CN1538974A - Hydrolysis polycondensation starch, process for producing the same and molded article made of hydrolysis polycondensation starch - Google Patents
Hydrolysis polycondensation starch, process for producing the same and molded article made of hydrolysis polycondensation starch Download PDFInfo
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- CN1538974A CN1538974A CNA028154371A CN02815437A CN1538974A CN 1538974 A CN1538974 A CN 1538974A CN A028154371 A CNA028154371 A CN A028154371A CN 02815437 A CN02815437 A CN 02815437A CN 1538974 A CN1538974 A CN 1538974A
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- C08B31/00—Preparation of derivatives of starch
Abstract
Hydrolyzed and condensation-polymerized starch obtained by introducing a flexible and linear organic group into at least a part of a main chain of starch, for example, a group represented by -O-(C=O)-O-, -((O-R1)x-(O-(C=O-R2)y)m-Oz-, or -CH2-(C=O)-CHR3-O- into at least a part of a main chain of starch. In each of the formulae, R1 and R2 denote an alkylene group of a carbon number at least 1 or an arylene group of a carbon number at least 6. The symbols x, y, and z denote 0 or 1. The value of x+y equals 1 or 2. The symbol m denotes an integer of 1 to 3100. R3 denotes hydrogen atom, an alkyl group of a carbon number at least 1, an aryl group of a carbon number at least 6, or an alkoxyl group of a carbon number of at least 1.
Description
Technical field
The present invention relates to hydrolytie polycondensation starch, its manufacture method, with the farinaceous fibre product of aforementioned hydrolytie polycondensation, film or sheet-like formed product and molded product.Hydrolytie polycondensation starch of the present invention, for example, as used for cosmetic tackifier, food tackifier, wafer, edibility material, reach the extrusion moulding product of fibre product, film, sheet material, pipe, rod etc., the raw material of molded, shaped articles and injection molded article uses.
Background technology
Do not have the polymkeric substance that thermoplastic starch is economy, but can not be in general polymkeric substance purposes, for example aspects such as film, fiber, moulding product are used.The motion of existing many use Starch Production thermoplastic articles.
As such modified starch hydroxyalkyl starch, acetic ester starch or carbamate starch are arranged.These modified starches make by first hydroxyl and the reactions such as urea, epoxide, carbamate or isocyanic ester formation material that make starch.Yet the chemical starch that this class denaturation method is produced is uneconomical, generally is not used in aforementioned and so on purposes.
The side chain that starch has amylopectin to form is owing to be that huge polymkeric substance does not show thermoplasticity.And the obstructions such as hydrogen bond between the first hydroxyl become thermoplasticity.By making the first hydroxyl reaction of starch, carry out sex change, lose hydrogen bond force, then starch presents thermoplasticity.
On the other hand, generate α-change starch during the starch heating, revert to β-change starch during cooling.Lotus root starch be starch in the presence of water, the heating become pasty state, can present thermoplastic example in appearance.Special fair 7-74241 communique has been put down in writing water has been added in the starch, at high temperature makes hydrolyzed starch, makes the dry synthetic body that dissolves.But do not proceed polycondensation after not putting down in writing hydrolysis.
In addition, special fair 7-57827 communique has been put down in writing starch and Biodegradable resin has been carried out the blended method.Be that water is added in the starch, at high temperature make hydrolyzed starch, make the method for dry synthetic molten mass.
That is, starch is added the water hydrolysis, make hydrolyzed starch.Put down in writing this hydrolyzed starch and presented thermoplasticity.And put down in writing amylatic molecular weight and drop to 1/5000 from 1/2 of the initial stage, present thermoplasticity.Because do not stipulate the absolute value of molecular weight, this also leaves query technically.
In addition, also record makes this hydrolyzed starch moisture absorption 18 weight %, mixes other resin, uses injection moulding machine trial-production dumbbell-shaped test piece.This test piece hygroscopic deformation is little.But, comparing with common plastics, 18 weight % have been sizable value, are not general values.
The method that in existing many reports are reported in jar, under the supercritical state of carbonic acid gas-water system starch is hydrolyzed.For example, the spy opens the sex change that flat 11-92501 communique has proposed polyose in the densification fluid.Yet this motion only discloses in jar, the huge macromolecule hydrolysis of starch is become to be lower than under the supercritical state of carbonic acid gas-water system the method for the molecule of oligopolymer, and how can be hydrolyzed into low molecular compound effectively is main problem.Therefore, record will not be hydrolyzed as high molecular starch, continuously the low molecule of gained be carried out the method for polycondensation again.
In addition, the spy opens the renovation process that the 2001-253967 communique has proposed crosslinked polymer material.Wherein put down in writing single screw rod of crosslinked polymer material and water supply or twin screw extruder, aforementioned water becomes in aforementioned forcing machine under the condition of supercritical water or subcritical water and is hydrolyzed, and cuts off the method for crosslink part.Wherein do not put down in writing CO 2 supercritical or the precritical method of utilizing carbonic acid gas-water system.In addition, the method that does not also have record that the crosslink part that cuts off is carried out polycondensation again.
General thermal plastic high polymer has the character of easy fusion adhesion under the high temperature more than the softening temperature.Therefore, this gluing in order to prevent, carry out chilling usually.As everyone knows, when for example making the pellet of nylon, polyester etc., with the polymer-extruded one-tenth of fused section shape, in cold water, carry out chilling from nozzle, below temperature drops to softening temperature after with the cutter cut-out, prevent the adhesion of pellet.Yet, adopt water-cooled must carry out drying before the fusion once more, this is disadvantageous economically.Also be not reported in and prevent the method for adhering more than the thermoplastic resin softening temperature.
The object of the present invention is to provide novel hydrolytie polycondensation starch and inexpensive method of manufacturing thereof.
The object of the present invention is to provide have thermoplasticity, flexibility and practical sufficient mechanical properties, and cheap hydrolytie polycondensation starch and manufacture method thereof especially also are difficult to the hydrolytie polycondensation starch and the manufacture method thereof of adhering more than softening temperature.
The object of the present invention is to provide to have sufficient service performance, and cheap, have fibre product, film and the sheet forming goods and a molded, shaped articles of biological degradability again.
Summary of the invention
The present invention relates to a part of introducing-type (1) in the starch main chain: the base that-O-(C=O)-O-represents, formula (2) :-((O-R
1)
x-(O-(C=O)-R
2)
m-O
zThe base and formula (3) :-CH of-expression
2-(C=O)-CHR
3The hydrolytie polycondensation starch of at least a kind of base selecting in the group that the base that-O-represents is formed.R
1Expression C
1Above alkylidene group or C
6Above arylidene.R
2Expression C
1Above alkylidene group or C
6Above arylidene.X represents 0 or 1.Y represents 0 or 1.X+y is 1 or 2.M represents 1～3100 integer, and z represents 1 or 2.R
3Expression hydrogen atom, C
1Above alkyl, C
6Above aryl or C
1Above alkoxyl group.
The present invention relates to crosslinked aforementioned hydrolytie polycondensation starch.
Hydrolytie polycondensation starch of the present invention preferably 20 ℃ of temperature, was placed 24 hours under the condition of relative humidity 60%, and in fact reaching constant equilibrated moisture rate is 1～6 weight %.The swelling rate that hydrolytie polycondensation starch of the present invention preferably floods after 1 hour in the water of 25 ℃ of temperature is 150～400%.Hydrolytie polycondensation starch of the present invention preferably presents and melts sex change.
Hydrolytie polycondensation starch of the present invention, for example, can by make starch and the compound that forms shown in the formula (1) base, form the compound of base shown in the formula (2) and form at least a kind compound selecting in the group that the compound of base shown in the formula (3) forms in the presence of water, 100～350 ℃ react down, perhaps in the presence of water and carbon dioxide gas, become at carbon dioxide gas under the condition of supercritical state or subcritical state its reaction is made.
The manufacture method of hydrolytie polycondensation starch of the present invention, preferably starch with from the compound that forms shown in the formula (1) base, form the compound of base shown in the formula (2) and form in the reaction of at least a kind the compound of selecting the group that the compound of base shown in the formula (3) forms and use forcing machine, at 100～250kg/cm
2(extrude under the pressure before=9.8～24.5MPa) the nozzle.
Hydrolytie polycondensation starch of the present invention uses as the material that forms fibre product, film or sheet forming goods and molded, shaped articles.
