JPH0388817A - Production of lignin-containing flame-retardant polyurethane - Google Patents
Production of lignin-containing flame-retardant polyurethaneInfo
- Publication number
- JPH0388817A JPH0388817A JP24863887A JP24863887A JPH0388817A JP H0388817 A JPH0388817 A JP H0388817A JP 24863887 A JP24863887 A JP 24863887A JP 24863887 A JP24863887 A JP 24863887A JP H0388817 A JPH0388817 A JP H0388817A
- Authority
- JP
- Japan
- Prior art keywords
- lignin
- polyurethane
- diisocyanate
- retardant
- solvent
- 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 25
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 21
- 239000004814 polyurethane Substances 0.000 title claims abstract description 21
- 239000003063 flame retardant Substances 0.000 title claims abstract description 18
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 10
- 229920005862 polyol Polymers 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- -1 polyol compound Chemical class 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 abstract description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract description 3
- 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 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 238000003797 solvolysis reaction Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material 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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- SUYARWBGPSQLRC-UHFFFAOYSA-N [bis(2-hydroxyethyl)amino]methylphosphonic acid Chemical compound OCCN(CCO)CP(O)(O)=O SUYARWBGPSQLRC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 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
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000003756 stirring Methods 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
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はリグニンを含む難燃性ポリウレタンの製造方法
、さらに詳しくは、リグニンとジイソシアネートを反応
型難燃剤の存在下に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 The present invention relates to a method for producing flame-retardant polyurethane containing lignin, and more specifically, to a method for producing polyurethane by polymerizing lignin and diisocyanate in the presence of a reactive flame retardant. .
［従来技術］
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、難燃性を有するリグニンを含むポリウレタンは知ら
れていない。[Prior Art] Various types of polyurethane have been known in the past, but polyurethane containing lignin, which has flame retardant properties, is not known.
［目 的］
本発明者らは、リグニンを含むポリウレタンの難燃化に
ついて鋭意研究を重ねた結果、反応型難燃剤の添加によ
って、難燃性に優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至った。[Purpose] As a result of extensive research into flame retardant polyurethane containing lignin, the present inventors discovered that polyurethane with excellent flame retardancy can be obtained by adding a reactive flame retardant.1 The present invention I was able to complete it.
即ち、本発明によれば、ジイソシアネートにリグニンを
反応型難燃剤及び溶媒の存在下で重合反工業リグニンす
なわち、ソーダリグニン、クラフトリグニン、ソルボシ
スリグニン等である。That is, according to the present invention, lignin is polymerized with diisocyanate in the presence of a reactive flame retardant and a solvent to produce anti-industrial lignin, such as soda lignin, kraft lignin, and sorbosis lignin.
本発明においては、前記のような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９０重量％以上である。In the present invention, the above-mentioned lignin is used as a polyurethane raw material, and its purity is usually 70% by weight or more, preferably 90% by weight or more.
本発明によりポリウレタンを好ましく製造するには、先
ず、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、１０
−１００℃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、ポ
リメリック４，４°−ジフェニルメタンジイソシアネー
ト等がある。To preferably produce polyurethane according to the present invention, first, lignin is dissolved in an organic solvent such as tetrahydrofuran or dioxane, a diisocyanate component is added, and lignin is dissolved in an organic solvent such as tetrahydrofuran or dioxane.
Polymerize at -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, for example, 4,
Examples include 4°-diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and polymeric 4,4°-diphenylmethane diisocyanate.
割合にするのがよい。It is better to make it a percentage.
