JPS63182327A - Production of polyurethane containing lignin - Google Patents
Production of polyurethane containing ligninInfo
- Publication number
- JPS63182327A JPS63182327A JP62014972A JP1497287A JPS63182327A JP S63182327 A JPS63182327 A JP S63182327A JP 62014972 A JP62014972 A JP 62014972A JP 1497287 A JP1497287 A JP 1497287A JP S63182327 A JPS63182327 A JP S63182327A
- Authority
- JP
- Japan
- Prior art keywords
- lignin
- polyurethane
- diisocyanate
- solvolysis
- component
- 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
- 229920005610 lignin Polymers 0.000 title claims abstract description 33
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 24
- 239000004814 polyurethane Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- -1 polyol compound Chemical class 0.000 claims abstract description 9
- 229920005862 polyol Polymers 0.000 claims abstract description 8
- 238000003797 solvolysis reaction Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 abstract description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YFMUYJJUVCWKIE-UHFFFAOYSA-N chloroethane;ethanol Chemical compound CCO.CCCl YFMUYJJUVCWKIE-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明はリグニンを含むポリウレタンの製造方法、さら
に詳しくは、ソルボリシスリグニンとジイソシアネート
を重合反応させてポリウレタンを製造する方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing polyurethane containing lignin, and more particularly to a method for producing polyurethane by polymerizing solvolysis lignin and diisocyanate.
従来、ポリウレタンとしては各種のものが知ら、れてい
るが５分子量分別などを施さず、単離したリグニンをそ
のままハードセグメント成分として含むものは知られて
いない。Conventionally, various types of polyurethane have been known, but none are known that contain isolated lignin as a hard segment component without being subjected to 5-molecular weight fractionation or the like.
一方、リグニン成分は木材等のパルプ原料の中に含まれ
、ソルボリシスパルプ製造の際に副産物（ソルボリシス
リグニン）として得られている天然高分子であり、その
主鎖中には剛直な芳香環が含まれている。On the other hand, the lignin component is a natural polymer that is contained in pulp raw materials such as wood and obtained as a by-product (solvolysis lignin) during the production of solvolysis pulp, and its main chain contains a rigid aromatic ring. It is.
本発明者らは、ソルボリシスリグニンの有効利用につい
て鋭意研究を重ねた結果、このものは、ポリウレタンの
バードセグメント成分としてすぐれた効果を示し、そし
て、このリグニン成分をハードセグメント成分として含
むポリウレタンは、リグニンを含まない従来のポリウレ
タンに比べ。As a result of extensive research into the effective use of solvolysis lignin, the present inventors found that this material has excellent effects as a bird segment component in polyurethane, and polyurethanes containing this lignin component as a hard segment component Compared to conventional polyurethane that does not contain
機械的及び熱的性質に著しくすぐれていることを見出す
と共に、またポリエーテルやポリエステル等のポリオー
ル化合物をソフトセグメント成分として用い、それらの
両成分の配合比を変化させることにより、物性の制御さ
れたポリウレタンが得られることを見出し１本発明を完
成するに到った。In addition to discovering that it has outstanding mechanical and thermal properties, we have also achieved controlled physical properties by using a polyol compound such as polyether or polyester as a soft segment component and changing the blending ratio of both components. They discovered that polyurethane can be obtained and completed the present invention.
即ち１本発明によれば、ジイソシアネートにソルボリシ
スリグニンを溶媒の存在下で重合反応させることを特徴
とするリグニンを含むボリウしたンの製造方法が提供さ
れる。According to one aspect of the present invention, there is provided a method for producing polyurethane containing lignin, which comprises subjecting diisocyanate to a polymerization reaction of solvolysis lignin in the presence of a solvent.
本発明において、ポリウレタンのハードセグメント成分
として用いるソルボリシスリグニンは、有機溶媒又は有
機溶媒と水との混合溶媒中で木材等のパルプ原料から常
法によるソリポリシスパルプを製造する工程において、
その有機溶媒層に抽出されるものである。この溶媒層か
らソルボリシスリグニンを回収するには、溶媒層をベン
ゼン中に注ぎ、粗ソルボリシスリグニンを得る１次に、
酢酸−水混合溶媒（容量混合比＝９： １）と水系によ
る再沈殿により精製ソルボリンスリグニンを得る。In the present invention, solvolysis lignin used as a hard segment component of polyurethane is produced in the process of producing solvolysis pulp from pulp raw materials such as wood by a conventional method in an organic solvent or a mixed solvent of an organic solvent and water.
It is extracted into the organic solvent layer. To recover solvolysis lignin from this solvent layer, first, pour the solvent layer into benzene to obtain crude solvolysis lignin.
Purified sorbolin lignin is obtained by reprecipitation with an acetic acid-water mixed solvent (volume mixing ratio = 9:1) and an aqueous system.
また、このソルボリシスリグニンをさらに精製するには
、ｌ、 ２−ａクロルエタン−エタノール混合溶媒（容
量混合比＝２： １）とエチルエーテルによる再沈殿を
行う。Further, in order to further purify this solvolysis lignin, reprecipitation is performed using a l,2-a chloroethane-ethanol mixed solvent (volume mixing ratio = 2:1) and ethyl ether.
本発明においては、前記のようにして得られる精製ソル
ボリシスリグニンをポリウレタン原料として用いるが、
その純度は、通常、７０重量％以上、好ましくは９０１
１以上である。このソルボリシスリグニンは、パルプ原
料にもよるが、平均分子１５００〜１００００を有し、
１グラム当りの水酸基綿量２〜２０ミリモルを有する。In the present invention, the purified solvolysis lignin obtained as described above is used as a polyurethane raw material.
Its purity is usually 70% by weight or more, preferably 901% by weight or more.
It is 1 or more. This solvolysis lignin has an average molecular weight of 1,500 to 10,000, depending on the pulp raw material,
It has a hydroxyl group content of 2 to 20 mmol per gram.
本発明によりポリウレタンを好ましく３Ｉ！ｉｌするに
は、先ず、ソルボリシスリグニンをテトラヒドロフラン
やジオキサン等の有機溶媒中に溶解し、ジイソシアネー
ト成分を加え、ｌＯ〜１００’Ｃで重合させる。この場
合、ジイソシアネート成分は、ポリウレタンの製造に従
来用いられている芳香族系、脂肪族系、複素環系のもの
が用いられる。このようなジイソシアネートの具体例と
しては、例えば、４．４′−ジフェニルメタンジイソシ
アネート、トリレンジイソシアネート、ヘキサメチレン
ジイソシアネート等がある。According to the invention, polyurethane is preferably 3I! To il, first, solvolysis lignin is dissolved in an organic solvent such as tetrahydrofuran or dioxane, a diisocyanate component is added, and polymerization is carried out at 10 to 100'C. In this case, as the diisocyanate component, aromatic, aliphatic, or heterocyclic diisocyanate components conventionally used in the production of polyurethane are used. Specific examples of such diisocyanates include 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and the like.
ソルボリシスリグニンとジイソシアネート成分とを重合
反応させる場合、イソシアネート基の量は、ソルボリシ
スリグニン中の全水酸基量の０．５〜３倍当量の割合に
するのがよい。When solvolysis lignin and a diisocyanate component are polymerized, the amount of isocyanate groups is preferably 0.5 to 3 equivalents of the total amount of hydroxyl groups in solvolysis lignin.
また、本発明においては、前記のようにしてソルボリシ
スリグニンとジイソシアネート成分と反応させた後、ポ
リオール化合物をソフトセグメント成分として反応させ
ることにより、ソフトセグメント成分を含むポリウレタ
ンを得ることができる。この場合、ポリオール化合物と
しては、従来一般に用いられているポリエーテル系やポ
リエステル系のものが用いられ、例えば、ポリオキシプ
ロピレングリコールや、ポリオキシエチレングリコール
、ポリプロピレングリコール、ポリエチレングリコール
、アジピン酸とエチレングリコールとを縮合させて得ら
れるポリエステル系グリコール等が挙げられる。このよ
うなポリウレタンを得る場合、イソシアネート基の量は
、ソルボリシスリグニンの水酸基量とポリオール化合物
の水酸基量の合計に対して、０．２〜３倍当量の割合で
ある。Further, in the present invention, a polyurethane containing a soft segment component can be obtained by reacting solvolysis lignin with a diisocyanate component as described above and then reacting with a polyol compound as a soft segment component. In this case, as the polyol compound, conventionally commonly used polyether and polyester compounds are used, such as polyoxypropylene glycol, polyoxyethylene glycol, polypropylene glycol, polyethylene glycol, adipic acid and ethylene glycol. Examples include polyester glycols obtained by condensing these. When obtaining such a polyurethane, the amount of isocyanate groups is in a proportion of 0.2 to 3 times the equivalent of the total amount of hydroxyl groups in the solvolysis lignin and the hydroxyl group in the polyol compound.
