JPH0248012B2 - - Google Patents
Info
- Publication number
- JPH0248012B2 JPH0248012B2 JP58242243A JP24224383A JPH0248012B2 JP H0248012 B2 JPH0248012 B2 JP H0248012B2 JP 58242243 A JP58242243 A JP 58242243A JP 24224383 A JP24224383 A JP 24224383A JP H0248012 B2 JPH0248012 B2 JP H0248012B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose acetate
- molecular weight
- low molecular
- diisocyanate
- degree
- 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 - Lifetime
Links
- 229920002301 cellulose acetate Polymers 0.000 claims description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims description 12
- 229920001400 block copolymer Polymers 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 15
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 tin carboxylate Chemical class 0.000 description 3
- 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 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QJNLUNBGDFUULX-UHFFFAOYSA-N 4-n,4-n'-dimethyl-3h-pyridine-4,4-diamine Chemical compound CNC1(NC)CC=NC=C1 QJNLUNBGDFUULX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Description
【発明の詳細な説明】
本発明は、低分子量酢酸セルロースを一成分と
する共重合体の製法に関するものであり、詳しく
は低分子量酢酸セルロースと、分子末端に水酸基
又はアミノ基を有する高分子の官能基とを、ジイ
ソシアナートとの反応を介して結合させたブロツ
ク共重合体の製法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a copolymer containing low molecular weight cellulose acetate as one component. The present invention relates to a method for producing a block copolymer in which a functional group is bonded to a block copolymer through a reaction with a diisocyanate.
酢酸セルロースは熱可塑性高分子物質の一つと
して、プラスチツクス、フイルム、繊維、半透膜
などに工業的に利用されており、透明性、着色
性、印刷適性、耐衝撃性、感触の良さなどに優れ
た特徴がある。しかしながら、単独では熱可塑性
が充分でないため、プラスチツクス用途には可塑
剤と混合して加工する必要がある。現在酢酸セル
ロースに対し、充分な親和性を有する可塑剤は見
出されておらず、成型加工後に可塑剤が拡散移動
し相接する他の材料に移行してその物性を損ねた
り酢酸セルロース成型体内部に歪を生じるなどの
問題がある。 Cellulose acetate is a thermoplastic polymer substance that is used industrially in plastics, films, fibers, semipermeable membranes, etc., and is known for its transparency, colorability, printability, impact resistance, and good feel. has excellent characteristics. However, since it does not have sufficient thermoplasticity when used alone, it is necessary to process it by mixing it with a plasticizer for plastics applications. Currently, no plasticizer has been found that has sufficient affinity for cellulose acetate, and after the molding process, the plasticizer diffuses and moves to other adjacent materials, impairing their physical properties. There are problems such as internal distortion.
現在使用されているような低分子可塑剤に代つ
て、酢酸セルロースに対する親和性が高く、且つ
現在使用されている可塑剤に比し分子量の高い高
分子改質剤の開発は、極めて有用なことと考えら
れる。 It would be extremely useful to develop a polymeric modifier that has a high affinity for cellulose acetate and has a higher molecular weight than the currently used plasticizers in place of the currently used low-molecular plasticizers. it is conceivable that.
このような高分子改質剤は、分子中に酢酸セル
ロース構造部分を有するとともに、セルロース骨
格よりも可撓性に富む構造部分を併せ有するもの
が適当と考えられ、そのような化合物は、ブロツ
ク重合体あるいはグラフト重合体の製造によつて
達成できると考えられる。しかしながら工業的に
生産されている酢酸セルロースをそのまゝ共重合
成分とした場合は、生成物の重合度が高すぎた
り、架橋などの副反応が起つたり、反応溶媒の選
択範囲が狭いなどの問題があり、実際的でない。 Such a polymer modifier is considered to be suitable for having a cellulose acetate structural part in the molecule, as well as a structural part that is more flexible than the cellulose skeleton. It is believed that this can be achieved by the production of coalescence or graft polymers. However, if industrially produced cellulose acetate is directly used as a copolymerization component, the degree of polymerization of the product may be too high, side reactions such as crosslinking may occur, or the selection range of reaction solvents may be narrow. This is problematic and impractical.
これに対し、工業的に生産されている酢酸セル
ロースに対し、その数分の１乃至1/10程度の重合
度を有する低分子量酢酸セルロースを出発原料と
してグラフト或はブロツク共重合体を得る方法が
考えられる。このような低分子量酢酸セルロース
でも、生成物の分子構造中に存在すれば高分子酢
酸セルロースとの高い親和性をもたらすのに充分
なものであると考えられる。 On the other hand, there is a method to obtain graft or block copolymers using low molecular weight cellulose acetate as a starting material, which has a degree of polymerization that is about 1/10 to 1/10 that of industrially produced cellulose acetate. Conceivable. Even such low molecular weight cellulose acetate is considered to be sufficient to provide high affinity with high molecular weight cellulose acetate if it exists in the molecular structure of the product.
このような低分子量酢酸セルロースを一成分と
する共重合体の製法としては、特公昭45−3399号
公報に、分子内に約２個の遊離水酸基を有する低
分子量三酢酸セルロースと２個の水酸基を有する
ポリエーテル又はポリエステルとを、ジイソシア
ネートを介して結合させてブロツク共重合体を得
る方法が示されている。しかしながらこの方法は
低分子量酢酸セルロースと、ポリエステル又はポ
リエーテルとをジイソシアナートとを触媒の共存
下溶媒中で反応させるものであつて、各成分同志
の結合や高重縮合が起り反応の制御が困難なもの
である。 As for a method for producing such a copolymer containing low molecular weight cellulose acetate as one component, Japanese Patent Publication No. 1983-3399 describes a method for producing a copolymer containing low molecular weight cellulose triacetate, which has approximately two free hydroxyl groups in the molecule, and a copolymer containing two free hydroxyl groups. A method is disclosed in which a block copolymer is obtained by bonding a polyether or a polyester having the following properties via a diisocyanate. However, in this method, low molecular weight cellulose acetate, polyester or polyether, and diisocyanate are reacted in a solvent in the presence of a catalyst, and bonding between each component and high polycondensation occur, making it difficult to control the reaction. It's difficult.
本発明者らは、架橋反応や高次の縮合反応や副
反応などを起さず、低分子酢酸セルロースと可撓
性分子鎖を有する化合物を結合させ、目的とする
共重合体を効率よく得る方法を見出した。 The present inventors efficiently obtain the desired copolymer by bonding low-molecular cellulose acetate with a compound having a flexible molecular chain without causing cross-linking reactions, higher-order condensation reactions, or side reactions. I found a way.
即ち本発明は、低分子酢酸セルロースの遊離水
酸基に対し、過剰量のジイソシアナートを加えて
反応させ、未反応ジイソシアナートを減圧蒸留で
除いた後高分子量のアルコール又はアミンを加え
て反応させることを特徴とするブロツク又はグラ
フト共重合体の製造方法に関するものである。 That is, in the present invention, an excess amount of diisocyanate is added to the free hydroxyl groups of low-molecular cellulose acetate to react, and after removing unreacted diisocyanate by vacuum distillation, a high-molecular-weight alcohol or amine is added and reacted. The present invention relates to a method for producing a block or graft copolymer characterized by the following.
本発明に使用する低分子量酢酸セルロースはエ
ステル置換度2.5以上、数平均重合度５〜50の酢
酸セルロースである。重合度５以下では、共重合
体の酢酸セルロースに対する親和性が低くなり、
重合度50以上では反応時の粘性が高くなり反応の
制御が困難になる。酢酸セルロース分子内の遊離
水酸基は１以上、10以下が好ましい。水酸基が多
すぎるとゲル化が起りやすく、生成物が酢酸セル
ロースに対し親和性が低いものとなる。エステル
置換度の望ましい範囲は、上記の重合度と遊離水
酸基数の関係で定まつてしまうが、結果的にエス
テル置換度2.5以上、特に2.7以上が好ましい。 The low molecular weight cellulose acetate used in the present invention is cellulose acetate having a degree of ester substitution of 2.5 or more and a number average degree of polymerization of 5 to 50. When the degree of polymerization is 5 or less, the affinity of the copolymer for cellulose acetate decreases,
If the degree of polymerization is 50 or more, the viscosity during the reaction becomes high, making it difficult to control the reaction. The number of free hydroxyl groups in the cellulose acetate molecule is preferably 1 or more and 10 or less. If there are too many hydroxyl groups, gelation tends to occur and the product has low affinity for cellulose acetate. The desirable range of the degree of ester substitution is determined by the relationship between the degree of polymerization and the number of free hydroxyl groups, but as a result, the degree of ester substitution is preferably 2.5 or more, particularly 2.7 or more.