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
リオール化合物及び反応型難燃剤を反応させることによ
り、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
、ポリプロピレングリコールや、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。また
反応型難燃剤としては従来一般に用いられている含リン
型ポリオール、含ハロゲン型ポリオール、インシアヌレ
ート環を有する化合物等が用いられ、たとえばビス（２
−ヒドロキシエチル）アミノメチルホスホン酸ジエチル
、ホンスン酸エステル型ポリエチレングリコール等が挙
げ対して、０．２〜３倍当量の割合である。また、ポリ
オール化合物は、ソルボリシスリグニン１００重量部に
対し０〜９５重量部、好ましくは０〜９０重量部の割合
で用いられる。また、反応型難燃剤はリグニン１００に
対し０．１〜５０部の割合に用いられる。Moreover, in the present invention, polyurethane can be obtained by reacting solvolysis lignin with a diisocyanate component as described above and then reacting a polyol compound and a reactive flame retardant. In this case, as the polyol compound, conventionally commonly used polyether and polyester compounds are used, such as polypropylene glycol, polyethylene glycol, and polyester glycol obtained by condensing adipic acid and ethylene glycol. etc. In addition, as reactive flame retardants, conventionally commonly used phosphorus-containing polyols, halogen-containing polyols, compounds having an incyanurate ring, etc. are used, such as bis(2
-Hydroxyethyl)aminomethylphosphonate, honsunate type polyethylene glycol, etc., in a proportion of 0.2 to 3 equivalents. The polyol compound is used in an amount of 0 to 95 parts by weight, preferably 0 to 90 parts by weight, based on 100 parts by weight of solvolysis lignin. The reactive flame retardant is used in an amount of 0.1 to 50 parts per 100 parts of lignin.
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、８０〜１５０℃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 80 to 150°C after removing the solvent.
［効 果］
本発明によれば、難燃性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。[Effects] According to the present invention, polyurethane with excellent flame retardancy can be produced industrially and at low cost.
また、本発明のポリウレタンにおいては、ハードセグメ
ント成分としてのポリオール化合物成分を含有させ、そ
の両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。Further, in the polyurethane of the present invention, its properties can be easily controlled by containing a polyol compound component as a hard segment component and changing the ratio of both components.
［実施例コ
次に本発明を実施例によりさらに詳細に説明すに得られ
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
３ｇをテトラヒドロフランに撹拌しつつ溶解して濃度約
２０重量％の溶液を作った。[Example] Next, the present invention will be described in more detail with reference to Examples. 3 g of solvolysis lignin separated and purified from the obtained cresol layer was dissolved in tetrahydrofuran with stirring to prepare a solution having a concentration of about 20% by weight.
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４００）及びビス（４
−ヒドロキシエチル）アミノメチルホスホン酸ジエチル
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。重合溶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１２０℃で３時間加熱して硬
化させた。To this, 4.4''-diphenylmethane diisocyanate (hereinafter simply abbreviated as DMI) was added in the proportion shown in Table 1 and polymerized at 60°C for 1 hour. After that, polyethylene glycol (diol, average molecular weight 400) and (4
Diethyl -hydroxyethyl)aminomethylphosphonate was added in the proportions shown in Table 1, and the mixture was further polymerized at 60°C for 1 hour. The polymerization solution was poured onto a glass plate and the solvent was evaporated to obtain a film. This was cured by heating at 120° C. for 3 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）平均分子量： １．８Ｘ１０”（２）水酸基当
量ニア、０ミリ当量／ｇＳＬ：ソルボシスリグニン
ＰＯ：ポリエチレングリコール
Ｐ−ＰＯ：ビス（２−ヒドロキシエチル）ツメチルホス
ホン酸ジエチル
アミ
ＭＤＩ ： ４．４’−ジフェニルメタンジイソシア
ネート
ＮＣ○／○Ｈ：反応原料におけるイソシアネート基と水
酸基の当量比
表１に示すように、Ｐ−Ｐ○１０％の酸素指数は、Ｐ−
Ｐ○０％のそれよりも大きく、難燃性が向上している。(1) Average molecular weight: 1.8X10" (2) Hydroxyl group equivalent near, 0 meq/gSL: Sorbocis lignin PO: Polyethylene glycol P-PO: Bis(2-hydroxyethyl)tumethylphosphonic acid diethylamide MDI: 4.4 '-Diphenylmethane diisocyanate NC○/○H: equivalent ratio of isocyanate groups to hydroxyl groups in the reaction raw material As shown in Table 1, the oxygen index of P-P○10% is P-
It is larger than that of P○0%, and the flame retardance is improved.
定性的には、Ｐ−ＰＯが０％のポリウレタンは空気中で
可燃性であり、一方Ｐ−Ｐ○が１０％のポリウレタンは
自己消火性である。従って、反応型難燃剤の添加によっ
て難燃性のリグニンを含むポリウレタンが得られる。Qualitatively, polyurethane with 0% P-PO is flammable in air, while polyurethane with 10% P-P○ is self-extinguishing. Therefore, by adding a reactive flame retardant, a polyurethane containing flame-retardant lignin can be obtained.
表１ ＮＣ○１０Ｈ＝ １．２．ＳＬ含有率２０％。Table 1 NC○10H=1.2. SL content 20%.
Ｐ−ＰＯ０％（ＰＥＧ１００％）及び ｐ−ｐ○１０％（ＰＥ０９０％）の酸素指数ａ）ＪＩＳ Ｋ２７０１に準じて測定した。P-PO0% (PEG100%) and Oxygen index of p-p○10% (PE090%) a) JIS Measured according to K2701.
Claims (2)
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
ンを含む難燃性ポリウレタンの製造方法。(1) A method for producing a flame-retardant polyurethane containing lignin, which comprises polymerizing diisocyanate with lignin and a reactive flame retardant in the presence of a solvent.
及び反応型難燃剤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難燃性ポリウレタンの製造
方法。(2) A method for producing a flame-retardant polyurethane containing lignin, which comprises polymerizing diisocyanate with lignin, a polyol compound, and a reactive flame retardant in the presence of a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24863887A JPH0388817A (en) | 1987-10-01 | 1987-10-01 | Production of lignin-containing flame-retardant polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24863887A JPH0388817A (en) | 1987-10-01 | 1987-10-01 | Production of lignin-containing flame-retardant polyurethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0388817A true JPH0388817A (en) | 1991-04-15 |
| JPH0512363B2 JPH0512363B2 (en) | 1993-02-17 |
Family
ID=17181087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24863887A Granted JPH0388817A (en) | 1987-10-01 | 1987-10-01 | Production of lignin-containing flame-retardant polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0388817A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2689366A1 (en) * | 1992-04-02 | 1993-10-08 | Bono Pierre | Bio:destructible cellular support for soilless - made from powdered pure lignin and polyurethane binder |
| US5396746A (en) * | 1994-01-07 | 1995-03-14 | Whitmer; Bruce F. | Molding construction |
| JP2012092282A (en) * | 2010-09-30 | 2012-05-17 | Hitachi Chemical Co Ltd | Resin composition, and molded body |
| JP2012193337A (en) * | 2011-03-01 | 2012-10-11 | Ricoh Co Ltd | Flame retardant resin composition and molded product |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63182327A (en) * | 1987-01-23 | 1988-07-27 | Agency Of Ind Science & Technol | Production of polyurethane containing lignin |
-
1987
- 1987-10-01 JP JP24863887A patent/JPH0388817A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63182327A (en) * | 1987-01-23 | 1988-07-27 | Agency Of Ind Science & Technol | Production of polyurethane containing lignin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2689366A1 (en) * | 1992-04-02 | 1993-10-08 | Bono Pierre | Bio:destructible cellular support for soilless - made from powdered pure lignin and polyurethane binder |
| US5396746A (en) * | 1994-01-07 | 1995-03-14 | Whitmer; Bruce F. | Molding construction |
| JP2012092282A (en) * | 2010-09-30 | 2012-05-17 | Hitachi Chemical Co Ltd | Resin composition, and molded body |
| JP2012193337A (en) * | 2011-03-01 | 2012-10-11 | Ricoh Co Ltd | Flame retardant resin composition and molded product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0512363B2 (en) | 1993-02-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |