CN102199221A - Cellulose derivative and manufacture method for cellulose derivative - Google Patents
Cellulose derivative and manufacture method for cellulose derivative Download PDFInfo
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- CN102199221A CN102199221A CN2011100740252A CN201110074025A CN102199221A CN 102199221 A CN102199221 A CN 102199221A CN 2011100740252 A CN2011100740252 A CN 2011100740252A CN 201110074025 A CN201110074025 A CN 201110074025A CN 102199221 A CN102199221 A CN 102199221A
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Abstract
The invention is advantaged by simply and easily synthetizing a cellulose derivative provided with good thermoplasticity and heat resistance. The invention aims at providing a manufacture method for a cellulose derivative, the cellulose derivative is provided with (A) an alkyl group, (B) a group comprising acyl group-CO-RBI and alkyleneoxy-RB2-O- (RB1 represents the alkyl group, RB2 represents an alkylene group) and (C) acyl group-CO-RC (RC represents the alkyl group) as substituent groups, and satisfies the following formula, DS (A)=0-2.2, MS (B)=0.1-1.9, DS (C)=0.5-1.7, In the above formula, DS (A) and MS (B) respectively represent substitution degree of substituent groups (A) and (C), and MS (B) represents mole substitution degree of the substituent group (B). The manufacture method is provided with the following steps of: (1) making the cellulose and a glucose residue relative to the above cellulose be in an alkali reaction with at least 2.0 mole equivalent to obtain alkalic cellulose; (2) making the alkalic cellulose and each glucose residue relative to the above cellulose be in a halogenated hydrocarbon with at least 2.0 mole equivalent and an alkylene oxide reaction with at least 0.1 mole equivalent to obtain cellulose ether; (3) and performing esterification of the cellulose ether.
Description
Technical field
The present invention relates to the manufacture method of plain derivative of a kind of tencel and derivatived cellulose.
Background technology
In the member that constitutes electric/electronic devices such as duplicating machine, printer, consider from aspects such as the desired characteristic of member, functions, use various materials.For example; in the member of the effect of the driving machine of taking in electric/electronic device etc. and this driving machine of performance protection in (basket), (patent documentations 1) such as general more use PC (polycarbonate) resin, ABS (acrylonitrile-butadiene-styrene (ABS)) resin, PC/ABS.These resins are synthetic by the compound that with the oil is raw material.
Fossil resources such as oil are main component with buried subterranean carbon all the year round.After being the goods burning of raw material with this fossil resource, Carbon emission is in atmosphere, and at this moment, non-existent carbon sharply gives off with the form of carbonic acid gas in the atmosphere originally, becomes a reason that causes global warming.Therefore, though PC resin, ABS resin etc. have excellent characteristic as electric/electronic device with the material of member, because of its with fossil resource as raw material, consider not preferred from the viewpoint that prevents global warming.
With respect to this, plant is that raw material generates by photosynthesis with Atmospheric Carbon Dioxide and water.Therefore, even the resin that is obtained by plant burning back generates carbonic acid gas, described carbonic acid gas also is equivalent to the carbonic acid gas that just has in the atmosphere originally, therefore, can think the not increase and decrease of Atmospheric Carbon Dioxide total amount.Consider that from this respect the resin that derives from plant is called as so-called " neutral carbon " material.Now, replacement derives from the resin of oil and uses the resin that derives from plant to become the task of top priority that prevents global warming.
For example, a kind of method (patent documentation 2) that reduces the oil usage quantity in the PC resin in its part material by the resource of using starch etc. to derive from plant has been proposed.But in the method, reduction is insufficient, requires the further resin of exploitation oil usage quantity minimizing.
Patent documentation 1: Japanese kokai publication sho 56-55425 communique
Patent documentation 2: TOHKEMY 2008-24919 communique
Summary of the invention
The inventor etc. are conceived to use Mierocrystalline cellulose as the neutral carbon resin.But Mierocrystalline cellulose does not generally have thermoplasticity, therefore, is difficult to by shapings such as heating, is not suitable for the processing that is shaped.In addition, promptly allow to give thermoplasticity, also have the problem of poor heat resistance.
In addition, be raw material with the Mierocrystalline cellulose, carry out building-up reactions and when being processed into new derivatived cellulose, need change the reaction conditions of each building-up reactions significantly.This is because Mierocrystalline cellulose is acknowledged as the resin that is difficult to react usually.Therefore, during through a plurality of operation, each operation all needs to take out the fibrin reaction thing, then, changes container, carries out reaction process in different reaction systems.For example, Mierocrystalline cellulose etherificate and esterification are carried out under alkalescence, acidic conditions respectively, and this is more common as industrial making method.Need then different reaction system (for example, being tied to the reaction system of acid solvent), proceed reaction carrying out a temporary transient reactant that takes out in reaction system back from the reaction of basic solvent.Therefore, cellulosic processing expends time in, and equipment is also relatively large, is unfavorable for industrial production.
The objective of the invention is to, a kind of manufacture method that has good thermoplastic and thermotolerance and make the derivatived cellulose of the processing that is suitable for being shaped easily is provided.
Above-mentioned problem can be reached by following method.
＜1〉manufacture method of a kind of derivatived cellulose, described derivatived cellulose have (A) alkyl, (B) comprises acyl group-CO-R
B1And alkylene oxide group-R
B2Group (the R of-O-
B1The expression alkyl, R
B2The expression alkylidene group) and (C) acyl group-CO-R
C(R
CThe expression alkyl), and satisfy following formula as substituting group,
DS(A)＝0～2.2、MS(B)＝0.1～1.9、DS(C)＝0.5～1.7
[in the above-mentioned formula, DS (A) and DS (C) represent the substitution value of substituting group (A), (C) respectively, the molar substitution of MS (B) expression substituting group (B).]
It is characterized in that possessing following operation:
(1) makes Mierocrystalline cellulose and be the alkali reaction of at least 2.0 molar equivalents, obtain first operation of alkali cellulose with respect to above-mentioned cellulosic each glucosyl residue;
(2) make described alkali cellulose and be the halon of at least 2.0 molar equivalents with respect to above-mentioned cellulosic each glucosyl residue and be the alkylene oxide reaction of at least 0.1 molar equivalent, obtain second operation of ether of cellulose;
(3) described ether of cellulose is carried out the 3rd operation of esterification.
＜2〉as＜1〉manufacture method of described derivatived cellulose, it is characterized in that, after above-mentioned second operation, from reaction vessel, do not take out ether of cellulose and directly carry out the 3rd operation.
＜3〉as＜1〉or＜2〉described derivatived cellulose manufacture method, it is characterized in that the alkali that uses in above-mentioned first operation is highly basic.
＜4〉as＜1〉manufacture method of described derivatived cellulose, it is characterized in that DS (A)=1.2～2.2, MS (B)=0.1～1.0, DS (C)=0.5～1.7.
＜5〉as＜1〉manufacture method of described derivatived cellulose, it is characterized in that DS (A)=1.2～2.2, MS (B)=0.1～0.6, DS (C)=0.7～1.7.
＜6〉as＜1〉manufacture method of described derivatived cellulose, it is characterized in that DS (A)=1.2～1.6, MS (B)=0.1～0.3, DS (C)=1.0～1.7.
＜7〉as＜1 〉～＜6 in the manufacture method of each described derivatived cellulose, it is characterized in that described (B) R
B2Carbonatoms be 2～4.
＜8〉as＜1 〉～＜7 in the manufacture method of each described derivatived cellulose, it is characterized in that the carbonatoms of described (A) alkyl is 1～3.
＜9〉as＜1 〉～＜8 in the manufacture method of each described derivatived cellulose, it is characterized in that described (C) R
CCarbonatoms be 1～4.
The manufacture method of derivatived cellulose of the present invention can be synthesized easily and had good matrix band outward appearance and inflexible derivatived cellulose.
Embodiment
Below, to the manufacture method of derivatived cellulose of the present invention and utilize the derivatived cellulose of this manufacture method manufacturing to be elaborated.
The manufacture method of＜derivatived cellulose 〉
The manufacture method of derivatived cellulose of the present invention comprises makes Mierocrystalline cellulose and first operation that obtains alkali cellulose with respect to above-mentioned cellulosic each glucosyl residue at least for the alkali reaction of 2.0 molar equivalents.Comprise by make the alkali cellulose that obtains by first operation with respect to above-mentioned cellulosic each glucosyl residue for the halon of at least 2.0 molar equivalents and obtain second operation of ether of cellulose at least for the alkylene oxide reaction of 0.1 molar equivalent.Via first operation that alkalizes with utilize excessive halon and alkylene oxide carries out second operation of etherification reaction, can from reaction vessel, not take out reaction system and directly carry out esterification after it.Among the present invention,, can from reaction vessel, not take out reaction system ground and make derivatived cellulose with good thermotolerance etc. by making cellulosic reaction activation.
[first operation]
First operation of the present invention is by making Mierocrystalline cellulose and the operation that obtains alkali cellulose with respect to above-mentioned cellulosic each glucosyl residue at least for the alkali reaction of 2.0 molar equivalents.
Cellulosic manufacture method of the present invention is raw material with the Mierocrystalline cellulose, does not take out Mierocrystalline cellulose and can carry out etherificate and esterification from reaction vessel, therefore can make derivatived cellulose of the present invention well.Unqualified as cellulosic raw material, for example can enumerate: cotton, cotton linter (for example velveteen), paper pulp (for example wood pulp) etc.
In with the cellulosic operation of derivatived cellulose alkalization alkalize of the present invention, use alkali.Alkali can use known weak base, and alkaline any, but preferably use highly basic.
As highly basic, can use for example alkali hydroxide.As alkali hydroxide, can use sodium hydroxide, potassium hydroxide, lithium hydroxide etc., but preferred sodium hydroxide.In addition, alkali hydroxide uses with the form of the aqueous solution, and its concentration is preferably more than the 10 weight %, more preferably 20～80 weight %.
Addition as the alkali that alkalizes adds excessive alkali.This is for after etherificate described later, does not take out from reaction vessel and directly carries out esterification.As the addition of alkali of alkalization, need add alkali more than 2.0 molar equivalents with respect to cellulosic each glucosyl residue of reaction.Amount as the alkali that adds more specifically, is preferably 2.0～10.0 molar equivalents, and more preferably 3.0～10.0 molar equivalents most preferably are 6.0～10.0 molar equivalents.
The temperature of reaction of first operation is considered from the viscosity of cellulosic reaction soln and the viewpoint of speed of response, is preferably 5～70 ℃, but considers more preferably 20～50 ℃ from reactive viewpoint.
The reaction times of first operation is preferably 0.5～2 hour, in order to suppress the generation of by product, is preferably 0.5～1 hour.
First operation of the present invention can only be carried out once in manufacture method of the present invention, also can carry out repeatedly.When repeatedly handling, after the first all operations finishes, can obtain the target alkali cellulose and get final product.
As the solvent of first operation of the present invention, unqualified, preferably water.First operation and second operation are preferably carried out with the reaction system of the two-phase system of the solvent that forms second operation described later and water/organic solvent.
As pressure of the present invention, unqualified, be preferably airtight or overheated and degree that rise naturally, particularly, preferred 0.1～5.0MPa, more preferably 0.1～3.5MPa, further preferred 0.1～2.5MPa.
The alkali cellulose that is obtained by first operation is the dissociated state of cellulosic hydroxyl (for example, when using sodium hydroxide, being the sodium cellulosate alkoxide).
[second operation]
Second operation be meant by make the alkali cellulose that obtains by first operation with respect to above-mentioned cellulosic each glucosyl residue for the halon of at least 2.0 molar equivalents and obtain the operation of ether of cellulose at least for the alkylene oxide reaction of 0.1 molar equivalent.
In the operation of the alkali cellulose etherificate that in first operation, obtains, use halon and alkylene oxide.After first operation, carry out second operation, also can after first operation, suit to add other operation.As other operation, for example can be refrigerating work procedure, also can be the substituent reaction that imports other.
For with the Mierocrystalline cellulose etherificate, can use halon.As concrete halon, preferred C
nH
2n+1Halon or its derivative shown in-the X (X is halogen atoms such as fluorine, chlorine, bromine, iodine).Particularly, n is preferred 1～4, and more preferably 1～3, most preferably 1～2.
As the addition of the halon that uses in second operation, use the halon excessive with respect to raw cellulose.This is directly to carry out esterification in order not take out from reaction vessel after etherificate described later.As the addition of halon, need add halon more than 2.0 molar equivalents with respect to each glucosyl residue of reaction.As the amount of the halon that adds, more specifically, preferred 2.0～10 molar equivalents, more preferably 3.0～10 molar equivalents, most preferably 6.0～9.0 molar equivalents.
For with the Mierocrystalline cellulose etherificate, use alkylene oxide.The carbonatoms of alkylene oxide for example is 1～7, more specifically, is preferably 1～5, more preferably 1～4.As the example of alkylene oxide, use oxyethane, propylene oxide, butylene oxide ring etc.
As the addition of the alkylene oxide that uses in second operation, need add alkylene oxide more than 0.1 molar equivalent with respect to each glucosyl residue of reaction.Amount as the alkylene oxide that adds more specifically, is preferably 0.1～8.0 molar equivalent, and more preferably 0.2～5.0 molar equivalent most preferably is 0.3～3.0 molar equivalent.
The temperature of reaction of second operation is preferably 40～130 ℃, more preferably 50～120 ℃.Be more than 40 ℃ the time, the velocity of diffusion of etherifying agent accelerates, and considers and preferred from reactive viewpoint.Be below 130 ℃ the time, the viewpoint of pressing in the reaction system considers, side reaction is suppressed and preferred.
The reaction times of second operation to be to be preferably 4～10 hours total time, more preferably 6～8 hours.The reaction times of the 3rd operation is preferably 3～12 hours, more preferably 4～8 hours.
Second operation of the present invention can only be carried out once in manufacture method of the present invention, also can carry out repeatedly.When repeatedly handling, after the second all operations finishes, can obtain the plain ether of target fibers and get final product.
The solvent of second operation can use aromatic hydrocarbon solvents such as benzene or toluene.The viewpoint of the vapour pressure of the halon during from the reduction etherificate is considered, especially preferably uses toluene.The solvent of second operation can be a kind or 2 kinds, but is preferably formed two-phase system.
The hydrogen atom that the compound that obtains in second operation for example can obtain the contained hydroxyl of Mierocrystalline cellulose is replaced by the alkyl of carbonatoms 1～4 and the ether of cellulose that obtains or hydroxy alkyl cellulose etc.
Particularly, can enumerate: methylcellulose gum, ethyl cellulose, propyl cellulose, butyl cellulose, allylcellulose, Natvosol, Walocel MT 20.000PV etc.
The unreacted alkylene oxide of second operation also can exist with the form of polyvalent alcohol.
[the 3rd operation]
The 3rd operation is the operation of instigating the ether of cellulose that obtained by second operation to carry out esterification.
The ether of cellulose that obtains in second operation does not take out from reaction vessel and directly carries out the esterification of the 3rd operation.In esterification step, can use alkali and acid anhydrides.Can after second operation, carry out the 3rd operation, also can after second operation, suitably add other operation.
As the alkali that is used for the Mierocrystalline cellulose esterification, for example can use: amines such as pyridine, lutidine, dimethyl aminopyridine, triethylamine, diethyl butylamine, diazabicyclo undecylene, alkaline carbonates such as salt of wormwood, triethylamine etc.Wherein, amines such as preferred pyridine, dimethyl aminopyridine, triethylamine.
As the addition that is used for the alkali of Mierocrystalline cellulose esterification, be 2.0～10.0 molar equivalents preferably with respect to the ether of cellulose that obtains in second operation.
As acid anhydrides, the carboxylic acid anhydride that for example can use the carboxylic acid by carbonatoms 4～18 to form.As this carboxylic acid anhydride, for example can enumerate: acetic anhydride, propionic anhydride, butyryl oxide, valeric anhydride, caproic anhydride, heptylic anhydride, caprylic anhydride, 2 ethyl hexanoic acid acid anhydride, nonanoic anhydride, capric anhydride, lauric anhydride, myristic anhydride, palmitic anhydride, stearic anhydride, propionic anhydride etc.Preferred especially acetic anhydride, butyryl oxide, propionic anhydride etc.
As the addition of acid anhydrides, be preferably 2.0～10.0 molar equivalents.
The temperature of reaction of the 3rd operation is preferably 20～70 ℃, more preferably 30～60 ℃.Be more than 20 ℃ the time, the velocity of diffusion of esterifying agent accelerates, and considers and preferred from reactive viewpoint.Be below 70 ℃ the time, side reaction is suppressed and preferred.
The 3rd operation of the present invention can only be carried out once in manufacture method of the present invention, also can carry out repeatedly.When repeatedly handling, after the 3rd all operations finished, the derivatived cellulose that can obtain target got final product.
[derivatived cellulose]
The derivatived cellulose that utilizes manufacture method of the present invention to obtain has
A) alkyl,
B) comprise acyl group-CO-R
B1And alkylene oxide group-R
B2Group (the R of-O-
BThe expression alkyl),
C) acyl group :-CO-R
C(R
CThe expression alkyl).
That is the Mierocrystalline cellulose { (C of derivatived cellulose of the present invention,
6H
10O
5)
nContained hydroxyl hydrogen atom to small part by above-mentioned A) alkyl, above-mentioned B) comprise acyl group (CO-R
B) and alkylene oxide group (R
B2-O-) group and above-mentioned C) acyl group (CO-R
C) replace.
More specifically, derivatived cellulose of the present invention has the repeating unit shown in the following general formula (2).
General formula (2)
In the above-mentioned formula, R
2, R
3And R
6Represent hydrogen atom, A respectively independently) alkyl, B) comprise acyl group (CO-R
B) and alkylene oxide group (R
B2-O-) group and C) acyl group (CO-R
C).R
BAnd R
CThe expression alkyl.Wherein, R
2, R
3And R
6At least a portion represent alkyl, and R
2, R
3And R
6At least a portion represent to comprise acyl group (CO-R
B) and alkylene oxide group (R
B2-O-) group, and R
2, R
3And R
6At least a portion represent acyl group (CO-R
C).These organic groups have to replace or do not have replacement all can.
For derivatived cellulose of the present invention, at least a portion of the hydroxyl by making β-glucose ring is as mentioned above utilized A) alkyl, B) comprise acyl group (CO-R
B) and alkylene oxide group (R
B2-O-) group and C) acyl group (CO-R
C) carry out etherificate and esterification, can show thermoplasticity, applicable to the processing that is shaped.
In addition, this derivatived cellulose also can show good intensity and thermotolerance as molding, and is particularly useful as heat-formable material.And then therefore Mierocrystalline cellulose, is neutral carbon for deriving from the composition of plant fully, can reduce the load to environment significantly.
Need to prove, said among the present invention " Mierocrystalline cellulose " be meant into a plurality of glucose via β-1, the macromolecular compound of 4-glycosidic link bonding, and do not have replacement with the hydroxyl of 2,3,6 carbon atom bondings of cellulosic glucose ring.In addition, " hydroxyl that Mierocrystalline cellulose is contained " is meant the hydroxyl with 2,3,6 carbon atom bondings of cellulosic glucose ring.
Above-mentioned derivatived cellulose comprises above-mentioned A in arbitrary part of its integral body) alkyl, B) contain acyl group (CO-R
B) and alkylene oxide group (R
B2-O-) group and C) acyl group (CO-R
C) get final product, can constitute by identical repeating unit, also can constitute by multiple repeating unit.In addition, above-mentioned derivatived cellulose needn't contain above-mentioned A in a repeating unit)～C) substituent all.
As mode more specifically, when for example the alkylene oxide group that has of derivatived cellulose is 2 kinds, can enumerate following mode.
(1) by R
2, R
3And R
6A part by A) repeating unit that replaces of alkyl,
And R
2, R
3And R
6A part by B) comprise acyl group (CO-R
B) and alkylene oxide group (R
B2The repeating unit that-O-) group replaces,
And R
2, R
3And R
6A part by C) acyl group (CO-R
C) derivatived cellulose that constitutes of the repeating unit that replaces.
(2) by the R of a repeating unit
2, R
3And R
6Any by A) alkyl,
B) comprise acyl group (CO-R
B) and alkylene oxide group (R
B2-O-) group and
C) acyl group (CO-R
C) replace (that is, in a repeating unit, having above-mentioned A)～C) substituent all) the derivatived cellulose that constitutes of repeating unit of the same race.
(3) the position of substitution or the substituent diverse repeating unit derivatived cellulose of bonding at random.
In addition, on the part of derivatived cellulose, also can comprise the repeating unit that do not have to replace (that is, and in above-mentioned general formula (1), R
2, R
3And R
6All are repeating units of hydrogen atom.)
As above-mentioned A) alkyl, can be in aliphatic group and the aromatic group any.During for aliphatic group, in straight chain, side chain and the ring-type any can be, also unsaturated link(age) can be contained.As aliphatic group, for example can enumerate: alkyl, cycloalkyl, thiazolinyl, alkynyl etc.As aromatic group, for example can enumerate: phenyl, naphthyl, phenanthryl, anthryl etc.
As above-mentioned A) alkyl, preferred aliphat group, more preferably alkyl, the alkyl (low alkyl group) of further preferred carbonatoms 1～4.Particularly, preferable methyl, ethyl, propyl group, more preferably methyl, ethyl, most preferable.
At above-mentioned B) acyl group (CO-R
B1) in, R
B1The expression alkyl.R
B1Can be in aliphatic group and the aromatic group any.During for aliphatic group, can be in straight chain, side chain and the ring-type any, also can have unsaturated link(age).As aliphatic group and aromatic group, can enumerate above-mentioned group.
As R
B1, particularly be alkyl or aryl.As alkyl or aryl, particularly be the alkyl or the aryl of carbonatoms 1～12, be preferably the alkyl of carbonatoms 1～12, the alkyl of carbonatoms 2～4 more preferably most preferably is the alkyl (that is propyl group) of carbonatoms 3.
Particularly, as R
B1, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, hexyl, heptyl, 2-ethylhexyl, the tertiary butyl, different heptyl etc.R
BBe preferably ethyl, propyl group, most preferably be propyl group.
Above-mentioned as B) comprise acyl group (CO-R
B1) and alkylene oxide group (R
B2-O-) group is preferably the group that comprises the structure shown in the following general formula (1).
General formula (1)
In the formula, R
B2The expression alkylidene group can be with alkylene oxide group (R
B2-O-) comprise a plurality ofly, also can only comprise one.X represents 1～10 integer, preferred x=1～5, more preferably x=1～3.
Above-mentioned B) group more specifically can be with following general formula (1 ') or general formula (1 ") expression.In the formula, n represents 2～4 integer independently, preferably represents 2～3 integer.M represents 1～4 integer independently, preferably represents 1～3 integer.
General formula (1 ')
[in the formula, x represents 1～5 integer, preferably represents 1～3 integer.]
General formula (1 ")
[in the formula, x represents 1～5 integer, preferably represents 1～3 integer.]
In the formula, R
B1With above-mentioned equivalent in meaning, preferred range is also identical.The upper limit of n is not particularly limited, and according to the variations such as import volume of alkylene oxide group, for example is about 10.
In derivatived cellulose of the present invention, can mix and contain the above-mentioned B that only comprises an alkylene oxide group) group (n is 1 group in above-mentioned general formula (1 ')) and comprise the above-mentioned B of 2 above alkylene oxide group) group (n is the group more than 2 in above-mentioned general formula (1 ')).
Above-mentioned as C) acyl group (CO-R
C) in, R
CThe expression alkyl.As R
CShown alkyl can use and above-mentioned R
B1The group that cited group is identical.R
CPreferred range also with above-mentioned R
B1Identical.
Above-mentioned as A) alkyl, above-mentioned R
B1And above-mentioned R
CShown alkyl and alkylidene group can further have substituting group, also can unsubstituted, but preferred unsubstituted.
R particularly
B1And R
CWhen further having substituting group, preferably do not comprise and give water-soluble such substituting group for example sulfonic group, carboxyl etc.By not comprising these groups, can obtain water-insoluble cellulose derivatives and reach by its shaped material that forms.
Above-mentioned as A) alkyl, R
B1, R
C, and alkylidene group when further having substituting group, as substituting group further, for example can enumerate: halogen atom (for example fluorine atom, chlorine atom, bromine atoms, iodine atom), hydroxyl, alkoxyl group (carbonatoms of moieties is preferably 1～5), thiazolinyl etc.Need to prove when above-mentioned R is a group beyond the alkyl, also can have alkyl (preferred carbonatoms 1～5) as substituting group.
In addition, when derivatived cellulose of the present invention is used as shaped material, be preferably water-insoluble, therefore, preferably do not have water-soluble substituting groups such as carboxyl in fact.Derivatived cellulose can not have water-insoluble by not comprising carboxyl in fact, thereby is more suitable in the processing that is shaped.
Herein " not having carboxyl in fact " not only comprises the situation that derivatived cellulose of the present invention does not have carboxyl fully, also comprises derivatived cellulose of the present invention has the carboxyl of trace in water-fast scope situation.For example, in Mierocrystalline cellulose, comprise carboxyl sometimes, use it sometimes and imported above-mentioned A as raw material)～C) substituent derivatived cellulose comprises carboxyl, and these situations all are included in " derivatived cellulose that does not have carboxyl in fact ".
In addition, " water-insoluble " is meant that the solubleness in 25 ℃ 100 mass parts water is below 5 mass parts.
A in the derivatived cellulose) alkyl, B) comprise acyl group (CO-R
B1) and alkylene oxide group (C
nH
2n-O-) group, and C) acyl group (CO-R
C) the position of substitution, and unitary each the substituent number (substitution value) of each β-glucose ring be DS (A)=0～2.2, MS (B)=0.1～1.9, DS (C)=0.5～1.7.
For example, the A) number of the substitution value DS (A) of alkyl (in the repeating unit) alkyl) be preferably 0～2.2 with respect to the A of 2,3 of β-glucose ring and 6 s' hydroxyl, more preferably 1.2～2.2, most preferably be 1.2～1.6.
B) comprise acyl group (CO-R
B) and alkylene oxide group (C
nH
2n-substitution value the DS (B) (in the repeating unit, with respect to the B of 2,3 of the cellulosic structure of β-glucose ring and 6 s' hydroxyl) of group O-) comprises the number of acyl group and inferior ethoxyl) preferred 0＜DS (B).By 0＜DS (B), can reduce the melt initiation temperature degree, therefore, can more easily carry out thermoforming.
C) acyl group (CO-R
C) the number of substitution value DS (C) (in the repeating unit) acyl group with respect to the C of 2,3 of the cellulosic structure of β-glucose ring and 6 s' hydroxyl) be 0.1＜DS (C).Particularly, be preferably 0.5～1.7, more preferably 0.7～1.7, most preferably be 1.0～1.7.
The number of the hydroxyl that the nothing that exists in the derivatived cellulose in addition, replaces also is not particularly limited.The substitution value DSh of hydrogen atom (in the polymerized unit, 2,3 and 6 s' hydroxyl does not have the ratio of replacement) can be in 0～1.5 scope, can be preferably in 0～0.6 scope.By making DSh below 0.6, can improve the flowability of heat-formable material, or the foaming that causes of the suction of the heat-formable material when suppressing to quicken to be shaped because of pyrolysated etc.
In addition, derivatived cellulose of the present invention also can have above-mentioned A) alkyl, B) comprise acyl group (CO-R
B) and alkylene oxide group (C
nH
2n-O-) group, and C) acyl group (CO-R
C) in addition substituting group.As the substituent example that can have, for example can enumerate: hydroxyethyl, hydroxyl ethoxy ethyl, hydroxyl-oxethyl ethoxyethyl group.Therefore, the summation of all substituent each substitution values that derivatived cellulose has is 3, and (DS (A)+DS (B)+DC (C)+DSh) is below 3.
In addition, the alkylene oxide group (C in the group above-mentioned B)
nH
2n-O-) import volume is with molar substitution (MS: expression (Mierocrystalline cellulose association compile, Mierocrystalline cellulose dictionary P142) the substituent importing mole number of each glucosyl residue).Preferred 0＜the MS of molar substitution MS (B) (B) of alkylene oxide group, more preferably 0.1～1.9, more preferably 0.1～1.0, most preferably be 0.1～0.6.
For the molecular weight of derivatived cellulose, number-average molecular weight (Mn) is preferably 5 * 10
3～1000 * 10
3Scope, more preferably 10 * 10
3～800 * 10
3Scope, most preferably 10 * 10
3～500 * 10
3Scope.In addition, weight-average molecular weight (Mw) is preferably 7 * 10
3～10000 * 10
3Scope, more preferably 100 * 10
3～5000 * 10
3Scope, most preferably 500 * 10
3～5000 * 10
3Scope.By making molecular-weight average, can improve plasticity, mechanical strength of molding etc. in this scope.
Molecular weight distribution (MWD) is preferably in 1.1～10.0 scope, more preferably in 2.0～8.0 scope.By making molecular weight distribution, can improve plasticity etc. in this scope.
The mensuration of number-average molecular weight of the present invention (Mn), weight-average molecular weight (Mw) and molecular weight distribution (MWD) can use gel permeation chromatography (GPC) to carry out.Particularly, can be with N-Methyl pyrrolidone as solvent, use polystyrene gel, use by the conversion molecular weight calibration curve that curve obtains in advance that constitutes of standard monodisperse polystyrene and obtain.
The purposes of the derivatived cellulose that obtains among the present invention is not particularly limited, for example, as molding, can enumerate the interior dress of electric/electronic device (household electrical appliances, OA media relevant device, optics with equipment and signal equipment etc.) or adorn member, automobile, mechanical component, residential housing outward with material etc.Wherein, from having good thermotolerance and the less viewpoint of the load of environment being considered that the outer dress part (particularly basket) that can preferably use as for example electric/electronic devices such as duplicating machine, printer, computer, TV uses.
Above-mentioned molding also can contain as required filler, fire retardant, other polymkeric substance, softening agent, stablizer (antioxidant, UV light absorber etc.), releasing agent, antistatic agent, flame retardant, processing aid, Antidrip agent, antiseptic-germicide, mould inhibitor, comprise the various additives such as tinting material of dyestuff or pigment.
[embodiment]
Below, enumerate embodiment and comparative example specifically describes the present invention, but scope of the present invention is not limited to embodiment shown below.
＜synthesis example 1:P-1's is synthetic 〉
In autoclave (withstand voltage nitre industry system, simple type autoclave TEM-D3000M), the paper pulp 100g that weighing is pulverized, aqueous sodium hydroxide solution (sodium hydroxide 148g/ water 150ml, be 6.1 molar equivalents with respect to cellulosic each glucosyl residue) stir 1 hour (first operation) down nitrogen atmosphere, 45 ℃.After placing cooling, be cooled to-40 ℃ with dry ice/methanol bath, and then, add toluene 150ml, methyl chloride 186g (existing is 6 molar equivalents for cellulosic each glucosyl residue), propylene oxide 20g (is 0.6 molar equivalent with respect to cellulosic each glucosyl residue), 60 ℃ stir down 1 hour, stir 6 hours (second operation) down at 90 ℃.After returning to room temperature, remaining gas in the discharge system, and then, add acetic anhydride 300ml, triethylamine 150ml again, stirred 6 hours down at 50 ℃.After returning to room temperature, the limit is stirred the limit fast it is put in the 6L water, obtains brown solid (the 3rd operation) thus.Then, carry out 3 times and clean the operation of the brown solid obtain with 6L hot water, and then, carry out the operation of cleaning with methyl alcohol 2L/ water 6L mixed solvent for 3 times more repeatedly, obtain pale solid.Filter the pale solid that obtains by suction filtration, and under 100 ℃, carry out vacuum-drying in 6 hours, obtain the plain derivative of target fibers (P-1, substitution value, molecular weight are as described in Table 1) (receipts amount 145g) of pale powder.
＜synthesis example 2:P-2's is synthetic 〉
In synthesis example 1, with the temperature of reaction of second operation change to 60 ℃ following 1 hour, 100 ℃ following 6 hours, in addition same as described above, obtain the plain derivative of target fibers (P-2, substitution value, molecular weight are as described in Table 1) (receipts amount 138g) of pale powder.
＜synthesis example 3:P-3's is synthetic 〉
In synthesis example 2, the sodium hydroxide that uses in first operation changed to the methyl chloride that uses in 222g (is 9.1 molar equivalents with respect to cellulosic each glucosyl residue), second operation changes to 278g (is 6.1 molar equivalents with respect to cellulosic each glucosyl residue), propylene oxide changes to 25g (is 0.7 molar equivalent with respect to cellulosic each glucosyl residue), in addition same as described above, the plain derivative of target fibers (P-3, substitution value, molecular weight are as described in Table 1) that obtains pale powder (135g).
＜synthesis example 4:P-4's is synthetic 〉
In synthesis example 1, the methyl chloride that uses in second operation is changed to monochloroethane 235g (is 6 molar equivalents with respect to cellulosic each glucosyl residue), temperature of reaction, and to change to 60 ℃ of following 1 hours, 120 ℃ following 6 hours, in addition same as described above, the plain derivative of target fibers (P-4, substitution value, molecular weight are as described in Table 1) that obtains pale powder (148g).
＜synthesis example 5:P-5's is synthetic 〉
In synthesis example 1, the methyl chloride that uses in second operation is changed to N-PROPYLE BROMIDE 450g (is 6 molar equivalents with respect to cellulosic each glucosyl residue), temperature of reaction, and to change to 60 ℃ of following 1 hours, 100 ℃ following 6 hours, in addition same as described above, the plain derivative of target fibers (P-5, substitution value, molecular weight are as described in Table 1) that obtains the chocolate powder (163g).
＜synthesis example 6:P-6's is synthetic 〉
In synthesis example 4, the acetic anhydride that uses in the 3rd operation is changed to propionic anhydride, in addition same as described above, the plain derivative of target fibers (P-6, substitution value, molecular weight are as described in Table 1) that obtains pale powder is (155g).
＜synthesis example 7:P-7's is synthetic 〉
In synthesis example 3, the methyl chloride that uses in second operation is changed to monochloroethane 355g (is 9 molar equivalents with respect to cellulosic each glucosyl residue), propylene oxide to change to oxybutylene 20g (is 0.5 molar equivalent with respect to cellulosic each glucosyl residue), temperature of reaction to change to 60 ℃ of following 1 hours, 120 ℃ following 6 hours, in addition same as described above, the plain derivative of target fibers (P-7, substitution value, molecular weight are as described in Table 1) that obtains pale powder (128g).
＜synthesis example 8:P-8's is synthetic 〉
In synthesis example 3, the quantitative change that the methyl chloride that uses in second operation is changed to monochloroethane 235g (is 6 molar equivalents with respect to cellulosic each glucosyl residue), propylene oxide is 60g (is 1.7 molar equivalents with respect to cellulosic each glucosyl residue) more, in addition same as described above, the plain derivative of target fibers (P-8, substitution value, molecular weight are as described in Table 1) that obtains pale powder (156g).
The synthesis example 1:H-1's of＜comparative compound is synthetic 〉
In synthesis example 1, the sodium hydroxide that uses in the 1st operation is changed to 40g (is 1.6 molar equivalents with respect to cellulosic each glucosyl residue), the methyl chloride that uses in second operation changes to 45g (is 1.5 molar equivalents with respect to cellulosic each glucosyl residue), propylene oxide changes to 300g (is 8.5 molar equivalents with respect to cellulosic each glucosyl residue), with temperature of reaction change to 60 ℃ following 1 hour, 80 ℃ following 3 hours, 100 ℃ following 3 hours, in addition same as described above, obtain the comparative compound (H-1 of yellow-white amorphous solid, substitution value, molecular weight is as described in Table 1) (230g).
The synthesis example 2:H-2's of＜comparative compound is synthetic 〉
In synthesis example 1, the sodium hydroxide that uses in the 1st operation is changed to 40g (is 1.6 molar equivalents with respect to cellulosic each glucosyl residue), propylene oxide changes to 290g (is 8.2 molar equivalents with respect to cellulosic each glucosyl residue), methyl chloride changes to monochloroethane 60g (is 1.5 molar equivalents with respect to cellulosic each glucosyl residue), with temperature of reaction change to 60 ℃ following 1 hour, 80 ℃ following 3 hours, 120 ℃ following 3 hours, in addition same as described above, obtain the comparative compound (H-2 of beige amorphous solid, substitution value, molecular weight is as described in Table 1) (183g).
The synthesis example 3:H-3's of＜comparative compound is synthetic 〉
In autoclave (withstand voltage nitre industry system, simple type autoclave TEM-D3000M), the paper pulp 100g that weighing is pulverized, aqueous sodium hydroxide solution (sodium hydroxide 45g/ water 150ml, be 1.8 mole with respect to cellulosic each glucosyl residue) stir 1 hour (first operation) down nitrogen atmosphere, 45 ℃.After placing cooling, be cooled to-40 ℃ with dry ice/methanol bath, and then, add toluene 150ml, monochloroethane 70g (is 1.8 moles with respect to cellulosic each glucosyl residue), propylene oxide 20g (is 0.6 mole with respect to cellulosic each glucosyl residue), stir 1 hour, 90 ℃ down at 60 ℃ and stir 6 hours (second operation) down.After returning to room temperature, remaining gas in the discharge system, the limit is stirred the limit fast it is put in the 5L hot water, obtains gelatinous solid.With the gelatinous solid filtered while hot that obtains, then, usefulness 5L hot water cleans 3 times, and descends dry 6 hours at 100 ℃, obtains white solid 110g thus.The white solid that obtains is transferred in the three-necked flask of 5L, and added pyridine 2L, at room temperature make its dissolving.And then, add acetic anhydride 0.5L, under 50 ℃, make its reaction 6 hours.After returning to room temperature, the limit is stirred the limit fast reaction mixture is put in the 10L methyl alcohol, obtains white-yellowish solid thus.After the white-yellowish solid filtration that obtains, repeat 3 operations again with methanol=2L/2L mixed solvent cleaning, filter the white-yellowish solid that obtains by suction filtration, 80 ℃ of following vacuum-dryings 6 hours, obtain the comparative compound (H-4, substitution value, molecular weight are as described in Table 1) (receipts amount 140g) of the target of yellow-white powder thus.
Need to prove, to the above compound that obtains, the hydroxyl (R that substituted cellulose is contained
2, R
3And R
6) functional group kind, and DS and MS utilize Cellulose Communication 6,73-79 (1999) and Chrality 12 (9), the method described in the 670-674, by
1H-NMR or
13C-NMR observation and the result who determines are as described in Table 1.
The physical property measurement of＜derivatived cellulose 〉
To the derivatived cellulose that obtains, number-average molecular weight (Mn), weight-average molecular weight (Mw) are shown in table 1.Need to prove that their measuring method is as described below.
[molecular weight]
The mensuration of number-average molecular weight (Mn), weight-average molecular weight (Mw) is used gel permeation chromatography (GPC).Particularly, N-Methyl pyrrolidone as solvent, is used polystyrene gel, utilize by the conversion molecular weight calibration curve that curve obtains in advance that constitutes of standard monodisperse polystyrene and obtain.GPC equipment uses HLC-8220GPC (eastern Cao's corporate system).
＜embodiment 1: the making of the molding that derivatived cellulose constitutes 〉
＜test film is made 〉
The above-mentioned derivatived cellulose that obtains (P-1) is supplied to injection molding machine ((strain) well unit makes made, semi-automatic injection molding forming mill), according to the forming temperature shown in the table 1 (bowl temperature), 60 ℃ of die temperatures, injection pressure 1.5kgf/cm
2, be configured as the multi-usage test film (pliability test sheet) of 4 * 10 * 80mm.
＜embodiment 2～8, comparative example 1～4 〉
Operate equally with embodiment 1, use derivatived cellulose (P-2)～(P-8), comparative compound (H-1)～(H-2), (H-4) Vltra tears (H-3, this grease of pine system 90MP4000), be shaped, make test film according to the molding condition of table 1.
The physical property measurement of＜test film 〉
To the test film that obtains,, measure bending elastic modulus and matrix band outward appearance according to following method.The result is as shown in table 1.
[bending elastic modulus (rigidity)]
With JISK7171 is benchmark, utilizes flexing machine, measures bending elastic modulus.
[matrix band outward appearance]
To the test film that obtains, carry out the sense evaluation to the outward appearance of matrix band is following.
A: transparent and homogeneous.
B: translucent.
C: white opacity.
A～B is the practical no problem scope that.
As shown in Table 1, by implementing manufacture method of the present invention, can provide a kind of reaction system ground that from reaction vessel, do not take out to make the method for the derivatived cellulose of having given good matrix band outward appearance and high rigidity (bending elastic modulus) easily.
Claims (9)
1. the manufacture method of a derivatived cellulose is characterized in that, has following (A), (B), (C) in this derivatived cellulose as substituting group,
(A) alkyl;
(B) comprise acyl group-CO-R
B1And alkylene oxide group-R
B2The group of-O-, wherein, R
B1The expression alkyl, R
B2The expression alkylidene group; And
(C) acyl group-CO-R
C, R
CThe expression alkyl,
And this derivatived cellulose is satisfied following formula,
DS(A)＝0～2.2
MS(B)＝0.1～1.9
DS(C)＝0.5～1.7
In the above-mentioned formula, DS (A) and DS (C) represent the substitution value of substituting group (A), (C) respectively, the molar substitution of MS (B) expression substituting group (B),
The manufacture method of this derivatived cellulose has following operation:
(1) first operation: make Mierocrystalline cellulose and obtain soda cellulose for the alkali reaction of at least 2.0 molar equivalents with respect to described cellulosic each glucosyl residue,
(2) second operations: make described soda cellulose with respect to described cellulosic each glucosyl residue for the halon of at least 2.0 molar equivalents and for the alkylene oxide reaction of at least 0.1 molar equivalent obtains ether of cellulose, and
(3) the 3rd operations: described ether of cellulose is carried out esterification.
2. the manufacture method of derivatived cellulose according to claim 1 is characterized in that, after described second operation, ether of cellulose is not directly carried out the 3rd operation from the reaction vessel taking-up.
3. the manufacture method of derivatived cellulose according to claim 1 and 2 is characterized in that, the alkali that uses in described first operation is highly basic.
4. the manufacture method of derivatived cellulose according to claim 1 is characterized in that, DS (A)=1.2～2.2, MS (B)=0.1～1.0, DS (C)=0.5～1.7.
5. the manufacture method of derivatived cellulose according to claim 1 is characterized in that, DS (A)=1.2～2.2, MS (B)=0.1～0.6, DS (C)=0.7～1.7.
6. the manufacture method of derivatived cellulose according to claim 1 is characterized in that, DS (A)=1.2～1.6, MS (B)=0.1～0.3, DS (C)=1.0～1.7.
7. according to the manufacture method of each described derivatived cellulose in the claim 1,2,4,5 and 6, it is characterized in that described (B) R
B2Carbonatoms be 2～4.
8. according to the manufacture method of each described derivatived cellulose in the claim 1,2,4,5 and 6, it is characterized in that the carbonatoms of described (A) alkyl is 1～3.
9. according to the manufacture method of each described derivatived cellulose in the claim 1,2,4,5 and 6, it is characterized in that described (C) R
CCarbonatoms be 1～4.
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| CN104245741A (en) * | 2012-03-27 | 2014-12-24 | 陶氏环球技术有限责任公司 | A process of preparing an ester of a cellulose ether |
| CN105745013A (en) * | 2013-12-04 | 2016-07-06 | 陶氏环球技术有限责任公司 | Process for preparing a mixture of a cellulose derivative and a liquid diluent |
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| KR101837634B1 (en) * | 2011-12-20 | 2018-03-13 | 롯데정밀화학 주식회사 | Acetylated cellulose ether, method of preparing the acetylated cellulose ether and articles comprising the same |
| KR101837635B1 (en) * | 2011-12-30 | 2018-03-13 | 롯데정밀화학 주식회사 | Method of preparing acetylated cellulose ether and acetylated cellulose ether prepared by using the method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226981A (en) * | 1977-09-28 | 1980-10-07 | Shin-Etsu Chemical Co., Ltd. | Ether-ester derivatives of cellulose and their applications |
| JPH05339301A (en) * | 1992-06-05 | 1993-12-21 | Shin Etsu Chem Co Ltd | Preparation of cellulose carboxylate derivative |
| JP2005194302A (en) * | 2003-12-26 | 2005-07-21 | Daicel Chem Ind Ltd | Cellulose ester resin composition |
| CN101260158A (en) * | 2008-04-14 | 2008-09-10 | 浙江中维药业有限公司 | Method for preparing hydroxypropylmethylcellulose |
| JP2010031558A (en) * | 2008-07-29 | 2010-02-12 | Takigami Steel Construction Co Ltd | Seismic strengthening structure and seismic strengthening method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5915922B2 (en) * | 1975-08-14 | 1984-04-12 | 旭化成株式会社 | Production method of thermoplastic cellulose ester |
| DE10060470A1 (en) * | 2000-12-05 | 2002-06-06 | Bayer Ag | Thermoplastic and water-soluble cellulose ether esters |
| CN1507453A (en) * | 2001-05-21 | 2004-06-23 | 陶氏环球技术公司 | Process for preparing alkyl hydroxyalkyl cellulose ethers |
-
2010
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-
2011
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226981A (en) * | 1977-09-28 | 1980-10-07 | Shin-Etsu Chemical Co., Ltd. | Ether-ester derivatives of cellulose and their applications |
| JPH05339301A (en) * | 1992-06-05 | 1993-12-21 | Shin Etsu Chem Co Ltd | Preparation of cellulose carboxylate derivative |
| JP2005194302A (en) * | 2003-12-26 | 2005-07-21 | Daicel Chem Ind Ltd | Cellulose ester resin composition |
| CN101260158A (en) * | 2008-04-14 | 2008-09-10 | 浙江中维药业有限公司 | Method for preparing hydroxypropylmethylcellulose |
| JP2010031558A (en) * | 2008-07-29 | 2010-02-12 | Takigami Steel Construction Co Ltd | Seismic strengthening structure and seismic strengthening method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104245741A (en) * | 2012-03-27 | 2014-12-24 | 陶氏环球技术有限责任公司 | A process of preparing an ester of a cellulose ether |
| US9453081B2 (en) | 2012-03-27 | 2016-09-27 | Dow Global Technologies Llc | Process of preparing an ester of a cellulose ether |
| CN105745013A (en) * | 2013-12-04 | 2016-07-06 | 陶氏环球技术有限责任公司 | Process for preparing a mixture of a cellulose derivative and a liquid diluent |
| CN105745013B (en) * | 2013-12-04 | 2019-02-26 | 陶氏环球技术有限责任公司 | The method for being used to prepare the mixture of cellulose derivative and liquid diluent |
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| JP2011195788A (en) | 2011-10-06 |
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