TW201918502A - 製造內酯共聚物之方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 229920001577 copolymer Polymers 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 26
- 239000011541 reaction mixture Substances 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000002516 radical scavenger Substances 0.000 claims abstract description 15
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 11
- 150000002596 lactones Chemical class 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 4
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 10
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 6
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- -1 aromatic carbodiimide Chemical class 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229920000704 biodegradable plastic Polymers 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- XLDBGFGREOMWSL-UHFFFAOYSA-N n,n'-bis[2,6-di(propan-2-yl)phenyl]methanediimine Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C=NC1=C(C(C)C)C=CC=C1C(C)C XLDBGFGREOMWSL-UHFFFAOYSA-N 0.000 claims description 3
- FYGFQAJDFJYPLK-UHFFFAOYSA-N 3-butyloxiran-2-one Chemical compound CCCCC1OC1=O FYGFQAJDFJYPLK-UHFFFAOYSA-N 0.000 claims description 2
- 238000010146 3D printing Methods 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 claims description 2
- 239000004831 Hot glue Substances 0.000 claims description 2
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- PLONEVHFXDFSLA-UHFFFAOYSA-N ethyl hexanoate;tin(2+) Chemical compound [Sn+2].CCCCCC(=O)OCC PLONEVHFXDFSLA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 239000007943 implant Substances 0.000 claims description 2
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- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- 229960000380 propiolactone Drugs 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229920001281 polyalkylene Polymers 0.000 claims 1
- 239000012190 activator Substances 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- HMOZDINWBHMBSQ-UHFFFAOYSA-N 2-[3-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC(C=2OCCN=2)=C1 HMOZDINWBHMBSQ-UHFFFAOYSA-N 0.000 description 1
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BTFJIXJJCSYFAL-UHFFFAOYSA-N arachidyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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Abstract
本發明揭示一種藉由使包含至少一種內酯單體、至少一種第二單體及至少一種催化劑及視需要之至少一種引發劑/活化劑及/或至少一種抗氧化劑之反應混合物共聚合來製造內酯共聚物之方法,其中利用有效量之至少一種除酸劑預處理該反應混合物,且其中該共聚合係在有效量之該至少一種除酸劑的存在下進行。
Description
本發明係關於一種方法,其中藉由使包含至少一種內酯單體、至少一種第二單體及至少一種催化劑及視需要之至少一種引發劑/活化劑及/或至少一種抗氧化劑之反應混合物共聚合而獲得內酯共聚物,其中利用有效量之至少一種除酸劑預處理該反應混合物,且其中該共聚合係在有效量之該至少一種除酸劑的存在下進行。
自例如內酯、交酯及乙交酯產生之可生物降解共聚物被廣泛地用於例如生醫應用,諸如組織工程及藥物傳遞系統、黏著劑及生物分解塑膠中。製造方法係技藝中所熟知,且例如包括在一或多種催化劑(諸如包含有機金屬化合物及錯合物之催化劑)之存在下的開環無規或嵌段共聚合。
對於限制催化劑之用量存在特定的需求及期望,因其將使終產物更為環保及可接受。再一問題為基於例如乳酸及/或乙醇酸之單體(諸如交酯及乙交酯)會在水分之存在下形成游離酸。此會在運送及儲存及尤其在(共)聚合製程中引起問題。於(共)聚合製程中注意到的典型效應為反應時間顯著地增加且將需要較大量的催化劑及因此需要催化劑去活化劑。現意料之外地停止發現在至少一 種內酯及至少一種第二單體之共聚合中利用除酸劑處理及存在除酸劑將導致製程呈現降低量的催化劑及/或較短的反應時間,因催化劑將不會被存在於用過原料及/或於共聚合期間原位產生之酸性催化劑去活化劑消耗。較少量的催化劑意謂要添加較少量的催化劑去活化劑來停止共聚合。此外,意料之外地發現該處理及存在導致較短的反應/加工時間。
在本發明之較佳具體例中,該至少一種除酸劑係選自例如至少一種單體、寡聚或聚合碳二醯亞胺,諸如芳族碳二醯亞胺,其可適當地以雙-(2,6-二異丙基苯基)碳二醯亞胺及聚-雙-(2,6-二異丙基苯基)碳二醯亞胺、及/或至少一種伸芳基唑啉(諸如1,3-伸苯基雙-唑啉)為例。然而,該除酸劑不限於此等例示的化合物。除酸劑係以對應於例如所獲得反應混合物之酸值及原位形成之酸性催化劑去活化劑的有效量適當地添加至該反應混合物。
在本發明之具體例中,該至少一種內酯單體係α-乙內酯、β-丙內酯、γ-丁內酯、δ-戊內酯及/或最佳地ε-己內酯。在該等具體例中,該至少一種第二單體係適當地選自由(甲基)丙烯酸羥烷酯、乙交酯、乙醇酸酯、交酯、乳酸酯、烷二醇或氧化烯烴、碳酸伸烷酯及/或氫呋喃所組成之群。該第二單體可舉下列但不限於彼等為例:D-或L-交酯、聚乙二醇或聚氧化乙烯、單、寡或聚烷二醇及氧化烯烴、單、寡或聚碳酸伸烷酯(諸如碳酸三伸乙酯)、及/或四氫呋喃。
本發明之方法係適當地及較佳地在150-250℃(諸如160-200℃)之反應溫度下,及在該內酯單體對該第二單體介於90: 10與10:90之間(諸如80:20、75:25、60:40、50:50、40:60、25:75及20:80)之進料比下進行。在各種具體例中,所產生之共聚物係具有(例如,但不限於)介於500與50000之間(諸如2000-20000)g/mol之分子量(Mn)的無規或嵌段共聚物。
在較佳具體例中,於本發明方法中所使用之催化劑係包含至少一種有機金屬化合物或錯合物(諸如含錫、鋅、鋁及/或鉬之化合物或錯合物)的催化劑。最佳的催化劑係辛酸亞錫,諸如乙基己酸錫(II)。催化劑係以催化有效量存在,諸如25-250或75-150ppm,並以一或多個部分加入。
在本方法之具體例中,最佳的共聚物係藉由使ε-己內酯及具有下式之D-或L-交酯共聚合來獲得。
適當的引發劑/活化劑例如係在下列之中:烷基、烷基芳基及聚醚醇,諸如正丁醇、第三丁醇、月桂醇、鯨蠟醇(1-十六醇)、硬脂醇及/或二十醇,及適當的抗氧化劑例如係在下列之中:經取代酚及苯二胺及其衍生物,諸如N,N’-二-2-丁基-1,4-苯二胺、2,6-二-第三丁基-4-甲基酚、2,4-二甲基-6-第三丁基酚、2,4-二甲基-6-第三丁基酚、2,4-二甲基-6-第三丁基酚及2,6-二-第三丁基-4-甲基酚、2,6-二-第三丁基酚、3,9-雙(2,4-二-第三丁基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、及/或烷基氫醌(諸如第三丁基氫 醌)及/或烷基化(諸如丁基化)羥基苯甲醚及羥基甲苯。
在再一態樣中,本發明係關於藉由如上文所揭示之方法獲得之內酯共聚物於熱塑性塑料(包括生物分解塑膠)、用於3D印刷之組成物、熱熔膠、醫療植入物及其他技藝中已知於其中利用內酯共聚物之應用領域中的用途。
不作進一步闡述,咸信熟悉技藝人士可使用先前描述,將本發明利用至其最完整程度。下文中,實施例1係在本發明範疇外之比較例,及實施例2及3係本發明之具體例。在所有實施例中使用不含水分及氧之原料。該等實施例顯示可降低催化劑、及因此催化劑去活化劑之量,且利用除酸劑預處理反應混合物及於共聚合期間存在除酸劑可減少反應/加工時間。實施例進一步顯示該等減少不會對所產生之產物有負面影響。在以下進行的實驗中,酸值被認為適中。根據本發明,據估計當在反應物中存在較高酸值時,將達成甚至更大的時間節約。在本發明之範疇中,亦可限制催化劑之用量,及因此亦限制催化劑去活化劑之用量,來自環境以及加工觀點進一步改良終產物。
將196.7克之ε-己內酯單體(Perstorp UK)、295.1克之L-交酯單體(Puralact® L,Corbion,UK)、12.2克作為引發劑/活化劑之鯨蠟醇及1.5克作為抗氧化劑之Irgafos® 126(BASF,德國)加至設有 加熱裝置、攪拌器、溫度探針、真空設備及氮入口之反應容器中,並混合。測得反應混合物之酸值為0.4mg KOH/g。現在氮氣吹掃下將反應混合物加熱至160℃並添加75ppm作為催化劑之辛酸亞錫(DABCO® T9,Evonik,UK)。隨後將反應混合物加熱至180℃並施加真空以得到回流。1小時後,將另一75ppm之該辛酸亞錫添加至反應混合物且於2.5小時後添加又另一75ppm之該辛酸亞錫。於6小時後達成完全真空(<50毫巴(mbar))且無回流,指示沒有或少量的原料殘留於反應混合物中。最後,摻混340ppm之催化劑去活化劑(ABK AX-71,Adeka Palmarole,法國)並將所產生之產物排放至聚矽氧盤中。
分析產生產物具有0.3%之己內酯及2.98%之交酯單體。
將196.7克之ε-己內酯單體(Perstorp UK)、295.1克之L-交酯單體(Puralact® L,Corbion,UK)、12.2克作為引發劑/活化劑之鯨蠟醇及1.5克作為抗氧化劑之Irgafos® 126(BASF,德國)加至設有加熱裝置、攪拌器、溫度探針、真空設備及氮入口之反應容器中,並混合。測得反應混合物之酸值為0.34mg KOH/g且用1.70克之除酸劑(Stabaxol® 1,Rhein Chemie,德國)處理反應混合物。將現具有酸值<0.01mg KOH/g之反應混合物在氮氣下加熱至160℃並添加75ppm作為催化劑之辛酸亞錫(DABCO® T9,Evonik,UK)。隨後將反應混合物加熱至180℃並施加真空以得到回流。1小時後,將另一75ppm之該辛酸亞錫添加至反應混合物。於2小時後達成完全真空 (<50毫巴)且無回流,指示沒有或少量的原料殘留於反應混合物中。最後,摻混225ppm之催化劑去活化劑(ABK AX-71,Adeka Palmarole,法國)並將所產生之產物排放至聚矽氧盤中。
分析產生產物具有0.24%之己內酯及2.19%之交酯單體。
將196.7克之ε-己內酯單體(Perstorp UK)、295.1克之L-交酯單體(Puralact® L,Corbion,UK)、12.2克作為引發劑/活化劑之鯨蠟醇及1.5克作為抗氧化劑之Irgafos® 126(BASF,德國)加至設有加熱裝置、攪拌器、溫度探針、真空設備及氮入口之反應容器中,並混合。測得反應混合物之酸值為0.31mg KOH/g且用1.55克之除酸劑(Stabaxol® 1,Rhein Chemie,德國)處理反應混合物。將現具有酸值<0.01mg KOH/g之反應混合物在氮氣下加熱至160℃並添加150ppm作為催化劑之辛酸亞錫(DABCO® T9,Evonik,UK)。隨後將反應混合物加熱至180℃並施加真空以得到回流。於105分鐘後達成完全真空(<50毫巴)且無回流,指示沒有或少量的原料殘留於反應混合物中。最後,摻混225ppm之催化劑去活化劑(ABK AX-71,Adeka Palmarole,法國)並將所產生之產物排放至聚矽氧盤中。
分析產生產物具有0.28%之己內酯及1.98%之交酯單體。
Claims (15)
- 一種製造內酯共聚物之方法,其係藉由使包含至少一種內酯單體、至少一種第二單體及至少一種催化劑及視需要之至少一種引發劑及/或至少一種抗氧化劑之反應混合物共聚合,其特徵在於以有效量之至少一種除酸劑預處理該反應混合物,且該共聚合係在有效量之該至少一種除酸劑的存在下進行。
- 如請求項1之方法,其中,該除酸劑係單體、寡聚或聚合碳二醯亞胺。
- 如請求項1之方法,其中,該除酸劑係芳族碳二醯亞胺,諸如雙-(2,6-二異丙基苯基)碳二醯亞胺及/或聚-雙-(2,6-二異丙基苯基)碳二醯亞胺。
- 如請求項1之方法,其中,該至少一種內酯單體係α-乙內酯、β-丙內酯、γ-丁內酯、δ-戊內酯及/或ε-己內酯。
- 如請求項1之方法,其中,該至少一種第二單體係選自由下列所組成之群:(甲基)丙烯酸羥烷酯,乙交酯,乙醇酸酯,交酯,乳酸酯,單、寡或聚烷二醇或氧化烯烴,單、寡或聚碳酸伸烷酯及/或氫呋喃。
- 如請求項1之方法,其中,該內酯單體係ε-己內酯且該第二單體係下式之D-或L-交酯
- 如請求項1之方法,其中,該共聚物係在介於90:10與10: 90之間之該至少一種內酯單體對該至少一種第二單體的進料比下產生。
- 如請求項1之方法,其中,該共聚合係在150-250℃之反應溫度下進行。
- 如請求項1之方法,其中,該共聚物係無規共聚物。
- 如請求項1之方法,其中,該共聚物係嵌段共聚物。
- 如請求項1之方法,其中,該共聚物具有介於500與50000g/mol之間的分子量(Mn)。
- 如請求項1之方法,其中,該至少一種催化劑包含至少一種有機金屬化合物或錯合物。
- 如請求項12之方法,其中,該有機金屬化合物或錯合物係含錫、鋅、鋁及/或鉬之化合物或錯合物。
- 如請求項1之方法,其中,該催化劑係辛酸亞錫,諸如乙基己酸錫(II)。
- 一種請求項1至14中任一項之方法所獲得內酯共聚物之用途,其係用於熱塑性塑料,包括生物分解塑膠、用於3D印刷之組成物、熱熔膠及/或醫療植入物中。
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