CN107805284A - One kind is used for the rabbit hair and crude oil starch base natural polymer emulsifying agent and preparation method thereof - Google Patents
One kind is used for the rabbit hair and crude oil starch base natural polymer emulsifying agent and preparation method thereof Download PDFInfo
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- CN107805284A CN107805284A CN201610817980.3A CN201610817980A CN107805284A CN 107805284 A CN107805284 A CN 107805284A CN 201610817980 A CN201610817980 A CN 201610817980A CN 107805284 A CN107805284 A CN 107805284A
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- stearate
- starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/11—Starch or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
- D06M2101/12—Keratin fibres or silk
Abstract
The invention discloses a kind of preparation method of CMS stearate：Using starch as matrix, by etherification reaction and ester exchange reaction, starch base natural polymer emulsifying agent CMS stearate is prepared.In first step etherification reaction：100 parts of native cornstarch, 13~15 parts of chloroacetic acid, 7~8 parts of sodium hydroxide, 18~20 parts of ethanol, 18~20 parts of deionized water, reaction temperature are 48~52 DEG C.In second step esterification：100 parts of starch after etherificate, 162~169 parts of stearic acid, 16~17 parts of enuatrol, 8~9 parts of sodium carbonate, 830~840 parts of deionized water, when reaction temperature is 118 DEG C 122 DEG C, the CMS stearate substitution value of preparation can reach 0.356.Each component in the emulsifying agent pair and crude oil formula has very strong emulsifiability, it is by increasing the viscosity with crude oil emulsion, make emulsion-stabilizing, it is favorably improved the binding ability of emulsion and wool fibre surface, improve oil applying rate, rabbit fur fibre cohesive force after oiling is remarkably reinforced, and spinnability significantly improves.
Description
Technical field
The present invention relates to the exploitation of natural polymer additive in the rabbit hair and crude oil, specially a kind of CMS is stearic
Acid esters emulsifying agent and preparation method thereof.
Background technology
It is a kind of indispensable important auxiliary agent that woolen industry is added in spinning process with crude oil.It is in wool fibre
In combing and spinning process, cohesive force between reinforcing fiber is played, reduces fibre damage, and keeps fiber softening and the mesh of elasticity
's；It can also reduce simultaneously in combing and spinning process because of electrostatic caused by friction, reduce fly phenomenon and winding needle cloth phenomenon, from
And spinning is smoothed out, improve row yielding and production efficiency.
Importance for rabbit hair spinning processing, and crude oil is also self-evident.Rabbit fur fibre surface is smooth, friction system
Number is small, and light specific gravity, resistance is big, and fibre cohesion is poor during spinning processing, easy fracture, to fly hair serious, and electrostatic is serious.Therefore,
Make the rabbit hair spinning be smoothed out, in addition to a rational processing technology is formulated, pair and crude oil it is also proposed many particular/special requirements.
It is fine should also to possess stronger raising in addition to it should possess the infiltration of common and crude oil, lubrication and the performance of softness for the rabbit hair and crude oil
Coefficient of friction, increase collection of filaments ability, stronger antistatic effect are tieed up, while must also be had and easily be removed, be degradable, without flaw
The features such as dirt.
With regard to and crude oil for, its composition can be divided into two major parts：Basic finish and additive.Basic finish is and hair
The bulk composition of finish, primarily serves smoothing effect, therefore also known as smooth agent.Although additive with proportion in crude oil agent not
Greatly, but playing such as increases obvolvent, antistatic, the easily effect such as wetting, infiltration, emulsification, and makees in above-mentioned effect, and to emulsify
With the most prominent.Therefore, additive is mostly some surface reactive materials, therefore also known as emulsifying agent.
According to molecular size range, surface reactive material can be divided into low molecule emulsifying agent (molecular weight 100~1000), in point
Sub- emulsifying agent (molecular weight 1000~10000) and macromolecule emulsifier (molecular weight is more than 10000).Wherein macromolecule emulsifier
Though surface-active protrudes not as the above two, in emulsification, solubilising it is especially scattered, it is stable etc. there is unique efficiency, ten
Dividing has development prospect.Macromolecule emulsifier by sources divides, and can be divided into and natural be macromolecule emulsifier and synthesis is macromolecule
Emulsifying agent.Regardless of whether from the ready availability of resource, or to environment, the security of human body, compatibility and sustainable development side
Face considers, be naturally that advantage possessed by macromolecule emulsifier all synthesizes is that macromolecule emulsifier can not compare.
China's starch resource enriches, and prepares macromolecule emulsifier, and nearly ten using this cheap renewable resource
The important development direction of macromolecule emulsifier product over year.Starch-based high molecular emulsifying agent not only shows good thickening, divided
The performance such as scattered, emulsification, solubilising, film forming, protecting colloid, but also generally there is the conventional surface such as biodegradable, safe to use
Premium properties not available for activating agent, there are high industrial application value and good economical, societal benefits.
The content of the invention
In view of the shortcomings of the prior art, the technical problem that intends to solve of the present invention is：There is provided a kind of for the rabbit hair and crude oil shallow lake
Powder base natural polymer subsystem emulsifying agent (CMS stearate) and preparation method thereof.The macromolecular emulsifying agent have with
Lower advantage：
1) effect with crude oil external phase of emulsion viscosity is improved, suitable for doing tackifier and stabilizer；
2) there are change and the hydromechanical characteristic of crude oil emulsion, the viscoplasticity regulator as finish；
3) there are certain tackness and intensity to rabbit fur fibre, the binding agent as fiber；
4) easily fiber surface absorption and interior phase particle surface absorption, and according to its concentration be used as flocculating agent, dispersant and
Deflocculant；
5) emulsifying ability is strong, there is extremely strong emulsifying effectiveness to basic finish；
6) also there is good wetting, moisture-absorbing moisture-keeping, antistatic, defoaming effect.
The starch base natural polymer emulsifying agent has that technique is simple, reaction condition delays due to being prepared using conventional equipment
With, process is easy to control, product is easily separated, repeatable height, and pollution-free in production process, it is safe the features such as.
The technical scheme that the present invention solves the starch technical problem is to design a kind of starch base natural polymer emulsification
Agent, it is characterised in that the material quality of the emulsifying agent forms number and is：
In first step etherification reaction：
100 parts of native cornstarch, 13~15 parts of chloroacetic acid, 7~8 parts of sodium hydroxide, 18~20 parts of ethanol, deionized water
18~20 parts.
In second step esterification：
100 parts of etherification starch, 162~169 parts of stearic acid, 16~17 parts of enuatrol, 8~9 parts of sodium carbonate, deionized water
830~840 parts.
The technical scheme that the present invention solves the preparation method technical problem is to design a kind of starch base natural polymer breast
The preparation method of agent, the preparation method using starch base natural polymer emulsifying agent of the present invention material quality composition and
Following processing step：
(1) alkalize：Starch suspension is made in the cornstarch of the number and deionized water, is transferred to two mouthfuls of 500mL
In flask, 18~20 parts of deionized waters and the alkaline solution of 7~8 sodium hydroxide parts configuration will be used, and pass through constant pressure funnel 2-3
It is added dropwise in flask in minute, is then alkalized 50~60 minutes at 33~37 DEG C.
(2) it is etherified：, will be molten with 18~20 parts of ethanol and etherifying agent that 13~15 parts of monoxone is configured to after alkalization terminates
Liquid, it is added dropwise to by constant pressure funnel within 4-6 minutes in flask.Then reacted 3~3.5 hours at 48~52 DEG C.Instead
PH=6.5~7, filtering are adjusted with 1N hydrochloric acid solutions after should terminating, product is washed with the ethanol water that volume fraction is 85%
Extremely (examined without chlorion with silver nitrate solution).