現在工業的に使用されている酢酸セルロース
は、重合度が100〜400の範囲のものであり、これ
を解重合して低重合度酢酸セルロースを得る。 Cellulose acetate currently used industrially has a degree of polymerization in the range of 100 to 400, and is depolymerized to obtain cellulose acetate with a low degree of polymerization.
酢酸セルロースの低分子量化は特公昭45−3399
号公報にも示されているが酢酸セルロースを酢酸
溶液中で適量の水或いは無水酢酸に加えて触媒
（濃硫酸、過塩素酸）の存在で処理することによ
つてえられる。 The reduction of the molecular weight of cellulose acetate was published in 1973-3399.
As disclosed in the above publication, cellulose acetate is obtained by treating cellulose acetate in an acetic acid solution in addition to an appropriate amount of water or acetic anhydride in the presence of a catalyst (concentrated sulfuric acid, perchloric acid).
上記低分子量酢酸セルロースの遊離水酸基に対
し過剰量のジイソシアナートを添加して反応さ
せ、未反応のジイソシアナートを減圧留去する
と、低分子酢酸セルロースの水酸基がカルバモイ
ル化し、且つジイソシアナートの一方のイソシア
ナートが残つている形のものがえられる。反応触
媒としてピリジン、ジメチルアミノピリジンなど
のアミノ塩基、カルボン酸スズなどのルイス酸な
どを共存させるのが好ましい。この反応に使用す
るジイソシアナートは、未反応のものを留去する
ことが必要であり分子量200以下程度のものが好
ましい。例えばトリレンジイソシアナート、フエ
ニレンジイソシアナート、ヘキサメチレンジイソ
シアナートなどがある。 When an excess amount of diisocyanate is added and reacted with the free hydroxyl groups of the low molecular weight cellulose acetate, and unreacted diisocyanate is distilled off under reduced pressure, the hydroxyl groups of the low molecular weight cellulose acetate are carbamoylated, and the diisocyanate is A form in which one isocyanate remains is obtained. It is preferable to coexist an amino base such as pyridine or dimethylaminopyridine, or a Lewis acid such as tin carboxylate as a reaction catalyst. The diisocyanate used in this reaction preferably has a molecular weight of about 200 or less since it is necessary to distill off unreacted substances. Examples include tolylene diisocyanate, phenylene diisocyanate, and hexamethylene diisocyanate.
上記によつて得た低分子量酢酸セルロースから
のイソシアナート化合物は、適当な溶媒中、分子
末端に水酸基又はアミノ基を有する高分子と反応
させる。この分子末端に官能基を有する高分子
は、反応生成物における可撓性分子鎖となるもの
であり、分子量は100以上であることが望ましい。
一方、分子量が２万以上になると生成物の酢酸セ
ルロースに対する相溶性が低下するので、分子量
は100〜２万の範囲が適当である。イソシアナー
ト変性した酢酸セルロースに対する該高分子の使
用比率については、該高分子が一官能の場合は理
論量の小過剰量を使用すればよいが、多官能の場
合は大過剰量を使用して、架橋反応や、分子量の
必要以上の増大を避けることが望ましい。 The isocyanate compound obtained from the low molecular weight cellulose acetate obtained above is reacted with a polymer having a hydroxyl group or an amino group at the molecular end in a suitable solvent. The polymer having a functional group at the molecular end serves as a flexible molecular chain in the reaction product, and preferably has a molecular weight of 100 or more.
On the other hand, when the molecular weight exceeds 20,000, the compatibility of the product with cellulose acetate decreases, so the appropriate molecular weight is in the range of 100 to 20,000. Regarding the ratio of the polymer to the isocyanate-modified cellulose acetate, if the polymer is monofunctional, a small excess of the theoretical amount may be used, but if it is polyfunctional, a large excess should be used. It is desirable to avoid cross-linking reactions and unnecessarily increasing the molecular weight.
本発明の方法によれば、目的とするブロツク共
重合体を効率良く製造できる。 According to the method of the present invention, the desired block copolymer can be efficiently produced.
本発明の方法によつて得られる共重合体は、酢
酸セルロースの高分子可塑剤としての利用のほ
か、酢酸セルロースと他の高分子とのポリマーブ
レンドにおける相溶性改良剤など、種々の用途が
期待される。 The copolymer obtained by the method of the present invention is expected to have various uses, including as a polymer plasticizer for cellulose acetate and as a compatibility improver in polymer blends of cellulose acetate and other polymers. be done.
実施例
低分子量三酢酸セルロースの製造
三酢酸セルロース（数平均重合度110、D.
S.2.94）60ｇを酢酸600mlに溶解し、80℃に昇温
した後、無水酢酸9.9ml、濃硫酸3.0ml、水3.6mlを
加え、撹拌下に80℃で３時間保持した。溶液を30
℃まで冷却した後過剰量の酢酸マグネシウム水溶
液を加え系内の硫酸を中和した。中和後の溶液を
２−プロパノール（IPA）１中に加え、生成す
る低分子量三酢酸セルロースの沈澱を別した。
該沈澱は水１中に分散させ、別する操作を２
回繰返して洗滌し、別後真空乾燥した。さらに
クロロホルム300mlに溶解しIpA1500ml中に加え
て再沈澱させる精製法を２回くりかえした後真空
乾燥した。収量56ｇ（収率93％）であつた。Example Production of low molecular weight cellulose triacetate Cellulose triacetate (number average degree of polymerization 110, D.
S.2.94) 60g was dissolved in 600ml of acetic acid and heated to 80°C, then 9.9ml of acetic anhydride, 3.0ml of concentrated sulfuric acid, and 3.6ml of water were added, and the mixture was maintained at 80°C for 3 hours with stirring. solution 30
After cooling to ℃, an excess amount of an aqueous magnesium acetate solution was added to neutralize the sulfuric acid in the system. The neutralized solution was added to 1 part of 2-propanol (IPA), and the precipitate of low molecular weight cellulose triacetate produced was separated.
The precipitate was dispersed in 1 part of water and 2 separate operations were performed.
It was washed several times, separated and vacuum dried. Furthermore, the purification method of dissolving in 300 ml of chloroform, adding to 1500 ml of IpA, and reprecipitation was repeated twice, followed by vacuum drying. The yield was 56 g (yield 93%).
かくして得た低分子量三酢酸セルロースは、ク
ロロホルム溶液の蒸気圧浸透圧法による測定では
数平均重合度27であつた。この1H−NMRスペ
クトル及び1Rスペクトルをそれぞれ第１図及び
第２図に示す1H−NMRスペクトルにおける特
性シグナルはすべて三酢酸セルロースの構造にも
とづいて説明できる。なお1Rスペクトルには
3500cm-1に弱いＯ−Ｈ伸縮振動にもとづく吸収が
みられる。 The low molecular weight cellulose triacetate thus obtained had a number average degree of polymerization of 27 as measured by vapor pressure osmosis method of a chloroform solution. The characteristic signals in the 1H-NMR spectra shown in FIGS. 1 and 2, respectively, can be explained based on the structure of cellulose triacetate. Furthermore, in the 1R spectrum,
Absorption based on weak O-H stretching vibrations is seen at 3500 cm -1 .
この低分子量三酢酸セルロースを、Malmの方
法（Anal.Chem.26 188（1954））に従いピリジン
中90℃にて大過剰のフエニルイソシアナートで処
理して、遊離水酸基をフエニルカルバモイル化
し、272nｍの紫外線吸収強度から含有フエニル
カルバモイル量を求めた。この値はフエニルイソ
シアナート処理剤の遊離水酸基量に対するもので
あり、その結果は低分子量三酢酸セルロース１モ
ルあたり4.5個であつた。 This low molecular weight cellulose triacetate was treated with a large excess of phenyl isocyanate in pyridine at 90°C according to the method of Malm (Anal. The amount of phenylcarbamoyl contained was determined from the ultraviolet absorption intensity of . This value is based on the amount of free hydroxyl groups in the phenyl isocyanate treatment agent, and the result was 4.5 free hydroxyl groups per mole of low molecular weight cellulose triacetate.
ブロツクコポリマーの合成
上記で合成した低分子量三酢酸セルロース2.0
ｇをジクロルメタン100mlに溶解し、蒸溜により
50mlを除去した。この操作により溶液内の水が共
沸により除去される。残つた低分子量三酢酸セル
ロース溶液に、４，４−ジメチルアミノピリジン
55mgと、トリレンジイソシアナート１mlを加え、
乾燥した窒素雰囲気下室温（20〜30℃）にて２日
間静置し反応させた。次に溶媒を減圧下留去し、
さらに室温にて揮発性物質を減圧下除去して、低
分子量三酢酸セルロースとトリレンジイソシアナ
ートの反応生成物をフラスコ底部に残した。Synthesis of block copolymer Low molecular weight cellulose triacetate 2.0 synthesized above
Dissolve g in 100ml of dichloromethane and distill it.
50ml was removed. Through this operation, water in the solution is removed azeotropically. Add 4,4-dimethylaminopyridine to the remaining low molecular weight cellulose triacetate solution.
Add 55 mg and 1 ml of tolylene diisocyanate,
The reaction mixture was allowed to stand for 2 days at room temperature (20 to 30°C) under a dry nitrogen atmosphere. Next, the solvent was distilled off under reduced pressure,
Further, volatile substances were removed under reduced pressure at room temperature, leaving a reaction product of low molecular weight cellulose triacetate and tolylene diisocyanate at the bottom of the flask.
別に平均分子量5000のポリエチレングリコール
モノメチルエーテル6.0ｇを100mlの乾燥ジクロル
メタンに溶解し、溶液から50mlの溶媒を留去する
ことにより水を除去した。この溶液にジメチルア
ミノピリジン50mgを加え、前記の低分子量三酢酸
セルロースとジイソシアナートの反応生成物を保
持しているフラスコ中に移し、全体を撹拌した後
２日間室温（25〜30℃）にて静置下に反応させ
た。反応溶液を200mlの石油エーテル中に加え、
生成した沈澱を別し、乾燥した後１の水に投
入して洗滌し、再び別し、乾燥した。収量7.4
ｇの粗生成物を得た。 Separately, 6.0 g of polyethylene glycol monomethyl ether having an average molecular weight of 5000 was dissolved in 100 ml of dry dichloromethane, and water was removed by distilling off 50 ml of the solvent from the solution. Add 50 mg of dimethylaminopyridine to this solution, transfer it to the flask holding the reaction product of low molecular weight cellulose triacetate and diisocyanate, stir the whole thing, and then let it stand at room temperature (25-30°C) for 2 days. The reaction mixture was allowed to stand still. Add the reaction solution into 200ml petroleum ether,
The formed precipitate was separated, dried, poured into water from Step 1 for washing, separated again, and dried. Yield 7.4
g of crude product was obtained.
上記粗生成物420mgを20mlのジメチルスルホキ
サイド中に懸濁し、100℃にて３分間加熱すると
透明な溶液となつた。この溶液を凍結乾燥して溶
媒を除去し、残つた固形分を水で抽出し、水抽出
物204mgと水不溶物216mgを得た。水抽出物は、
1Rスペクトルから未反応のポリエチレングリコ
ールであることをみとめた。 420 mg of the above crude product was suspended in 20 ml of dimethyl sulfoxide and heated at 100°C for 3 minutes to form a clear solution. This solution was freeze-dried to remove the solvent, and the remaining solid content was extracted with water to obtain 204 mg of water extract and 216 mg of water-insoluble matter. The water extract is
It was confirmed from the 1R spectrum that it was unreacted polyethylene glycol.
上記水不溶物の上記分別手段にもとづく計算収
量は3.8ｇである。このものはクロロホルム、塩
化メチレン、熱ジメチルスルホキシドに溶解す
る。蒸気圧浸透圧法により求めた分子量は17000
であつた。その1H−NMRスペクトル及び1Rス
ペクトルをそれぞれ第３図及び第４図に示す。
NMRスペクトル（δ、CDCl3）における3.2〜
5.4ppmのマルチスプレツト及び2.15ppm、
2.02ppm、1.96ppmの３つのシンプレツトは酢酸
セルロース構造部分、3.66ppmの強いシンプレツ
トはポリエチレングリコールの構造部分の存在を
示す。また1Rスペクトルにおいて1700cm-1、及
び1540cm-1の吸収はウレタン結合のＣ＝Ｏ伸縮振
動及びNH変角振動にもとづくものであり、1150
cm-1、960cm-1の吸収はベンゼン環のCH変角振動
にもとづく吸収である。 The calculated yield of the water-insoluble material based on the above separation method is 3.8 g. It dissolves in chloroform, methylene chloride, and hot dimethyl sulfoxide. Molecular weight determined by vapor pressure osmosis method is 17000
It was hot. The 1H-NMR spectrum and 1R spectrum are shown in FIGS. 3 and 4, respectively.
3.2 in NMR spectrum (δ, CDCl3 )
5.4ppm multispread and 2.15ppm,
The three simplets at 2.02 ppm and 1.96 ppm indicate the presence of cellulose acetate structural parts, and the strong simplet at 3.66 ppm indicates the presence of polyethylene glycol structural parts. In addition, the absorption at 1700 cm -1 and 1540 cm -1 in the 1R spectrum is based on the C=O stretching vibration and NH bending vibration of the urethane bond, and the 1150
The absorption at cm -1 and 960 cm -1 is based on the CH bending vibration of the benzene ring.
これらの結果から、生成物は低分子量酢酸セル
ロースとポリエチレングリコールがジイソシアナ
ートを介して結合したブロツク共重合体であると
判明される。該生成物のクロロホルム溶液からの
流延フイルムは透明で、三酢酸セルロースフイル
ムよりも可撓性に富んでいる。またそのジメチル
スルホキシド溶液を水に投入すると、固形分は微
細懸濁の状態となりその懸濁状態は安定である。 These results reveal that the product is a block copolymer in which low molecular weight cellulose acetate and polyethylene glycol are bonded via diisocyanate. Films cast from chloroform solutions of the product are clear and more flexible than cellulose triacetate films. When the dimethyl sulfoxide solution is poured into water, the solid content becomes a fine suspension and the suspension is stable.
第１図は実施例で得た低分子量三酢酸セルロー
スのプロトンNMRスペクトル、第２図は同じ低
分子量三酢酸セルロースの赤外吸収スペクトルで
ある。第３図は実施例で得たブロツク共重合体の
プロトンNMRスペクトル、第４図は同じブロツ
ク共重合体の赤外吸収スペクトルである。
FIG. 1 shows a proton NMR spectrum of the low molecular weight cellulose triacetate obtained in the example, and FIG. 2 shows an infrared absorption spectrum of the same low molecular weight cellulose triacetate. FIG. 3 shows the proton NMR spectrum of the block copolymer obtained in the example, and FIG. 4 shows the infrared absorption spectrum of the same block copolymer.
