CN110128591A - A method of improving and keep carboxymethyl starch with high substitution degree viscosity - Google Patents
A method of improving and keep carboxymethyl starch with high substitution degree viscosity Download PDFInfo
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Abstract
The invention belongs to the technical fields of converted starch, disclose the method for a kind of raising and holding carboxymethyl starch with high substitution degree viscosity.Method: 1) mixing carboxymethyl starch with water, obtains gelatinized corn starch；2) monomer is mixed with gelatinized corn starch as a solution, the pH of regulation system is 7.5~9.5, then in an inert atmosphere, initiator is added, 3~8h is reacted at 50~80 DEG C, adjusts the pH of reaction product to neutrality, subsequent processing obtains composite modified carboxymethyl starch；The monomer is one kind of acrylamide or acrylic acid.Method of the invention improves the viscosity of carboxymethyl starch, reaches 5~24 times of different degree of substitution original carboxymethyl starch, solves the problems, such as that carboxymethyl starch viscosity is improved with degree of substitution and reduced.The composite modified carboxymethyl starch obtained by the method for the invention is with the improve of degree of substitution, and viscosity can maintain always higher level, with good viscosity stability.
Description
Technical field
The invention belongs to the technical fields of converted starch, and in particular to a kind of compound by be grafted to carboxymethyl starch
It is modified, to improve and keep carboxymethyl starch viscosity, the especially method of carboxymethyl starch with high substitution degree viscosity.
Background technique
Carboxymethyl starch is starch by a kind of modified obtained anion converted starch of carboxymethyl etherification, is had non-
Often it is widely applied field.In performance, when the etherificate degree of substitution of carboxymethyl starch reaches 0.1, it can be swollen in cold water
At uniform gelatinized corn starch, liquid function admirable is pasted, using upper also very convenient.
But after the etherificate degree of substitution of carboxymethyl starch reaches about 0.2, continues to increase degree of substitution, will not only increase
Add viscosity, will appear the raising with degree of substitution instead, the shortcomings that reaction control constantly reduces, and also degree of substitution is higher, viscosity
It is lower.
Lacking for rapid decrease occurs for this increase with degree of substitution of carboxymethyl starch with high substitution degree, the viscosity for pasting liquid
It falls into, greatly reduces its thickening properties, directly affect the performances such as its freeze-thaw stability, flocculability and absorption property, limit significantly
Application of the carboxymethyl starch in fields such as sizing agent, flocculant and spinning sizing agents.How to overcome drawbacks described above, prepares simultaneously
It is always the Scientific And Technical brainstorm subject of the technical field with high substituted degree and highly viscous carboxymethyl modified starch.
In order to improve and promoted the viscosity and viscosity stability of carboxymethyl starch with high substitution degree, the current country has multinomial grind
Study carefully report, such as it is carried out using crosslinking agent such as epoxychloropropane, sodium trimetaphosphate, sodium tripolyphosphate, calgon secondary
Modified, preparation is crosslinked composite modified carboxymethyl starch etc., and the purpose is to the methods by being crosslinked to increase its viscosity.In patent application
In " preparation method of High Viscosity Crosslinked Carboxymethyl Starch " (104311681 A of CN), use epoxychloropropane as crosslinking agent,
Prepare crosslinked carboxymethyl fecula；At patent application " preparation method of superelevation viscosity sodium carboxymethyl starch " (105859895 A of CN)
In, use sodium trimetaphosphate as crosslinking agent preparation crosslinked carboxymethyl fecula sodium etc..Above-mentioned method of modifying is viscous to carboxymethyl starch
The promotion of degree and stability has some improvement and helps, but does not reach the degree of meet demand, especially high substitution
The problem of degree carboxymethyl starch viscosity is decreased obviously still needs to be resolved.
The present invention be grafted to carboxymethyl starch composite modified, is successfully prepared a kind of while having high substituted degree and height
Viscosity, and the composite modified carboxymethyl starch that the viscosity stability that is not decreased obviously by increasing for degree of substitution of viscosity is excellent.
