GB2158081A - Graft polymer of cellulose and caprolactone - Google Patents
Graft polymer of cellulose and caprolactone Download PDFInfo
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- GB2158081A GB2158081A GB08508466A GB8508466A GB2158081A GB 2158081 A GB2158081 A GB 2158081A GB 08508466 A GB08508466 A GB 08508466A GB 8508466 A GB8508466 A GB 8508466A GB 2158081 A GB2158081 A GB 2158081A
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- graft polymer
- cellulose
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- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 61
- 229920002678 cellulose Polymers 0.000 title claims abstract description 24
- 239000001913 cellulose Substances 0.000 title claims abstract description 14
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 description 18
- 150000001721 carbon Chemical group 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 229920002301 cellulose acetate Polymers 0.000 description 10
- 239000000178 monomer Substances 0.000 description 8
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- -1 cyclic ester Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- JUJWROOIHBZHMG-RALIUCGRSA-N pyridine-d5 Chemical compound [2H]C1=NC([2H])=C([2H])C([2H])=C1[2H] JUJWROOIHBZHMG-RALIUCGRSA-N 0.000 description 1
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Engineering & Computer Science (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Polyesters Or Polycarbonates (AREA)
- External Artificial Organs (AREA)
- Materials For Medical Uses (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
A graft polymer of cellulose has such a structure that all or some of the hydrogen atoms in the hydroxy groups have been substituted by a graft chain group of the formula: <IMAGE> m being an integer of at least 1, and at least one of any balance of unreacted hydroxyl hydrogen atoms has been substituted by a group of the formula: <IMAGE> n being an integer of at least 1
Description
SPECIFICATION
Graft polymer of cellulose
The present invention relates to a cellulose ester having an ester group derived from caprolactone as a graft chain. More particularly, the invention relates to a cellulose ester which has as a graft chain an ester group derived from caprolactone and having a primary hydroxyl group at one end thereof, and which is useful as a coating resin or moulding material.
The inventors have succeeded in producing on an industrial scale a graft polymer comprising a cellulose ester having a graft chain comprising -caprolactone, which is industrially highly useful and has not been disclosed in any literature, and also in elucidating the structure of the graft polymer. Further, the inventors have found that the graft polymer is tough and flexible and it is useful as a coating resin or moulding.
The invention provides a new polymer grafted on cellulose or a cellulose ester, a graft polymer of cellulose in which all or a part of the hydrogen atoms of the hydroxy groups of the cellulose has been substituted by a graft chain group of the formula (Ill) as defined below and at least one of any balance has been substituted by a group of the formula (IV) as defined below. In other words, the invention polymer may be defined by using the formulae (I) and (11) as defined below. The free bond at the right of the formulae (I) and (II) may be attached to hydrogen, the group of the formula (lV) or the group of the formula (III) and the free bond on the left may be attached to hydroxy, -O-(lV) or -O-(lll).
In a particular embodiment the present invention provides a new graft polymer composed of a number of units of formula (I):
wherein at least one of R1, R2 and R3 represents a group of the formula (III):
wherein m is an integer of at least 1, at least one of any balance ofF1, R2 and F3 represents a group of the formula (IV):
wherein n is an integer of at least 1 and any balance of R1, F2 and R3 represents H, and, if desired, a number of units of formula (it):
wherein at least one of R4, Rs and F6 represents
p being an integer of at least 1 and any balance of R4, F5 and F6 represents H.
In the graft polymer of the present invention, all the glucose rings may be bonded with a graft chain composed of an e-caprnlactone monomer, namely, the graft polymer may be composed of only the units of the above formula (I), or alternatively it may be composed of both the units of the above formula (I) and the units of the above formula (it).
Both polymers are included in the graft polymers of the present invention and they have high toughness and flexibility.
It is believed that the high flexibility of the graft polymer of the present invention is due to the presence of a relatively bulky group, i.e. a graft chain composed of e-caprolactone having a primary hydroxyl group at one end thereof, attached to the glucose ring. Further, it is believed that the primary hydroxyl group, being present at a position distant from the glucose ring, has a reactivity higher than that of a hydroxyl group directly bonded with the glucose ring such as the one remaining in cellulose acetate or cellulose acetate butyrate. Therefore, it is preferable that the graft chain of the graft polymer of the present invention is composed of at least one e-caprolactone monomer unit, more preferably a plurality of -caprolactone monomer units.
To obtain the graft polymer of the present invention having a high mechanical strength, it is preferred that the graft polymer is composed of at least 20 units of formula (I) or at least 20 units of formulae (I) and (II) taken together. Particularly, the graft polymer composed of 50 to 250 units on average of formula (I) or 50 to 250 units on average of formulae (I) and (II) taken together is preferred for obtaining sufficient flexibility and toughness. Though the proportion of the units of formula (I) to the units of formula (II) is not limited in the invention, it may generally be in the range of 80120 to 20180.
The invention will be further illustrated by reference to the accompanying drawings in which:
Figure 1 is a 7H-NMR spectrum of the graft polymer obtained in Example 1;
Figure 2 is a 13C-N M R spectrum of the same graft polymer;
Figure 3 is an IR absorption spectrum of the same graft polymer; and
Figure 4 is a gas chromatogram of the same graft polymer.
The graft polymer of the present invention can be identified by a known means of analysis, such as '3C-NMR spectroscopy, 1H-NMR spectroscopy, infrared absorption spectroscopy or gas chromatography.
For example, according to the 73C-NMR spectroscopy, the graft polymer can be identified based on signals shown below, since it has the following structure in it's molecule:
in which at least one of F1, R2 and F3 represents
(11) (12) (13) (14) (15) (16) (21) (22) (23) (24) (25) (26) being 0 or an integer of at least 1, at least one of the balance of R1, R2 and F3 represents
being an integer of at least 1, and the balance of Rs,R2 and F3 represents H, the numerals in the parentheses below the carbon atoms refer to the respective positions of the carbon atoms.
The signals of carbon atom (1), carbon atoms (2) to (5) and carbon atom (6) are observed at 100 to 106 ppm, 72 to 83 ppm and 60 to 65 ppm, respectively. The signal of C=O of the acyl group bonded with the glucose ring by an ester bond, i.e. carbon atom (7), is observed at 169 to 171 ppm.
In the graft chain composed of e-caprolactone, signals of carbon atoms (12)to (15) and (22) to (25) are observed at 24to 36 ppm, those of carbon atoms (16) and (26) are observed at 61 to 65 ppm and those of carbon atoms (11) and (21) are observed at 173 to 174 ppm.
Though a signal of the carbon of the carboxyl group, i.e. the carbon of sC=O is observed at 175
to 176 ppm when the graft chain has a terminal carboxyl group, no corresponding signal is observed
in the graft polymer of the present invention, since the terminal group of the graft chain thereof is a
hydroxyl group.
The above-mentioned characteristic features are recognized in the 13C-NMR spectrum of the graft
polymer of the present invention.
The graft polymer of the present invention can be produced by various processes including a
process disclosed in the specification of our Japanese Patent Application No. 197333/82, now
published on May 18, 1984 with A publication No. 86621/84. In this process, a cyclic ester is
subjected to a ring-opening reaction in the presence of a cellulose ester having a hydroxyl group in
the molecule, which is obtained by esterifying cellulose with an aliphatic carboxylic acid, by using a
catalyst generally used in the ring-opening reaction of cyclic esters, such as an organic acid, an
inorganic acid, an organotin compound, a tin salt of an organic acid, an alkali metal, an organic alkali
metal compound, an alkylaluminum, an organotitanium compound or a halide such as tin chloride,
at a temperature of 120 to 230"C for about 0.1 to 96 h (as for the catalysts used in the ring-opening
reaction of cyclic esters, see Takeo Saegusa, "Koza, Jugo hanno-ron 7. Kaikan jugo (II), published by
Kagaku Dojin Co., Ltd., 1973, pp. 104 to 128).
Cellulose esters to be used in the production of the graft polymer of the present invention
according to the above-mentioned process include one which has a non-acylated hydroxyl group,
prepared from an aliphatic carboxylic acid of the general formula:
wherein q represents an integer of at least 1, and cellulose. A cellulose ester containing 1 to 20 wt. % of the hydroxyl group is preferred. Particularly preferred are those which can be handled easily and which are commercially available at a relatively low cost, such as cellulose acetate, cellulose propionate, cellulose
butyrate, cellulose acetate propionate and cellulose acetate butyrate.
As for the molecular weight of the cellulose esters, those having at least 20 glucose units on average are
preferred in general. When the number of the cellulose units is less than 20, the mechanical toughness of the
graft polymer of the present invention may be deteriorated in some cases.
When the graft polymer of the present invention is obtained in the form of a mixture thereof with a non-grafted cellulose ester and/or a non-grafted -caprolactone homopolymer, the graft polymer can be isolated therefrom in pure form buy a known method generally employed in isolating a graft polymer, e.g.
solvent fractionation.
When the graft polymer of the present invention is used as a coating resin, it exhibits an excellent compatibility with other thermoplastic resins to form a coating film having excellent properties. When the
graft polymer is used as a molding material,the use of a plasticizer such as a phthalate is unnecessary, since it has a high flexibility which cannot be obtained when the cellulose ester is used alone.
The primary hydroxyl group positioned attheterminal of the graft chain of the graft polymer has such a high reactivity that it can react with an isocyanate, acid halide or epoxy group. Therefore, it is possible that the graft polymer is further reacted to effect a chemical modification or reticulation.
Further, the graft polymer may be used as a raw material for fibers, separating membranes,films and
medical materials.
The following examples will further illustrate the graft polymers of the present invention. Unless otherwise
stated, parts and percentages are given by weight.
Example 1
100 parts of -caprolactone and 0.0110 part of tetrabutyl titanate, (C4Hg0)4Ti, were placed in a sufficiently dried reactor provided with a stirrer, a thermometer and a reflux condenser in a dry nitrogen atmosphere.
The mixture was heated to 120"C. 100 parts of cellulose acetate which had been dried sufficiently (a product
of Daicel Chemical Industries, Ltd. having a degree of acetylation of 45.4%, a degree of substitution of 1.75
and an average degree of polymerization of about 100) was added slowly thereto and the mixture was stirred until substantially homogeneous mixture was obtained. Then, the temperature was elevated to 1 60"C and the reaction was continued et that temperature for 14 h to obtain a light yellow, transparent polymer.
5 parts of this polymer were dissolved in 95 parts of acetone. The solution was added dropwise slowly to a large excess of a solvent mixture of diethyl ether and benzene in a volume ratio of 50/50. A polymer thus precipitated was fractionated and reprecipitated from the mixture of diethyl ether and benzene three times to obtain a graft polymer.
The molecular weight of the graft polymer was determined according to gel permeation chromatography with a high-performance liquid chromatograph LC-SA (a product of Shimadzu Seisakusho Ltd.) using a column of Shodexs PAK A-80M (a product of Showa Denko K.K., Ltd.) and a differential refractometer
ERC-7510 (a product of Eruma Kogaku K.K.).1 me/min of tetrahydrofu ran was used as the eluent and the column temperature was 40"C. The number-average molecular weight was 3.2 x 104 and the weight-average molecular weight was 15.7 x 104 (against a polystyrene standard).The results of elementary analysis were as follows:
carbon: 53.93 % hydrogen: 6.92 % Figure 1 is a 1H-NMR spectral chart of the fractionated graft polymer obtained with a nuclear magnetic resonance spectrometer MH-100 of Nihon Denshi Co., Ltd. (100 MH2, 60"C) using deuterated dimethyl sulfoxide (CD3-SOCD3) as the solvent.
Among the protons in a polyester segment
formed by the ring-opening polymerization of e-caprolactone (the numerals belowthe respective protons refer to the positions of the protons), the signal of the methylene proton ) was observed at 3.9 to 4.2 ppm, that of methylene proton 1 was observed at 2.1 to 2.5 and that of methylene protons ) to (E) was observed at 1.3 to 1.8 ppm. The signal of the methyl proton of the acetyl group of cellulose acetate used was observed at 1.8 to 2.1 ppm and the broad signal of the proton in the anhydroglucose unit was observed at 2.9 to 5.6 ppm (the signal at 2.5 to 2.6 ppm was assignable to the methyl proton of dimethyl sulfoxide contained in the solvent).
Figure 2 is a 73C-NMR spectral chart of the fractionated graft polymer obtained with a nuclear magnetic resonance spectrometerJNM GX-270 of Nihon Denshi Co., Ltd. (67.8MHz, 80"C) using pyridine-d5f (C5D5N) as the solvent.
Said graft polymer has the following structure in its molecule:
wherein at least one of R1, R2 and Rg represents
(lox12) (13) (14) (15) (16) (21I22) (23) (24) (25) (26) at least one of the balance of R1, R2 and F3 represents
H, and the numerals in the parentheses below the carbon atoms refer to the respective positions of the carbon atoms. More particularly, (1) to (8) refer to carbon atoms of the cellulose acetate itself, (11) to (16) refer to carbon atoms of the graft chain segment excluding the caprolactone monomer unit at the graft chain terminal and (21) to (26) refer to carbon atoms of the segment of the caprolactone monomer unit at the graft chain terminal.
Therefore, the signals on the 13C-NMR spectral chart in Figure 2 may be summarized as shown in the following Table 1.
TABLE 1
Position of carbon Chemical shift (ppm) (1) 101-106 (2) (3) l 72 ~ 83 (4) (5) (6) 62.5 -- 64 (7) 169-171 (8) 2022 (11) 173.3 (12) 34.3 (13) 25 (14) 28.8 (15) 25.9 (16) 64.3 (21) 173.5 (22) 34.6 (23) 25.4 (24) 26.2 (25) 33.3 (26) 62 In Figure 2, a signal at 62.0 ppm is assigned to carbon atom (26) of the methylene group adjacent to the primary hydroxyl group at the terminal of the graft chain. No signal of the carbon atom of the carboxyl group
at the terminal of the graft chain in the graft polymer at a chemical shift of 174 to 176 ppm was observed in the chart of Figure 2. It maybe concluded, therefore, that the graft chain terminal of the graft polymer comprised only the primary hydroxyl group.
In the 13C-NMR spectrum of cellulose acetate used in the production of the graft polymer, a signal assigned to carbon atom (6) bonded with the hydroxyl group was observed at 60 60 62 ppm. On the other hand, no signal was observed at 60 to 62 ppm in the spectrum of said graft polymer. It may be concluded, accordingly, that the carbon atom (6) of the resulting graft polymer is bonded with the acetyí group or the graft chain.
Signals of carbon atom (11) of the graft polymer are observed at 101 to 106 ppm. Among them, a signal at 101 to 102 ppm is assigned to the carbon atom (1) observed when carbon atom (2) is not bonded with the hydroxyl group and that at 104 to 106 ppm is assigned to the carbon atom (1) observed when carbon atom (2) is bonded with the hydroxyl group. In the carbon atom (1), the proportion of the carbon atom to which the signal at 101 to 102 ppm is assigned is higher in the graft polymer than in the cellulose acetate used for the production of the graft polymer.
These facts suggest that the hydroxyl groups remaining in the cellulose acetate used in the graft polymer are bonded with the graft chain composed of e-caprolactone.
From the ratio of the intensity of the signals of carbon atoms (21) to (26) to that of carbon atoms (11) to (16) in the terminal E-caprolactone monomer unit and the non-terminal E-caprolactone monomer units in the graft chain of the graft polymer, it was found that the graft chain of the graft polymer was composed of 4 to 5 e-caprolactone monomer units as shown below:
The infrared absorption spectrum of the fractionated graft polymer was determined by the potassium bromide tablet method (device: A-3 of Nihon Bunko Co., Ltd.). Figure 3 is a chart of the results.In Figure 3, an absorption due to an O-H stretching vibration of the hydroxyl group is observed at about 3300 to 3600 cm~', an absorption due to a C-H stretching vibration of the methylene group is observed at about 2800 to 3000 cm~1 and that due to a C=O stretching vibration of the ester group is observed at about 1720 to 1740 cm.
Further, an absorption due to a C-O stretching vibration of the saturated primary alcoholic hydroxyl group is observed at around 1050 cam~'.
The fractionated graft polymer was subjected to pyrolysis gas chromatography [pyrolysis device: a Curie point pyrolyzer JHP 2 (a product of Nihon Bunseki Kogyo Co.), pyrolysis temp.: 590"C; pyrolysis time: 3 sec; gaschromatograph: a gaschromatographJGC-20 K(a product of Nihon Denshi Co.); column: PEG 20 M 10 %/Chromosorb W-AW (stainless column 2 m); column temperature: 70 to 230OC (elevation rate: 8DC/min); carrier gas: 60 me/min helium gas; detector FID]. As shown in Figure 4, a peak due to the polyester segment composed of e-caprnlactone was observed (development time: 27 to 28 min).A peak observed after a development time of 15 to 16 min was due to cellulose acetate.
The acid value of the fractionated graft polymer was measured to reveal that it was less than 0.1 (KOH mglg). Thus, it is reasonable to consider that the terminal group of the polyester segment composed of caprnlactone was not the carboxyl group but the hydroxyl group. This fact coincided with the results of the above-mentioned 13C-NMR spectroscopy. From the results of the elementary analysis of the graft polymer, it was found that one glucose ring of the cellulose acetate used in this polymer is bonded with 1.24 (on average) graft chains composed of e-caprolactone. Thus, it may be concluded from the results of the elementary analysis and 13C-NMR spectroscopy that the graft polymer is composed of the units of formulas (I) and (II) in a ratio of 24.8 to 31/75.2 to 69.
Claims (4)
1. A graft polymer of cellulose in which all or some of the hydrogen atoms of the hydroxy groups of the cellulose have been substituted by a graft chain group of the formula (lli):
wherein mis an integer of at least 1,
and when only some of the said hydrogen atoms are so substituted at least one of the balance has been substituted by a group of the formula livy:
wherein n is an integer of at least 1.
2. A graft polymer of cellulose as claimed in claim 1, in which said polymer has a number of units of the formula (I):
wherein at least one of R1, R2 and F3 represents
m being an integer of at least 1, at least one of any balance of F1, R2 and F3 represents
wherein n is an integer of at least 1 and the balance if any, of F1, R2 and F3 represent H.
3. A graft polymer of cellulose as claimed in claim 2, in which said polymer further has a number of units oftheformula (II):
wherein at least one of R4 and F5 and Fe represents
wherein p is an integer of at least 1 and any balance of R4, R5 and F6 represents H.
4. A graft polymer of cellulose substantially as hereinbefore described with reference to the accompanying Examples and drawings.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59069104A JPH0647601B2 (en) | 1984-04-09 | 1984-04-09 | Novel graft polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8508466D0 GB8508466D0 (en) | 1985-05-09 |
| GB2158081A true GB2158081A (en) | 1985-11-06 |
Family
ID=13392982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08508466A Withdrawn GB2158081A (en) | 1984-04-09 | 1985-04-01 | Graft polymer of cellulose and caprolactone |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH0647601B2 (en) |
| DE (1) | DE3512079C2 (en) |
| GB (1) | GB2158081A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5100435A (en) * | 1990-12-04 | 1992-03-31 | Kimberly-Clark Corporation | Meltblown nonwoven webs made from epoxy/pcl blends |
| US5247013A (en) * | 1989-01-27 | 1993-09-21 | Mitsui Toatsu Chemicals, Inc. | Biocompatible polyester and production thereof |
| EP0584677A1 (en) * | 1992-08-26 | 1994-03-02 | Wolff Walsrode Aktiengesellschaft | Biologically dégradable thermoplastic cellulose esters and process for producing the same |
| EP0639600A3 (en) * | 1993-08-20 | 1995-05-17 | Nippon Paint Co Ltd | Composition of biodegradable resin and anti-soil paint. |
| US5698612A (en) * | 1995-12-22 | 1997-12-16 | Bayer Akteingesellschaft | Thermoplastically workable, biodegradable moulding compositions |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69030786T2 (en) * | 1989-01-27 | 1998-02-19 | Mitsui Toatsu Chemicals | METHOD FOR PRODUCING A BIOCompatible POLYESTER |
| WO1999023118A1 (en) * | 1997-11-05 | 1999-05-14 | Bio-Tec Biologische Naturverpackungen Gmbh & Co.Kg | The reaction of a polyhydroxy polymer or a derivative thereof with a lactone |
| JP2001181302A (en) * | 1999-12-24 | 2001-07-03 | Daicel Chem Ind Ltd | Method for producing cyclic ester-modified cellulose derivative |
| JP5219352B2 (en) * | 2006-02-24 | 2013-06-26 | 株式会社ダイセル | Modified glucan derivative and optical molded article |
| KR20080096600A (en) * | 2006-02-24 | 2008-10-30 | 다이셀 가가꾸 고교 가부시끼가이샤 | Modified Glucan Derivatives and Molded Forms thereof |
| TW200745171A (en) * | 2006-05-09 | 2007-12-16 | Daicel Chem | Hydroxyl acid modified glucan derivative and moldings thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58225101A (en) * | 1982-06-22 | 1983-12-27 | Daicel Chem Ind Ltd | Cellulose ester derivative and its preparation |
| CA1212618A (en) * | 1982-10-07 | 1986-10-14 | Roderick J. Macdonald | Flare stack ignitor |
| JPS60188401A (en) * | 1984-03-09 | 1985-09-25 | Daicel Chem Ind Ltd | Fatty acid cellulose ester-thermoplastic molding material |
-
1984
- 1984-04-09 JP JP59069104A patent/JPH0647601B2/en not_active Expired - Fee Related
-
1985
- 1985-04-01 GB GB08508466A patent/GB2158081A/en not_active Withdrawn
- 1985-04-02 DE DE19853512079 patent/DE3512079C2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5247013A (en) * | 1989-01-27 | 1993-09-21 | Mitsui Toatsu Chemicals, Inc. | Biocompatible polyester and production thereof |
| US5100435A (en) * | 1990-12-04 | 1992-03-31 | Kimberly-Clark Corporation | Meltblown nonwoven webs made from epoxy/pcl blends |
| EP0584677A1 (en) * | 1992-08-26 | 1994-03-02 | Wolff Walsrode Aktiengesellschaft | Biologically dégradable thermoplastic cellulose esters and process for producing the same |
| EP0639600A3 (en) * | 1993-08-20 | 1995-05-17 | Nippon Paint Co Ltd | Composition of biodegradable resin and anti-soil paint. |
| US5698612A (en) * | 1995-12-22 | 1997-12-16 | Bayer Akteingesellschaft | Thermoplastically workable, biodegradable moulding compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60212422A (en) | 1985-10-24 |
| DE3512079A1 (en) | 1985-10-17 |
| DE3512079C2 (en) | 1993-10-21 |
| GB8508466D0 (en) | 1985-05-09 |
| JPH0647601B2 (en) | 1994-06-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |