CN1114837A - 含木质素的聚合物的制备方法 - Google Patents
含木质素的聚合物的制备方法 Download PDFInfo
- Publication number
- CN1114837A CN1114837A CN94190707A CN94190707A CN1114837A CN 1114837 A CN1114837 A CN 1114837A CN 94190707 A CN94190707 A CN 94190707A CN 94190707 A CN94190707 A CN 94190707A CN 1114837 A CN1114837 A CN 1114837A
- Authority
- CN
- China
- Prior art keywords
- compound
- functional group
- xylogen
- oxygen
- polymkeric substance
- 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
- 238000000034 method Methods 0.000 title claims description 16
- 229920005610 lignin Polymers 0.000 title abstract description 9
- 229920000642 polymer Polymers 0.000 title abstract description 4
- 108090000790 Enzymes Proteins 0.000 claims abstract description 14
- 102000004190 Enzymes Human genes 0.000 claims abstract description 14
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 102000003992 Peroxidases Human genes 0.000 claims description 4
- 102000003425 Tyrosinase Human genes 0.000 claims description 4
- 108060008724 Tyrosinase Proteins 0.000 claims description 4
- 108040007629 peroxidase activity proteins Proteins 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 150000002527 isonitriles Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 125000004355 nitrogen functional group Chemical group 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 108010029541 Laccase Proteins 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- -1 acryl Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001409 amidines Chemical class 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920005654 Sephadex Polymers 0.000 description 1
- 229920002684 Sepharose Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- XELZGAJCZANUQH-UHFFFAOYSA-N methyl 1-acetylthieno[3,2-c]pyrazole-5-carboxylate Chemical compound CC(=O)N1N=CC2=C1C=C(C(=O)OC)S2 XELZGAJCZANUQH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/22—Preparation of oxygen-containing organic compounds containing a hydroxy group aromatic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Zoology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Microbiology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Compounds Of Unknown Constitution (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Enzymes And Modification Thereof (AREA)
Abstract
如此制备含木质素和有机化合物的聚合物，即在自由基氧化酶和形成其被酶作用物的氧化剂存在下聚合木质素和有机化合物，该有机化合物含有至少3个碳原子以及氧、氮和/或重键官能团。
Description
本发明涉及一种含木质素和有机化合物的聚合物的制备方法以及按该方法制备的聚合物。
由US—A4687828已知木质素—(2—丙烯酰胺)—(Na—2，2—二甲基—3—亚氨基—4—氧代己—5—烯—1—磺酸酯)的接枝共聚物及其制造方法。按该方法不能制造其它聚合物。