The viscosity of composite modified carboxymethyl starch of the invention reaches the former carboxylic of different degree of substitution close to even more than 20000mPas
5~24 times of methyl starch.Composite modified carboxymethyl starch prepared by the present invention, not only viscosity increases substantially, but also with taking
The raising of Dai Du keeps stablizing.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a kind of raisings and the high substitution of holding
Spend the method for carboxymethyl starch viscosity.The present invention carries out graft modification to carboxymethyl starch using monomer, improves and keep carboxylic first
Base starch, especially carboxymethyl starch with high substitution degree viscosity.
The purpose of the present invention is achieved through the following technical solutions:
A method of improving and keep carboxymethyl starch with high substitution degree viscosity, comprising the following steps:
1) carboxymethyl starch is mixed with water, obtains gelatinized corn starch；
2) monomer is mixed with gelatinized corn starch as a solution, the pH of regulation system is 7.5~9.5, then in inertia atmosphere
Under enclosing, initiator is added, 3~8h is reacted at 50~80 DEG C, adjusts the pH of reaction product to neutrality, subsequent processing is answered
Close modified carboxy methyl starch.
The mass volume ratio of carboxymethyl starch described in step 1) and water is (10~100) g:(200~800) mL；
Carboxymethyl starch described in step 1) includes cornstarch, tapioca, potato starch, wheaten starch, rice
One or more of carboxymethyl starch made by starch and/or wax (glutinous) cornstarch, carboxymethyl takes in carboxymethyl starch
Dai Du is 0.1~2.0.
Monomer described in step 2) is one kind of acrylamide or acrylic acid；When monomer is acrylamide, solution third
Acrylamide aqueous solution；Mass ratio=1:1~1:3 of acrylamide and water in acrylamide aqueous solution；When monomer is acrylic acid,
Solution is the sodium hydroxide solution of acrylic acid；The mass ratio of acrylic acid and sodium hydroxide solution in the sodium hydroxide solution of acrylic acid
=1:1~1:4；The mass concentration of sodium hydroxide solution is 20%~40%；
The mass ratio of carboxymethyl starch is 0.5:1~2:1 in monomer described in step 2) and gelatinized corn starch；
The pH of regulation system described in step 2) refers to for 7.5~9.5 to be adjusted using sodium hydroxide solution；Hydroxide
The mass concentration of sodium solution is 10%~30%；
Inert atmosphere is nitrogen atmosphere in step 2).
Initiator described in step 2) is potassium peroxydisulfate；The initiator is added in form of an aqueous solutions, draws in aqueous solution
The mass ratio for sending out agent and water is (5~12): 100.
The pH that reaction product is adjusted in step 2) refers to neutrality to be adjusted using sulfuric acid solution.
The dosage of initiator described in step 2) is the 0.6%~6% of carboxymethyl starch quality；
Subsequent processing described in step 2) refer to use volume fraction settle, filter for 95% ethanol water, volume point
Number is the washing of 90% ethanol water, dry, crushing, sieving.
Method of the invention can be improved carboxymethyl starch viscosity, and with the raising of degree of substitution, viscosity is able to maintain
Stablize, the low phenomenon of current high substituted carboxymethyl starch reaction control is avoided, in addition, the carboxymethyl starch being prepared also has
Other better performances, such as higher transparency and better water-retaining property.
Compared with prior art, the present invention has the advantage that
(1) present invention in a manner of graft copolymerization, introduces polyacrylamide, polypropylene in carboxymethyl starch molecule
Sour branch can improve the performance indexes of former carboxymethyl starch comprehensively.
(2) the composite modified carboxymethyl starch of the method for the present invention preparation can increase substantially the viscous of carboxymethyl starch paste liquid
Degree, and the amplitude improved reaches 5~24 times of different degree of substitution carboxymethyl starch.
(3) raising of the composite modified carboxymethyl starch of the method for the present invention preparation with degree of substitution, carboxymethyl starch paste liquid
Viscosity can maintain higher level always, have good viscosity stability.
(4) the composite modified carboxymethyl starch of the method for the present invention preparation also has higher transparency and better water-retaining property
The advantages that.
Detailed description of the invention
Fig. 1 is composite modified carboxymethyl starch prepared by the present invention and unmodified carboxymethyl starch (former carboxymethyl starch)
Viscograph under different degree of substitution；Wherein curve (1) is composite modified carboxymethyl starch, and curve (2) is that former carboxymethyl forms sediment
Powder.
Specific embodiment
Present invention is further described in detail combined with specific embodiments below, but embodiments of the present invention are not limited to
This.
Embodiment 1
(1) the carboxymethyl cornstarch and the uniformly mixed acquisition gelatinized corn starch of 500mL water for being 0.6 by 40g degree of substitution；
(2) 40g acrylamide is mixed with 40g water, solution is added in gelatinized corn starch liquid to being completely dissolved for stirring, stirring
Uniformly；Then the sodium hydroxide solution that mass concentration is 10% is added dropwise, adjusts the pH=7.5 of reaction system；
(3) nitrogen, time 30min are slowly filled with；
(4) 0.24g potassium peroxydisulfate is mixed with 4.8g water, stirring adjusts initiator solution addition to being completely dissolved
In the gelatinized corn starch of pH value and it is uniformly mixed；
(5) 50 DEG C of insulation reaction 5h obtain reaction product；
(6) after reaction, the pH of sulfuric acid solution adjusting reaction product is added dropwise to neutrality, the use of volume fraction is 95% second
Alcohol solution sedimentation, filtering, volume fraction are the washing of 90% ethanol water, 55 DEG C of dryings, crushing, sievings, obtain compound change
Property carboxymethyl starch.
The composite modified carboxymethyl starch of former carboxymethyl starch and preparation is made into the paste liquid that mass fraction is 3%, wait paste
It the use of rotational viscometer tested viscosity is respectively 3090mPas and 24700mPas, increasing multiplying power is about 8 times after changing completely；
It the use of the transparency that ultraviolet specrophotometer tests two kinds of paste liquid is respectively 18.40% and 19.97%, increasing multiplying power is about 1.1
Times；After taking two kinds of paste liquid 10mL to be centrifuged 1h under the conditions of 2500r/min respectively, be precipitated water volume be respectively 5.9mL and
1.8mL, it is about 2.00 times that water-retaining property, which increases multiplying power,.
Embodiment 2
(1) carboxymethyl cassava starch and the uniformly mixed acquisition gelatinized corn starch of 800mL water for being 0.1 by 60g degree of substitution；
(2) 90g acrylamide is mixed with 140g water, solution is added in gelatinized corn starch liquid to being completely dissolved for stirring, stirring
Uniformly；Under agitation, the sodium hydroxide solution that mass concentration is 30% is added dropwise into the gelatinized corn starch liquid that monomer is added, adjusts
The pH=8.5 of reaction system；
(3) nitrogen, time 30min are slowly filled with；
(4) 0.6g potassium peroxydisulfate is mixed with 5.4g water, the shallow lake for adjusting pH value is added to being completely dissolved in solution by stirring
In paste mixing and it is uniformly mixed；
(5) 60 DEG C of insulation reaction 3h obtain reaction product；
(6) after reaction, the pH of sulfuric acid solution adjusting reaction product is added dropwise to neutrality, is sunk using 95% ethanol water
Drop, filtering, the washing of 90% ethanol water, 55 DEG C of dryings, crushing, sievings, obtain composite modified carboxymethyl starch.
Embodiment 3
(1) the carboxymethyl wheaten starch and the uniformly mixed acquisition gelatinized corn starch of 600mL water for being 1.2 by 20g degree of substitution；
(2) 10g acrylamide is mixed with 30g water, solution is added in gelatinized corn starch liquid to being completely dissolved for stirring, stirring
Uniformly；
(3) under agitation, the sodium hydroxide solution that mass concentration is 20% is added dropwise into gelatinized corn starch liquid, adjusts reaction
The pH=9 of system；
(4) nitrogen, time 30min are slowly filled with；
(5) 1.2g potassium peroxydisulfate is mixed with 12g water, the shallow lake for adjusting pH value is added to being completely dissolved in solution by stirring
In paste mixing and it is uniformly mixed；
(6) 70 DEG C of insulation reaction 3h obtain reaction product；
(7) after reaction, the pH of sulfuric acid solution adjusting reaction product is added dropwise to neutrality, is sunk using 95% ethanol water
Drop, filtering, the washing of 90% ethanol water, 55 DEG C of dryings, crushing, sievings, obtain composite modified carboxymethyl starch.
Embodiment 4
(1) carboxymethyl potato starch and the uniformly mixed acquisition gelatinized corn starch of 800mL water for being 0.7 by 30g degree of substitution；
It (2) is that 20% sodium hydroxide solution mixes with 60g mass concentration by 60g acrylic acid, stirring, will be molten to being uniformly mixed
Liquid is added in gelatinized corn starch liquid, stirs evenly；
(3) under agitation, it is molten that the sodium hydroxide that mass concentration is 15% is added dropwise into the gelatinized corn starch liquid that monomer is added
Liquid adjusts the pH=7.5 of reaction system；
(4) nitrogen, time 30min are slowly filled with；
(5) 0.2g potassium peroxydisulfate is mixed with 2.5g water, the shallow lake for adjusting pH value is added to being completely dissolved in solution by stirring
In paste mixing and it is uniformly mixed；
(6) 50 DEG C of insulation reaction 5h obtain reaction product；
(7) after reaction, the pH of sulfuric acid solution adjusting reaction product is added dropwise to neutrality, is sunk using 95% ethanol water
Drop, filtering, the washing of 90% ethanol water, 55 DEG C of dryings, crushing, sievings, obtain composite modified carboxymethyl starch.
Embodiment 5
(1) the carboxymethyl waxy corn starch and the uniformly mixed acquisition gelatinized corn starch of 600mL water for being 1.0 by 70g degree of substitution；
(2) 140g acrylamide is mixed with 280g water, solution is added in gelatinized corn starch liquid, stirs to being completely dissolved by stirring
It mixes uniformly；
(3) under agitation, it is molten that the sodium hydroxide that mass concentration is 15% is added dropwise into the gelatinized corn starch liquid that monomer is added
Liquid adjusts the pH=8.5 of reaction system；
(4) nitrogen, time 30min are slowly filled with；
(5) 0.5g potassium peroxydisulfate is mixed with 8g water, the starch for adjusting pH value is added to being completely dissolved in solution by stirring
In paste and it is uniformly mixed；
(6) 70 DEG C of insulation reaction 4h obtain reaction product；
(7) after reaction, the pH of sulfuric acid solution adjusting reaction product is added dropwise to neutrality, is sunk using 95% ethanol water
Drop, filtering, the washing of 90% ethanol water, 55 DEG C of dryings, crushing, sievings, obtain composite modified carboxymethyl starch.
The composite modified carboxymethyl starch of former carboxymethyl starch and preparation is made into the paste liquid that mass fraction is 3%, wait paste
After changing completely, using rotational viscometer tested viscosity, as a result respectively 1056mPas and 25050mPas；Viscosity increases again
Rate is about 24 times；The use of the transparency that ultraviolet specrophotometer tests two kinds of paste liquid is respectively 16.30% and 21.70%, increases
Multiplying power is about 1.33 times；After taking two kinds of paste liquid 10mL to be centrifuged 1h under the conditions of 2500r/min respectively, water volume, which is precipitated, is respectively
6.6mL and 3.6mL, it is about 1.80 times that water-retaining property, which increases multiplying power,.
Embodiment 6
(1) carboxymethyl cassava starch and the uniformly mixed acquisition gelatinized corn starch of 700mL water for being 0.5 by 60g degree of substitution；
(2) 75g acrylamide is mixed with 120g water, solution is added in gelatinized corn starch liquid to being completely dissolved for stirring, stirring
Uniformly；
(3) under agitation, it is molten that the sodium hydroxide that mass concentration is 10% is added dropwise into the gelatinized corn starch liquid that monomer is added
Liquid adjusts the pH=7.5 of reaction system；
(4) nitrogen, time 30min are slowly filled with；
(5) 0.36g potassium peroxydisulfate is mixed with 6g water, the shallow lake for adjusting pH value is added to being completely dissolved in solution by stirring
In paste mixing and it is uniformly mixed；
(6) 80 DEG C of insulation reaction 3h obtain reaction product；
(7) after reaction, the pH of sulfuric acid solution adjusting reaction product is added dropwise to neutrality, is sunk using 95% ethanol water
Drop, filtering, the washing of 90% ethanol water, 55 DEG C of dryings, crushing, sievings, obtain composite modified carboxymethyl starch.
Embodiment 7
It (1) is that 1.8 carboxymethyl rice starch and 200mL water are uniformly mixed and obtain gelatinized corn starch by 10g degree of substitution；
(2) 15g acrylamide is mixed with 45g water, solution is added in gelatinized corn starch liquid to being completely dissolved for stirring, stirring
Uniformly；
(3) under agitation, the hydroxide that mass concentration is 25% is slowly added into the starch system that monomer is added
Sodium solution adjusts the pH=9 of reaction system；
(4) nitrogen, time 30min are slowly filled with；
(5) 0.6g potassium peroxydisulfate is mixed with 5.4g water, the shallow lake for adjusting pH value is added to being completely dissolved in solution by stirring
In paste mixing and it is uniformly mixed；
(6) 50 DEG C of insulation reaction 7h obtain reaction product；
(7) after reaction, the pH of reaction product is adjusted to neutrality, uses the sedimentation of 95% ethanol water, filtering, 90%
Ethanol water washing, 55 DEG C of dryings, crushing, sievings, obtain composite modified carboxymethyl starch.
Embodiment 8
(1) the carboxymethyl cornstarch and the uniformly mixed acquisition gelatinized corn starch of 800mL water for being 0.8 by 100g degree of substitution；
(2) 100g acrylamide is mixed with 100g water, solution is added in gelatinized corn starch liquid, stirs to being completely dissolved by stirring
It mixes uniformly；
(3) under agitation, it is molten that the sodium hydroxide that mass concentration is 20% is added dropwise into the gelatinized corn starch liquid that monomer is added
Liquid adjusts the pH=8 of reaction system；
(4) nitrogen, time 30min are slowly filled with；
(5) 0.6g potassium peroxydisulfate is mixed with 6g water, the starch for adjusting pH value is added to being completely dissolved in solution by stirring
In paste and it is uniformly mixed；
(6) 60 DEG C of insulation reaction 4h obtain reaction product；
(7) after reaction, the pH of sulfuric acid solution adjusting reaction product is added dropwise to neutrality, is sunk using 95% ethanol water
Drop, filtering, the washing of 90% ethanol water, 55 DEG C of dryings, crushing, sievings, obtain composite modified carboxymethyl starch.
The composite modified carboxymethyl starch of former carboxymethyl starch and preparation is made into the paste liquid that mass fraction is 3%, wait paste
After changing completely, using rotational viscometer tested viscosity, as a result respectively 1162mPas and 18700mPas, viscosity increase again
Rate is about 16 times；The use of the transparency that ultraviolet specrophotometer tests two kinds of paste liquid is respectively 18.73% and 21.3%, increases again
Rate is about 1.13 times；After taking two kinds of paste liquid 10mL to be centrifuged 1h under the conditions of 2500r/min respectively, water volume, which is precipitated, is respectively
6.3mL and 2.8mL, it is about 1.88 times that water-retaining property, which increases multiplying power,.
Embodiment 9
(1) the carboxymethyl rice starch and the uniformly mixed acquisition gelatinized corn starch of 400mL water for being 0.4 by 80g degree of substitution；
(2) 60g acrylamide is mixed with 90g water, solution is added in gelatinized corn starch liquid to being completely dissolved for stirring, stirring
Uniformly；
(3) under agitation, it is molten that the sodium hydroxide that mass concentration is 10% is added dropwise into the gelatinized corn starch liquid that monomer is added
Liquid adjusts the pH=8.5 of reaction system；
(4) nitrogen, time 30min are slowly filled with；
(5) 0.48g potassium peroxydisulfate is mixed with 6g water, the shallow lake for adjusting pH value is added to being completely dissolved in solution by stirring
In paste mixing and it is uniformly mixed；
(6) 50 DEG C of insulation reaction 5h obtain reaction product；
(7) after reaction, the pH of sulfuric acid solution adjusting reaction product is added dropwise to neutrality, is sunk using 95% ethanol water
Drop, filtering, the washing of 90% ethanol water, 55 DEG C of dryings, crushing, sievings, finally obtain composite modified carboxymethyl starch.
The composite modified carboxymethyl starch of former carboxymethyl starch and preparation is made into the paste liquid that mass fraction is 3%, wait paste
After changing completely, using rotational viscometer tested viscosity, as a result respectively 2975mPas and 21100mPas, viscosity increase again
Rate is about 7 times；The use of the transparency that ultraviolet specrophotometer tests two kinds of paste liquid is respectively 15.10% and 17.40%, increases again
Rate is about 1.15 times；After taking two kinds of paste liquid 10mL to be centrifuged 1h under the conditions of 2500r/min respectively, water volume, which is precipitated, is respectively
6.1mL and 2.3mL, it is about 1.97 times that water-retaining property, which increases multiplying power,.
Embodiment 10
(1) the carboxymethyl waxy corn starch and the uniformly mixed acquisition gelatinized corn starch of 500mL water for being 2.0 by 50g degree of substitution；
(2) 80g acrylamide is mixed with 80g water, solution is added in gelatinized corn starch liquid to being completely dissolved for stirring, stirring
Uniformly；
(3) under agitation, it is molten that the sodium hydroxide that mass concentration is 15% is added dropwise into the gelatinized corn starch liquid that monomer is added
Liquid adjusts the pH=9.5 of reaction system；
(4) nitrogen, time 30min are slowly filled with；
(5) 0.4g potassium peroxydisulfate is mixed with 4g water, the starch for adjusting pH value is added to being completely dissolved in solution by stirring
In paste and it is uniformly mixed；
(6) 70 DEG C of insulation reaction 3h obtain reaction product；
(7) after reaction, the pH of sulfuric acid solution adjusting reaction product is added dropwise to neutrality, is sunk using 95% ethanol water
Drop, filtering, the washing of 90% ethanol water, 55 DEG C of dryings, crushing, sievings, obtain composite modified carboxymethyl starch.
Embodiment 11
(1) the carboxymethyl cornstarch and the uniformly mixed acquisition gelatinized corn starch of 500mL water for being 0.2 by 30g degree of substitution；
(2) 30g acrylamide is mixed with 30g water, solution is added in gelatinized corn starch liquid to being completely dissolved for stirring, stirring
Uniformly；Then the sodium hydroxide solution that mass concentration is 10% is added dropwise, adjusts the pH=7.5 of reaction system；
(3) nitrogen, time 30min are slowly filled with；
(4) 0.18g potassium peroxydisulfate is mixed with 3.6g water, stirring adjusts initiator solution addition to being completely dissolved
In the gelatinized corn starch of pH value and it is uniformly mixed；
(5) 50 DEG C of insulation reaction 5h obtain reaction product；
(6) after reaction, the pH of sulfuric acid solution adjusting reaction product is added dropwise to neutrality, the use of volume fraction is 95% second
Alcohol solution sedimentation, filtering, volume fraction are the washing of 90% ethanol water, 55 DEG C of dryings, crushing, sievings, obtain compound change
Property carboxymethyl starch.
The composite modified carboxymethyl starch of former carboxymethyl starch and preparation is made into the paste liquid that mass fraction is 3%, wait paste
It the use of rotational viscometer tested viscosity is respectively 4870mPas and 26000mPas, increasing multiplying power is about 5 times after changing completely；
It the use of the transparency that ultraviolet specrophotometer tests two kinds of paste liquid is respectively 14.21% and 62.73%, increasing multiplying power is more about
4.4 again；After taking two kinds of paste liquid 10mL to be centrifuged 1h under the conditions of 2500r/min respectively, it is respectively 6.2mL and 2.6mL that moisture, which is precipitated,
It is about 1.94 times that water-retaining property, which increases multiplying power,.
Performance test: influence of the degree of substitution to viscosity:
The preparation of composite modified carboxymethyl starch:
The carboxymethyl starch of 40g different degree of substitution (degree of substitution is respectively 0.2,0.4,0.6,0.8,1.0) and 600g are steamed
Distilled water is uniformly mixed and (is warming up to 55 DEG C, sufficiently gelatinization 50min), obtains gelatinized corn starch；Weighing acrylamide solid, (acrylamide is solid
Body is 1:1 with carboxymethyl starch mass ratio) it is mixed with distilled water (mass ratio of acrylamide and distilled water is 1:1), stirring is extremely
It is completely dissolved, acrylamide solution is added in gelatinized corn starch liquid, stir 10min, be adjusted to the pH=7.5 of system, be then charged with
Nitrogen, time 30min；Potassium peroxydisulfate solid (potassium peroxydisulfate and the proportion of acylamide 0.006:1) is weighed, distilled water is added
Potassium persulfate solution addition is contained monomer to dissolving completely by (mass ratio of potassium peroxydisulfate and distilled water is 0.06:1), stirring
Gelatinized corn starch liquid in, the insulated and stirred at 55 DEG C, reaction 4 hours after take out, precipitated, wadded a quilt with cotton with 95% ethanol water
Shape precipitating, filtering are that 90% ethanol water washs with volume fraction, 24 hours dry at 55 DEG C, obtain carboxymethyl starch
Acrylamide grafted copolymer (i.e. composite modified starch).
3% paste liquid is respectively prepared in the carboxymethyl starch of the composite modified carboxymethyl starch of above-mentioned preparation and different degree of substitution
And test its viscosity.Test results are shown in figure 1.Fig. 1 be composite modified carboxymethyl starch prepared by the present invention with it is unmodified
Viscograph of the carboxymethyl starch (former carboxymethyl starch) under different degree of substitution；Wherein curve (1) is composite modified carboxymethyl
Starch, curve (2) are former carboxymethyl starch.
The viscosity of composite modified carboxymethyl starch of the invention reaches different substitutions close to even more than 20000mPas
5~24 times or more for spending former carboxymethyl starch.In contrast, the viscosity without composite modified carboxymethyl starch, with substitution
Degree is increased and is gradually reduced, shown in curve (2) as shown in figure 1.Pass through carboxymethyl starch and composite modified carboxymethyl starch viscosity
Comparison display, the composite modified carboxymethyl starch of the method for the present invention preparation, not only viscosity increases substantially, but also not with substitution
The raising of degree and be decreased obviously.These advantages are beneficial to expand carboxymethyl starch with high substitution degree in the application of different field, mention
The value of high carboxymethyl starch.
Claims (10)
1. a kind of method of raising and holding carboxymethyl starch with high substitution degree viscosity, it is characterised in that: the following steps are included:
1) carboxymethyl starch is mixed with water, obtains gelatinized corn starch；
2) monomer being mixed with gelatinized corn starch as a solution, the pH of regulation system is 7.5~9.5, then in an inert atmosphere,
Initiator is added, 3~8h is reacted at 50~80 DEG C, adjusts the pH of reaction product to neutrality, subsequent processing obtains composite modified
Carboxymethyl starch；
Monomer described in step 2) is one kind of acrylamide or acrylic acid.
2. the method for improving according to claim 1 and keeping carboxymethyl starch with high substitution degree viscosity, it is characterised in that: step
2) mass ratio of carboxymethyl starch is 0.5:1~2:1 in monomer described in and gelatinized corn starch；
Degree of substitution by carboxymethyl is 0.1~2 in carboxymethyl starch described in step 1).
3. the method for improving according to claim 1 and keeping carboxymethyl starch with high substitution degree viscosity, it is characterised in that: step
2) initiator described in is potassium peroxydisulfate；The dosage of initiator described in step 2) be carboxymethyl starch quality 0.6%~
6%.
4. the method for improving according to claim 1 and keeping carboxymethyl starch with high substitution degree viscosity, it is characterised in that: step
2) monomer described in is one kind of acrylamide or acrylic acid；When monomer is acrylamide, solution is acrylamide aqueous solution；
When monomer is acrylic acid, solution is the sodium hydroxide solution of acrylic acid.
5. the method for improving according to claim 4 and keeping carboxymethyl starch with high substitution degree viscosity, it is characterised in that: propylene
Mass ratio=1:1~1:3 of acrylamide and water in amide aqueous solution；
Mass ratio=1:1~1:4 of acrylic acid and sodium hydroxide solution in the sodium hydroxide solution of acrylic acid；Sodium hydroxide solution
Mass concentration be 20%~40%.
6. the method for improving according to claim 1 and keeping carboxymethyl starch with high substitution degree viscosity, it is characterised in that: step
1) mass volume ratio of carboxymethyl starch described in and water is (10~100) g:(200~800) mL.
7. the method for improving according to claim 1 and keeping carboxymethyl starch with high substitution degree viscosity, it is characterised in that: step
2) initiator described in is added in form of an aqueous solutions；The pH of regulation system described in step 2) refers to for 7.5~9.5 using hydrogen
Sodium hydroxide solution is adjusted.
8. the method for improving according to claim 7 and keeping carboxymethyl starch with high substitution degree viscosity, it is characterised in that: step
2) initiator described in is added in form of an aqueous solutions, and the mass ratio of initiator and water is (5~12) in aqueous solution: 100；
The pH of regulation system described in step 2) refers to for 7.5~9.5 to be adjusted using sodium hydroxide solution；Sodium hydroxide is molten
The mass concentration of liquid is 10%~30%.
9. the method for improving according to claim 1 and keeping carboxymethyl starch with high substitution degree viscosity, it is characterised in that: step
2) pH that reaction product is adjusted in refers to neutrality to be adjusted using sulfuric acid solution；
Subsequent processing described in step 2), which refers to, uses that volume fraction is settled for 95% ethanol water, filtered, volume fraction is
The washing of 90% ethanol water, drying.
10. a kind of composite modified carboxymethyl starch, it is characterised in that: obtained by any one of claim 1~9 the method.
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| CN117164765A (en) * | 2023-11-01 | 2023-12-05 | 中国核电工程有限公司 | Nuclear engineering concrete temperature-control corrosion-resistant component and preparation method and application thereof |
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| CN103342779A (en) * | 2013-05-23 | 2013-10-09 | 内蒙古大学 | Novel technology of preparing super absorbent resin by using carboxymethyl potato starch ether sodium |
| JP2014532792A (en) * | 2011-11-04 | 2014-12-08 | アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップＡｋｚｏ Ｎｏｂｅｌ Ｃｈｅｍｉｃａｌｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｂ．Ｖ． | Grafted dendritic copolymer and method for producing the same |
| CN108383224A (en) * | 2018-04-12 | 2018-08-10 | 王建玲 | A kind of flocculant of environmentally protective degerming |
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| JP2014532792A (en) * | 2011-11-04 | 2014-12-08 | アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップＡｋｚｏ Ｎｏｂｅｌ Ｃｈｅｍｉｃａｌｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｂ．Ｖ． | Grafted dendritic copolymer and method for producing the same |
| CN103342779A (en) * | 2013-05-23 | 2013-10-09 | 内蒙古大学 | Novel technology of preparing super absorbent resin by using carboxymethyl potato starch ether sodium |
| CN108383224A (en) * | 2018-04-12 | 2018-08-10 | 王建玲 | A kind of flocculant of environmentally protective degerming |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117164765A (en) * | 2023-11-01 | 2023-12-05 | 中国核电工程有限公司 | Nuclear engineering concrete temperature-control corrosion-resistant component and preparation method and application thereof |
| CN117164765B (en) * | 2023-11-01 | 2024-02-23 | 中国核电工程有限公司 | Nuclear engineering concrete temperature-control corrosion-resistant component and preparation method and application thereof |
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