Hydrolytie polycondensation starch of the present invention is thermoplastic, also is difficult to adhesion under the temperature more than the softening temperature, preferably presents thixotropy.Hydrolytie polycondensation starch of the present invention can be considered by making the part in the starch main chain have softish line style organic radical shown in formula (1), formula (2) or the formula (3), having improved the obviously shortcoming of big this starch of water absorbability, is thermoplasticity, the starch with flexibility.That is, by the base of introducing-type (1), formula (2) or formula (3) expression, make a part in the starch main chain that upright and outspoken grape sugar chain constitutes have the soft of similar hinge, it is soft that main chain becomes.The main chain that flexibility increases becomes little pompon shape easily.The entanglement that becomes a globular main chain and other main chains is few, can slide between main chain as a result.This phenomenon is considered to become hydrolytie polycondensation starch of the present invention and presents thermoplastic cause.
By starch and the compound that forms base shown in formula (1), formula (2) or the formula (3) are being reacted under the condition as the aforementioned, starch produces hydrolysis reaction, the polycondensation of dewatering of the starch of hydrolysis and the compound that forms shown in formula (1), formula (2) or the formula (3) base generates hydrolytie polycondensation starch of the present invention.
The simple declaration of accompanying drawing
Fig. 1 is the graphic representation that the hydrolytie polycondensation starch of the expression embodiment of the invention 1 manufacturing adopts Fourier's infrared spectrophotometer measurement result.
Fig. 2 is the expression embodiment of the invention 1 hydrolytie polycondensation starch of making and the graphic representation that adopts the Fourier transform infrared spectrophotometer measurement result as the W-Gum of raw material.
The optimum implementation of invention
The part of hydrolytie polycondensation starch of the present invention in the starch main chain has the structure of base shown in introducing-type (1), formula (2) or the formula (3).Hydrolytie polycondensation starch of the present invention has formula (10) :-G-M
n-shown in repeating unit.G represents to remove 1 of the glucose divalent base with 4 hydroxyls.The base of M expression (1), formula (2) or formula (3) expression.N represents the integer more than 1.When n is a integer more than 2, a plurality of M can be mutually the same also can be different.
As the R in the formula (2)
1, C such as ethylene, trimethylene, tetramethylene are for example arranged
1More than the straight chain shape alkylidene group of (common below 12); Phenylene, diphenylene, biphenylene alkylidene group C such as (for example, biphenylene methylene radical, 2,2-biphenylene propylidene)
6More than the arylidene of (common below 15).
As the R in the formula (2)
2, for example have 1,1-ethylidene, 1,1-propylidene, propylene, 1,1-butylidene, 1,2-butylidene, 1,3-butylidene etc. has C
1More than the alkylidene group of (common below 12) alkyl; C such as phenylene, biphenylene alkylidene group (for example biphenylene methylene radical, 2,2-biphenylene propylidene)
6More than the arylidene of (logical when below 15).
R
2For the hydrolytie polycondensation starch of alkylidene group than having flexibility and the high tendency of biological degradability for the hydrolytie polycondensation starch of arylidene.
Base as formula (2) expression has formula (4) :-(O-(C=O)-R
2)
mBase (x=0, y=1, z=0), the formula (5) of-expression :-(O-(C=O)-R
2)
mThe base that-O-represents (x=0, y=1, z=1), formula (6) :-(O-R
1)
mBase (x=1, y=0, z=0), the formula (7) of-expression :-(O-R
1-O-(C=O)-R
2)
mBase (x=1, y=1, z=0), the formula (8) of-expression :-(O-R
1)
mBase that-O-represents (x=1, y=0, z=1) and formula (9) :-(O-R
1)-O-(C=O)-R
2)
mThe base that-O-represents (x=1, y=1, z=1).
Base as formula (4) expression has aliphatic ester group (R
2Be alkylidene group), aromatic series ester group (R
2Be arylidene), monoesters base (m=1), two ester groups (m=2), three ester groups (m=3), polyester base (m is 2～3100 integer, especially 4～3100 integer) are arranged.
Base as formula (5) expression has aliphatic ester ether (R
2Be alkylidene group), aromatic ester ether (R
2Be arylidene), monoesters ether (m=1), diester ether (m=2), three ester ethers (m=3), polyester ether (m is 2～3100 integer, especially 4～3100 integer) are arranged.
Base as formula (6) expression has monoalkyl ether (R
1Be alkylidene group, m=1), dialkyl group ether (R
1Be alkylidene group, m=2), trialkyl ether (R
1Be alkylidene group, m=3), multi-alkyl ether base (R
1Be 2～3100 integer, especially 4～3100 integer for alkylidene group, m), single aryl ether (R
1Be arylidene, m=1), diaryl ether (R
1Be arylidene, m=2), triaryl ether (R
1Be arylidene, m=3), polyaryl ether (R
1For arylidene, m 2～3100 integer, especially 4～3100 integer).
Base as formula (7) expression has single alkylidene group ester group (R
1Be alkylidene group, m=1), two alkylidene group ester group (R
1Be alkylidene group, m=2), three alkylene ester base (R
1Be alkylidene group, m=3), polyalkylene ester group (R
1Be 2～3100 integer, especially 4～3100 integer for alkylidene group, m), single arylidene ester group (R
1Be arylidene, m=1), two arylidene ester group (R
1Be arylidene, m=2), Sanya aryl ester group (R
1Be arylidene, m=3), many arylidene ester group (R
1For arylidene, m 2～3100 integer, especially 4～3100 integer).
Base as formula (8) expression has monoalkyl two ether (R
1Be alkylidene group, m=1), dialkyl group two ether (R
1Be alkylidene group, m=2), trialkyl two ether (R
1Be alkylidene group, m=3), many alkyl two ether (R
1For alkylidene group, m are 2～3100 integer, 4～3100 integer especially), single aryl two ether (R
1Be arylidene, m=1), diaryl two ether (R
1Be arylidene, m=2), triaryl two ether (R
1Be arylidene, m=3), polyaryl two ether (R
1For arylidene, m are 2～3100 integer, 4～3100 integer especially).
Base as formula (9) expression has single alkylene ester ether (R
1Be alkylidene group, m=1), two alkylene ester ether (R
1Be alkylidene group, m=2), three alkylene ester ether (R
1Be alkylidene group, m=3), polyalkylene ester ether (R
1For alkylidene group, m are 2～3100 integer, 4～3100 integer especially), single arylidene ester ether (R
1Be arylidene, m=1), two arylidene ester ether (R
1Be arylidene, m=2), Sanya aryl ester ether (R
1Be arylidene, m=3).Many arylidene ester ether (R
1For arylidene, m are 2～3100 integer, 4～3100 integer especially).
As the R in the formula (3)
3, for example, hydrogen atom is arranged; C such as methyl, ethyl, n-propyl, sec.-propyl
1More than the alkyl of (common below 3); C such as phenyl
6More than the aryl of (common below 8); C such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy
1More than the alkoxyl group of (common below 3).Base as formula (3) expression for example, has diformazan ketone group (R
3Be hydrogen atom), ethyl-methyl ketone group (R
3Be methyl), methyl methoxy ylmethyl ketone group (R
3Be methoxyl group).
Hydrolytie polycondensation starch of the present invention, can a part of introducing-type (1), formula (2) or formula (3) in the starch main chain shown in more than a kind or 2 kinds of base.As the hydrolytie polycondensation starch more than 2 kinds of base shown in introducing-type (1), formula (2) or the formula (3), basic hydrolytie polycondensation starch shown in base shown in the base that has formula shown in (1) and the formula (2) or the formula (3) is arranged; Basic hydrolytie polycondensation starch shown in the base that has formula shown in (2) and the formula (3) is arranged; The hydrolytie polycondensation starch that the base that has formula shown in (2) more than two kinds is arranged; The hydrolytie polycondensation starch that the base that has formula shown in (3) more than 2 kinds is arranged; The hydrolytie polycondensation starch that base shown in the base that has formula shown in (1), the formula (2) and base shown in the formula (3) are arranged.
Part in the starch main chain has imported the base shown in the formula (1), and this can be by measuring 1745～1755cm that distinctive CO stretching vibration forms when adopting infrared spectrophotometer to measure to the unexistent carbonyldioxy of starch
-1Absorption band confirm.
Base (y=1) shown in a part of introducing-type (4) in the starch main chain, formula (5), formula (7) and the formula (9), this (is for example using solvent, ortho-cresol) extraction is unreacted from the hydrolytie polycondensation starch of gained (for example forms compound basic shown in formula (4), formula (5), formula (7) and the formula (9), poly(lactic acid)) afterwards, the employing infrared spectrophotometer is measured, can be by the unexistent ester group of starch being measured 1730～1740cm that distinctive CO stretching vibration forms
-1Absorption band confirm.In addition, R
3Be 1, during the 1-ethylidene (for example, when gathering alpha-hydroxypropionic acid) as the compound use that forms base shown in the aforementioned formula (5), from the hydrolytie polycondensation starch of gained, extract out after the unreacted poly-alpha-hydroxypropionic acid, adopt NMR to measure, can confirm by the methyl of poly-alpha-hydroxypropionic acid is measured distinctive peak value.
Base (x=1) shown in a part of introducing-type (6) in the starch main chain, formula (7), formula (8) or the formula (9), this can (for example use solvent, boiled water) extraction is unreacted from the hydrolytie polycondensation starch of gained (for example forms compound basic shown in formula (6), formula (7), formula (8) and the formula (9), n-propyl alcohol) afterwards, in NMR measures, for example, R
1During for trimethylene, the methylene radical of the unexistent propyl alcohol of starch is measured distinctive peak value confirm.
Base shown in a part of introducing-type (3) in the starch main chain, this can be when adopting infrared spectrophotometer to measure, by 1715～1725cm to the distinctive CO stretching vibration formation of the based assays shown in the formula (3)
-1Absorption band confirm.Starch and the compound (for example, glycerine) that forms shown in the formula (3) base there is not this absorption band.
Consider from hydrolytie polycondensation Thermoplasticity of Starch viewpoint, the base of formula (1), formula (2) or formula (3) expression, with respect to 100 moles of the glucose units of starch, preferably by total formula weight, the ratio with 50～100, especially 70～100 imports.The import volume of formula (1), formula (2) and base shown in the formula (3) after a little while, the hydrolytie polycondensation Thermoplasticity of Starch is low, import volume forms the compound of base shown in formula (1), formula (2) or the formula (3) for a long time and separates out from end article sometimes.
The amount of base shown in introducing-type in the main chain of hydrolytie polycondensation starch (1), formula (2) or the formula (3), even the trace of observing with infrared spectrophotometer, that is, even a few %, also this effect occurs.The low photometer of sensitivity is viewed as shoulder shape sometimes.Along with the import volume in the basal orientation main chain shown in formula (1), formula (2) or the formula (3) increases, the hydrolytie polycondensation Thermoplasticity of Starch improves.The import volume of formula (1), formula (2) and base shown in the formula (3) after a little while, the hardening of hydrolytie polycondensation starch, import volume has the tendency of deliquescing for a long time.
Hydrolytie polycondensation starch of the present invention can be made by the compound reaction that makes starch and the compound that forms shown in the formula (1) base, forms the compound (forming the compound of base shown in formula (4), formula (5), formula (6), formula (7), formula (8) or the formula (9)) of base shown in the formula (2) or form base shown in the formula (3).
As main raw material starch, can use the starch of general use.For example, produce with the potato class of cereal, potato and the pearl powder etc. of corn and so on by barley, rye, black wheat, wheat, rice.The kind of raw starch does not have particular restriction among the present invention.But be conceived to good economy performance and preferably use W-Gum.
The molecular weight of starch is very big, for example is about 20,000,000, and is different according to the kind of starch.
As the base of formula (1) expression, promptly form the compound of carbonyldioxy, can use the carbonated through adding heat release carbonic acid gas such as carbonic acid gas or yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, lime carbonate, Calcium hydrogen carbonate etc.
Compound as forming base shown in the formula (4) for example, has formula (11): H-(C=O)-R
3-(O-(C=O)-R
3)
M-1The compound that-OH represents.
In the base of formula (4) expression, as forming aliphatics monoesters base (R
3Be alkylidene group, m=1) compound, for example, hydroxyalkyl aldehyde such as hydroxy-acetaldehyde, glycollic aldehyde, acetaldol, Glycerose are arranged.In the base of formula (4) expression, as forming aromatic series monoesters base (R
2Be arylidene, m=1) compound, for example, hydroxyalkyl aryl aldehyde such as methylol benzyl aldehyde, hydroxyethyl benzyl aldehyde, hydroxypropyl benzyl aldehyde are arranged.
In the base of formula (4) expression, as the compound that forms two ester groups (m=2), three ester groups (m=3), polyester base (m is 2～3100 integer, especially 4～3100 integer) etc., the ester that hydroxyalkyl aldehyde such as hydroxy-acetaldehyde list lactate, hydroxy-acetaldehyde lactyl-lactic acid ester, hydroxy-acetaldehyde three lactates, the many lactates of hydroxy-acetaldehyde and aliphatic carboxylic acid for example, are arranged.
Compound as forming base shown in the formula (5) for example, has formula (12): H-(O-(C=O)-R
3)
mThe compound that-OH represents.In the base of formula (5) expression, as forming aliphatic ester ether (R
2Be alkylidene group) compound, for example, hydroxyalkyl carboxylic acid such as alpha-hydroxypropionic acid (lactic acid), ethylene lactic acid, Alpha-hydroxy butyric acid, beta-hydroxy-butanoic acid, gamma-hydroxybutyric acid and polycondensate thereof (for example, poly-alpha-hydroxypropionic acid) are arranged.In the base of formula (5) expression, as forming aromatic series monoesters ether (R
3Be arylidene) compound, for example, hydroxyalkyl aryl carboxylic acids such as methylol carboxylic acid benzyl, hydroxyethyl carboxylic acid benzyl, hydroxypropyl carboxylic acid benzyl are arranged.
Compound as forming base shown in the formula (6) for example, has formula (13): H-(O-R
1)
mThe compound that-H represents.In the base of formula (6) expression, as forming alkylether radicals (R
1Be alkylidene group, m=1) compound, for example, alcohol such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol are arranged.
Compound as forming base shown in the formula (7) for example, has formula (14): H-(R
1-O-(C=O)-R
3)
mThe compound that-OH represents.
In the base of formula (7) expression, as alkyl ester ether (R
1Be alkylidene group, m=1), dialkyl ether (R
1Be alkylidene group, m=2), trialkyl ester ether (R
1Be alkylidene group, m=3), multi-alkyl ester ether (R
1Be alkylidene group, m is 2～3100 integer, especially during 4～3100 integer), for example, ethyl lactate is arranged, the lactyl-lactic acid ethyl ester, three ethyl lactates, many ethyl lactates, propyl lactate, the lactyl-lactic acid propyl ester, three propyl lactates, many propyl lactates, n-Butyl lactate, the lactyl-lactic acid butyl ester, three n-Butyl lactates, many n-Butyl lactates, the Alpha-hydroxy ethyl butyrate, two Alpha-hydroxy ethyl butyrates, three Alpha-hydroxy ethyl butyrates, many Alpha-hydroxies ethyl butyrate, the Alpha-hydroxy propyl butyrate, two Alpha-hydroxy propyl butyrates, three Alpha-hydroxy propyl butyrates, many Alpha-hydroxies propyl butyrate, the Alpha-hydroxy butyl butyrate, two Alpha-hydroxy butyl butyrates, three Alpha-hydroxy butyl butyrates, the alkyl ester of hydroxy acids such as many Alpha-hydroxies butyl butyrate.
Compound as forming base shown in the formula (8) for example, has formula (15): H-R
4-(C=O)-and compound, formula (16) that OH represents: H-(O-R
1)
m-OH.-R
4-CH
2-be equivalent to R
1As the base of formula (8) expression, promptly form the compound of alkylether radicals, for example, aliphatic carboxylic acids such as propionic acid, butyric acid (butyric acid, isopropylformic acid), valeric acid, caproic acid, lauric acid, oleic acid, stearic acid are arranged; Ethylene glycol, propylene glycol, butyleneglycol, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene glycol and 1,2-propylene glycol multipolymer.
Compound as forming base shown in the formula (9) for example, has formula (17): H-R
1-O-(C=O)-R
5-(C=O)-compound that O-H represents.R
5,-R
5-CH
2-be equivalent to the R in the formula (2)
3As the compound that forms base shown in the formula (9), for example, dicarboxylic acid alkyl esters such as ethyl maleate, toxilic acid list propyl ester, butyl maleate, ethyl succinate, succsinic acid propyl ester, succinic acid butyl ester, ethyl fumarate, fumaric acid propyl ester, fumaric acid butyric acid, hexanodioic acid ethyl ester, hexanodioic acid propyl ester, hexanodioic acid butyl ester are arranged.
Compound as forming base shown in the formula (3) for example, has formula (18): X-O-CH
2-CH (OH)-CHR
3The compound that-O-Y represents (X and Y represent hydrogen atom or acyl group respectively).Compound as forming base shown in the formula (3) for example, has 1-AKGs such as 1-alkyl glycerols such as glycerine, 1-methylglycerin(e), 1-methoxyl group glycerine, or these ester.Glycerine or its ester moiety import the back formation dimethyl ketone (R in the formula (3) in the starch main chain
3Be hydrogen atom).1-alkyl glycerol and ester thereof import the back formation alpha-alkyl methyl ketone group (R in the formula (3) in the starch main chain
3Be alkyl).The back forms the alkoxy methyl ketone group (R in the formula (3) in the main chain of 1-AKGs and ester importing starch thereof
3Be alkoxyl group).As ester, for example, the glyceryl ester (direactive glyceride, two glyceryl ester etc.) of aliphatics organic acids such as lauric acid, stearic acid, oleic acid, linolic acid etc. is arranged.Use the occasion of ester, consider that preferred reaction free organic acid (especially low-molecular-weight organic acid) does not have bad influence to the characteristic of end article.
As the compound that forms base shown in formula (1), formula (2) or the formula (3), by using the composition that exists in the whole food, it is good to obtain security, the hydrolytie polycondensation starch to environment.
By making starch and the compound that forms shown in formula (1), formula (2) or the formula (3) base, in the presence of water, 100-350 ℃, preferred 135-155 ℃ of reaction down, the base of a part of introducing-type (1), formula (2) or formula (3) expression that can be in the starch main chain.Reactivity reduced when temperature of reaction was too low, and when temperature of reaction was too high, gained hydrolytie polycondensation starch produced painted sometimes, and molecular weight obviously reduces, embrittlement.
By making starch and the compound that forms base shown in formula (1), formula (2) or the formula (3), in the presence of water and carbon dioxide gas, carbon dioxide gas (for example becomes under the condition of supercritical state or subcritical state, under the condition of 100～350 ℃ of temperature, preferred 135～155 ℃, reaction top pressure 7.48～29.4MPa, preferred 15.7～23.5MPa) react the base of a part of introducing-type (1), formula (2) or formula (3) expression that can be in the starch main chain.Existing carbonic acid gas also works the compound of base shown in the formula that forms (1).Carbonic acid gas is a supercritical state under the condition of temperature more than 31.1 ℃, more than the pressure 7.48MPa, under the condition of temperature more than 31.1 ℃, insufficient pressure 7.48MPa and 31.1 ℃ of temperature less thaies.Under the condition more than the pressure 7.48MPa is subcritical state.The carbonic acid gas of supercritical state or subcritical state promotes the hydrolysis reaction of starch, the polycondensation of dewatering of the starch that helps hydrolysis simultaneously and the compound that forms base shown in the formula (1), and help crosslinking reaction as linking agent.The usage quantity of carbonic acid gas is a benchmark with water, for example preferred 0.1-3 weight %.Carbonic acid gas is owing to play catalyst action during amylolysis, so even trace is also brought into play effect.
The reaction top pressure for example, can be 76～300kg/cm
2(=7.5～29.4MPa), be preferably 160～240kg/cm
2(=15.7～23.5MPa).Reactivity reduced when pressure was too low.When pressure was too high, gained hydrolytie polycondensation starch produced painted sometimes, and molecular weight obviously reduces, embrittlement.Reaction times for example can for 1～10 minute, be preferably 3～5 minutes.Time, gained hydrolytie polycondensation starch produced painted sometimes when oversize, and molecular weight obviously reduces, embrittlement.Time reactivity reduction too in short-term, the hydrolytie polycondensation starch that can not obtain to have abundant performance sometimes.
The usage quantity of water for example with respect to starch 100 weight parts (dewatering exceptionally), amounts to 30～80 weight parts with moisture (common 12～13 weight %) contained in the starch, is preferably 50～70 weight parts.The usage quantity of the water reactivity of starch after a little while reduces.Dehydration polycondensation rate reduced when the usage quantity of water was too many, and the recovery of molecular weight is few, and the tendency of the molecular weight reduction of gained hydrolytie polycondensation starch is arranged.In addition, the energy that dewaters required in order to reclaim hydrolytie polycondensation starch increases, and economy is bad.
By starch and the compound that forms base shown in formula (1), formula (2) or the formula (3) are reacted under aforementioned each condition, carry out the hydrolysis reaction of starch main chain and the starch and the dehydration polycondensation that forms the compound of base shown in formula (1), formula (2) or the formula (3) of hydrolysis continuously, the base of a part of introducing-type (1) in the starch main chain, formula (2) or formula (3) expression.Think that the side chain of starch is cut off with the hydrolysis reaction of starch main chain, the decrease in molecular weight of starch, starch is near the straight chain shape simultaneously, in addition, by the base of introducing-type (1), formula (2) or formula (3) expression, hydrophobic property and flexibility, hydrolytie polycondensation starch presents thermoplasticity.
Form the part of the compound of base shown in formula (1), formula (2) or the formula (3) and hydroxyl, especially the hydroxyl of glucose unit and carry out dehydration reaction formation side chain, the hydrolytie polycondensation Thermoplasticity of Starch is improved with methylol.
Starch and the reactivity that forms the compound of base shown in formula (1), formula (2) or the formula (3), can calculate the unreacted amount that forms based compound shown in formula (1), formula (2) or the formula (3) and infer by measure the reduction rate and the moisture amount of hydrolytie polycondensation starch by TGA, dsc analysis.
In the presence of water, under high pressure and the high shear force, can make the starch hydrolysis by heating.For make starch under high pressure the short period of time be hydrolyzed, the polycondensation of then dewatering then, starch and the compound reaction that forms shown in formula (1), formula (2) or the formula (3) base, the preferred successive reaction machine that uses dehydration with the vented extruder type.Preferably use forcing machine as the reaction machine, for example 2 venting port forcing machines or 3 venting port forcing machines.Employed screw rod is preferably twin screw in order only to make to supply with partly to feed well, after this is made of single screw rod to head.3 venting port forcing machines for example, preferably by the screw rod supply unit, shear mixing compression unit, open exhaust portion, mixing compression unit, vacuum pump suction exhaust portion, mixing compression unit, the suction and discharge portion of vacuum pump, mixing compression unit and constitute.
Use the occasion of forcing machine as the reaction machine, for example, preferably at 100～250kg/cm
2(extrude under the pressure before=9.8～24.5MPa) the nozzle.
It is crosslinked that hydrolytie polycondensation starch of the present invention can use linking agent to carry out.By crosslinked between the methylol that makes hydrolytie polycondensation starch, can suppress water-swellable, improve water tolerance.Even the very little effect that also presents the swelling of abundant inhibition water of crosslinked degree.Water-swellable reduces with crosslinked increase.Water swelling rate for example can (for example, 25 ℃ be flooded 1 hour in) the water, the weight and the adiabatic drying weight of its swelling front and back are calculated by being determined at normal temperature.
As linking agent, for example, can use phosphoric acid class, polycarboxylic acid class, hydroxycarboxylic acid, epoxide, acid anhydrides, isocyanic ester, silanization thing etc.As linking agent, for example, the phosphoric acid salt of tripoly phosphate sodium STPP etc. is arranged; The polycarboxylic acid of oxalic acid, toxilic acid, hexanodioic acid, phthalic acid, succsinic acid etc.; The polycarboxylate of hexanodioic acid calcium, caoxalate, calcium maleate, calcium phthalate, calcium succinate etc.; The hydroxycarboxylic acid of lactic acid etc.; The hydroxycarboxylate of calcium lactate etc.; Carbonic acid gas; The supercarbonate of sodium bicarbonate, Calcium hydrogen carbonate etc.; The epoxide of one glycidyl ether etc.; The acid anhydrides of succinyl oxide, maleic anhydride etc.; Hexamethylene diisocyanate, Toluene-2,4-diisocyanate, the isocyanic ester of 4-vulcabond etc.; The silanization thing of vinyl trimethylsilane etc.; Six hydrogen-1,3,5-triacryl-s-triazine.Linking agent can use a kind separately, or uses mixing more than 2 kinds.
Add linking agent in hydrolytie polycondensation starch, undertaken mixingly by heating (for example 100～180 ℃), it is crosslinked that hydrolytie polycondensation starch is carried out.The addition of linking agent is a benchmark with the hydrolytie polycondensation starch before crosslinked, preferred 0.01～3 weight %.The addition of linking agent has the water-swellable that suppresses hydrolytie polycondensation starch, improves the little tendency of water tolerance effect after a little while, the hydrolytie polycondensation starch dissolution in water, water-swellable infinity sometimes.When the addition of linking agent was too many, the hydrolytie polycondensation Thermoplasticity of Starch reduced with mobile reduction, processibility sometimes.
Use forcing machine, in the presence of water, make starch and (for example form compound basic shown in the formula (1), when carbon dioxide gas) reacting, and in the presence of water and carbon dioxide gas, make starch and form compound basic shown in formula (2) or the formula (3) when reacting, for example, make the preceding pressure of nozzle maintain 160kg/cm
2More than the (=15.7MPa), cause rapidly dehydration, can make that part causes the crosslinked of carbonic acid gas between the methylol of glucose unit by in atmosphere, extrude instantaneously.Because the carbonic acid of this part is crosslinked, can obtain enough cross-linking densities, presents thixotropic hydrolytie polycondensation starch more than softening temperature.This crosslinking reaction is owing to be the crosslinking reaction that the dehydration between methylol causes, therefore more promptly dewater, promptly, more promptly reduce pressure from high pressure more, then hydrolytie polycondensation cross-linking of starch density is high more, water-swellable is low, water tolerance is high, hydrolytie polycondensation starch is difficult to adhere more.
For example, use hot cutter contact with the head of forcing machine to cut off the pellet of the crosslinked hydrolytie polycondensation starch of acquisition, the some air limits of injection, limit fall, even for example be parked under the state in a receiving plate that is arranged under the 1m, because inadhesion, so directly applying pressure carries spraying machine to carry.In addition, use this pellet to adopt the blown film device in the system film, even for example the film blister film at distance head 1m rear is adjacent to also inadhesion from the both sides pressurization.Crosslinked hydrolytie polycondensation starch is difficult to adhesion, and this estimation is owing to crosslinkedly have a thixotropic cause of reversible.
Hydrolytie polycondensation starch of the present invention, for example, weight-average molecular weight can be 30000～500000, is preferably 50000～200000.The hydrolytie polycondensation starch that molecular weight is low has the low tendency of mechanical properties, the hydrolytie polycondensation starch that molecular weight is high mobile sometimes low, be difficult to moulding.
The molecular weight of hydrolytie polycondensation starch, because the temperature of reaction when improving starch with the compound reaction that forms base shown in formula (1), formula (2) or the formula (3), or because the raising reaction pressure has the tendency of reduction.
Hydrolytie polycondensation starch of the present invention preferably 20 ℃ of temperature, was placed 24 hours under the condition of relative humidity 60%, and in fact reaching constant equilibrated moisture rate is 1～6 weight %.
Hydrolytie polycondensation starch of the present invention, the swelling rate of dipping after 1 hour preferably 150～400% in 25 ℃ water.The hydrolytie polycondensation starch water tolerance that aforementioned swelling rate is too high is low, and the pellet tendency of adhesion is easily arranged, and the hydrolytie polycondensation starch that the swelling rate is too low has mobile low tendency.For example, crosslinked by carrying out between the methylol that makes hydrolytie polycondensation starch glucose unit, can reduce aforementioned swelling rate.
Hydrolytie polycondensation starch of the present invention preferably has thixotropy.For example, crosslinked hydrolytie polycondensation starch presents the reversible thixotropy.Crosslinked hydrolytie polycondensation starch only is heated to more than the softening temperature, because crosslinkedly do not cut off, so because original shape is kept in the little englobement of surface tension, but flow distortion easily when under this state, applying slight loading.Still keep distortion when removing loading, present the reversible thixotropy.
Hydrolytie polycondensation starch of the present invention is not owing to starch exists with particle, so the transparency is good.Hydrolytie polycondensation starch of the present invention, the mist degree that for example uses spectrophotometer that the sheet material of the thick 1mm of hot-pressing is recorded are the excellent value below 30.Mist degree, (total light transmittance (%) and Td (diffusion transmitance (%)) can be calculated as mist degree (%)=Td ÷ Tt * 100 for example to use ス ガ trier corporate system HGM-2DP to measure Tt.When the sheet material of hydrolytie polycondensation starch of the present invention was immersed in the water, because swelling poor of part, the part that produces specific refractory power was poor, causes scattering of light, gonorrhoea slowly, but through super-dry, the partial error of specific refractory power disappears, and becomes transparent again.
The general polymkeric substance additive that uses in can adding in the hydrolytie polycondensation starch of the present invention.As these additives, for example, can enumerate the additive of tinting material (pigment, dyestuff), antiseptic-germicide, deodorizer, sanitas, insect-proof agent, static inhibitor, photostabilizer, heat-resistant agent, antiblocking agent etc.These additive can use separately, can also use together more than 2 kinds.The use of relevant these additives should be considered according to purposes, makes it the characteristic as food, and as the characteristic of medicine, the biological degradability when discarded etc. does not have detrimentally affect.
By in hydrolytie polycondensation starch of the present invention, adding the softening agent of aliphatics organic acid and glyceryl ester thereof etc., can improve thermoplasticity.Can further improve thermoplasticity by the use level that increases softening agent.
Form the reactivity of the compound of base shown in formula (1), formula (2) or the formula (3), can infer with the decrement that adopts TGA, dsc analysis to measure gained hydrolytie polycondensation starch.For example, cooperate the starch of 70 weight % and the glycerine of 30 weight %, the hydrolytie polycondensation starch that makes is carried out permanent rate decrement up to the temperature that begins to decompose (about 270 ℃) by certain speed.This reduction rate comprises the moisture reduction rate, approximately is 15 weight %.Because it is 4～5 weight % that hydrolytie polycondensation starch reaches constant equilibrated moisture containing ratio, therefore estimate the approximately unreacted glycerine of residual 10 weight %, the glycerine reaction of all the other about 20 weight % imports the part in the starch main chain, perhaps forms side chain.
Hydrolytie polycondensation starch of the present invention can be used as the raw material use of extrusion moulding product, molded, shaped articles and the injection-molded article of the fibre product, film, sheet material, pipe, rod of non-woven fabrics that dry type non-woven fabrics, Wet-laid non-woven fabric, heat that fiber constitutes melts bonded nonwoven, chemical adhesion non-woven fabrics etc. and cloth etc. etc.
Hydrolytie polycondensation starch of the present invention, for example can adopt melt-spinning to carry out spinning.That is, use forcing machine with hydrolytie polycondensation starch carry out fusion, mixing, knit from spray while measure with toothed gear pump spin, oiling be after coiling can obtain long filament.This long filament is stretched again, or mixed fine with other fiber, or carry out false twisting processing or hand over sth. made by twisting processing etc., can make various fibre products.
As the material that melt-spinning is used, preferred molten viscosity 10～500, more preferably 200～400 hydrolytie polycondensation starch.The melt viscosity of hydrolytie polycondensation starch can be used in the discharge (g) that flowed out 10 minutes from the aperture of diameter 2mm under the condition of 190 ℃ of temperature, loading 2.16kg and determine.Melt viscosity less than 100 or surpass 500 hydrolytie polycondensation starch, the spinning property when making fibre product is low.
For example, when the air-flow (air) of use rectification cooled off spun, slowly the refrigerative method had the tendency of good spinnability than quick cooling.Utilize air-flow to remove in the hydrolytie polycondensation starch and contain moisture.Also can stretch simultaneously or after the spinning with spinning.The tensile break strength of undrawn yarn for example is about 0.2g/d, and tension fracture elongation rate for example is about 530%.By being stretched, undrawn yarn can improve fibre strength.Consider from the viewpoint that improves fibre strength, preferably under the temperature more than the second-order transition temperature of hydrolytie polycondensation starch, undrawn yarn is stretched.By undrawn yarn is stretched, for example can obtain tensile break strength more than 2g/d, can obtain fiber more than the 3g/d according to the difference of stretching condition.
After hydrolytie polycondensation starch of the present invention carried out spinning, boundling became fibrous bundle, and thermal stretch can obtain staple fibre after oiling, reel and cut.Packing immediately after cutting the staple fibre of acquisition, cutting usually.Staple fibre can adopt blending and other blending in of fibers to use.
Use the weaving silk of hydrolytie polycondensation starch fiber of the present invention to hand over sth. made by twisting or to carry out the doubling use with other silk.The fiber of hydrolytie polycondensation starch of the present invention and general long filament or weaving silk similarly can be used to make cloth.The staple fibre of hydrolytie polycondensation starch of the present invention, with general staple fibre similarly, can adopt needle punching, air method, jet net-spraying method, paper process, be used to make non-woven fabrics.
Use hydrolytie polycondensation starch of the present invention can make film and sheet forming product.For example, hydrolytie polycondensation starch of the present invention is carried out extrusion moulding, can make film and sheet material by adopting T font head.When adopting T font head manufactured film or sheet material, by regulating the thickness that extrusion capacity and pulling speed can be controlled gained film or sheet material.The film of hydrolytie polycondensation starch of the present invention and sheet material also can adopt blow moulding manufacturing.When adopting blow moulding to make film or sheet material, the preferred viscosity of using in operation, the MI value is 1～10, especially 1～5 hydrolytie polycondensation starch.
When making hydrolytie polycondensation starch film of the present invention or sheet material, the extrusion temperature selective hydrolysis polycondensation starch fusing point of hydrolytie polycondensation starch up and down 20 ℃ with interior scope, for example, preferred 140～180 ℃.
By hydrolytie polycondensation starch film of the present invention or the sheet material that adopts T font head or blow moulding to make stretched, can make oriented film or stretched sheet.Temperature when hydrolytie polycondensation starch film of the present invention and sheet material are stretched is preferably more than the second-order transition temperature, to the scope greater than 30 ℃ of this temperature.
To hydrolytie polycondensation starch of the present invention stretched sheet not, for example adopt vacuum forming can make molded product.For example, use infrared heater that the sheet material of thick 0.2～2mm is heated to more than the second-order transition temperature, move on on the vacuum forming mould, inhale by mould and paste the shape that can be processed into sheet material mould.
Poly(lactic acid) is the Biodegradable resin that is widely known by the people, tension fracture elongation rate under unstretched state is very little, be 2～3% and matter is crisp is not durable under the normal temperature, in addition, even vacuum forming obtains stretching though be out of shape big part, the part of die edge does not almost stretch, therefore residual not stretched portion, this part matter is crisp and be not durable.And hydrolytie polycondensation starch of the present invention is stretched sheet not, and its tension fracture elongation rate is more than 20% at normal temperature (for example 25 ℃), and stretched portion does not have for actual use mechanical properties yet out of question yet.
Below, describe the present invention in detail with embodiment.
Embodiment 1: the hydrolytie polycondensation starch with base shown in the formula (3)
With W-Gum 100 weight parts, with starch in usually the moisture of contained 12～13 weight % amounts to 70 weight part ion exchanged waters and glycerine 50 weight parts, butyleneglycol 10 weight parts mix, supply to the single screw extrusion machine that has three grades of venting ports of 45mm.Adopt open gland pump, oil diffusion pump to dewater from venting port.The screw rod of design forcing machine make it through supply, mixing, compression, from the venting port dehydration, mixing, from the venting port dehydration, mixing, from the process of venting port dehydration, compression, can obtain effect not second to common twin screw extruder.
The melting effect of screw rod contains sooty polyethylene 2 weight parts by sneaking in water white transparency polypropylene 100 weight parts, mixing back exists part to confirm with microscopic examination comparison sooty.
Showing about about 30 microns size greatly with opticmicroscope affirmation polyethylene in polypropylene disperses equably.
At 150 ℃ of maximum heating temperatures, pressure 230kg/cm
2With the starch hydrolysis, then make the starch of hydrolysis and glycerine promptly carry out open type dehydration polycondensation under the condition of (=22.5MPa).Total residence time is 3 minutes, and raw material supplying speed is 50kg/ hour.After using 100 purpose strainers to filter the hydrolytie polycondensation starch that generates, extrude, be processed into pellet with hot cutter from the nozzle of diameter 1mm.The MI value (180 ℃) of the hydrolytie polycondensation starch pellet that makes is 5, presents good thermoplastic.
Make film by gained hydrolytie polycondensation starch pellet, use Fourier's infrared spectroscopy degree meter to carry out FT-IR and measure, confirm the 1724.9cm that basic distinctive CO stretching vibration forms shown in the unexistent formula of starch (3)
-1Absorption band.Fig. 1 shows with infrared spectrophotometer and carries out the measurement result that FT-IR measures.For the purpose of comparison, gained hydrolytie polycondensation starch is carried out FT-IR measurement result of measuring and the W-Gum that uses as raw material with infrared spectrophotometer be shown in Fig. 2 contrastively with the measurement result that Fourier transform infrared spectrophotometer carries out FT-IR mensuration.
Among Fig. 1 and Fig. 2, the 3294cm of hydrolytie polycondensation starch
-1Absorb the O-H of expression hydrogen bond, 2929cm
-1Absorption represent CH
2The C-H of base, 1724.9cm
-1Absorption represent the C=O of dimethyl ketone group, 1646cm
-1Absorption show the existence of crystal water.Among Fig. 2, the 3295cm of W-Gum
-1Absorb the O-H of expression hydrogen bond, 2929cm
-1Absorption represent CH
2The C-H of base, 1645cm
-1Absorption show the existence of crystal water.W-Gum is not represented the 1724.9cm that the C=O of dimethyl ketone group exists
-1Near absorption.
FT-IR measures and uses パ one キ Application ェ Le マ one corporate system Fourier transform infrared spectrophotometer.
Embodiment 2 and 3: hydrolytie polycondensation starch with base shown in the formula (3)
Except the residence time be 3 minutes (embodiment 2) with 5 minutes (embodiment 3), other are processed into pellet similarly to Example 1, the result is identical with embodiment 1, is confirmed to be to have hydrolytie polycondensation starch basic shown in thermoplasticity and the introducing-type (3).
The moulding of＜sheet material 〉
The T font head extrusion device that uses the 0.5mm slit is extruded under 160 ℃ of head temperatures, makes the about 400 microns not stretched sheet of thickness.The tensile break strength and the tension fracture elongation rate of resulting sheet are as follows, demonstrate the intensity of anti-practicality.Constant moisture rate after 20 ℃ of temperature, relative humidity are placed 24 hours 60% time is as follows.
| Tensile break strength | Tension fracture elongation rate | Moisture rate | |
| Embodiment 1 | ????0.5N/mm 2 | ????125％ | ????6％ |
| Embodiment 2 | ????0.8N/mm 2 | ????88％ | ????5％ |
| Embodiment 3 | ????1.1N/mm 2 | ????71％ | ????4％ |
The moulding of＜film 〉
Not stretched sheet at 90 ℃ the following embodiment 3 of heating chamber temperature stretches 4 times, makes the monodirectional tension film of 100 microns of thickness.The tensile break strength of gained film is 9.9N/mm
2, tension fracture elongation rate is 25%, expresses the intensity of anti-practicality.
Embodiment 4: the hydrolytie polycondensation starch with base shown in the formula (1)
Except the sodium bicarbonate 10 weight parts replacement glycerine that uses the generation carbonic acid gas reacted, other carried out similarly to Example 1.When the hydrolytie polycondensation starch of gained adopts infrared spectrophotometer to measure, because 1745～1755cm that the distinctive CO stretching vibration of new discovery carbonyldioxy forms
-1Absorption band can be confirmed the part base that introducing-type (1) :-O-(C=O)-O-represents in the starch main chain.Starch does not have this absorption band.The MI value of gained hydrolytie polycondensation starch is 23.
Embodiment 5: the hydrolytie polycondensation starch with base shown in the formula (5)
Be equivalent to equimolar poly-alpha-hydroxypropionic acid and replace glycerine reacts except use is converted into monomeric unit, other carry out similarly to Example 1.After using ortho-cresol from gained hydrolytie polycondensation starch, to extract unreacted poly-alpha-hydroxypropionic acid out, use infrared spectrophotometer to measure, because 1730～1740cm that the distinctive CO stretching vibration of new discovery ester group forms
-1Absorption band, (the O-(C=O)-CH (CH that can confirm that the part in the starch main chain imports
3))
mThe base that-O-represents.Starch does not have this absorption band.In addition, from gained hydrolytie polycondensation starch, extract unreacted poly-alpha-hydroxypropionic acid out, detect the peak of the methyl existence that shows poly-alpha-hydroxypropionic acid after NMR analyzes.
Embodiment 6: the hydrolytie polycondensation starch with base shown in the formula (6)
Except using equimolar n-propyl alcohol to replace glycerine reacts, other carry out similarly to Example 1.After from gained hydrolytie polycondensation starch, extracting unreacted n-propyl alcohol with boiled water out, analyze, detect the peak that the methylene radical that shows the unexistent n-propyl alcohol of starch exists, can confirm that the part in the main chain of starch has imported O-CH through NMR
2-CH
2-CH
2The base of-expression.
Embodiment 7: have formula (5) and hydrolytie polycondensation starch basic shown in the formula (6)
Except the n-propyl alcohol that uses half mole number and the poly-alpha-hydroxypropionic acid that is equivalent to half mole number that is converted into monomeric unit replace outside glycerine reacts, other carry out similarly to Example 1.From gained hydrolytie polycondensation starch, extract unreacted n-propyl alcohol out with boiled water, after extracting unreacted poly-alpha-hydroxypropionic acid out with ortho-cresol then, analyze through NMR, detect the peak of the methylene radical existence of the n-propyl alcohol that shows that starch does not have, can confirm that a part has imported O-CH in the starch main chain
2-CH
2-CH
2The base of-expression.In addition, the hydrolytie polycondensation starch that makes adopts infrared spectrophotometer to measure, because 1730～1740cm that the distinctive CO stretching vibration of new discovery ester group forms
-1Absorption band, (the O-(C=O)-CH (CH that can confirm that the part in the starch main chain imports
3))
mThe base that-O-represents.
Embodiment 8～11: crosslinked
In the hydrolytie polycondensation starch that embodiment 1 makes, change addition and add tripoly phosphate sodium STPP, use single screw mixing forcing machine, carry out at 130 ℃ mixing, with dried cutter manufacturing pellet.The measurement result of gained pellet water-swellable is as follows.The little pellet of water-swellable does not have adhesion problems more with hot cutter granulation the time.In addition, make sheet material similarly to Example 1.
| The tripoly phosphate sodium STPP addition | Water-swellable | |
| Embodiment 8 | 0.03 weight % | Dissolving, infinity |
| Embodiment 9 | 0.05 weight % | ????630％ |
| Embodiment 10 | 1 weight % | ????160％ |
| Embodiment 11 | 3 weight % | ????20％ |
The manufacturing of＜molded product 〉
The hydrolytie polycondensation starch of use embodiment 8 is made the not stretched sheet of thick 1mm, after using infrared heater to be heated to 90 ℃ (more than second-order transition temperatures), move on on the normal temperature vacuum forming mould, aspirate with vacuum pump from mold bottom, sheet material is formed with the same shape of mould, use the band knife mold to prune, make molded product.The shape of mould is that the corner angle R of base and opening portion is 5mm, the square of the every limit 5cm of opening surface, the every limit 3cm in base, whether well use the degree of depth to be respectively 3 moulds interval 1cm mould side by side of 2cm, 4cm and 6cm, visually judge the moulding of degree of depth difference, any degree of depth of result all can.This sheet material does not produce destruction, does not produce wall part as thin as a wafer, good forming ability yet.
Embodiment 12: the hydrolytie polycondensation starch with base shown in the formula (8)
Similarly to Example 1, except the positive butyleneglycol replacement glycerine of mole numbers such as use, other carry out similarly to Example 1.Use boiled water from gained hydrolytie polycondensation starch, to extract unreacted positive butyleneglycol out, adopt the NMR analyzing and testing to go out to show the peak that the methylene radical of the unexistent positive butyleneglycol of starch exists, can confirm that the part in the starch main chain has imported O-CH
2-CH
2-CH
2-CH
2The base that-O-represents.
＜softening temperature, fail temperature 〉
Adopt system DSC6200 of Seiko electronics corporation and Seiko electronics corporation to make the result that hydrolytie polycondensation starch that SSC5200 makes embodiment 1～12 is analyzed, softening temperature is that 42～80 ℃, fail temperature are 278～299 ℃.
＜biological degradability 〉
The sheet material that embodiment 1～12 is made drops into commercially available home-use mixing machine, gets a part of sample, the reduction of working sample in per termly 8 hours.Estimate the biological degradability of sheet material with this reduction rate.The combination treatment temperature remains on 40～50 ℃, and blended kind bacterium is divided the use wheat-flour with nutrition.Any sample all can not become the hydrolytie polycondensation samples with starch after 48 hours, demonstrated favorable biological degradability.
Embodiment 13: the manufacturing of fibre product
Use the hydrolytie polycondensation starch fusion of the MI value 32 that forcing machine makes embodiment 12, under 180 ℃ of nozzle temperatures, carry out the undrawn yarn of spinning, oiling, manufacturing circle with toothed gear pump while measuring with the common spinning nozzle of circle.Observed moisture evaporation during spinning, but spinning has not been had detrimentally affect.4.4 times of stretching ratios, make the drawn yarn of fiber 250D/16F of the present invention under 90 ℃ of conditions of heating piece temperature then.The fusing point that DSC measures in the nitrogen environment atmosphere does not appear in this fiber.The tensile break strength of this fiber is 1.8g/d, and tension fracture elongation rate is 22%.
The possibility of utilizing on the industry
Hydrolytie polycondensation starch of the present invention is different from starch, owing to have thermoplasticity, thus can be used as the in the past alternative materials of thermoplastic resin, for example, as the materials'use of making various moulded products and using.
Hydrolytie polycondensation starch of the present invention is different from starch, owing to do not need to carry out drying when making various products formeds with materials'use, so good economy performance. Therefore hydrolytie polycondensation starch of the present invention can easily make its biodegradation owing to similarly have biological degradability with starch in mixing.
Claims (19)
1. hydrolytie polycondensation starch is a part of introducing-type (1) in the starch main chain: the base that-O-(C=O)-O-represents, formula (2) :-((O-R
1)
x-(O-(C=O)-R
2)
y)
m-O
zThe base and formula (3) :-CH of-expression
2-(C=O)-CHR
3The hydrolytie polycondensation starch of at least a kind of base selecting in the group that the base that-O-represents is formed [in the formula (2), R
1Expression C
1Above alkylidene group or C
6Above arylidene; R
2Expression C
1Above alkylidene group or C
6Above arylidene; X represents 0 or 1; Y represents 0 or 1; X+y is 1 or 2; M represents 1～3100 integer; Z represents 0 or 1; In the formula (3), R
3Expression hydrogen atom, C
1Above alkyl, C
6Above aryl or C
1Above alkoxyl group].
2. the described hydrolytie polycondensation starch of claim 1, wherein, the base of introducing-type (1) expression.
3. the described hydrolytie polycondensation starch of claim 1, wherein, introducing-type (4) :-(O-(C=O)-R
2)
mThe base of-expression [x in the formula (2) is 0, y is 1, z be 0 o'clock] is as the base of formula (2) expression.
4. the described hydrolytie polycondensation starch of claim 1, wherein, introducing-type (5) :-(O-(C=O)-R
2)
mThe base that-O-represents [x is 0 in the formula (2), y is 1, z be 1 o'clock] is as the base of formula (2) expression.
5. the described hydrolytie polycondensation starch of claim 1, wherein, introducing-type (6) :-(O-R
1)
mThe base of-expression [x in the formula (2) is 1, y is 0, z be 0 o'clock] is as the base of formula (2) expression.
6. the described hydrolytie polycondensation starch of claim 1, wherein, introducing-type (7) :-(O-R
1-O-(C=O)-R
2)
mThe base of-expression [x in the formula (2) is 1, y is 1, z be 0 o'clock] is as the base of formula (2) expression.
7. the described hydrolytie polycondensation starch of claim 1, wherein, introducing-type (8) :-(O-R
1)
mThe base that-O-represents [x in the formula (2) is 1, y is 0, z be 1 o'clock] is as the base of formula (2) expression.
8. the described hydrolytie polycondensation starch of claim 1, wherein, introducing-type (9) :-(O-R
1-O-(C=O)-R
2)
mThe base that-O-represents [x in the formula (2) is 1, y is 1, z be 1 o'clock] is as the base of formula (2) expression.
9. the described hydrolytie polycondensation starch of claim 1, wherein, the base of introducing-type (3) expression.
10. crosslinked claim 1,2,3,4,5,6,7,8 or 9 described hydrolytie polycondensation starch.
11. claim 1,2,3,4,5,6,7,8,9 or 10 described hydrolytie polycondensation starch wherein, 20 ℃ of temperature, were placed 24 hours under the condition of relative humidity 60%, in fact reaching constant equilibrated moisture rate is 1～6 weight %.
12. claim 1,2,3,4,5,6,7,8,9,10 or 11 described hydrolytie polycondensation starch, wherein, the swelling rate of dipping after 1 hour is 150～400% in the water of 25 ℃ of temperature.
13. present thixotropic claim 1,2,3,4,5,6,7,8,9,10,11 or 12 described hydrolytie polycondensation starch.
14. the manufacture method of hydrolytie polycondensation starch, be make starch with from the compound that forms shown in formula (1) :-O-(C=O)-O-base, form formula (2) :-((O-R
1)
x-(O-(C=O)-R
2)
y)
m-O
z-represent the compound of base and form formula (3) :-CH
2-(C=O)-CHR
3At least a kind the compound of selecting in the group that the compound of base is formed shown in-the O-in the presence of water, 100～350 ℃ down the manufacture method of the hydrolytie polycondensation starch of reaction [in the formula (2), R
1Expression C
1Above alkylidene group or C
6Above arylidene; R
2Expression C
1Above alkylidene group or C
6Above arylidene; X represents 0 or 1; Y represents 0 or 1; X+y is 1 or 2; M represents 1～3100 integer; Z represents 0 or 1; In the formula (3), R
3Expression hydrogen atom, C
1Above alkyl, C
6Above aryl or C
1Above alkoxyl group].
15. the manufacture method of hydrolytie polycondensation starch, be make starch with from the compound that forms shown in formula (1) :-O-(C=O)-O-base, form formula (2) :-((O-R
1)
x-(O-(C=O)-R
2)
y)
m-O
z-represent the compound of base and form formula (3) :-CH
2-(C=O)-CHR
3-O-represents at least a kind of compound selecting in the group that the compound of base forms, in the presence of water and carbon dioxide gas, carbon dioxide gas be the hydrolytie polycondensation starch that reacts under the condition of supercritical state or subcritical state manufacture method [in the formula (2), R
1Expression C
1Above alkylidene group or C
6Above arylidene; R
2Expression C
1Above alkylidene group or C
6Above arylidene; X represents 0 or 1; Y represents 0 or 1; X+y is 1 or 2; M represents 1～3100 integer; Z represents 0 or 1; In the formula (3), R
3Expression hydrogen atom, C
1Above alkyl, C
6Above aryl or C
1Above alkoxyl group].
16. the manufacture method of claim 14 or 15 described hydrolytie polycondensation starch, wherein, starch with from the compound that forms shown in the formula (1) base, form the compound of base shown in the formula (2) and form in the reaction of at least a kind of compound selecting the group that the compound of base shown in the formula (3) forms and use forcing machine, at 100～250kg/cm
2Nozzle before extrude under the pressure.
17. fibre product is made by claim 1,2,3,4,5,6,7,8,9,10,11,12 or 13 described hydrolytie polycondensation starch.
18. film or sheet forming product are made by claim 1,2,3,4,5,6,7,8,9,10,11,12 or 13 described hydrolytie polycondensation starch.
19. molded product are made by claim 1,2,3,4,5,6,7,8,9,10,11,12 or 13 described hydrolytie polycondensation starch.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001238707 | 2001-08-07 | ||
| JP238707/2001 | 2001-08-07 |
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| Publication Number | Publication Date |
|---|---|
| CN1538974A true CN1538974A (en) | 2004-10-20 |
| CN100340579C CN100340579C (en) | 2007-10-03 |
Family
ID=19069581
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|---|---|---|---|
| CNB028154371A Expired - Fee Related CN100340579C (en) | 2001-08-07 | 2002-08-05 | Hydrolysis polycondensation starch, process for producing the same and molded article made of hydrolysis polycondensation starch |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3539955B2 (en) |
| CN (1) | CN100340579C (en) |
| TW (1) | TWI244487B (en) |
| WO (1) | WO2003014164A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113273678A (en) * | 2021-04-29 | 2021-08-20 | 南昌大学 | Preparation method of instant pure kudzu powder with natural particle structure retained |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005336423A (en) * | 2004-05-31 | 2005-12-08 | Hideko Yamaguchi | Method for manufacturing water-resistant, transparent, thermoplastic organic composition, and thermoplastic organic composition obtained thereby |
| GB2423252B (en) * | 2005-02-18 | 2007-10-17 | Engelhard Lyon | Cross-linked polymer of carbohydrate, notably based on polysaccharides, and/or on oligosaccharides and/or on polyols |
| US10920044B2 (en) | 2015-06-30 | 2021-02-16 | BiologiQ, Inc. | Carbohydrate-based plastic materials with reduced odor |
| US20170002184A1 (en) | 2015-06-30 | 2017-01-05 | BiologiQ, Inc. | Articles Formed with Biodegradable Materials and Strength Characteristics of Same |
| US11926929B2 (en) | 2015-06-30 | 2024-03-12 | Biologiq, Inc | Melt blown nonwoven materials and fibers including starch-based polymeric materials |
| US11359088B2 (en) | 2015-06-30 | 2022-06-14 | BiologiQ, Inc. | Polymeric articles comprising blends of PBAT, PLA and a carbohydrate-based polymeric material |
| US11674014B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Blending of small particle starch powder with synthetic polymers for increased strength and other properties |
| US11046840B2 (en) | 2015-06-30 | 2021-06-29 | BiologiQ, Inc. | Methods for lending biodegradability to non-biodegradable plastic materials |
| US11111363B2 (en) | 2015-06-30 | 2021-09-07 | BiologiQ, Inc. | Articles formed with renewable and/or sustainable green plastic material and carbohydrate-based polymeric materials lending increased strength and/or biodegradability |
| US11111355B2 (en) | 2015-06-30 | 2021-09-07 | BiologiQ, Inc. | Addition of biodegradability lending additives to plastic materials |
| US11149144B2 (en) | 2015-06-30 | 2021-10-19 | BiologiQ, Inc. | Marine biodegradable plastics comprising a blend of polyester and a carbohydrate-based polymeric material |
| US10995201B2 (en) | 2015-06-30 | 2021-05-04 | BiologiQ, Inc. | Articles formed with biodegradable materials and strength characteristics of the same |
| US11926940B2 (en) | 2015-06-30 | 2024-03-12 | BiologiQ, Inc. | Spunbond nonwoven materials and fibers including starch-based polymeric materials |
| US11674018B2 (en) | 2015-06-30 | 2023-06-13 | BiologiQ, Inc. | Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics |
| US11879058B2 (en) | 2015-06-30 | 2024-01-23 | Biologiq, Inc | Yarn materials and fibers including starch-based polymeric materials |
| US10752759B2 (en) | 2015-06-30 | 2020-08-25 | BiologiQ, Inc. | Methods for forming blended films including renewable carbohydrate-based polymeric materials with high blow up ratios and/or narrow die gaps for increased strength |
| US10919203B2 (en) | 2015-06-30 | 2021-02-16 | BiologiQ, Inc. | Articles formed with biodegradable materials and biodegradability characteristics thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3720663A (en) * | 1971-06-24 | 1973-03-13 | Nat Starch Chem Corp | Preparation of starch esters |
| DE4001251A1 (en) * | 1990-01-18 | 1991-07-25 | Basf Lacke & Farben | COATING MEASURES, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DE4038732A1 (en) * | 1990-12-05 | 1992-06-11 | Henkel Kgaa | MATERIALS AND / OR COMPONENTS MODIFIED BY SYNTHETIC POLYMER COMPOUNDS AND DRY-BASED METHOD AND METHOD OF MANUFACTURING THEM |
| JP4345944B2 (en) * | 2000-02-18 | 2009-10-14 | キヤノン株式会社 | POLYMER COMPOUND, PROCESS FOR PRODUCING THE SAME, MOLDED ARTICLE, AND METHOD FOR RECYCLING WASTE PAPER |
-
2002
- 2002-08-05 CN CNB028154371A patent/CN100340579C/en not_active Expired - Fee Related
- 2002-08-05 TW TW91117554A patent/TWI244487B/en not_active IP Right Cessation
- 2002-08-05 WO PCT/JP2002/007955 patent/WO2003014164A1/en active Application Filing
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|---|---|---|---|---|
| CN113273678A (en) * | 2021-04-29 | 2021-08-20 | 南昌大学 | Preparation method of instant pure kudzu powder with natural particle structure retained |
| CN113273678B (en) * | 2021-04-29 | 2022-06-14 | 南昌大学 | Preparation method of instant pure kudzu powder with natural particle structure retained |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI244487B (en) | 2005-12-01 |
| WO2003014164A1 (en) | 2003-02-20 |
| CN100340579C (en) | 2007-10-03 |
| JP3539955B2 (en) | 2004-07-07 |
| JPWO2003014164A1 (en) | 2004-11-25 |
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