由EP—A 91102118.6已知本质素和丙烯酸酯或甲基丙烯酸酯的接枝共聚物。它们必须在无氧气氛下制造，按该方法仅能制造含丙烯酸或甲基丙烯酸的衍生物。
本发明的任务是制造聚合物和其制造方法，该聚合物由木质素和有机化合物组成，该聚合物可以以简单方式生产和在制造时不必无氧气氛。
通过具有主权利要求特征标记的一类方法来完成该任务。
按照本发明的方法，全部有机化合物与木质素反应，所述有机化合物含有至少3个碳原子和至少一个氧和/或氮和/或至少一个重键官能团。对于该方法来说不需要无氧气氛。
用作原料的木质素可以是天然植物木质素，例如木材的木质素。但是，尤其使用的是在纤维素生产时同时大量产生的，例如以亚硫酸酯木质素或碱木质素[牛皮纸木质素(kraftlignin)]。因此，本发明公开了一种能使用到目前为止正难以利用的废料产物的可能性。
已经指出，含有低于3个碳原子的有机化合物难以与木质素聚合反应。特别简单的是用丙烯酰基衍生物或用含5个或更多碳原子的有机化合物进行聚合反应。
适于聚合反应的尤其是含至少三个碳原子的下述物质：
含氧官能团的物质，象例如羰基化合物，尤其醛和酮；羟基化合物，尤其一元或多元醇；醚化合物，尤其单或多醚，环氧化合物。
含氮官能团的物质，象例如胺，亚胺，酰胺，脒类，腈，异腈，偶氮化合物。
含至少一个重键官能团的物质，象例如含至少一个双键和/或三键的、优选含C—C双键的化合物。
该化合物还可含有多个上述的官能团，象例如是羧酸，羧酸酐，酰胺，脒类，尿素，羧酸酯，过氧化物。另外，化合物中还可以含有其它官能团，象例如羧卤化物，硫醇和类似物。
所有所述的化合物可以以脂族、芳香、环脂族或杂环化合物的形式存在。
作为自由基氧化酶可以使用下述化合物：
过氧化物酶，如锰一过氧化物酶，小红萝卜—过氧化物酶；酚氧化酶，如虫漆酶，Thyrosinase。
在实施聚合反应时必须存在氧化剂，对于相应的酶该氧化剂形成被酶作用物。在使用过氧化物酶时氧化剂是过氧化氢，在使用酚氧化酶时它是氧。此外，无机过氧化物和有机过氧化物和氢过氧化物适用作被酶作用物。然而，不同的酶和被酶作用物可以作为混合物加到聚合反应中。
可以在水溶剂和/或有机溶剂或在用这样溶剂形成的分散液中进行该反应。在使用有机溶剂时，优选酶以酶—母体—络合物的形式加入，象在DE 3827001C1中所述。
按照本发明的方法，所有与木质素聚合的有机化合物含有至少3个、优选多于5个碳原子。还可聚合高分子原料，例如糖，淀粉，纤维素，半纤维素或所述原料的衍生物，以及合成的聚合物。仅在空间阻碍的情况下才能影响聚合反应。
在聚合中使用的木质素溶解或悬浮在所用的溶剂中，添加共聚物组分和加入含酶混合物以及添加辅被作用物，例如氧或过氧化氢。在使用酚氧化酶时，在反应空间存在的空气氧常常就是以使聚合反应开始。可在室温下进行该反应。在较高的温度可加速反应，因此，可在高达70至80℃温度范围内、优选高达60℃进行该反应。此外，可在绝热或等温条件下和在增压或减压下进行该聚合反应。在温度超过80℃时酶一般将失活。一般几小时或几天后结束聚合反应。
下面将借助实施例更详细说明本发明，在实施例中包含的所有说明被认为是本发明的本质。
实施例1
有机溶解木质素与葡糖的聚合
将1g具有克分子量为约6000的有机溶胶本质素悬浮在20ml水中并加入1g用C14标记的葡糖，然后加入虫漆酶溶液，直到溶液中达到1000U/ml浓度。该溶液在室温聚合4个小时。
通过加入pH值为2的酸沉淀生成的聚合物和在碱中溶解生成的沉淀物。再用酸沉淀，直到水相不再呈放射性。
在生成的聚合物中，纤维素共价连接在木质素上。通过测量沉淀物中的放射性来证明。因此，在Sephadex LH 20(隔离界限20000)上进行沉淀物的凝胶色谱并测量高分子馏份的放射性。共聚物的分子量在20000以上。
实施例2
有机溶胶木质素与草香酸的聚合
相应于实施例1用1g有机溶胶木质素与用C14标记的1g草香酸在二噁烷作溶剂中进行聚合。加入Dextrangel VomTyp Sepharose CL 6B的以母体—络合物形式存在的酶。
象例1那样描述聚合物的特征。
实施例3
有机溶胶木质素与山梨醇的聚合
象例1那样将有机溶胶木质素与山梨醇聚合。如例1中那样描述聚合物的特征。
实施例4
有机溶胶木质素与丙烯酰胺的聚合
在1000U/ml虫漆酶存在下于7∶3的二噁烷—水中将0.4g有机溶胶木质素与3.2g丙烯酰胺聚合3小时。在此情况下，在反应开始20分钟长的时间加入氧。如例2那样以酶—母体—络合物形式加入虫漆酶。
用层析分离生成的聚合物。用盐酸沉淀溶解部分。它含有两个馏分，一个馏分具有克分子量超过12000，它由402mg含75.1％丙烯酸酯成分的聚合物组成。第二馏份由535mg具有克分子量超过20000和含14.8％丙烯酸酯成份的聚合物组成。
Claims (8)
1.含木质素和有机化合物的聚合物的制备方法，其特征在于，在自由基氧化酶和形成其被酶作用物的氧化剂存在下，将木质素与有机化合物聚合，该有机化合物含有至少3个碳原子以及至少一个氧官能团和/或氮官能团和/或至少一个重键官能团。
2.按照权利要求1的方法，其特征在于，使用过氧化酶和/或酚氧化酶作为自由基氧化酶。
3.按照权利要求1的方法，其特征在于，使用氧或/或过氧化氢作为氧化剂。
4.按照权利要求1的方法，其特征在于，用含有羟基，羰基和/或醚官能团的化合物作为含氧官能团的化合物。
5.按照权利要求1的方法，其特在于，用含胺、亚胺、酰胺、腈、异腈和/或偶氮官能团的化合物作为含氮官能团的化合物。
6.按照权利要求1的方法，其特征在于，用含至少一个双键和/或三键、优选含C—C双键的化合物作为含重键官能团的化合物。
7.按照权利要求1的方法，其特征在于，在水和/或有机溶剂中进行聚合反应。
8.按权利要求1至7的一项或多项得到的木质素和有机化合物的聚合物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4331878.9 | 1993-09-20 | ||
| DE4331878A DE4331878A1 (de) | 1993-09-20 | 1993-09-20 | Verfahren zur Herstellung von ligninhaltigen Polymeren |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1114837A true CN1114837A (zh) | 1996-01-10 |
| CN1042544C CN1042544C (zh) | 1999-03-17 |
Family
ID=6498097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94190707A Expired - Fee Related CN1042544C (zh) | 1993-09-20 | 1994-09-20 | 含木质素和有机化合物的聚合物和其制备方法 |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5608040A (zh) |
| EP (1) | EP0669953B1 (zh) |
| JP (1) | JPH08505780A (zh) |
| CN (1) | CN1042544C (zh) |
| AT (1) | ATE167208T1 (zh) |
| AU (1) | AU693479B2 (zh) |
| BR (1) | BR9405608A (zh) |
| CA (1) | CA2150012A1 (zh) |
| DE (2) | DE4331878A1 (zh) |
| FI (1) | FI108143B (zh) |
| NZ (1) | NZ273947A (zh) |
| RU (1) | RU2165978C2 (zh) |
| WO (1) | WO1995008588A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897596A (zh) * | 2019-03-28 | 2019-06-18 | 贵州大学 | 一种杉木树皮人造板胶粘剂 |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19700907A1 (de) * | 1997-01-14 | 1998-07-16 | Neste Oy | Zwischenprodukt für die Herstellung von Ligninpolymerisaten und dessen Verwendung zur Herstellung von Holzwerkstoffen |
| DE19756172A1 (de) * | 1997-12-17 | 1999-06-24 | Stockhausen Chem Fab Gmbh | Verfahren zur Pfropfung von Lignin, danach hergestellte Polymerisate und deren Verwendung |
| US5939089A (en) * | 1998-04-09 | 1999-08-17 | Lignotech Usa, Inc. | Method for providing a stable protective coating for UV sensitive pesticides |
| EP1686138A4 (en) * | 2003-10-31 | 2007-04-18 | Ebara Corp | METHOD FOR SEPARATING AND OBTAINING ACID / SUGAR SOLUTION AND A LIGNOPHENOL DERIVATIVE FROM LIGNOCELLULOSIC SUBSTANCE |
| JP4874255B2 (ja) * | 2004-09-24 | 2012-02-15 | 株式会社日本触媒 | クラフトリグニンを利用した分散剤および新規なリグニン誘導体 |
| JP4135760B2 (ja) * | 2006-11-28 | 2008-08-20 | 富士ゼロックス株式会社 | リグノフェノール誘導体、重合体、樹脂組成物および樹脂成形体 |
| CN101234865A (zh) * | 2007-08-22 | 2008-08-06 | 陈国忠 | 一种利用纸浆稀黑液改性接枝羰基脂肪族制备混凝土高效减水剂的方法 |
| MY163510A (en) * | 2009-09-07 | 2017-09-15 | Univ Sains Malaysia | A method for preparing a gelling and viscosifying agent for drilling mud and the product thereof |
| DE102010008393A1 (de) * | 2010-02-10 | 2011-10-06 | Technische Universität Dresden | Substrat zur Bodenverbesserung mit Wasser speichernder Eigenschaft, Verfahren zur Herstellung und dessen Verwendung |
| US9914870B2 (en) | 2013-01-22 | 2018-03-13 | Carnegie Mellon University | Lignin-containing polymers and compositions including lignin-containing polymers |
| JP2015003955A (ja) * | 2013-06-19 | 2015-01-08 | 独立行政法人産業技術総合研究所 | リグニンの分解方法 |
| EP3219747B1 (de) | 2016-03-15 | 2018-10-17 | Sika Technology AG | Enzymatisch modifizierte lignine |
| DE102017128339A1 (de) | 2017-11-29 | 2019-05-29 | Deutsche Institute Für Textil- Und Faserforschung Denkendorf | Modifiziertes Lignin, Verfahren zu dessen Herstellung und Verwendung |
| AT522066A1 (de) * | 2019-01-24 | 2020-08-15 | Univ Wien Bodenkultur | Verfahren zur Herstellung eines Lignosulfonat-Polymers |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3037992C2 (de) * | 1980-10-08 | 1983-04-21 | Gesellschaft für Biotechnologische Forschung mbH (GBF), 3300 Braunschweig | Verfahren zur Herstellung eines Bindemittels für Holzwerkstoffe |
| DE3644397C1 (de) * | 1986-12-24 | 1988-05-05 | Pfleiderer Fa G A | Emissionsarmes Bindemittel fuer holz- und cellulosehaltige Werkstoffe |
| US5138007A (en) * | 1988-12-19 | 1992-08-11 | Meister John J | Process for making graft copolymers from lignin and vinyl monomers |
-
1993
- 1993-09-20 DE DE4331878A patent/DE4331878A1/de not_active Withdrawn
-
1994
- 1994-09-20 BR BR9405608-0A patent/BR9405608A/pt not_active IP Right Cessation
- 1994-09-20 US US08/436,367 patent/US5608040A/en not_active Expired - Fee Related
- 1994-09-20 WO PCT/EP1994/003142 patent/WO1995008588A1/de active IP Right Grant
- 1994-09-20 DE DE59406212T patent/DE59406212D1/de not_active Expired - Fee Related
- 1994-09-20 CA CA002150012A patent/CA2150012A1/en not_active Abandoned
- 1994-09-20 NZ NZ273947A patent/NZ273947A/en unknown
- 1994-09-20 AU AU77830/94A patent/AU693479B2/en not_active Ceased
- 1994-09-20 CN CN94190707A patent/CN1042544C/zh not_active Expired - Fee Related
- 1994-09-20 AT AT94928381T patent/ATE167208T1/de not_active IP Right Cessation
- 1994-09-20 EP EP94928381A patent/EP0669953B1/de not_active Expired - Lifetime
- 1994-09-20 RU RU95112463/04A patent/RU2165978C2/ru not_active IP Right Cessation
- 1994-09-20 JP JP7509560A patent/JPH08505780A/ja active Pending
-
1995
- 1995-05-19 FI FI952463A patent/FI108143B/fi not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897596A (zh) * | 2019-03-28 | 2019-06-18 | 贵州大学 | 一种杉木树皮人造板胶粘剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE167208T1 (de) | 1998-06-15 |
| US5608040A (en) | 1997-03-04 |
| CA2150012A1 (en) | 1995-03-30 |
| FI952463A (fi) | 1995-07-11 |
| EP0669953B1 (de) | 1998-06-10 |
| DE59406212D1 (de) | 1998-07-16 |
| DE4331878A1 (de) | 1995-03-23 |
| WO1995008588A1 (de) | 1995-03-30 |
| FI952463A0 (fi) | 1995-05-19 |
| CN1042544C (zh) | 1999-03-17 |
| AU7783094A (en) | 1995-04-10 |
| NZ273947A (en) | 1996-08-27 |
| EP0669953A1 (de) | 1995-09-06 |
| AU693479B2 (en) | 1998-07-02 |
| RU2165978C2 (ru) | 2001-04-27 |
| BR9405608A (pt) | 1999-09-08 |
| JPH08505780A (ja) | 1996-06-25 |
| FI108143B (fi) | 2001-11-30 |
| RU95112463A (ru) | 1997-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1042544C (zh) | 含木质素和有机化合物的聚合物和其制备方法 | |
| Mai et al. | Chemoenzymatical grafting of acrylamide onto lignin | |
| CN1092084A (zh) | 一种与淀粉化学结合的可生物降解聚乙烯组合物及其制备方法 | |
| CN1037352C (zh) | 与淀粉结合的可生物降解聚乙烯组合物及其制法和用途 | |
| US6410618B2 (en) | Polymeric composite material and method of manufacturing the same | |
| Ajima et al. | Polymerization of 10-hydroxydecanoic acid in benzene with polyethylene glycol-modified lipase | |
| Olsson et al. | Lipase-catalyzed synthesis of an epoxy-functionalized polyester from the suberin monomer cis-9, 10-epoxy-18-hydroxyoctadecanoic acid | |
| US4765901A (en) | Method for purifying waste water | |
| US6013774A (en) | Biodegradable plastics and composites from wood | |
| Coats et al. | Production of natural fiber reinforced thermoplastic composites through the use of polyhydroxybutyrate-rich biomass | |
| Hall et al. | Enzymatic transformations of lignin | |
| CA1203189A (en) | Biologically produced acid precipitable polymeric lignin | |
| Pareek et al. | Degradation of lignin and lignin model compound under sulfate reducing condition | |
| CN1250482A (zh) | 木质素聚合物制备用中间产物及其用于木质材料生产的用途 | |
| Landucci | Reaction of p-hydroxycinnamyl alcohols with transition metal salts 3. Preparation and NMR characterization of improved DHPs | |
| CN1036998C (zh) | 一种用作光稳定剂的含受阻胺侧基的共聚物的制法 | |
| CN1243524A (zh) | 制备木质素聚合产物用的中间产物及其供制造以植物纤维、防水纸及纸板为原料制造复合材料以及以木质素衍生物为原样制造热固性塑料用试剂的应用 | |
| JP3179563B2 (ja) | 生分解性組成物 | |
| AU588295B2 (en) | Coating composition containing polymeric surfactant | |
| Young et al. | Craig Clemons | |
| EP0555117A1 (fr) | Résines vinylesters constituées d'un ou plusieurs monomères acryliques et d'au moins une macromolécule compatible et copolymérisable, et leurs utilisations | |
| PYCNOPORUS | FBSB 2008 16 | |
| CN1537886A (zh) | 增强可生物降解薄膜塑性的方法 | |
| CN1762953A (zh) | 用于富集、分离、纯化香兰素的分子印迹材料 | |
| JPH085974B2 (ja) | 光崩壊性樹脂フイルム |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C53 | Correction of patent of invention or patent application | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: PATENTEE; FROM: ALOYS HEYOTMANN TO: SIDUKHAUSON LIMITED PARTNERSHIP |
|
| CP03 | Change of name, title or address |
Address after: German Clay Field Patentee after: Stockhauson GmbH & Co. Address before: German Gottingen Patentee before: Aloys Huettermann |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |