JPS60252622A - Preparation of novel lactone polymer - Google Patents
Preparation of novel lactone polymerInfo
- Publication number
- JPS60252622A JPS60252622A JP11013984A JP11013984A JPS60252622A JP S60252622 A JPS60252622 A JP S60252622A JP 11013984 A JP11013984 A JP 11013984A JP 11013984 A JP11013984 A JP 11013984A JP S60252622 A JPS60252622 A JP S60252622A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- lactone
- parts
- polyester
- lactones
- 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
- 150000002596 lactones Chemical class 0.000 title claims abstract description 51
- 229920000642 polymer Polymers 0.000 title claims description 24
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 14
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 12
- 229920001225 polyester resin Polymers 0.000 claims abstract description 9
- 239000004645 polyester resin Substances 0.000 claims abstract description 9
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 8
- 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 8
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 abstract description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001361 adipic acid Substances 0.000 abstract description 4
- 235000011037 adipic acid Nutrition 0.000 abstract description 4
- 239000000049 pigment Substances 0.000 abstract description 4
- 239000002270 dispersing agent Substances 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract description 3
- 229920001634 Copolyester Polymers 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- -1 epsilon-caprolactone Chemical class 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 4
- 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 4
- 239000003999 initiator Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- SZCWBURCISJFEZ-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) 3-hydroxy-2,2-dimethylpropanoate Chemical compound OCC(C)(C)COC(=O)C(C)(C)CO SZCWBURCISJFEZ-UHFFFAOYSA-N 0.000 description 1
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000012644 addition polymerization 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
- 238000003287 bathing Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 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 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 229940108184 stannous iodide Drugs 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】 （技術の背景） 本発明は、新規なラクトン重合体の製造方法に関する。[Detailed description of the invention] (Technical background) The present invention relates to a novel method for producing lactone polymers.
さらに詳しくは、エステル鎖と、ラクトン鎖とのエステ
ル交換反応を起させ、多塩基酸／多価アルコール／ラク
トンのランダム共重合ポリエステルの製造方法に関する
。More specifically, the present invention relates to a method for producing a polybasic acid/polyhydric alcohol/lactone random copolyester polyester by causing a transesterification reaction between an ester chain and a lactone chain.
（従来技術およびその欠点）
従来から知られているラクトン重合体は、エチレングリ
コール、ジエチレングリコール、ネオペンチルグリコー
ル、トリメチロールプロパン等ノ多価アルコールを開始
剤としてラクトン類を開環付加重合させることにより得
られる末端が水酸基のいわゆるポリエステルポリオール
である。これらは、ポリウレタンの原料としてウレタン
エラストマー、ウレタンフオーム、接着剤、塗料等に広
く用いられている。また、各種プラスチ・ツクの可塑剤
、変性剤、無機光てん剤の分散性付与剤、熱硬化性樹脂
の可とう仕付与剤、収縮性改良剤としても注目されてい
る。この末端が水酸基であるラクトン重合体をプラスチ
ックの改質剤、ｍ機充てん剤の分散性付与剤、熱硬化性
樹脂の収縮性改良剤可とシ性付与剤等に用いる場合、改
良しようとする樹脂によっては非常に相浴性が悪かった
シ。(Prior art and its drawbacks) Conventionally known lactone polymers are obtained by ring-opening addition polymerization of lactones using polyhydric alcohols such as ethylene glycol, diethylene glycol, neopentyl glycol, and trimethylolpropane as an initiator. This is a so-called polyester polyol having a hydroxyl group at the end. These are widely used as raw materials for polyurethane, such as urethane elastomers, urethane foams, adhesives, and paints. It is also attracting attention as a plasticizer and modifier for various plastics, a dispersibility imparting agent for inorganic brightening agents, a flexibility imparting agent for thermosetting resins, and a shrinkage improver. When this lactone polymer whose terminal end is a hydroxyl group is used as a modifier for plastics, a dispersibility imparting agent for machine fillers, a shrinkage improver for thermosetting resins, and a shrinkability imparting agent, etc., the improvement is attempted. Depending on the resin, the bathing properties were very poor.
分散性が良くないという問題点を持っている。It has the problem of poor dispersibility.
これらの欠点を改良するために末端の水酸基をカルボン
酸基に置き換える種々の工夫がなされている。例えば、
コハク酸、フタル酸、マレイン酸等の多価カルボン［ｆ
−開始剤にしてラクトン類を開環重合させる仁とにより
カルボキシル末端ヲ有するラクトン重合体ケ得る試みが
なされている。In order to improve these drawbacks, various efforts have been made to replace the terminal hydroxyl group with a carboxylic acid group. for example,
Polyvalent carboxylic acid [f] such as succinic acid, phthalic acid, maleic acid, etc.
- Attempts have been made to obtain lactone polymers having carboxyl terminals by ring-opening polymerization of lactones as an initiator.
また、末端水酸基のラクトン重合体に無ホコハク酸、無
水フタル酸、無水マレイン酸等の多価カルボン酸無水物
を開環反応させ同様に末端カルボン酸基を有するラクト
ン重合体を得る試みもなされている。しかし、これらの
方法はいずれも反応時間が非常に長く、かつ、工業的生
産工程を考えた場合工程が繁雑であったり用いる触媒に
よってはラクトン重合体そのものが持つ物性を低下させ
る原因となるといった問題点を有している。In addition, attempts have also been made to similarly obtain lactone polymers having terminal carboxylic acid groups by ring-opening reaction with polycarboxylic anhydrides such as phosuccinic anhydride, phthalic anhydride, and maleic anhydride on lactone polymers having terminal hydroxyl groups. There is. However, all of these methods have problems such as extremely long reaction times, complicated processes when considering industrial production processes, and depending on the catalyst used, the physical properties of the lactone polymer itself may be deteriorated. It has points.
これらの背景から本発明者らは鋭意検討した結果、ラク
トン重合体にカルボン酸基ケ容易に導入する方法を見い
出し本発明に到達した。Based on these backgrounds, the inventors of the present invention have made extensive studies and have found a method for easily introducing a carboxylic acid group into a lactone polymer, resulting in the present invention.
（本発明の構成）
すなわち本発明は、多価アルコールと多塩基酸又はその
酸無水物とから合成された、末端カルボン酸基を有する
ポリエステル樹脂とラクトン類から合成されるラクトン
重合体の製造方法に関する。(Structure of the present invention) That is, the present invention provides a method for producing a lactone polymer synthesized from a polyester resin having a terminal carboxylic acid group, which is synthesized from a polyhydric alcohol and a polybasic acid or its acid anhydride, and lactones. Regarding.
本発明のラクトン重合体は多価アルコールと多塩基酸又
はその酸無水物とから合成された両末端にカルボン酸基
を有するポリエ”ステル樹脂と、ラクトン類を触媒存在
下において、同時に反応器に仕込み、まず開環隼合開始
剤とラクトン類との開環重合を行なわぜる。さらに、反
応を続けるとポリエステル樹脂とラクトン重合体のエス
テル結合がエステル交換反応奮起としランタン、重合体
の１分子内にカルボン酸基および水酸基をどちらも１個
以上有するラクトン重合体’に４ることかできる。The lactone polymer of the present invention is produced by combining a polyester resin synthesized from a polyhydric alcohol and a polybasic acid or its acid anhydride and having carboxylic acid groups at both ends, and lactones in the presence of a catalyst in a reactor. First, ring-opening polymerization is performed between the ring-opening initiator and the lactones.Furthermore, as the reaction continues, the ester bond between the polyester resin and the lactone polymer stimulates a transesterification reaction, and one molecule of lanthanum and polymer is produced. A lactone polymer having at least one carboxylic acid group and one or more hydroxyl group can also be used.
本発明におけるラクトン類は、甲の中に４ Ｊ’−以上
、好捷しくは、６またけ、そハフ以上の炭素伸子を持つ
。好ましいラフ）・ンけ、５員環から８員環のラクトン
であシ、例えばε−カプロラクトン、δ−バレロラクト
ン、ｒ−ブチロラクトン等がある。The lactones according to the present invention have carbon fibers of 4 J' or more, preferably 6 or more, in the shell. Preferred lactones include 5- to 8-membered ring lactones, such as ε-caprolactone, δ-valerolactone, r-butyrolactone, and the like.
又、本発明に用いる多価アルコールとしては、２価、３
価、さらに４価」以上のアルコールを含み、例、ｔ ハ
エチレングリコール、プロピレンクリコール、１．３−
フチレンゲリコール、２−メチルプロパンジオール、１
．４−ブチ１７ングリコール、ネオペンチルグリコール
、１．６−へギザングリコール。In addition, the polyhydric alcohols used in the present invention include dihydric and trihydric alcohols.
Including alcohols with a valence of 4 or higher, such as ethylene glycol, propylene glycol, 1.3-
Fthylene gelicol, 2-methylpropanediol, 1
．． 4-buty-17 glycol, neopentyl glycol, 1,6-buty-17 glycol.
１．２−ドデカンジオール、グリセリン、トリメチロー
ルプロパン、トリメチロールエタン、ペンタエリスリト
・−ル、ジペンタエリスリトール、ヒドロキシピバリン
酸ネオペンチルグリコールエステル、１．４シクロへギ
ザンジメタノール、ビスフェノールＡのエチレンオキシ
ド付加物、ビスフェノールＡのブロビレンオキシド付加
物、１．４−ヒドロキシハイドロキノン等を単独又は、
とわらを併用することができる。1.2-dodecanediol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, hydroxypivalic acid neopentyl glycol ester, 1.4cyclohexane dimethanol, addition of bisphenol A with ethylene oxide compound, bisphenol A brobylene oxide adduct, 1,4-hydroxyhydroquinone, etc. alone or
Can be used in combination with straw.
本発明の末端カルボン酸基を有するポリエステル樹脂の
第２の成分である多塩基酸又はその無水物としては、マ
レイン酸、コハク酸、フマル酸、アジピン酸、セバシン
酸、アゼライン酸、ドデカン２酸、フタル酸、イノフタ
ル酸、テレフタル酸、ヘキサヒドロフタル酸、メチルへ
キサヒドロフタル酸、テトラヒドロフタル酸、メチルテ
トラヒドロフタル酸、トリメリット酸又はそれらの無水
物等を単独又は、これらを併用することもてきる。Examples of the polybasic acid or anhydride thereof which is the second component of the polyester resin having a terminal carboxylic acid group of the present invention include maleic acid, succinic acid, fumaric acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, Phthalic acid, inophthalic acid, terephthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, trimellitic acid, or their anhydrides, etc. may be used alone or in combination. Ru.
本発明に於てはラクトン類がラクトン重合体中３０〜９
５重量％含むようにすることが必要である。In the present invention, lactones are present in the lactone polymer with a concentration of 30 to 9
It is necessary to contain 5% by weight.
ラクトン類が３０重量％より少ないと、生成した樹脂の
耐水性や低温特性が悪くなる。又、９５重量％よりも多
い場合は、ラクトン類の結晶性のため、溶剤への相溶性
が悪くな−〕たり、ラクトン重合体の融点が高くなって
好捷１．〈ない。If the content of lactones is less than 30% by weight, the water resistance and low temperature properties of the produced resin will deteriorate. If the amount exceeds 95% by weight, the compatibility with solvents may be poor due to the crystallinity of the lactones, or the melting point of the lactone polymer may become high, resulting in poor compatibility. <do not have.
さて、次に本発明のラクトン重合体を合成する方法を述
べる。Next, a method for synthesizing the lactone polymer of the present invention will be described.
先ず多価アルコールと、多塩基酸と、反応器に仕込む。First, polyhydric alcohol and polybasic acid are charged into a reactor.
この多価・アルコールのモ・ル数ｉｎとした時多塩基酸
のモル数ｋ ｎ ＋ １の比率で加える。反応温度は、
１００°Ｃ〜２３０℃が適切である。所定量の水が脱水
されれば両末端カルボン酸のポリエステルが得られる。When the number of moles of the polyhydric alcohol is expressed as in, the number of moles of the polybasic acid is k n + 1. The reaction temperature is
A temperature of 100°C to 230°C is suitable. When a predetermined amount of water is dehydrated, a polyester having carboxylic acid at both terminals is obtained.
この反応は無触媒で進行するが通常エステル化反応に使
用される触媒２用いても良い。例えば、硫酸、バラトル
エンスルフォン酸テトラブチルチタネート等のチタン化
合物などがあげられる。This reaction proceeds without a catalyst, but catalyst 2, which is commonly used in esterification reactions, may be used. Examples include sulfuric acid and titanium compounds such as valatoluenesulfonic acid tetrabutyl titanate.
この様Ｖして沓らｈた両末端カルボン酸のポリエステル
の分子昂−は、３００〜２０，０００、好捷しくは１．
０００〜５，０００である。The molecular weight of the polyester having carboxylic acid terminals on both ends, which has been washed in this manner, is 300 to 20,000, preferably 1.
000 to 5,000.
次いで、ラクトン類會樹脂中に、３０〜９５重量％、好
１しくけ６０〜９０重量係含重量うにポリエステル樹脂
にラクトン類、触媒、開壌重合開始剤を加え１反応させ
る。反応温度は、１３０℃〜２４０℃、好ましくは１６
０ ’Ｃ〜２３０ ’Ｃである。・又１反応中は、窒素
ガス等不活性ガスを通じるととが樹脂の色相等に良い結
果を与える。Next, lactones, a catalyst, and an open polymerization initiator are added to the polyester resin containing 30 to 95% by weight, preferably 60 to 90% by weight of the lactone resin, and a reaction is carried out. The reaction temperature is 130°C to 240°C, preferably 16°C.
0'C to 230'C.・Also, during the reaction, passing an inert gas such as nitrogen gas gives good results on the color of the resin.
この反応に用いる触媒どしては、テトラブチルチタネー
ト、テトラプロピルチタネート等のチタン化合物、ジブ
チルスズラウレート、オクチル酸スズ、ジブチルスズオ
キサイド、塩化第１スズ、臭化第１スズ、ヨウ化第１ス
ズ等があり、触媒使用量は０．０１〜５０ ｐｐｍ、好
ましくは０．１−１０ｐｐｍである。さらにとわらの触
媒の中で特にチタン系の化合物はエステル交換反応に対
しても十分な触媒活性を示す。Catalysts used in this reaction include titanium compounds such as tetrabutyl titanate and tetrapropyl titanate, dibutyltin laurate, tin octylate, dibutyltin oxide, stannous chloride, stannous bromide, stannous iodide, etc. The amount of catalyst used is 0.01-50 ppm, preferably 0.1-10 ppm. Furthermore, among Towara's catalysts, titanium-based compounds in particular exhibit sufficient catalytic activity for transesterification reactions.
本発明に用いる開環重合開始剤としては水、アルコール
類、カルボン酸類、アミン類、チオール類等、ラクトン
類の重合開始剤になるものであれば何をもちいてもさし
つかえはない、この活性水素を有する化合物は、ラクト
ン類の重合開始剤としての役割を果すものであるため、
その添加、量は、ラクトン類の重合を開始するのに必要
な最少量であることが好ましい。例えば・ラクトン類中
に微量含まれている不純物としての水であっても差しつ
かえはない。As the ring-opening polymerization initiator used in the present invention, any active hydrogen initiator may be used as long as it becomes a polymerization initiator for lactones, such as water, alcohols, carboxylic acids, amines, and thiols. Since the compound having the following functions as a polymerization initiator for lactones,
The amount added is preferably the minimum amount necessary to initiate polymerization of lactones. For example, there is no problem with water as an impurity contained in trace amounts in lactones.
また、有機モノカルボン酸の多価アルコールエステル中
に含まれる未反応多価アルコール成分であってもよい。Alternatively, it may be an unreacted polyhydric alcohol component contained in a polyhydric alcohol ester of an organic monocarboxylic acid.
活性水素を有する化合物成分の添加ｔが多いと、製品の
水酸基価や酸価が高くなるので好ましくない。従ってそ
の添加量は多価アルコール、多塩基酸または酸無水物、
ラクトン類を合わせた重量の０．１％から８％の範囲で
あることが好ましｂｏまた多価アルコール、多塩基酸又
は、その酸無水物から合成された両末端カルボン酸基會
持つポリエステル樹脂とあらかじめ合成しておいた高重
合度のラクトン重合物とのエステル交換反応を行なうこ
とによっても本発明の目的物を全く同じように合成する
こともできる。It is not preferable to add a large amount of the compound component having active hydrogen because the hydroxyl value and acid value of the product will increase. Therefore, the amount added is polyhydric alcohol, polybasic acid or acid anhydride,
It is preferably in the range of 0.1% to 8% of the total weight of the lactones.Also, polyester resins having carboxylic acid groups at both ends synthesized from polyhydric alcohols, polybasic acids, or their acid anhydrides. The object of the present invention can also be synthesized in exactly the same manner by conducting a transesterification reaction with a lactone polymer having a high degree of polymerization synthesized in advance.
両末端カルボン酸基のポリエステルと、ラクトン類を加
え、触媒と、開環重合開始剤を加え、反応温度１６０°
Ｃ〜２３０“Ｃで反応させると、まず。Add polyester with carboxylic acid groups at both ends and lactones, add catalyst and ring-opening polymerization initiator, and raise the reaction temperature to 160°.
When reacting at C~230"C, first.
ラクトン類の開環重合が起シ、ポリラクトンポリオール
ができる。ついで両末端カルボン酸基のポリエステル樹
脂のエステル知とラクトン鎖とのエステル交換反応が起
こシ、ランダム共重合ポリエステルを得ることができる
。Ring-opening polymerization of lactones occurs, producing polylactone polyol. Then, a transesterification reaction occurs between the ester group of the polyester resin having carboxylic acid groups at both terminals and the lactone chain, and a random copolymerized polyester can be obtained.
上記の如く充分にエステル交換反応を起はせ、ランダム
共重合体にすると々が低融点および溶剤との相溶性の良
いラクトン変性ポリエステルポリオールを合成するため
に必要である。As mentioned above, it is necessary to cause a sufficient transesterification reaction to form a random copolymer in order to synthesize a lactone-modified polyester polyol having a low melting point and good compatibility with solvents.
この様にして作られた、ラクトン重合体の分子量は１通
常、５００〜ｉ ｏ ｏ、ｏ ｏ ｏ程度である。分子
量の調節は１両末端カルボン酸のポリエステルの分子量
と重合開始剤と、ラクトン類のモル比を定めることによ
シ行なうことができる。The molecular weight of the lactone polymer produced in this manner is usually about 500 to io, ooo. The molecular weight can be adjusted by determining the molecular weight of the polyester having carboxylic acid at both terminals, the polymerization initiator, and the molar ratio of the lactones.
Ｃ本発明による効果）
本発明の新規なラクトン重合体は不飽和ポリエステルや
エポキシ樹脂の低収縮剤、熱可塑プラスチックスの可塑
剤、顔料分散剤、表面改質剤、ウレタン顔料分散性向上
剤、塗料の可撓性付与剤、顔料分散剤等、多くの分野に
極めて有利に利用され得る。C) Effects of the present invention) The novel lactone polymer of the present invention can be used as a low shrinkage agent for unsaturated polyesters and epoxy resins, as a plasticizer for thermoplastics, as a pigment dispersant, as a surface modifier, as a urethane pigment dispersion improver, It can be extremely advantageously used in many fields such as a flexibility imparting agent for paints and a pigment dispersant.
次に実施例を挙げて本発明の説明を行なうが、これらに
よって本発明を限定するものではない。Next, the present invention will be explained with reference to Examples, but the present invention is not limited by these.
なお１例中、部はいずれも重量部を示す。In addition, in one example, all parts indicate parts by weight.
実施例−１゜
撹拌機、温度計、窒素ガス導入管、脱水管付コンデンサ
ーのついた四ツ目フラスコ、にネオペンチルグリコール
２０８０部、アジピン酸３０６６部、テトラブチルチタ
ネー） ０．０５部を仕込み１４０℃から脱水が始まシ
、脱水が進むにつれて温度も２２０℃まで昇温し、脱水
量が７２０部に達するまで反応をさせた所、酸価（ＫＯ
Ｈｍ９／、！９）３４．６、平均分子量（ポリスチレン
換Ｘ ） ＭＮ−３７３０１Ｖ１．ｗ＝７５’９０ Ｍ
、ｗ／ＭＮ＝２．０３のポリエステルを得た。Example-1 2080 parts of neopentyl glycol, 3066 parts of adipic acid, and 0.05 parts of tetrabutyl titanate were added to a four-eye flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a condenser with a dehydration tube. Dehydration started at 140°C, and as dehydration progressed, the temperature rose to 220°C. When the reaction was allowed to occur until the amount of dehydration reached 720 parts, the acid value (KO
Hm9/,! 9) 34.6, average molecular weight (polystyrene-based X) MN-37301V1. w=75'90M
, a polyester having w/MN=2.03 was obtained.
別に同様の装置に、上記ポリエステル３００部、ε−カ
プロラクトン１７００部、ジエチレングリコール７．２
部、テトラブチルチタネート０．０２部を仕込み２１０
℃で１０時間反応させたところ、酸価（ＫＯＨｍｇ／
９ ） ５．０６、水酸基価（ＫＯＨ１１１９／７９）
４．９７、平均分子量（ポリスチレン換算） ＭＮ −
７６５０、Ｍｗ ＝ ２７８７０、Ｍｗ ／ ＭＮ、
＝ ３．６４融点４７℃〜４９℃のラクトン重合体を得
′に、。Separately, in a similar apparatus, 300 parts of the above polyester, 1700 parts of ε-caprolactone, and 7.2 parts of diethylene glycol were added.
210 parts, and 0.02 parts of tetrabutyl titanate.
When the reaction was carried out at ℃ for 10 hours, the acid value (KOHmg/
9) 5.06, hydroxyl value (KOH1119/79)
4.97, average molecular weight (polystyrene equivalent) MN −
7650, Mw = 27870, Mw / MN,
= 3.64 to obtain a lactone polymer with a melting point of 47°C to 49°C.
実施例−２
撹拌機、温度計、窒素ガス總入管、脱水管術コンデンザ
ーのついた四ツロフラスコに、ネオペンチルグリコール
７２８部、アジピン酸１１６８部、テトラブチルチタネ
ート０．０２部を仕込み１４０℃から脱水が始−！シ、
脱水が進むにつれて温度も２２０℃寸で昇温Ｌ、脱水量
が２５２部に達するまで反応をさせた所、酸価（ＫＯＨ
＃＋！；’／！９’） １１７ 。Example-2 728 parts of neopentyl glycol, 1168 parts of adipic acid, and 0.02 parts of tetrabutyl titanate were charged into a four-way flask equipped with a stirrer, a thermometer, a nitrogen gas inlet pipe, and a dehydration condenser, and dehydrated at 140°C. It's the beginning! C,
As the dehydration progresses, the temperature increases to 220°C. When the reaction is allowed to proceed until the dehydration amount reaches 252 parts, the acid value (KOH
＃＋! ;'/! 9') 117.
平均分子量（ポリスチレン換算） Ｍ、Ｎ＝ １４００
Ｍｗ ＝ ２２２０ Ｍｗ ／ ＭＮ ＝ １．．５８
のポリエステルを得た。Average molecular weight (polystyrene equivalent) M, N = 1400
Mw = 2220 Mw / MN = 1. ．． 58
of polyester was obtained.
別に同様の装置に、上記の反応で得たポリエステル３６
２部、ε−カプロラクトン］、 ８３８ ｓ、ジエチレ
ングリコール３，７部、テトラプ゛チルチタネート０．
０２部を仕込み２１０ ”Ｃで１０時間反応させたとこ
ろ、酸価（ＫＯＨ■／、！１ｔ）２２．４．水酸基価（
ＫＯＨｍ９／ 、９ ） ９．７６ 、平均分子量（ボ
ＩＪ スチレン換算）ＭＮ ＝６５１０． Ｍｗ＝１７
１００、Ｍｗ ／ ＭＮ ＝ ２．６２ 融点４５℃−
４７”Ｃのラクトン重合体を得た。Separately, in a similar apparatus, the polyester 36 obtained by the above reaction was
2 parts, ε-caprolactone], 838 s, 3.7 parts of diethylene glycol, 0.
When 02 parts were charged and reacted at 210"C for 10 hours, the acid value (KOH■/,!1t) was 22.4.Hydroxyl value (
KOHm9/, 9) 9.76, average molecular weight (BoIJ styrene equivalent) MN = 6510. Mw=17
100, Mw/MN = 2.62 Melting point 45℃-
A 47"C lactone polymer was obtained.
実施例−３
実施例−１の装置に１．４ブチレングリコ一ル９００部
、イノフタル酸１８２６部、テトラブチルチタネート０
．０２部を仕込み反応温度を２２０℃で反応を行ない、
脱水量が１８０部に達するまで反応に行ッｆｃ所、酸価
（ＫＯＨｍｙ ／ ９ ） ６２．８、平均分子量（ポ
リスチレン換算） ＭＮ ＝ ２０８０、Ｍｗ＝４５４
０． Ｍｗ／ＩＶｈ＝２．１．８ のポリエステルを得
た。Example-3 In the apparatus of Example-1, 900 parts of 1.4-butylene glycolyl, 1826 parts of inophthalic acid, and 0 parts of tetrabutyl titanate were added.
．． 02 parts were charged and the reaction was carried out at a reaction temperature of 220°C.
The reaction was continued until the amount of dehydration reached 180 parts, acid value (KOHmy/9) 62.8, average molecular weight (polystyrene equivalent) MN = 2080, Mw = 454.
0. A polyester having Mw/IVh=2.1.8 was obtained.
別に同様の装置に上記の反応で得たポリエステル１００
ｓ、ε〜カプロラクトン９００部、ジエチレングリコー
ル９．０部、テトラブチルチタネー） ０．０１部を仕
込み２２０℃で８時間反応させた所、酸価（ＫＯＨｍＱ
／ ９ ） ４．９、水酸基価（ＫＯＩｉη／！？）
１２．３、平均分子量（ポリスチレン換算）ＭＮ＝９２
１０． ｉＶ１ｍ＝２３４９０、Ｍｗ ／ ＭＮ −２
，５５ｍ点り９℃〜５３ ’Ｃのラクトン重合体全得た
。Separately, the polyester 100 obtained by the above reaction was placed in a similar apparatus.
s, ε ~ 900 parts of caprolactone, 9.0 parts of diethylene glycol, 0.01 part of tetrabutyl titanate) were charged and reacted at 220°C for 8 hours, and the acid value (KOHmQ
/ 9) 4.9, hydroxyl value (KOIiη/!?)
12.3, average molecular weight (polystyrene equivalent) MN=92
10. iV1m=23490, Mw/MN-2
A total of lactone polymer having a temperature of 9°C to 53'C was obtained at 55m point.
Claims (1)
された末端カルボン酸基を有するポリエステル樹脂とラ
クトン類から合成されるラクトン重合体の製造方法A method for producing a lactone polymer synthesized from a polyester resin having a terminal carboxylic acid group synthesized from a polyhydric alcohol and a polybasic acid or its acid anhydride, and lactones
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59110139A JPH0660236B2 (en) | 1984-05-30 | 1984-05-30 | Novel method for producing lactone polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59110139A JPH0660236B2 (en) | 1984-05-30 | 1984-05-30 | Novel method for producing lactone polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60252622A true JPS60252622A (en) | 1985-12-13 |
| JPH0660236B2 JPH0660236B2 (en) | 1994-08-10 |
Family
ID=14528016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59110139A Expired - Lifetime JPH0660236B2 (en) | 1984-05-30 | 1984-05-30 | Novel method for producing lactone polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0660236B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6351468A (en) * | 1986-08-20 | 1988-03-04 | Dainichi Color & Chem Mfg Co Ltd | Pigment composition |
| JPH02202915A (en) * | 1989-02-01 | 1990-08-13 | Toyobo Co Ltd | Production of block copolyester |
| EP0909789A3 (en) * | 1992-06-19 | 1999-06-09 | Eastman Chemical Company | Composition comprising poly (3-Hydroxylalkanoates) |
| JP2011517717A (en) * | 2008-04-18 | 2011-06-16 | コモンウェルス サイエンティフィック アンド インダストリアル リサーチ オーガニゼイション | Condensation polymers with modified properties |
| EP3670568A1 (en) * | 2018-12-21 | 2020-06-24 | Covestro Deutschland AG | Method for producing a polyester |
| CN114380993A (en) * | 2020-10-05 | 2022-04-22 | 财团法人工业技术研究院 | Copolymers and methods of forming the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5154641A (en) * | 1974-08-21 | 1976-05-13 | Ciba Geigy | |
| JPS5880321A (en) * | 1981-11-06 | 1983-05-14 | Daicel Chem Ind Ltd | Thermoplastic polyester resin and its production |
-
1984
- 1984-05-30 JP JP59110139A patent/JPH0660236B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5154641A (en) * | 1974-08-21 | 1976-05-13 | Ciba Geigy | |
| JPS5880321A (en) * | 1981-11-06 | 1983-05-14 | Daicel Chem Ind Ltd | Thermoplastic polyester resin and its production |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6351468A (en) * | 1986-08-20 | 1988-03-04 | Dainichi Color & Chem Mfg Co Ltd | Pigment composition |
| JPH02202915A (en) * | 1989-02-01 | 1990-08-13 | Toyobo Co Ltd | Production of block copolyester |
| EP0909789A3 (en) * | 1992-06-19 | 1999-06-09 | Eastman Chemical Company | Composition comprising poly (3-Hydroxylalkanoates) |
| JP2011517717A (en) * | 2008-04-18 | 2011-06-16 | コモンウェルス サイエンティフィック アンド インダストリアル リサーチ オーガニゼイション | Condensation polymers with modified properties |
| EP3670568A1 (en) * | 2018-12-21 | 2020-06-24 | Covestro Deutschland AG | Method for producing a polyester |
| CN114380993A (en) * | 2020-10-05 | 2022-04-22 | 财团法人工业技术研究院 | Copolymers and methods of forming the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0660236B2 (en) | 1994-08-10 |
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