また、ポリオール化合物は、ソルポリシスリグニン１０
０重景部に対し０−９５重エラ、好ましくは０−９０重
量部の割合で用いられる。In addition, the polyol compound is Solpolycislignin 10
It is used in a ratio of 0 to 95 parts by weight, preferably 0 to 90 parts by weight, based on 0 parts by weight.
前記の重合工程により得られたポリウレタンは、溶媒を
除いた後、８Ｇ−１５０℃に加熱することにより硬化さ
せることができる。The polyurethane obtained by the above polymerization step can be cured by heating to 8G-150°C after removing the solvent.
（効 果〕
本発明によれば、機械的、熱的にすぐれたポリウレタン
を工業的にかつ安価に製造することができる。また１本
発明のポリウレタンにおいては、ハードセグメント成分
としてのリグニン成分に加えて、ソフトセグメント成分
としてのポリオール化合物成分を含有させ、その同成分
の割合を変えることにより、その性状を容易に制御する
ことができる。(Effects) According to the present invention, it is possible to produce mechanically and thermally excellent polyurethane industrially and at low cost.In addition, in the polyurethane of the present invention, in addition to the lignin component as a hard segment component, By containing a polyol compound component as a soft segment component and changing the proportion of the same component, its properties can be easily controlled.
次に本発明を実施例によりさらに詳細に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例
ブナをクレゾール−水混合溶媒（容量混合比＝８：２）
中において１８０℃で５時間蒸解した後に得られるクレ
ゾール層から分離精製したソルボリシスリグニンをテト
ラヒドロフランに撹拌しつつ溶解して濃度約５重量算の
溶液を作った。これに、 ４．４’−ジフェニルメタン
ジイソシアネート（以下、単にＤＭＩ略記する）を表−
１に示す割合で加えて６０℃で１時間重合させた。その
後、ポリエチレングリコール（ジオール、平均分子４０
０）を表−１に示す割合で加えてさらに６０℃で１時間
重合させた１重合溶液をロータリーエバポレータを用い
て減圧濃縮し、得られた濃縮液をガラス板上に流して溶
媒を蒸発させてフィルムを得た。これを１００℃で５時
間加熱して硬化させた。Example Beech was mixed with cresol-water mixed solvent (volume mixing ratio = 8:2)
Solvolysis lignin, which was separated and purified from the cresol layer obtained after cooking at 180° C. for 5 hours, was dissolved in tetrahydrofuran with stirring to prepare a solution having a concentration of about 5% by weight. In addition, 4,4'-diphenylmethane diisocyanate (hereinafter simply abbreviated as DMI) was added to the table.
1 and polymerized at 60° C. for 1 hour. Then polyethylene glycol (diol, average molecular weight 40
0) in the ratio shown in Table 1 and further polymerized at 60°C for 1 hour. The polymerized solution was concentrated under reduced pressure using a rotary evaporator, and the resulting concentrated liquid was poured onto a glass plate to evaporate the solvent. I got the film. This was cured by heating at 100° C. for 5 hours.
なお、前記で用いたソルボリシスリグニンは次の性状を
有する。The solvolysis lignin used above has the following properties.
（１）平均分子慧：１．８Ｘ１０３
（２）水酸基当量ニア、Ｏ腸ａｑ／ｇ
次に、前記で得られた重合溶液中のポリウレタンの分子
量及び熱硬化フィルムの物性を表−１に示す。(1) Average molecular weight: 1.8 x 103 (2) Hydroxyl equivalent (near), O aq/g Next, Table 1 shows the molecular weight of the polyurethane in the polymerization solution obtained above and the physical properties of the thermoset film.
なお、前記表−１に示した符号は次の内容を有する。Note that the symbols shown in Table 1 above have the following contents.
ＳＬ：ソルボリシスリグニン
ＰＯ：ポリエチレングリコール
ＭＤＩ：４．４’−ジフェニルメタンジイソシアネート
ＮＧＯ１０ｉｌ：反応原料におけるイソシアネート基と
水酸基の当社比
Ｙ：降伏点に対する物性
Ｂ：破断点に対する物性SL: Solvolysis lignin PO: Polyethylene glycol MDI: 4.4'-diphenylmethane diisocyanate NGO10il: Our ratio of isocyanate groups to hydroxyl groups in the reaction raw material Y: Physical properties with respect to yield point B: Physical properties with respect to break point
Claims (2)
の存在下で重合反応させることを特徴とするリグニンを
含むポリウレタンの製造方法。(1) A method for producing polyurethane containing lignin, which comprises subjecting diisocyanate to a polymerization reaction of solvolysis lignin in the presence of a solvent.
オール化合物を溶媒の存在下で重合反応させることを特
徴とするリグニンを含むポリウレタンの製造方法。(2) A method for producing polyurethane containing lignin, which comprises polymerizing diisocyanate, solvolysis lignin, and a polyol compound in the presence of a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62014972A JPS63182327A (en) | 1987-01-23 | 1987-01-23 | Production of polyurethane containing lignin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62014972A JPS63182327A (en) | 1987-01-23 | 1987-01-23 | Production of polyurethane containing lignin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63182327A true JPS63182327A (en) | 1988-07-27 |
| JPH0512362B2 JPH0512362B2 (en) | 1993-02-17 |
Family
ID=11875891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62014972A Granted JPS63182327A (en) | 1987-01-23 | 1987-01-23 | Production of polyurethane containing lignin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63182327A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0388817A (en) * | 1987-10-01 | 1991-04-15 | Agency Of Ind Science & Technol | Production of lignin-containing flame-retardant polyurethane |
| FR2689366A1 (en) * | 1992-04-02 | 1993-10-08 | Bono Pierre | Bio:destructible cellular support for soilless - made from powdered pure lignin and polyurethane binder |
| JP2006111599A (en) * | 2004-10-18 | 2006-04-27 | Kansai Paint Co Ltd | Antiseptic agent |
| JP2006111600A (en) * | 2004-10-18 | 2006-04-27 | Kansai Paint Co Ltd | Termite-proofing agent |
| WO2014044234A1 (en) | 2012-09-21 | 2014-03-27 | SYNPO, akciová společnost | A method of preparation of polyurethane materials containing lignin, a polyurethane material prepared according to this method |
| CN111171258A (en) * | 2020-01-17 | 2020-05-19 | 中科院广州化学有限公司 | Polysiloxane-based polyurethane/lignin elastomer and preparation method and application thereof |
-
1987
- 1987-01-23 JP JP62014972A patent/JPS63182327A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0388817A (en) * | 1987-10-01 | 1991-04-15 | Agency Of Ind Science & Technol | Production of lignin-containing flame-retardant polyurethane |
| JPH0512363B2 (en) * | 1987-10-01 | 1993-02-17 | Kogyo Gijutsuin | |
| FR2689366A1 (en) * | 1992-04-02 | 1993-10-08 | Bono Pierre | Bio:destructible cellular support for soilless - made from powdered pure lignin and polyurethane binder |
| JP2006111599A (en) * | 2004-10-18 | 2006-04-27 | Kansai Paint Co Ltd | Antiseptic agent |
| JP2006111600A (en) * | 2004-10-18 | 2006-04-27 | Kansai Paint Co Ltd | Termite-proofing agent |
| WO2014044234A1 (en) | 2012-09-21 | 2014-03-27 | SYNPO, akciová společnost | A method of preparation of polyurethane materials containing lignin, a polyurethane material prepared according to this method |
| CN111171258A (en) * | 2020-01-17 | 2020-05-19 | 中科院广州化学有限公司 | Polysiloxane-based polyurethane/lignin elastomer and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0512362B2 (en) | 1993-02-17 |
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| EXPY | Cancellation because of completion of term |