CN105579140A - 用于制造含有催化活性的钛化合物的产品的方法 - Google Patents
用于制造含有催化活性的钛化合物的产品的方法 Download PDFInfo
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- CN105579140A CN105579140A CN201480045342.3A CN201480045342A CN105579140A CN 105579140 A CN105579140 A CN 105579140A CN 201480045342 A CN201480045342 A CN 201480045342A CN 105579140 A CN105579140 A CN 105579140A
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- 238000000034 method Methods 0.000 title claims abstract description 36
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 7
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 35
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
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- 235000011187 glycerol Nutrition 0.000 claims description 4
- 150000002576 ketones Chemical group 0.000 claims description 4
- -1 polyalcohol Chemical compound 0.000 claims description 4
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- 239000005864 Sulphur Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000001339 acylated starch Substances 0.000 description 1
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- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
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- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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Abstract
用于制造含有催化活性的钛化合物的产品的方法以及通过该方法获得的产品，该方法包括至少一个以下步骤，其中使该催化活性的钛化合物与底物在液相中接触，该液相包含溶剂和抑制剂，该溶剂具有羰基官能团和在所述羰基官能团的α-位上的C-H键，该抑制剂选自一种或多种酸和一种或多种醇或其混合物。
Description
本申请要求欧洲申请号13180138.3的优先权，出于所有的目的将此申请的全部内容通过引用结合在此。
本发明涉及用于制造含有催化活性的钛化合物的产品的方法以及含有底物和催化活性的钛化合物的产品。
已经提出含有催化活性的钛化合物的产品用于提供改善的底物(如，用作滤嘴丝束的纤维素乙酸酯)降解性；参见以本申请人名义的WO2010/017989。
本发明现在使得用于含有催化活性的钛化合物的产品的改进的制造方法以及含有底物和催化活性的钛化合物的改进的产品可供使用。
本发明因此涉及用于制造含有催化活性的钛化合物的产品的方法，该方法包括至少一个以下步骤，其中使该催化活性的钛化合物与底物在液相中接触，该液相包含溶剂和抑制剂，该溶剂具有羰基官能团和在所述羰基官能团的α-位上的C-H键，该抑制剂选自一种或多种酸和一种或多种醇或其混合物。
已经出乎意料地发现根据本发明的方法允许强烈降低所不希望的副产物的形成(特别是来自于溶剂的自缩合的)，同时保留所希望的钛化合物的催化活性，例如，用于加速底物(如生物基聚合物)的降解、特别是光催化降解。
“催化活性的钛化合物”应理解为具体指代能够加速反应(例如像有机化合物如特别是生物基聚合物的裂解)的钛化合物。一类特别的催化活性的钛化合物(所谓的光催化活性的钛化合物、特别是二氧化钛光催化剂)在辐射(如可见光或UV光)的存在下是显著地催化活性的。在本发明的意义上，含有TiO2颜料降低光催化活性的涂料不是光催化活性的钛化合物。优选的催化地钛化合物是纳米结构的。
“纳米结构的”应理解为是指该钛化合物由以下项组成或主要由以下项组成：任选团聚的微晶，这些微晶具有从1至150nm，优选从1至100nm，并且更优选从5至30nm的平均粒径。
特别优选将任选改性的纳米结构的二氧化钛作为催化活性的钛化合物。
在第一具体实施例中，该催化活性的钛化合物是纳米结构的氧化钛，该氧化钛包含一种或两种类型的氧化钛，特别是金红石和/或锐钛矿。
在第二具体实施例中，该催化活性的钛化合物是纳米结构的氧化钛，该氧化钛是用另外的元素如，碳、氮、硫、氟、碘、铝、铋、铁、钴、钒、铬、镍、锰、钨、钼、钽、铌、银、金或铂改性的。优选的是碳改性的纳米结构的氧化钛(如在以本申请人名义的WO-A-2010/017989中所披露的)和铁改性的二氧化钛(如在WO-A-2012/139726中所披露的)。
当使用碳掺杂的二氧化钛时，该碳掺杂的二氧化钛的微晶尺寸可以是从5至150nm，尤其从7至25nm。在单独的情况中，可能有利的或甚至必要的是研磨常规的商业粗颗粒碳改性的二氧化钛以便调节最佳晶粒尺寸。
经常地，该碳改性的二氧化钛具有3.0至5.0g/cm3，尤其3.5至4.2g/cm3的密度(ISO787，第10部分)。该碳改性的氧化钛优选具有大于100m2/g，尤其大于250m2/g的比表面积BET。经常地，此比表面积是等于或低于1000m2/g。优选地，该碳改性的二氧化钛的特征是与纯二氧化钛相比在[λ]>＝400nm范围内的显著的光吸收。
该碳改性的二氧化钛优选含有按重量计0.05％至5％，尤其按重量计从0.3％至1.5％的量的碳。
在根据本发明的方法中，该溶剂经常选自酮和酯(具有在羰基官能团的α-位上的C-H键)。优选的是酮溶剂，更特别优选的是C3-C6酮(特别是丙酮)。
在一个方面，该抑制剂是包含在该液相中的溶剂。在另一个方面，包含在该液相中的溶剂不同于该抑制剂。
在根据本发明方法的第一具体方面，该抑制剂包括酸。羧酸被适当地用作抑制剂。羟基羧酸是优选抑制剂。更具体地，优选的是选自以下项的抑制剂：乙醇酸、乳酸、苹果酸、柠檬酸、酒石酸、甘油酸、羟基丙酸、羟基丁酸、扁桃酸或其组合。
在根据本发明方法的第二具体方面，该抑制剂包括醇。多元醇是优选的抑制剂。更具体地，优选的是选自以下项的抑制剂：乙二醇、丙三醇、丙二醇、丁二醇、季戊四醇糖醇或其组合。
在根据本发明的方法中，该底物适当地是塑性材料，特别是任选改性的生物聚合物。优选地，该塑性材料是可光催化降解的塑性材料。优选地，该底物是酰化的多糖如，酰化淀粉或，特别地，酰化纤维素。
当使用纤维素酯作为该底物时，优选的是纤维素乙酸酯、纤维素丙酸酯、纤维素丁酸酯、乙酸丙酸纤维素和/或乙酸丁酸纤维素。纤维素乙酸酯是特别优选的。
当使用纤维素酯作为该底物时，平均取代度(DS)优选地是从1.5至3.0，尤其从2.2至2.7，纤维素乙酸酯尤其是这种情况。该纤维素酯中的最佳平均聚合度是从150至500，尤其是从180至280。
在根据本发明的方法中，用作抑制剂的酸的量通常是相对于催化活性的钛化合物的重量从0.5％重量至50％重量。优选地这个量是从1％重量到20％重量。
在根据本发明的方法中，用作抑制剂的醇的量通常是相对于催化活性的钛化合物的重量从0.5％重量至1000％重量。优选地这个量是从1％重量到100％重量。
通常，该液相含有相对于该液相的重量最高达4％重量的抑制剂和催化活性的钛化合物。优选地这个量是从0.2％-1％重量。
在根据本发明的方法中，底物的浓度通常是相对于该液相的总重量从10％重量至50％重量，优选从20％重量至35％重量。
在根据本发明的方法中，溶剂的浓度通常是相对于该液相的总重量从49％重量至89％重量，优选从64％重量至79％重量。
在具体的方面，该液相含有相对于该液相的总重量最高达2％重量的另外的添加剂如稳定剂、着色剂或颜料。
在第二具体方面，该液体包含最高达10％的软化剂。
根据本发明的方法通常是在从50℃至65℃的温度下进行。
该液相可以适当地通过挤出通过模具进行加工以便形成底物的薄膜或细丝。
在具体方面，根据本发明的方法包括(a)提供包含催化活性的钛化合物、溶剂和抑制剂的液相，以及(b)将步骤(a)中获得的液相添加到包含该底物和溶剂的第二液相中，以及任选地(c)将步骤(b)中获得的液相挤出通过模具以便形成含有底物、催化活性的钛化合物和抑制剂的产品的薄膜或优选地细丝。
在另一个具体方面，根据本发明的方法包括(a)提供包含催化活性的钛化合物、溶剂、抑制剂以及第一量的底物的液相，以及(b)将步骤(a)中获得的液相的至少一部份添加到包含第二量的底物和溶剂的第二液相中，以及任选地(c)将步骤(b)中获得的液相挤出通过模具以便形成含有底物、催化活性的钛化合物和抑制剂的产品的薄膜或优选地细丝。“第一量”旨在指代相对于步骤a)中获得的液相的总重量从0.1％重量至10％重量，优选从1％重量至9％重量，并且最优选从2％重量至7％重量的量的底物。
本发明还涉及产品，该产品含有底物、催化活性的钛化合物以及抑制剂，该抑制剂选自一种或多种酸和一种或多种醇或其混合物，该产品可以适当地通过根据本发明的方法来获得。
根据本发明的产品通常含有从50至100000ppm/wt，优选从100至2000ppm/wt的抑制剂。
根据本发明的产品通常含有少于1000ppm/wt，优选少于300ppm/wt，更优选少于200ppm/wt的溶剂自缩合产物(特别是二丙酮醇)。根据本发明的产品通常含有多于1ppm/wt的溶剂自缩合产物(特别是二丙酮醇)。
根据本发明的产品通常含有少于10000ppm/wt，优选少于5000ppm/wt的溶剂(特别是丙酮)。根据本发明的产品通常含有多于10ppm/wt的溶剂(特别是丙酮)。
根据本发明的产品中催化活性的钛化合物(特别是碳改性的钛)的含量通常是按重量计从0.1％至5％，尤其按重量计0.3％至1.5％。
可以将根据本发明的产品转化成模制体，如纤维，薄膜，尤其深拉薄膜，以上都用作包装材料，用于注塑模制的物品、厚壁模制体、颗粒、微珠、珠粒以及容器。将这些纤维进一步加工成滤嘴丝束是尤其有利的，用其生产用于滤嘴卷烟的由其制成的滤嘴棒和滤嘴塞(filterplug)。含有催化活性的钛化合物的滤嘴塞(在环境中被发现)在光的作用下比不含催化活性的钛化合物的那些显著地降解得快得多。这些模制体如纤维、薄膜(尤其深拉薄膜)、包装材料、注塑模制物品、颗粒、微珠、珠粒、容器、以及特别地滤嘴塞具有强烈降低的不希望的副产物(特别是来自溶剂的自缩合的)的含量，同时保留所希望的钛化合物的催化活性，例如，用于加速产品的降解。
如果通过引用结合在此的任何专利、专利申请、以及公开物的披露内容与本申请的说明发生冲突的程度到了可能导致术语不清楚，则本说明应该优先。
以下实例旨在说明本发明，而非限制本发明。
实例
实例1(参考)
将200mL的丙酮和5％重量的碳改性的TiO2光催化剂在不透光的烧瓶中混合。将所得到的悬浮液在环境温度下以200rpm搅拌。
实例2
将0.5％重量的丙二醇添加到不透光的烧瓶中的200mL的丙酮与5％重量的碳改性的TiO2光催化剂的混合物中。将所得到的悬浮液在环境温度下以200rpm搅拌。
实例3
将0.5％重量的丙三醇添加到不透光的烧瓶中的200mL的丙酮与5％重量的碳改性的TiO2光催化剂的混合物中。将所得到的悬浮液在环境温度下以200rpm搅拌。
实例4
将0.5％重量的乳酸添加到不透光的烧瓶中的200mL的丙酮与5％重量的碳改性的TiO2光催化剂的混合物中。将所得到的悬浮液在环境温度下以200rpm搅拌。
实例5
将0.5％重量的柠檬酸添加到不透光的烧瓶中的200mL的丙酮与5％重量的碳改性的TiO2光催化剂的混合物中。将所得到的悬浮液在环境温度下以200rpm搅拌。
实例6
将5％重量的碳改性的二氧化钛与3％重量的纤维素乙酸酯、0.5％重量的丙三醇以及其余部分的丙酮混合。使用珠磨机(WABDynomillMultilab，1,4l)研磨所得到的悬浮液。
将26重量份的具有2.45的DS的纤维素乙酸酯溶解在74重量份的96:4的丙酮/水的溶剂混合物中。将5.2％重量的二氧化钛悬浮液添加到此混合物中。
均化并且随后过滤所得到的纺丝原液。
通过干式纺丝程序由此纺丝原液生产具有3.0旦尼尔细丝的纤维。
实例7
将5％重量的碳改性的二氧化钛与3％重量的纤维素乙酸酯、0.5％重量的乳酸以及其余部分的丙酮混合。使用珠磨机(WABDynomillMultilab，1,4l)研磨所得到的悬浮液。
将26重量份的具有2.45的DS的纤维素乙酸酯溶解在74重量份的96:4的丙酮/水的溶剂混合物中。将5.2％重量的二氧化钛悬浮液添加到此混合物中。
均化并且随后过滤所得到的纺丝原液。
通过干式纺丝程序由此纺丝原液生产具有3.0旦尼尔单丝纤度的纤维。
22小时后从实例1至5取得样品，将该样品过滤并且通过气相色谱法进行分析。
用乙醇萃取来自实例6的滤嘴丝束，并且通过气相色谱法分析该萃取物。
结果汇总在表1中。
表1
Claims (17)
1.用于制造含有催化活性的钛化合物的产品的方法，该方法包括至少一个以下步骤，其中使该催化活性的钛化合物与底物在液相中接触，该液相包含溶剂和抑制剂，该溶剂具有羰基官能团和在所述羰基官能团的α-位上的C-H键，该抑制剂选自一种或多种酸和一种或多种醇或其混合物。
2.根据权利要求1所述的方法，其中该催化活性的钛化合物是纳米结构的钛化合物，优选地纳米结构的二氧化钛。
3.根据权利要求1或2所述的方法，其中该催化活性的钛化合物是碳改性的二氧化钛。
4.根据权利要求1至3中任一项所述的方法，其中该溶剂是酮，优选丙酮。
5.根据权利要求1至4中任一项所述的方法，其中该抑制剂包括酸，优选羧酸。
6.根据权利要求5所述的方法，其中该抑制剂包括羟基羧酸，优选柠檬酸。
7.根据权利要求1至6中任一项所述的方法，其中该抑制剂包括醇，特别是多元醇，优选丙三醇。
8.根据权利要求1至7中任一项所述的方法，其中该底物是生物聚合物，优选酰化的多糖。
9.根据权利要求1至8中任一项所述的方法，该方法包括(a)提供包含催化活性的钛化合物、溶剂和抑制剂以及任选地第一量的底物的液相，以及(b)将该在步骤(a)中获得的液相添加到包含第二量的底物和溶剂的第二液相中。
10.根据权利要求9所述的方法，其中该第一量的底物是相对于该在步骤(a)中获得的液相的总重量从0.1％重量至10％重量，优选从1％重量至9％重量，并且最优选从2％重量至7％重量的底物。
11.根据权利要求1至10中任一项所述的方法，其中用作抑制剂的酸的量是相对于催化活性的钛化合物的重量从0.5％重量至50％重量，优选从1％重量至20％重量，或其中用作抑制剂的醇的量是相对于催化活性的钛化合物的重量从0.5％重量至1000％重量，优选从1％重量至100％重量。
12.根据权利要求1至11中任一项所述的方法，其中底物的浓度是相对于该液相的总重量从10％重量至50％重量，优选从20％重量至35％重量。
13.含有底物、催化活性的钛化合物以及选自一种或多种酸和一种或多种醇或其混合物的抑制剂的产品，该产品可以根据依据权利要求1至12中任一项所述的方法获得。
14.根据权利要求13所述的产品，该产品包含从0.1％/wt至5％/wt的催化活性的钛化合物。
15.根据权利要求13或14所述的产品，该产品包含从50ppm/wt至100000ppm/wt的抑制剂。
16.根据权利要求13至15中任一项所述的产品，该产品包含少于1000ppm/wt的溶剂的自缩合产物，特别是二丙酮醇。
17.根据权利要求13至16中任一项所述的产品，该产品包含少于10000ppm/wt的溶剂，特别是丙酮。
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| CN102105074A (zh) * | 2008-08-14 | 2011-06-22 | 罗迪阿阿克土有限公司 | 可光降解塑料及其用途 |
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- 2014-07-31 WO PCT/EP2014/066529 patent/WO2015022201A1/en active Application Filing
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- 2014-07-31 KR KR1020167006241A patent/KR102188528B1/ko active IP Right Grant
- 2014-07-31 ES ES14745143T patent/ES2935895T3/es active Active
- 2014-07-31 CA CA2920558A patent/CA2920558A1/en not_active Abandoned
- 2014-07-31 CN CN201480045342.3A patent/CN105579140A/zh active Pending
- 2014-07-31 US US14/911,535 patent/US20160199826A1/en not_active Abandoned
-
2016
- 2016-02-12 PH PH12016500294A patent/PH12016500294A1/en unknown
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2019
- 2019-02-06 US US16/269,046 patent/US20190168201A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995029209A1 (en) * | 1994-04-21 | 1995-11-02 | Courtaulds Chemicals (Holdings) Limited | Pigment dispersions and pigmented products |
| EP0716117A1 (en) * | 1994-12-05 | 1996-06-12 | Daicel Chemical Industries, Ltd. | Cellulose ester compositions and shaped articles |
| CN1132220A (zh) * | 1994-12-05 | 1996-10-02 | 大世吕化学工业株式会社 | 纤维素酯组合物及成型制品 |
| CN102105074A (zh) * | 2008-08-14 | 2011-06-22 | 罗迪阿阿克土有限公司 | 可光降解塑料及其用途 |
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| Title |
|---|
| JUERGEN PULSSTEVEN A ET AL: "Degradation of Cellulose Acetate-Based Materials: A Review", 《JOURNAL OF POLYMERS AND THE ENVIRONMENT》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2935895T3 (es) | 2023-03-13 |
| BR112016003012B1 (pt) | 2021-06-01 |
| RU2016108662A3 (zh) | 2018-05-03 |
| RU2016108662A (ru) | 2017-09-19 |
| JP2016528037A (ja) | 2016-09-15 |
| PH12016500294A1 (en) | 2016-05-02 |
| RU2673526C2 (ru) | 2018-11-27 |
| KR102188528B1 (ko) | 2020-12-08 |
| JP6648017B2 (ja) | 2020-02-14 |
| MX2016001797A (es) | 2016-10-26 |
| EP3033174A1 (en) | 2016-06-22 |
| CA2920558A1 (en) | 2015-02-19 |
| WO2015022201A1 (en) | 2015-02-19 |
| US20190168201A1 (en) | 2019-06-06 |
| EP3033174B1 (en) | 2022-11-02 |
| US20160199826A1 (en) | 2016-07-14 |
| KR20160042980A (ko) | 2016-04-20 |
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Application publication date: 20160511 |