難い次
の種類の多価アルコールは、一部併用の形で利用するこ
とができる。In addition, diethylene glycol, dipropylene glycol, butanediol 1,3, butanediol 1.4, neopentyl glycol, bentanediol 1,5, hexanediol 1.6, and the following types of polyhydric compounds that have high boiling points and are difficult to exchange with glycols: Alcohol can be used in some combinations.
水素化ビスフェノールＡ、ビスフェノールＡエチトンオ
キシド付加物、ヒスフェノールＡプロピ；２ジオ六し１
；付加物、グリセリンジアリルエーテル、トリメチロー
ルプロパ〉・モノまたはシアリル上−チル。Hydrogenated bisphenol A, bisphenol A ethitone oxide adduct, hisphenol A propylene; 2-dio6-1
; adduct, glycerin diallyl ether, trimethylol propa〉mono or sialyl ester.
さらに、アルキレンモノエポキシ化合物も利用可能であ
る。それちの例には、エチレンオキシド、プロピレンオ
キシド、エビクロロヒドリン、フェニルグリシジルエー
テル、アリルグリシジルエーテル等があげられる。Additionally, alkylene monoepoxy compounds can also be used. Examples include ethylene oxide, propylene oxide, shrimp chlorohydrin, phenyl glycidyl ether, allyl glycidyl ether, and the like.
本発明の不飽和ポリエステルを製造する方法としては、
まず、
イ）不飽和ポリエステルの酸価を１５以下とするまでエ
ステル化し、この段階で
口）脱グリコール反応の触媒を加え、
ハ）５ Ｔｏｒｒ以下、好ましくはＩ Ｔｏｒｒ以下の
減圧として、脱グリコール反応を促進する。The method for producing the unsaturated polyester of the present invention includes:
First, a) esterify the unsaturated polyester until the acid value is 15 or less, add a catalyst for the deglycol reaction at this stage, and c) perform the deglycol reaction by reducing the pressure to 5 Torr or less, preferably I Torr or less. promote.
第１段階のエステル化は常法に従い、不活性気流中１６
０〜２３０℃の温度にて行われ、酸価１５以下、望まし
くは１０以下で実質的に不飽和ポリエステルを合成する
ことで行われる。The first step of esterification was carried out in accordance with a conventional method, with 16
It is carried out at a temperature of 0 to 230°C, and is carried out by synthesizing a substantially unsaturated polyester with an acid value of 15 or less, preferably 10 or less.
この時の分子量は１０００以上であることが必要である
。The molecular weight at this time needs to be 1000 or more.
第２段階の脱グリコール反応（エステル交換反応）は、
触媒の存在下、高減圧下で行われる。The second stage deglycol reaction (ester exchange reaction) is
It is carried out under high vacuum in the presence of a catalyst.
この時酸価が１５を超えると、脱グリコール反応が十分
に行われず、結果として所望の高分子量不飽和ポリエス
テルを合成することは困難なものとなる。If the acid value exceeds 15 at this time, the deglycol reaction will not be carried out sufficiently, and as a result, it will be difficult to synthesize the desired high molecular weight unsaturated polyester.
触媒としては、チタンの有機化合物が利用可能である。As a catalyst, an organic compound of titanium can be used.
例えばテトラブチルチタネート、テトラブルピルチタネ
ート、チタンのアセチルアセトネートである。使用量は
、不飽和ポリエステル１００重量部に対して０．０１重
量部以上、好ましくは０．０１〜０，５重量部、さらに
好ましくは０．１〜０．３重量部である。Examples include tetrabutyl titanate, tetrabutyl titanate, and titanium acetylacetonate. The amount used is 0.01 part by weight or more, preferably 0.01 to 0.5 part by weight, and more preferably 0.1 to 0.3 part by weight, per 100 parts by weight of the unsaturated polyester.
不飽和ポリエステルを溶解してポリエステル樹脂とする
ためのモノマーは、スチレンが代表的であるか、その他
にはビニルトルエン、メタクリル酸メチル ジアリルフ
タレート、ジアリルテレフタレート、などが用いられる
。The monomer for dissolving the unsaturated polyester to form a polyester resin is typically styrene, and other examples include vinyltoluene, methyl methacrylate diallyl phthalate, diallyl terephthalate, and the like.
本発明による高分子量不飽和ポリエステル樹脂は、従来
、一般タイブの不飽和ポリエステル樹脂の利用されてい
た用途に活用でき、その際、繊維補強材、フィラー、着
色剤、離型剤、安定剤を併用できることは勿論である。The high molecular weight unsaturated polyester resin according to the present invention can be used in applications for which conventionally general unsaturated polyester resins have been used. Of course it can be done.
「実施例〕
次に本発明の理解を助けるために、以下に実施例を示す
。実施例において部とあるのは、特記しない限り重量部
である。"Examples" Next, in order to help the understanding of the present invention, examples are shown below. In the examples, parts are parts by weight unless otherwise specified.
実−１−１
撹拌機、分溜コンデンサー、ガス導入管、温度計を付し
た３Ｉセパラブルフラスコに、プロビレ〉グリコール９
１５ｆ、イソフタル酸１２７８ｇを仕込み、１８０〜１
９０℃で窒素気流中でエステル化し、酸価２９．４ 迄
反応した後、フマル酸２６７ｇを加え、温度１９０〜２
０５°Ｃで酸価９．０までエステル化を進めた。Example-1-1 In a 3I separable flask equipped with a stirrer, fractionation condenser, gas inlet tube, and thermometer, add Probile glycol 9.
15f, 1278g of isophthalic acid, 180~1
After esterification in a nitrogen stream at 90°C and reaction until the acid value reached 29.4, 267g of fumaric acid was added and the temperature was 190-2.
Esterification was continued at 05°C until the acid value reached 9.0.
この段階で不飽和ポリエステル１０００ｇを取出しく分
子量２８００、第１図参照）、０．３ｇのハイドロキノ
〉・を含むスチレン７２５ｇに溶解して、低分子量不飽
和ポリエステル樹脂（Ａ）が、ハーゼ〉・色数２５０、
粘度５．３ボイズで得られた。At this stage, take out 1000 g of unsaturated polyester (molecular weight 2800, see Figure 1) and dissolve it in 725 g of styrene containing 0.3 g of hydroquino. number 250,
It was obtained with a viscosity of 5.3 voids.
残りの不飽和ポリエステルに、テトライゾプロピルチタ
ネート３ｙ、ハイドロキノン０．６１？を加ん、温ま２
００〜２０５℃、最終的には０．８Ｔｏｒｒまで減圧し
て、脱グリコール反応による高分子量化を行った。To the remaining unsaturated polyester, tetrazopropyl titanate 3y and hydroquinone 0.61? Add and warm 2
The pressure was reduced to 00 to 205° C. and finally to 0.8 Torr to increase the molecular weight by deglycol reaction.
最終分子量は７８００であった（第２図参照）。The final molecular weight was 7800 (see Figure 2).
これにスチレン１０００ＦＩを加え、高分子量不飽和ポ
リエステル樹脂（Ｂ）が、ガードナー色数２、粘度６．
９ボイスで得られた。これは、本発明の前記−数式にお
ける、ｍ＝３．３ および ｎ＝１に相当する。Styrene 1000FI is added to this, and the high molecular weight unsaturated polyester resin (B) has a Gardner color number of 2 and a viscosity of 6.
Obtained with 9 voices. This corresponds to m=3.3 and n=1 in the above formula of the present invention.
それぞれの樹脂１００部に、メチルエチルケトンパーオ
キシド１，５部、ナフテン酸コバルト（６％Ｃｏ）０．
５部を加え、テストピース型に注型してゲル化後、８０
℃２時間、１２０℃２時間の後硬化を行った。To 100 parts of each resin, 1.5 parts of methyl ethyl ketone peroxide and 0.0 parts of cobalt naphthenate (6% Co) were added.
After adding 5 parts and casting into a test piece mold to gel, 80
Post-curing was performed for 2 hours at 120°C and 2 hours at 120°C.
得られた注型硬化樹脂の物性は、第１表に吃られるよう
に、両者の間には著しい差が認められた。As shown in Table 1, there was a significant difference in the physical properties of the cast-cured resins obtained.
第１表
シｌ」
撹拌機、分溜コンデンサー、ガス導入管、温度計を付し
た３１セパラブルフラスコに、エチレングリコール２８
０ｇ、プロピレングリコール５５０Ｍ−ジメチルテレフ
タレート７７６ｇ、酢酸亜鉛５ｇを仕込み、１６０之１
８０℃で反応させ、メタノールの漏出が終了次第、イソ
フタル酸６６４ｇを加え、温度１８０〜１９０°Ｃでさ
らにニスチルｆヒを進め、酸価を２７．１とし、さらに
無水マレイン酸１９６ｇを加えて、窒素気流中酸価８５
となるまで反応させた。分子量は２６００であった
この不飽和ポリエステル１０００ｙを、０２ｇのハイド
ロキノンを含むスチレン７２５ｇに溶解して、低分子量
不飽和ポリエステル樹脂（Ｃ）がハーゼン色数２５０、
粘度６２ボイズて得られた。Table 1: Into a 31 separable flask equipped with a stirrer, fractionation condenser, gas inlet tube, and thermometer, add ethylene glycol 28
0g, propylene glycol 550M-dimethyl terephthalate 776g, zinc acetate 5g, 160-1
The reaction was carried out at 80°C, and as soon as the leakage of methanol was completed, 664 g of isophthalic acid was added, and Nistyl acid was further heated at a temperature of 180 to 190°C to give an acid value of 27.1. Furthermore, 196 g of maleic anhydride was added. Acid value 85 in nitrogen stream
The reaction was allowed to occur until . 1,000 y of this unsaturated polyester with a molecular weight of 2,600 was dissolved in 725 g of styrene containing 0.2 g of hydroquinone to obtain a low molecular weight unsaturated polyester resin (C) with a Hazen color number of 250,
A viscosity of 62 voids was obtained.
残りの不飽和ポリエステルにテトライソブ口ビルチタ不
−１□７ｙ−ハイドロキノン０．５ｇを加え、コンデン
サーを替えて、温度２００〜２０５℃、最終的に０．８
Ｔｏｒｒの減圧下で、脱グリコール反応を行い、分子量
７９００の高分子量不飽和ポリエステルとした。これは
、本発明の前記−数式における、ｍ＝４、ｎ＝１に相当
する。これにスチレン１１００ｇを加えて、高分子量不
飽和ポリエステル樹脂（Ｄ）が、ガードナー色数２、粘
度８１ボイズで得られた。Add 0.5 g of tetraisobutylene-1□7y-hydroquinone to the remaining unsaturated polyester, change the condenser, raise the temperature to 200-205°C, and finally 0.8
A deglycol reaction was performed under reduced pressure of Torr to obtain a high molecular weight unsaturated polyester having a molecular weight of 7900. This corresponds to m=4 and n=1 in the above formula of the present invention. 1100 g of styrene was added to this to obtain a high molecular weight unsaturated polyester resin (D) having a Gardner color number of 2 and a viscosity of 81 voids.
それぞれの樹脂１００部ずつに、３２５メ・ソシュのガ
ラスフレーク３０部、エロジル１部、シランカ、プリン
グ剤１部、シリコン消泡剤１０ｐｐ輪、チタン白１０部
、スチレン１０部を加え、混練してカラスフレークコン
パウンドを得た。To 100 parts of each resin, 30 parts of 325 Me Soche glass flakes, 1 part of Erosil, Silanka, 1 part of a pulling agent, 10 pp of silicone defoamer, 10 parts of titanium white, and 10 parts of styrene were added and kneaded. A crow flake compound was obtained.
このコン・パウンド１００部に、メチフレエチル・ケト
ンパーオキシト１部、ナフテン酸コ／＜／シト０．５部
を加え、ボンデライト鋼板上に２００μ肩の厚さに塗装
し、硬化させた。To 100 parts of this compound, 1 part of methifrethyl ketone peroxide and 0.5 part of naphthenic acid was added, and the mixture was painted on a Bonderite steel plate to a thickness of 200 μm and cured.
一夜放置後の塗膜物性、ならびに工ｌレコメーターによ
る接着強度は、第２表に示すとおりであって、低分子量
樹脂使用のガラスフレークコン／にランドは、全く実用
性が認められなかったか、高分子量不飽和ポリエステル
樹脂（Ｄ）を使用したタイプは、実用可能であった。The physical properties of the coating film after being left overnight, as well as the adhesive strength measured using a mechanical recorder, are as shown in Table 2.Glass flake con/Niland using low molecular weight resin was not recognized to be practical at all. The type using high molecular weight unsaturated polyester resin (D) was practical.
第２表
〔発明の効果〕
本発明は上記のように構成したので、従来得ることので
きなかった新規な高分子量の不飽和ポリエステルを提供
することができ、その優れた物性を利用して、広範な用
途に応用することができる８Table 2 [Effects of the Invention] Since the present invention is constructed as described above, it is possible to provide a novel high molecular weight unsaturated polyester that could not be obtained conventionally, and by utilizing its excellent physical properties, Can be applied to a wide range of applications8
第１図は、実施例１における低分子量不飽和ポリエステ
ルのＧＰＣ測定図である。
第２図は、実施例１における高分子量不飽和ポリエステ
ルのＧＰＣ測定図である。FIG. 1 is a GPC measurement diagram of the low molecular weight unsaturated polyester in Example 1. FIG. 2 is a GPC measurement diagram of the high molecular weight unsaturated polyester in Example 1.
Claims (2)
００以上に対応する数） で示される、数平均分子量が５０００以上の高分子量不
飽和ポリエステル。(1) The following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, G is a residue of α-glycol, m = more than 3 and less than 5, n = 1, M = number average molecular weight is 50
A high molecular weight unsaturated polyester having a number average molecular weight of 5,000 or more, represented by the number corresponding to 00 or more.
に、これと共重合するモノマーを配合した高分子量不飽
和ポリエステル樹脂。(2) A high-molecular-weight unsaturated polyester resin prepared by blending the high-molecular-weight unsaturated polyester according to claim 1 with a monomer that copolymerizes therewith.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2308810A JP2620406B2 (en) | 1990-11-16 | 1990-11-16 | Method for producing high molecular weight unsaturated polyester |
| US07/793,135 US5198529A (en) | 1990-11-16 | 1991-11-18 | High molecular unsaturated polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2308810A JP2620406B2 (en) | 1990-11-16 | 1990-11-16 | Method for producing high molecular weight unsaturated polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04183713A true JPH04183713A (en) | 1992-06-30 |
| JP2620406B2 JP2620406B2 (en) | 1997-06-11 |
Family
ID=17985585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2308810A Expired - Lifetime JP2620406B2 (en) | 1990-11-16 | 1990-11-16 | Method for producing high molecular weight unsaturated polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2620406B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04236221A (en) * | 1991-01-16 | 1992-08-25 | Showa Highpolymer Co Ltd | High-molecular weight unsaturated polyester resin |
| JP2013523962A (en) * | 2010-04-01 | 2013-06-17 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド | Branched polyester polymer and coating containing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5525451A (en) * | 1978-08-14 | 1980-02-23 | Asahi Chem Ind Co Ltd | Preparation of unsaturated polyester |
-
1990
- 1990-11-16 JP JP2308810A patent/JP2620406B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5525451A (en) * | 1978-08-14 | 1980-02-23 | Asahi Chem Ind Co Ltd | Preparation of unsaturated polyester |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04236221A (en) * | 1991-01-16 | 1992-08-25 | Showa Highpolymer Co Ltd | High-molecular weight unsaturated polyester resin |
| JP2013523962A (en) * | 2010-04-01 | 2013-06-17 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド | Branched polyester polymer and coating containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2620406B2 (en) | 1997-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH04183713A (en) | High-molecular weight unsaturated polyester | |
| JP2622030B2 (en) | Method for producing high molecular weight unsaturated polyester | |
| JP2620408B2 (en) | Method for producing high molecular weight unsaturated polyester | |
| JP2620407B2 (en) | Method for producing high molecular weight unsaturated polyester | |
| US5371172A (en) | High-molecular unsaturated polyester resin | |
| JP3198833B2 (en) | Method for producing unsaturated polyester resin | |
| JP2604069B2 (en) | Method for producing high molecular weight unsaturated polyester resin | |
| US5254643A (en) | High-molecular unsaturated polyester resin | |
| US3520950A (en) | Polyesters of metal phthalocyanine-octacarboxylic acid | |
| JP2004156005A (en) | Normal temperature curable resin composition, method for curing the same and cured material of the same | |
| JP2002226564A (en) | Method for producing curable resin | |
| US3535404A (en) | Unsaturated polyester resins containing tetracarboxylic acids or dianhydrides | |
| US5198529A (en) | High molecular unsaturated polyester | |
| JPH04285628A (en) | High-molecular weight unsaturated polyester resin | |
| JP3467884B2 (en) | Oligomer excellent in curability, method for producing the oligomer, curable resin composition using the oligomer, and cured product obtained by curing the composition | |
| JP3053544B2 (en) | Method for producing high molecular weight unsaturated polyester | |
| JPH0641283A (en) | Production of unsaturated polyester oligomer | |
| JPH03294322A (en) | Production of graft polymer | |
| JP2604070B2 (en) | Method for producing high molecular weight unsaturated polyester resin | |
| JPH0822908B2 (en) | High molecular weight unsaturated polyester resin | |
| JPH107777A (en) | Unsaturated polyester and unsaturated polyester resin composition containing the same | |
| JPH03153719A (en) | Production of high-molecular weight unsaturated polyester | |
| JPS6010534B2 (en) | Method for producing modified unsaturated polyester | |
| JPH0586173A (en) | High-molecular unsaturated polyester resin | |
| JPH06157731A (en) | Polyester acrylate resin composition |