(3) deionized water and etherificate of the number are sequentially added in the 100mL there-necked flasks equipped with vacuum distillation apparatus
Starch, 16~17 parts of enuatrols, is warming up to 108~112 DEG C in oil bath, after slowly steaming 68%~72% water, addition 8~
9 parts of catalyst sodium carbonate and 32~34 parts of methyl stearate, improve temperature and start to depressurize, continue to steam 18~20%
After moisture, 130~135 parts of methyl stearate is added, temperature is risen to 118~122 DEG C, reaction obtains thick for 3~3.5 hours
Product.Crude product is first washed 2 times with deionized water, 3~4 are washed with n-butanol/butyl acetate solution that volume ratio is 50/50
It is secondary, to remove unreacted methyl stearate, enuatrol and catalyst sodium carbonate, dry, crush at 60 DEG C, 65 mesh excessively divide sample
Sieve, that is, obtain powdered starch base natural polymer emulsifying agent (CMS stearate).
Compared with existing and crude oil technology, innovative point of the invention mainly has following aspect：
1st, the present invention exchanges two-step method using etherificate -ester and prepares starch base natural polymer emulsifying agent-CMS
Stearate.In the first step, the carboxy methylation of starch is completed by etherification reaction, introduces anionic group-COO-Na+；
By ester exchange reaction in second step, further introduced on natural polymer starch the ester group with longer hydrocarbon chain-
COOC18H37.The emulsifying agent has the structure of anion and nonionic surfactant concurrently, and has high-molecular surface active simultaneously
The characteristics of agent.It not only has the advantages of anion surfactant, such as good dissolubility, solubilising and antistatic behaviour, again
High stability with nonionic surfactant, high emulsifying power, while also have high molecular surfactant tackifying and
Polymolecularity, and due to being made of to use natural polymer starch as material, so the natural polymer subsystem emulsifying agent of kind structure
For wool spinning and the additive of crude oil, report is at home and abroad there is no, this is first innovative point of the present invention.
2nd, in application aspect, the surfactant of the present invention is used for the rabbit hair and crude oil, at the same give basic finish and
The specific formula of additive.The main constituents of wherein basic finish be vegetable oil (castor oil, sulfonated castor oil) with it is advanced
Fatty acid ester (important component of glycerin monostearate, margarine and butter), it is not only environment-friendly, it is easy to degrade, and have
There is good self-emulsifying function, simultaneously because having and basic finish with the emulsifying agent (CMS stearate) of the present invention
Very similar structure, i.e. emulsifiability are good, emulsion-stabilizing.Show by experiment, using the oil formula in the present invention to rabbit
After hair is oiled, the friction cohesive force of rabbit fur fibre is remarkably improved.
The starch base natural polymer emulsifying agent of the present invention has primarily served following effect：
A. by suitably increasing phase viscosity outside finish emulsion, emulsion intercalation method is improved, so as to improve the effect that oils；
B. the good affinity using emulsifying agent itself to wool fibre, increase fiber obvolvent is served, improves the collection of filaments
The effect of property；
C. emulsifying ability is strong, there is extremely strong emulsifying effectiveness to basic finish；
D. because emulsifying agent is per se with anionic group, certain antistatic behaviour can be also played during wool spinning, and
Moisture absorption and the performance of keeping humidity of wool top can be improved.
In summary factor, oiled using the starch base natural polymer emulsifying agent and oil formula of the present invention
Afterwards, have rabbit fur fibre coefficient of friction, collection of filaments ability and cohesive force to increase substantially, in spinning process, serve
Significantly reduce fibre damage, reduce the effect of fuds fuddled and spinning end breaking, so as to considerably improve the spinnability of the rabbit hair, this is this
Second innovative point of invention.
Brief description of the drawings
Fig. 1 is a kind of embodiment of starch base natural polymer emulsifying agent CMS stearate of the present invention and ative starch
Infrared spectrum comparison diagram；Wherein, curve A is the infrared spectrum of ative starch；Curve B is CMS stearate of the present invention
Infrared spectrum.See Fig. 1.
Table 1 is the content of ester group in starch base natural polymer emulsifying agent under the conditions of different esterifications, CMS
The substitution value of stearic acid ester group in stearate.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Substitution value | 0.356 | 0.085 | 0.211 |
Table 2 for the starch base natural polymer emulsifying agent of the addition present invention account for finish total amount 2% and 5% and crude oil formula with
Blank finish (being not added with CMS stearate), commercial finish emulsion apparent viscosity.
Table 2
| Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| Finish gross mass 2% | 6.0mPa.S | 2.5mPa.S | 3.0mPa.S |
| Finish gross mass 5% | 10.1mPa.5 | 2.5mPa.5 | 3.0mPa.S |
Table 3 (does not add for the starch base natural polymer emulsifying agent and crude oil formula of the present invention of addition 5% with blank finish
Add CMS stearate), commercial finish and fibre cohesion (coefficient of friction) data of the rabbit hair of not oiling.
Table 3
Table 4 is the starch base natural polymer emulsifying agent and crude oil formula of the invention of addition 2% and 5% and blank finish
(being not added with CMS stearate), the emulsion life span of commercial finish.
Table 4
| Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| Finish gross mass 2% | 3.5d | 1.5d | 7d |
| Finish gross mass 5% | 9d | 1.5d | 7d |
Embodiment：
The present invention is further discussed below with reference to embodiment and accompanying drawing.
A kind of starch base natural polymer emulsifying agent (CMS stearate) that the present invention designs, it is characterised in that
The material quality of the starch forms number：
In first step etherification reaction：
100 parts of native cornstarch, 13~15 parts of chloroacetic acid, 7~8 parts of sodium hydroxide, 18~20 parts of ethanol, deionized water
18~20 parts.
In second step esterification：
100 parts of etherification starch, 162~169 parts of stearic acid, 16~17 parts of enuatrol, 8~9 parts of sodium carbonate, deionized water
830~840 parts.
CMS stearate infrared spectrum of the present invention is analyzed as follows：
The stretching vibration of ative starch associate hydrogen bond O-H keys 3400~3200cm in infrared spectrogram (referring to Fig. 1)-1Locate table
Now strong absworption peak, 2930cm for a width-1Locate as starch carbon chain backbone c h bond symmetric vibration absworption peak, 1152~1015cm-1For starch ehter bond C-O-C antisymmetric stretching vibration absworption peaks.Pass through CMS stearate and ative starch infrared spectrum
Contrast finds that CMS stearate is in 1618cm-1Place and 1424cm-1The new absworption peak of the appearance at place, is carboxylic respectively
Hydrochlorate COO-Antisymmetry and symmetrical stretching vibration caused by；In addition CMS stearate is also in 1731cm-1There is C=in place
The stretching vibration absworption peak of O of bondings, in 1380cm-1There is methyl-CH in place3Flexural vibrations absworption peak, in 1248cm-1Place occurs
The stretching vibration absworption peaks of C-O singly-bounds, the characteristic absorption of ester group is absorbed as above.
Above-mentioned change shows, after being modified by etherificate with two steps of esterification, by anionic group carboxylic acid group and nonionic
The long hydrocarbon chain ester group of group is incorporated into native starch macromolecular.
The present invention devises the preparation method (abbreviation preparation method) of CMS stearate, the preparation method simultaneously
Using CMS stearate of the present invention material quality part array into following processing step：
(1) alkalize：Starch suspension is made in the cornstarch of the number and deionized water, is transferred to two mouthfuls of 500mL
In flask, 18~20 parts of deionized waters and the alkaline solution of 7~8 parts of sodium hydroxide configurations will be used, and pass through constant pressure funnel 2-3
It is added dropwise in flask in minute, is then alkalized 50~60 minutes at 33~37 DEG C.
(2) it is etherified：, will be molten with 18~20 parts of ethanol and etherifying agent that 13~15 parts of monoxone is configured to after alkalization terminates
Liquid, it is added dropwise to by constant pressure funnel within 4-6 minutes in flask.Then reacted 3~3.5 hours at 48~52 DEG C.Instead
PH=6.5~7, filtering are adjusted with 1N hydrochloric acid solutions after should terminating, product is washed with the ethanol water that volume fraction is 85%
Extremely (examined without chlorion with silver nitrate solution).
(3) deionized water and etherificate of the number are sequentially added in the 100mL there-necked flasks equipped with vacuum distillation apparatus
Starch, 16~17 parts of enuatrols, is warming up to 108~112 DEG C in oil bath, after slowly steaming 68%~72% water, addition 8~
9 parts of catalyst sodium carbonate and 32~34 parts of methyl stearate, improve temperature and start to depressurize, continue to steam 18~20%
After moisture, 130~135 parts of methyl stearate is added, temperature is risen to 118~122 DEG C, reaction obtains thick for 3~3.5 hours
Product.Crude product is first washed 2 times with deionized water, 3~4 are washed with n-butanol/butyl acetate solution that volume ratio is 50/50
It is secondary, to remove unreacted methyl stearate, enuatrol and catalyst sodium carbonate, dry, crush at 60 DEG C, 65 mesh excessively divide sample
Sieve, that is, obtain powdered starch base natural polymer emulsifying agent (CMS stearate).
The present invention is determined to the substitution value of CMS stearate.The measure of CMS stearate
Method referring especially to《The preparation of starch stearate》(University Of Tianjin's journal, volume 28,1995.11) and state of the People's Republic of China (PRC)
Family standard GB/T 5344-2008《The measure of animal and plant fat saponification number》(People's Republic of China's national development and reform committee member
Meeting, 2008.9).
CMS stearate preparation method experimental instrument and equipment of the present invention includes：Heat collecting type heated at constant temperature magnetic force stirs
Mix device, electric mixer, multiplex vavuum pump of circulating water type, air blast electrically heated drying cabinet, digital display gas bath constant temperature oscillator.Present invention system
Instrument and equipment used in Preparation Method is routine instrument device, and cost is low, easy to operate, technology maturation, suitable for industrialization promotion
Using.
It is of the invention right respectively in order to illustrate enhancing effect of the CMS stearate to rabbit fur fibre friction cohesive force
Added CMS stearate is used with crude oil, blank finish (being not added with CMS stearate) and woollen mill
The treated rabbit hair of business finish, and the raw wool without oiling have carried out sound friction testing, and specific method of testing is：
29mL distilled water is added in 50mL beakers, is derived from system and crude oil 0.9g, starch stearate 0.6g is in 60 DEG C of temperature
The lower stirring of degree makes it be dissolved completely in distilled water, prepares and crude oil concentration is 3%, additive starch stearate concentration is
5% emulsion.After natural cooling, 1g rabbit fur fibres are put into emulsion and soaked 12 hours, make emulsion uniform fold in fiber table
Face.Squeeze and go unnecessary emulsion to be put into afterwards in baking oven untill rabbit hair weight is 2.33g after immersion, sample is dried at a temperature of 60 DEG C
To 1.19g.Then the coefficient of friction of 20 rabbit fur fibres is tested, is averaged.Specifically method of testing is：
Laboratory apparatus is frictional coefficient of fiber tester.It is 30 revs/min to set metal friction rod rotating speed, and clips are
150mg。
According to formula：Coefficient of friction u=0.7329 [LgT2-Lg(T2-M)]
T2For initial tension, M is balance reading.
In order to illustrate that CMS stearate to improving the rabbit hair and crude oil emulsion rheological property, improves its external phase of emulsion
The effect of viscosity, the present invention to addition CMS stearate and crude oil, blank finish (it is hard to be not added with CMS
Resin acid ester) and woollen mill be tested with the viscosity of business finish, specific method of testing is：
29mL distilled water is added in 50mL beakers, is derived from system and crude oil 0.9g, starch stearate 0.6g is in 60 DEG C of temperature
The lower stirring of degree makes it be dissolved completely in distilled water, then using the table of NDJ-79 formulas rotary viscosimeter measure and crude oil emulsion
See viscosity.
In order to illustrate the emulsifiability of CMS stearate pair and crude oil emulsion basis finish, and enhancing emulsion is steady
Qualitatively effect, the present invention to addition CMS stearate and crude oil, blank finish (it is hard to be not added with CMS
Resin acid ester) and woollen mill be tested with the life span of the emulsion of business finish, specific method is：
29mL distilled water is added in 50mL beakers, is derived from system and crude oil 0.9g, starch stearate 0.6g is in 60 DEG C of temperature
The lower stirring of degree makes it be dissolved completely in distilled water, then that it is static at room temperature, and it is (raw to observe the time existing for emulsion-stabilizing
Deposit the time).Life span is longer, then emulsion is more stable.5 are shown in Table with crude oil specific formula.
Table 5
Embodiment 1
Starch suspension is made in 30g native cornstarch and 70ml ethanol solutions, is transferred in two mouthfuls of flasks of 250mL,
The sodium hydroxide 7.4g solution prepared with 18ml deionized waters, to be added dropwise in constant pressure funnel 2-3 minutes, then 35 DEG C
Silkization one hour.
After silkization terminates, the ethanol solution 18ml of the 13.98g containing monoxone is added, is added dropwise in five minutes.Temperature is risen to 50
DEG C reaction 3 hours.Reaction terminate after with 1N hydrochloric acid adjust pH=6.5-7, with 85% ethanol wash to without chlorion (with nitric acid
Silver-colored solution measure).
The starch after 23ml deionized waters, 4g etherificates is sequentially added in the 100mL there-necked flasks equipped with vacuum distillation apparatus
Product, 0.667g enuatrols are warming up to 100-110 DEG C in oil bath, and 0.33g catalyst carbonic acid is added after slowly steaming 80% water
Sodium and 1.334g methyl stearates, improve temperature and start to depressurize, after water is evaporated in system, add 5.336g stearic acid first
Ester, temperature is risen to 120 DEG C, reaction can obtain starch stearate in 3 hours.
The substitution value that the present embodiment is computed is listed in table 1.
Embodiment 2
Starch suspension is made in 30g native cornstarch and 70ml ethanol solutions, is transferred in two mouthfuls of flasks of 250mL,
The 7.4 parts of solution of sodium hydroxide prepared with 18ml deionized waters, to be added dropwise in constant pressure funnel 2-3 minutes, then 35
DEG C silkization one hour.
After silkization terminates, the ethanol solution 18ml of the 13.98g containing monoxone is added, is added dropwise in five minutes.Temperature is risen to 50
DEG C reaction 3 hours.Reaction terminate after with 1N hydrochloric acid adjust pH=6.5-7, with 85% ethanol wash to without chlorion (with nitric acid
Silver-colored solution measure).
The starch after 23ml deionized waters, 4g etherificates is sequentially added in the 100mL there-necked flasks equipped with vacuum distillation apparatus
Product, 0.667g enuatrols are warming up to 100-110 DEG C in oil bath, and 0.66g catalyst carbonic acid is added after slowly steaming 80% water
Sodium and 1.334g methyl stearates, improve temperature and start to depressurize, after water is evaporated in system, add 5.336g stearic acid first
Ester, temperature is risen to 120 DEG C, reaction can obtain starch stearate in 3 hours.
The substitution value that the present embodiment is computed is listed in table 1.
Embodiment 3
Starch suspension is made in 30g native cornstarch and 70ml ethanol solutions, is transferred in two mouthfuls of flasks of 250mL,
The 7.4 parts of solution of sodium hydroxide prepared with 18ml deionized waters, to be added dropwise in constant pressure funnel 2-3 minutes, then 35
DEG C silkization one hour.
After silkization terminates, the ethanol solution 18ml of the 13.98g containing monoxone is added, is added dropwise in five minutes.Temperature is risen to 50
DEG C reaction 3 hours.Reaction terminate after with 1N hydrochloric acid adjust pH=6.5-7, with 85% ethanol wash to without chlorion (with nitric acid
Silver-colored solution measure).
The starch after 23ml deionized waters, 4g etherificates is sequentially added in the 100mL there-necked flasks equipped with vacuum distillation apparatus
Product, 0.667g enuatrols are warming up to 100-110 DEG C in oil bath, and 0.33g catalyst carbonic acid is added after slowly steaming 80% water
Sodium and 1.8g methyl stearates, improve temperature and start to depressurize, after water is evaporated in system, add 7.0g methyl stearates,
Temperature rises to 120 DEG C, and reaction can obtain starch stearate in 3 hours.
The substitution value that the present embodiment is computed is listed in table 1.
Embodiment 4
29mL distilled water is added in 50mL beakers, is derived from system and crude oil 0.9g, starch methyl stearate 0.6g is at 60 DEG C
At a temperature of stirring it is dissolved completely in distilled water, prepare and crude oil concentration be 3%, additive starch stearate concentration is
2% emulsion.Then the measure apparent viscosity of emulsion, emulsifying effectiveness (emulsion life span) and to rabbit fur fibre frictional force with embracing
Enhancing effect with joint efforts.The present embodiment test result is shown in Table 2, table 3 and table 4 respectively.
Comparative example 1
In order to illustrate that the emulsifying effectiveness of CMS stearate pair and crude oil emulsion, stablizing effect and rabbit fur fibre rub
The enhancing effect of power and cohesive force is wiped, the present invention enters to the emulsion of blank finish (being not added with CMS stearate) simultaneously
Gone apparent viscosity test, life span test and to through oiling rabbit fur fibre sound friction testing test.Degreaser
It is not added with formula outside CMS stearate, remaining same embodiment 1.Its test result is shown in Table 2, table 3 and table 4 respectively.
Comparative example 2
In order to illustrate that the emulsifying effectiveness of CMS stearate pair and crude oil emulsion, stablizing effect and rabbit fur fibre rub
Wipe the enhancing effect of power and cohesive force, the present invention simultaneously to woollen mill with the emulsion of business finish carried out apparent viscosity test,
Life span is tested and the rabbit fur fibre sound frictional force friction testing through oiling is tested.Except with crude oil formula wool spinning
Station-service business oil formula substitutes outer, remaining same embodiment 1.Its test result is shown in Table 2, table 3 and table 4 respectively.
Comparative example 3
In order to illustrate that CMS stearate is same to rabbit fur fibre frictional force and the enhancing effect of cohesive force, the present invention
The rabbit fur fibre sound frictional force friction testing experiment that Shi Wei oils.Except cohesive force test object is with the rabbit fur fibre not oiled
Substitute outer, remaining same embodiment 1.Its test result is shown in Table 2, table 3 and table 4 respectively.
From the data in table 2, table 3 and table 4, starch base natural polymer emulsifying agent-CMS of the invention
Stearate, not only pair and crude oil basis finish has good emulsifying effectiveness, and can significantly increase and crude oil emulsion
Stability and the compatibility with rabbit fur fibre.After oiling, the friction cohesive force of rabbit fur fibre dramatically increases, the collection of filaments
It is remarkably reinforced.Why the starch base natural polymer emulsifying agent of the present invention has above-mentioned premium properties, and main cause has at 3 points：
Firstth, in starch base natural polymer emulsifying agent structure of the invention, at the same have anionic group carboxylic acid group with
The long hydrocarbon chain ester group of non-ionic group, therefore there is the advantages of anionic surface work and nonionic surfactant simultaneously, it is such as good
Dissolubility, wetability, antistatic behaviour and high emulsification efficiency, can make farthest to play with each component in crude oil formula
It is acted on.
Secondth, starch base natural polymer emulsifying agent of the invention also have simultaneously high molecular surfactant tackifying and
Polymolecularity.By increasing and the viscosity of crude oil emulsion, the diffusion coefficient of dispersed phase drop can be reduced, make droplet collision frequency with
Coalescence rate reduces, and is advantageous to the stabilization of emulsion.On the other hand, the increase of outer phase viscosity also contributes to increase each component in emulsion
With the binding ability on wool fibre surface, oil applying rate is improved.
3rd, the main functional group of starch base natural polymer emulsifying agent of the invention and the main component in basic finish
Chemical constitution there is higher similitude, be high-grade aliphatic ester.According to the similar principle that mixes, basic finish can be risen
To good solubilization, so as to further increase emulsification efficiency and stability with crude oil emulsion.
Summary reason, starch base natural polymer emulsifying agent of the invention, for improving the stabilization with crude oil emulsion
Property and with the compatibility of rabbit fur fibre there is remarkable result, the rabbit fur fibre after the present invention and crude oil formula oil rubs obvolvent
Power is dramatically increased, and the collection of filaments is remarkably reinforced, so as to drastically increase the spinnability of rabbit fur fibre.This proves the present invention's
CMS stearate is a kind of new type natural macromolecule emulsifier of great potential, in wool spinning oil particularly rabbit hair hair
Spin in oil formula, have a good application prospect.
Claims (3)
1. a kind of starch base natural polymer emulsifying agent, it is characterised in that anti-by being etherified the step of ester exchange two using starch as matrix
Ying Fa, prepare the emulsifying agent, a CMS stearate.
2. according to claim 1, in first step etherification reaction：100 parts of native cornstarch, 13~15 parts of chloroacetic acid, hydrogen
7~8 parts of sodium oxide molybdena, 18~20 parts of ethanol, 18~20 parts of deionized water, reaction temperature are 35 DEG C -50 DEG C.Second step esterification
In：100 parts of starch after etherificate, 162~169 parts of stearic acid, enuatrol 16-17 parts, 8~9 parts of sodium carbonate, deionized water 830
~840 parts, when reaction temperature is 100 DEG C -120 DEG C, the CMS stearate of preparation determines substitution by saponification method
Degree can reach 0.356.
3. according to claim 2, the rabbit hair of the invention and crude oil formula main constituents are vegetable oil and higher aliphatic
Acid esters, it is not only environment-friendly, it is easy to degrade.The starch base natural polymer emulsifying agent CMS stearate of the present invention,
It is similar to main component structure in formula, therefore emulsifiability is good, emulsion-stabilizing.It our experiments show that, using the finish in the present invention
After formula oils to the rabbit hair, the frictional force and cohesive force of rabbit fur fibre are remarkably improved.
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| CN201610817980.3A CN107805284A (en) | 2016-09-08 | 2016-09-08 | One kind is used for the rabbit hair and crude oil starch base natural polymer emulsifying agent and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073996A (en) * | 1992-07-21 | 1993-07-07 | 中国纺织大学 | Rabbit wool modifying and crude oil |
| KR100229359B1 (en) * | 1997-08-04 | 1999-12-01 | 임승택 | Process for producing octenyl succinic acid amylodextrin |
| CN102296464A (en) * | 2011-06-07 | 2011-12-28 | 东华大学 | Wook lubricating oil, preparation method for wook lubricating oil, and application of wook lubricating oil in improvement of fiber spinning performance |
-
2016
- 2016-09-08 CN CN201610817980.3A patent/CN107805284A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073996A (en) * | 1992-07-21 | 1993-07-07 | 中国纺织大学 | Rabbit wool modifying and crude oil |
| KR100229359B1 (en) * | 1997-08-04 | 1999-12-01 | 임승택 | Process for producing octenyl succinic acid amylodextrin |
| CN102296464A (en) * | 2011-06-07 | 2011-12-28 | 东华大学 | Wook lubricating oil, preparation method for wook lubricating oil, and application of wook lubricating oil in improvement of fiber spinning performance |
Non-Patent Citations (1)
| Title |
|---|
| 郭蕉兰 等: "羧甲基淀粉钠-脂肪酸淀粉酯性质的研究", 《食品科技》 * |
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