JP2969257B2 - Method for producing easily degradable polyurethane resin - Google Patents
Method for producing easily degradable polyurethane resinInfo
- Publication number
- JP2969257B2 JP2969257B2 JP7337887A JP33788795A JP2969257B2 JP 2969257 B2 JP2969257 B2 JP 2969257B2 JP 7337887 A JP7337887 A JP 7337887A JP 33788795 A JP33788795 A JP 33788795A JP 2969257 B2 JP2969257 B2 JP 2969257B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyurethane resin
- weight
- producing
- formula
- 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.)
- Expired - Fee Related
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 239000002685 polymerization catalyst Substances 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 claims description 2
- 230000004580 weight loss Effects 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 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 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000012773 agricultural material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000005003 food packaging material Substances 0.000 description 2
- 235000012015 potatoes Nutrition 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 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 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- LUEQEZXFYBLPOF-UHFFFAOYSA-M dibutyl-[dibutyl(chloro)stannyl]oxytin;hydrate Chemical compound O.CCCC[Sn](CCCC)O[Sn](Cl)(CCCC)CCCC LUEQEZXFYBLPOF-UHFFFAOYSA-M 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- -1 heterocyclic isocyanates 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
-
- 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
- C08G18/6484—Polysaccharides and derivatives thereof
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- 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
- C08G2230/00—Compositions for preparing biodegradable polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】 本発明は、従来のものに比
較して分解速度が速い易分解性ポリウレタン樹脂製造方
法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing an easily decomposable polyurethane resin having a higher decomposition rate than conventional ones.
【０００２】[0002]
【従来の技術】 従来、都市部では廃棄物の多くを焼却
せずに地中に埋めて処理しているが、次々と排出される
廃棄物の処分場の土地確保が益々困難になっている。特
にプラスチックスよりなる農業用資材・食品用及び梱包
用包装材等生分解性がない、或は分解速度の遅いものに
対する問題は極めて深刻になりつつある。2. Description of the Related Art Conventionally, in the urban area, much of the waste is buried in the ground without being incinerated and disposed of. However, it has become increasingly difficult to secure land at a disposal site for waste that is discharged one after another. . In particular, the problem of materials having no biodegradability or having a low decomposition rate, such as agricultural materials, foods, and packaging materials made of plastics, is becoming extremely serious.
【０００３】その対策として、農業用資材・食品用包装
材料及び梱包用包装材料として易分解性ポリウレタン樹
脂が提案されているが、なお生分解速度が遅く、地中に
埋めた場合、なかなか分解せず、分解速度の増大が求め
られており、また使用するジブチルスズジラウレート、
オクチル酸スズ等の有機スズ触媒の活性が低く、重合促
進のため多量に添加しなければならず、これが環境へ悪
影響を与えると言う問題点がある。As a countermeasure, an easily decomposable polyurethane resin has been proposed as an agricultural material / food packaging material and a packaging material, but the biodegradation rate is still slow. Without increasing the decomposition rate is required, also used dibutyltin dilaurate,
The activity of an organotin catalyst such as tin octylate is low, and it has to be added in a large amount to promote polymerization, which has a problem that it has an adverse effect on the environment.
【０００４】[0004]
【発明が解決しようとする課題】 解決しようとする課
題は、上記従来の分解性ポリウレタン樹脂は分解速度が
小さく、地中に埋めた場合、なかなか分解せず、また使
用するジブチルスズジラウレート、オクチル酸スズ等の
有機スズ触媒が環境へ悪影響を与えることであって、本
発明は上記問題を解決した、ポリウレタン樹脂製造方法
を提供するものである。The problem to be solved is that the conventional decomposable polyurethane resin has a low decomposition rate, does not readily decompose when buried in the ground, and is used in dibutyltin dilaurate and tin octylate. The present invention provides a method for producing a polyurethane resin, which solves the above-mentioned problems.
【０００５】[0005]
【課題を解決するための手段】 鎖式炭化水素の水素原
子Ｈを水酸基−ＯＨで置き換えたものがアルコールであ
り、ヒドロキシル基−ＯＨの数が２個以上で、且つ各ヒ
ドロキシル基がそれぞれ別の炭素原子に結合しているも
のを多価アルコールと呼んでいる。そして、ウレタン工
業では、ヒドロキシル基を両方の末端基に有する多価ア
ルコールをポリオールと呼んでいる。Means for Solving the Problems An alcohol is obtained by replacing a hydrogen atom H of a chain hydrocarbon with a hydroxyl group -OH, the number of hydroxyl groups -OH is two or more, and each hydroxyl group is different from each other. Those that are bonded to carbon atoms are called polyhydric alcohols. In the urethane industry, a polyhydric alcohol having a hydroxyl group at both terminal groups is called a polyol.
【０００６】−Ｎ＝Ｃ＝Ｏはイソシアネート基と呼ば
れ、イソシアネート基を２つ有する化合物はジイソシア
ネート、３つ有する化合物はトリイソシアネートと呼ば
れている。-N = C = O is called an isocyanate group, a compound having two isocyanate groups is called a diisocyanate, and a compound having three isocyanate groups is called a triisocyanate.
【０００７】アルコールとイソシアネートとの反応によ
って得られる結合−ＮＨ・ＣＯ・Ｏ−はウレタン結合と
呼ばれている。ポリウレタン樹脂はポリオールとイソシ
アネートを反応させて得られる高分子化合物で、主鎖が
ウレタン結合−ＮＨ・ＣＯ・Ｏ−で結ばれている。The bond -NH.CO.O- obtained by the reaction between an alcohol and an isocyanate is called a urethane bond. A polyurethane resin is a polymer compound obtained by reacting a polyol and an isocyanate, and has a main chain linked by a urethane bond —NH.CO.O—.
【０００８】炭水化物は構成している分子の数によって
単糖類，少糖類，多糖類に分類される。多糖類の一種の
澱粉類は、加水分解により最終的に多数の分子のブドウ
糖になる。[0008] Carbohydrates are classified into monosaccharides, oligosaccharides, and polysaccharides according to the number of constituent molecules. One type of polysaccharide, starch, is hydrolyzed to end up with a number of molecules of glucose.
【０００９】この発明は、澱粉類並びにポリオールとイ
ソシアネートを重合触媒により重合させるポリウレタン
樹脂製造方法であって、重合触媒が、一般式The present invention is a process for producing a polyurethane resin in which a starch, a polyol and an isocyanate are polymerized with a polymerization catalyst, wherein the polymerization catalyst has a general formula
【化２】 ［式中Ｒはメチル基,エチル基,プロピル基,ブチル基,オ
クチル基,アリル基,ベンジル基,フェニル基,ナフチル基
のいずれかを示し、Ｘはハロゲン類,チオシアノ基,ヒド
ロシル基,アルコキシ基,カルボキシル基のいずれかを示
す。］で表される１,３−置換−１,１,３,３−テトラオ
ルガノジスタノキサン化合物よりなる易分解性ポリウレ
タン樹脂製造方法である。Embedded image [In the formula, R represents any one of a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, an allyl group, a benzyl group, a phenyl group, a naphthyl group, and X represents a halogen, a thiocyano group, a hydrosyl group, an alkoxy group. , Indicates a carboxyl group. The method for producing an easily decomposable polyurethane resin comprising a 1,3-substituted-1,1,3,3-tetraorganodistanoxane compound represented by the following formula:
【００１０】前記重合触媒は、高い触媒活性を持つた
め、触媒の添加量が少なくてよく、得られたポリウレタ
ン樹脂を使用後廃棄しても環境に与える悪影響が従来の
ものに比べて著しく少なく、また得られたポリウレタン
樹脂は逆反応を起しやすく、そのため分解速度が速いと
言う特徴がある。Since the polymerization catalyst has high catalytic activity, the amount of catalyst added may be small, and even if the obtained polyurethane resin is discarded after use, the adverse effect on the environment is significantly less than that of the conventional one. Further, the obtained polyurethane resin has a feature that the reverse reaction is apt to occur and therefore the decomposition rate is high.
【００１１】なお、ポリオールとしては、ポリエチレン
グリコール等末端に水酸基を持つポリエーテル又はポリ
エステルを、またイソシアネートとしては、４，４−ジ
フェニルメタンジイソシアネート（ＭＤＩ）、ヘキサメ
チレンジイソシアネート等の芳香族系、脂肪族系および
複素環系のイソシアネートをそれぞれ使用する。一般的
に澱粉類として、コーン、米、小麦、タピオカ、かんし
ょならびにジャガイモなどに含まれる澱粉が挙げられ
る。The polyol is a polyether or polyester having a hydroxyl group at a terminal such as polyethylene glycol, and the isocyanate is an aromatic or aliphatic system such as 4,4-diphenylmethane diisocyanate (MDI) or hexamethylene diisocyanate. And heterocyclic isocyanates, respectively. Generally, starches include starch contained in corn, rice, wheat, tapioca, potatoes, potatoes, and the like.
【００１２】[0012]
【発明の実施の形態】（実施例） ポリエチレングリコール（分子量：４００） ２０重量
部と触媒（ジスタノキサン） ０．０２５重量部及び多
糖類（コーンスターチ） ３０重量部をディゾルバーミ
キサーを用いて均一に撹拌した後、４，４−ジフェニル
メタンジイソシアネート（ＭＤＩ） ２５重量部を加え
て撹拌する。なお、触媒のジスタノキサンとして、１−
クロロ−３−ヒドロキシ−１，１，３，３−テトラブチ
ルジスタノキサンを使用した。得られた混合物を長方形
の容器に流延してオーブン内で加熱し、８０℃に３０分
間保持し加硫する。得られた発泡体を２ミリの厚さに切
断し、土中に埋設し、減量率を調べた。(Examples) 20 parts by weight of polyethylene glycol (molecular weight: 400), 0.025 parts by weight of a catalyst (distannoxane) and 30 parts by weight of a polysaccharide (corn starch) were uniformly stirred using a dissolver mixer. Thereafter, 25 parts by weight of 4,4-diphenylmethane diisocyanate (MDI) is added and stirred. In addition, as a catalyst distanoxane, 1-
Chloro-3-hydroxy-1,1,3,3-tetrabutyldistannoxane was used. The obtained mixture is cast in a rectangular container, heated in an oven, kept at 80 ° C. for 30 minutes and vulcanized. The obtained foam was cut into a thickness of 2 mm, buried in the soil, and the weight loss rate was examined.
【００１３】（比較例１） 触媒として、実施例のジスタノキサンの代わりにオクチ
ル酸スズ ０．１重量部を加えたことを除き、実施例と
同一の配合・処理を行い、さらに実施例同様に得られた
発泡体を２ミリの厚さに切断し、土中に埋設し、減量率
を調べた。Comparative Example 1 The same blending and treatment as in the example was carried out except that 0.1 part by weight of tin octylate was added in place of the distanoxane of the example as a catalyst. The obtained foam was cut into a thickness of 2 mm, buried in the soil, and the weight loss rate was examined.
【００１４】発泡体の地中埋設３ケ月後の分解状況を減
量率で示すと、比較例１が６５％減量したに対して本発
明の樹脂は８５％減量し、大半が分解している。なお、
配合・減量率を纏めたものを表１に、比較例２,３と共
に示す。Decomposition of the foam three months after being buried in the ground is shown by a weight loss rate. In Comparative Example 1, the resin of the present invention was reduced by 85%, whereas the resin of the present invention was reduced by 85%, and most of the resin was decomposed. In addition,
Table 1 summarizes the compounding and weight loss ratios, together with Comparative Examples 2 and 3.
【００１５】[0015]
【表１】 [Table 1]
【００１６】表１において、実施例のポリエチレングリ
コール・ＭＤＩ・コンスターチ・ジスタノキサンの和は
２０＋２５＋３０＋０．０２５≒７５重量部である。３
ヶ月土中埋設後の減量率８５％ということは、実際の残
存重量部が７５×（１−０．８５）≒１１．２５重量部
である。埋設前のポリエチレングリコールとＭＤＩとの
和即ちウレタンポリマー分の重量部２０＋２５＝４５か
ら実際の残存重量部１１．２５を引いたウレタンポリマ
ーの減量分は４５−１１．２５＝３３．７５重量部とな
る。このウレタンポリマーの減量分を埋設前のウレタン
ポリマー分の重量部で割った３３．７５÷４５≒０．７
５即ち７５％がウレタンポリマーの減量率となる。同様
な計算を比較例１〜３についても行い、その結果を表２
に示す。In Table 1, the sum of polyethylene glycol, MDI, constarch, and distannoxane in the examples is 20 + 25 + 30 + 0.025 ≒ 75 parts by weight. 3
A weight loss rate of 85% after being buried in monthly soil means that the actual remaining weight is 75 × (1−0.85) ≒ 11.25 weight parts. The weight loss of the urethane polymer obtained by subtracting the actual remaining weight of 11.25 from the sum of polyethylene glycol and MDI before embedding, that is, 20 + 25 = 45 of the urethane polymer, is 45-11.25 = 33.75 parts by weight. Become. The weight loss of the urethane polymer was divided by the weight of the urethane polymer before embedding to obtain 33.75 / 45 / 0.7.
5 or 75% is the urethane polymer weight loss rate. Similar calculations were performed for Comparative Examples 1 to 3, and the results were shown in Table 2.
Shown in
【００１７】[0017]
【表２】 [Table 2]
【００１８】表２から明らかなように、触媒としてジス
タノキサンとコンスターチとを併用することによって、
ウレタンポリマー分の分解が促進されている。As is clear from Table 2, the combined use of distannoxane and constarch as catalysts
The decomposition of the urethane polymer is promoted.
【００１９】得られたポリウレタン樹脂は、農業用資材
・食品用及び梱包用包装材料として使用可能であり、必
要に応じて、さらにシリカ、タルク、珪藻土、ベントナ
イトならびにバーミュキュライトなどの天然鉱産物を添
加することによって、樹脂物性の改善や保水性の付与な
どの高付加価値化を図ることができる。The obtained polyurethane resin can be used as an agricultural material, food, and packaging material, and if necessary, may further contain natural mineral products such as silica, talc, diatomaceous earth, bentonite, and vermiculite. By adding, it is possible to attain high added value such as improvement of resin physical properties and provision of water retention.
【００２０】[0020]
【発明の効果】 本発明は以上のように構成されるた
め、得られたポリウレタン樹脂よりなる農業用資材・食
品用包装材及び梱包用包装材は生分解速度が大きく、使
用後廃棄しても、短期間に大半が分解消失すると共に、
有機スズ含量が従来品と比べて少なく、環境に与える悪
影響が従来のものに比べて著しく少ない。EFFECTS OF THE INVENTION Since the present invention is configured as described above, agricultural materials and food packaging materials and packaging materials made of the obtained polyurethane resin have a high biodegradation rate and can be disposed after use. , And most of them decompose and disappear in a short time,
Organic tin content is lower than conventional products, and the adverse effect on the environment is significantly less than conventional ones.
Claims (1)
トを重合触媒により重合させるポリウレタン樹脂製造方
法において、重合触媒が、一般式 【化１】 ［式中Ｒはメチル基,エチル基,プロピル基,ブチル基,オ
クチル基,アリル基,ベンジル基,フェニル基,ナフチル基
のいずれかを示し、Ｘはハロゲン類,チオシアノ基,ヒド
ロシル基,アルコキシ基,カルボキシル基のいずれかを示
す。］で表される化合物よりなる易分解性ポリウレタン
樹脂製造方法。1. A method for producing a polyurethane resin in which a starch and a polyol and an isocyanate are polymerized with a polymerization catalyst, wherein the polymerization catalyst has a general formula: [In the formula, R represents any one of a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, an allyl group, a benzyl group, a phenyl group, a naphthyl group, and X represents a halogen, a thiocyano group, a hydrosyl group, an alkoxy group. , Indicates a carboxyl group. A method for producing an easily decomposable polyurethane resin comprising the compound represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7337887A JP2969257B2 (en) | 1995-12-01 | 1995-12-01 | Method for producing easily degradable polyurethane resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7337887A JP2969257B2 (en) | 1995-12-01 | 1995-12-01 | Method for producing easily degradable polyurethane resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09157345A JPH09157345A (en) | 1997-06-17 |
| JP2969257B2 true JP2969257B2 (en) | 1999-11-02 |
Family
ID=18312940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7337887A Expired - Fee Related JP2969257B2 (en) | 1995-12-01 | 1995-12-01 | Method for producing easily degradable polyurethane resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2969257B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110423456A (en) * | 2019-08-13 | 2019-11-08 | 湖南工业大学 | A kind of preparation method of high intensity dual network biomass membrane material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3730953A (en) | 1970-12-28 | 1973-05-01 | Takeda Chemical Industries Ltd | Process for producing high molecular polyurethanes by reacting oxadiazinones with polyols in the presence of an organotin catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0493315A (en) * | 1990-08-10 | 1992-03-26 | Denki Kagaku Kogyo Kk | Production of resin composition |
| JPH04351623A (en) * | 1991-05-28 | 1992-12-07 | Nippon Kayaku Co Ltd | New block copolymer and production thereof |
-
1995
- 1995-12-01 JP JP7337887A patent/JP2969257B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3730953A (en) | 1970-12-28 | 1973-05-01 | Takeda Chemical Industries Ltd | Process for producing high molecular polyurethanes by reacting oxadiazinones with polyols in the presence of an organotin catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09157345A (en) | 1997-06-17 |
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