Claims (1)
50の酢酸セルロースにジイソシアナートを反応さ
せて、その遊離水酸基をカルバモイル化した後、
分子末端に水酸基又はアミノ基を有する高分子を
添加して残存イソシアナート基と反応させること
を特徴とする、低分子量酢酸セルロースを一成分
とするブロツク共重合体の製法。1 Degree of acetyl substitution 2.5 or more, number average degree of polymerization 5 or more
After reacting cellulose acetate with diisocyanate to carbamoylate its free hydroxyl groups,
A method for producing a block copolymer containing low molecular weight cellulose acetate as one component, which is characterized by adding a polymer having a hydroxyl group or an amino group at the end of the molecule and reacting with the remaining isocyanate groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58242243A JPS60135423A (en) | 1983-12-23 | 1983-12-23 | Production of copolymer having low-mw cellulose acetate as component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58242243A JPS60135423A (en) | 1983-12-23 | 1983-12-23 | Production of copolymer having low-mw cellulose acetate as component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60135423A JPS60135423A (en) | 1985-07-18 |
| JPH0248012B2 true JPH0248012B2 (en) | 1990-10-23 |
Family
ID=17086370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58242243A Granted JPS60135423A (en) | 1983-12-23 | 1983-12-23 | Production of copolymer having low-mw cellulose acetate as component |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60135423A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0539411U (en) * | 1991-10-28 | 1993-05-28 | 株式会社吉野工業所 | Compact container equipped with a reference plate removal mechanism |
| JPH0588407U (en) * | 1992-04-23 | 1993-12-03 | 株式会社資生堂 | Medium container extrusion device |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2675997B2 (en) * | 1988-05-16 | 1997-11-12 | 工業技術院長 | Novel polyurethane manufacturing method |
| US6303670B1 (en) | 2000-02-25 | 2001-10-16 | Nippon Paper Industries Co., Ltd. | Cellulose based coating composition curable with ultraviolet ray |
-
1983
- 1983-12-23 JP JP58242243A patent/JPS60135423A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0539411U (en) * | 1991-10-28 | 1993-05-28 | 株式会社吉野工業所 | Compact container equipped with a reference plate removal mechanism |
| JPH0588407U (en) * | 1992-04-23 | 1993-12-03 | 株式会社資生堂 | Medium container extrusion device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60135423A (en) | 1985-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0425505A (en) | Cyclodextrain polymer and production of cyclodextrin membrane | |
| JP4544842B2 (en) | Method for producing polyrotaxane | |
| JPH0376321B2 (en) | ||
| WO2007026578A1 (en) | Hydrophobic modified polyrotaxane and crosslinked polyrotaxane | |
| JPH09512847A (en) | polyester | |
| EP0502194A1 (en) | Cyclodextrin polymer and cyclodextrin film formed therefrom | |
| Lee et al. | Preparation and characterization of cyclodextrin polymer and its high-performance liquid-chromatography stationary phase | |
| JPH0248012B2 (en) | ||
| JP5204409B2 (en) | Pseudopolyrotaxane and polyrotaxane | |
| EP2432813B1 (en) | Stereocomplexes of poly-l-lactide urethane and poly-d-lactide urethane, and method for producing same | |
| JP2000086702A (en) | Crosslinked polymer including derivatives of bis-silane, bis-thioether, bis-sulfoxide, bis-sulfone and butanediyl of polysaccharide and oligosaccharide as base and its molding as support material | |
| JP2020033440A (en) | Functionalized cycloolefin polymer | |
| Kobayashi et al. | Grafting of 2-oxazolines onto cellulose and cellulose diacetate | |
| JP3018113B2 (en) | Method for lowering molecular weight of cellulose acetate, lactone-modified cellulose acetate and method for producing the same | |
| CN112194741A (en) | Polyethylene glycol derivative modified beta-cyclodextrin and preparation method and application thereof | |
| JPH0253822A (en) | Preparation of hydroxy-terminated aliphatic polyether | |
| JP3715358B2 (en) | Novel optically active phenylacetylene polymer and process for producing the same | |
| JPH0689099B2 (en) | Polysiloxane-polyurea block copolymer and method for producing the same | |
| KR100637683B1 (en) | Biodegradable Molecular Imprinted Polymer | |
| JPH04351623A (en) | New block copolymer and production thereof | |
| JPH08500325A (en) | Energetic polymer and method for producing the same | |
| JPH03221504A (en) | Synthesis of cyclodextrin polymer and production of cyclodextrin film | |
| JP3475434B2 (en) | How to introduce azo groups | |
| JP7168200B2 (en) | Functionalized cycloolefin polymer | |
| WO2024014395A1 (en) | Rotaxane compound |