CN106928398B - A kind of medical acrylic acid class thickener and preparation method thereof - Google Patents
A kind of medical acrylic acid class thickener and preparation method thereof Download PDFInfo
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- CN106928398B CN106928398B CN201710256545.2A CN201710256545A CN106928398B CN 106928398 B CN106928398 B CN 106928398B CN 201710256545 A CN201710256545 A CN 201710256545A CN 106928398 B CN106928398 B CN 106928398B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Abstract
The invention discloses a kind of preparation methods of medical acrylic acid class thickener, comprising the following steps: step 1: under nitrogen protection, the first monomer, solvent, dispersing agent being added into reactor, stirs and be warming up to 55~80 DEG C；Step 2: the initiator of 15~20wt% is added in a manner of dropwise addition respectively into the reactor of step 1, time for adding is 0.5~1 hour；Then it is added second comonomer and remaining initiator in a manner of dropwise addition, isothermal reaction 2~6 hours；The weight ratio of first monomer and second comonomer is 1:3~4；Step 3: filtering, and again disperse sediment solvent after reaction after being washed for several times with solvent；Step 4: the mixture of step 3 being dried in the form being spray-dried, the dust after collecting drying to obtain the final product.The object of the present invention is to provide a kind of preparation methods of medical acrylic acid class thickener that monomer residue is few, and the medical acrylic acid class thickener being prepared using this method.
Description
Technical field
The present invention relates to thickener field, especially a kind of medical acrylic acid class thickener and preparation method thereof.
Background technique
Medical acrylic acid class thickener is widely used in gel preparation, such as the ointment of external application and for taking orally
Fluid preparation such as slop, this requires monomer residue is less when acrylic thickener is in medical field.
In this field, monomer residue is mostly from polymerization temperature, post-processing temperature, the choosing for causing system in reduction polymer
It selects, set about in terms of the selection of emulsification system, improve product by high temperature, redox initiation system and microemulsified systems
Monomer residue.
In order to solve the problems, such as that monomer residue, Chinese patent ZL201210165229.1 disclose a kind of low monomer residue third
The preparation method of the ester modified waterborne polyurethane pressure-sensitive adhesives of olefin(e) acid, belongs to adhesive technology field.1) using homemade hydroxyl
Acrylate quasi-oligomer replaces acrylic ester monomer modified aqueous polyurethane, makes acrylate and polyurethane that grafting occur anti-
It answers, then forms reticular structure by cross-linking agents, reaction is more abundant compared with acrylic ester monomer is modified, realizes that monomer is residual
Allowance is low, and preparation process is simple, energy-saving and environment-friendly purpose；2) product is post-processed using redox initiation system, into
One step reduces level of residual monomers, obtains the green adhesive products of ultralow monomer residue；The program uses acrylic monomers with low
The form of polymers is added in reaction system, and uses redox initiation system to control the monomer residue of reaction system.But
Be for the acrylic thickener of medical grade, using acrylic acid oligomer can viscosity to product and light transmittance generate shadow
It rings.
Chinese patent ZL98811506.9 discloses one kind by acrylic acid and/or acrylic acid derivative production with low residual
Stay the water solubility of content of monomer or the method for water-swellable polymer product, the method is characterized in that, by nitrogenous compound plus
Enter into the monomer solution to be polymerize, and then heats polymer at a temperature of 120-240 DEG C.Polymerization produce produced
Object is suitable as flocculant, dispersing agent and absorbent.Monomer residual can be controlled in 10ppm hereinafter, the program solves well
Determined monomer residue in polymer the problem of, but the new problem of bring is that nitrogen compound is that polymer is brought not
The performance of the excessively high color that will affect product of determining medical-risk and heating temperature, viscosity etc..
Chinese patent ZL2011800254110 discloses a kind of for removing residual monomer from water-absorbing polymeric particles
Method, wherein water-absorbing polymeric particles equipped with rotary mixing tool mixing machine at least 60 DEG C at a temperature of in water
Heat treatment is carried out in the presence of steam.It include equipped with rotary mixing tool mixing machine in air-flow in the presence of heat treatment
Water-absorbing polymeric particles, temperature of water-absorbing polymeric particles during heat treatment are at least 60 DEG C and water capacity
It is at least 3 weight %, and the air-flow contains the every kg dry gas of at least 0.01kg vapor.The program has more outstanding
Residue removal effect, but the problem of depositing, is that traditional acrylic thickener is powder, in the air-flow containing vapor
In be easy reunite it is agglomerating, for the later period use it is very inconvenient.
Therefore, it is directed to for acrylic thickener, the change of Study Polymer Melts structure, and post-processes corresponding
Adjust the meaning that practicability is had more to the influence of monomer residue.
Summary of the invention
The present invention is intended to provide a kind of preparation method for the medical acrylic acid class thickener that monomer residue is few, and using should
The medical acrylic acid class thickener that method is prepared.
It is the specific scheme is that a kind of preparation method of medical acrylic acid class thickener, comprising the following steps:
Step 1: under nitrogen protection, the first monomer, solvent, dispersing agent being added into reactor, stir and be warming up to 55
~80 DEG C；First monomer is made of unsaturated carboxylic acid monomer and sucrose base allyl ether series crosslinking agent, sucrose base allyl
The weight of base ethers crosslinking agent accounts for the 1.0~1.2% of the first total weight of monomer；
Step 2: the initiator of 15~20wt% is added in a manner of dropwise addition respectively into the reactor of step 1, when dropwise addition
Between be 0.5~1 hour；Then second comonomer and remaining initiator are added in a manner of dropwise addition, reacts 2~6 hours；Described
Second comonomer is by unsaturated carboxylic acid monomer and with the polyalkenyl ether of two or three polymerizable ethylenical unsaturated double bonds；Institute
The weight for the polyalkenyl ether stated accounts for the 0.4~0.8% of second comonomer weight；
The weight ratio of first monomer and second comonomer is 1:3~4；
Step 3: and again disperse sediment solvent after being washed for several times with solvent；
Step 4: the mixture of step 3 being dried in the form being spray-dried, the dust after collecting drying to obtain the final product.
In the preparation method of above-mentioned medical acrylic acid class thickener, in the step 4, the charging speed of spray drying
Degree is 10-20ml/min, and inlet air temperature is 110~145 DEG C；Leaving air temp is 50-90 DEG C, atomizing pressure 0.3-0.7Mpa,
Carrier gas is inert gas.
Preferably, first sediment 1-2 times of solvent for being equivalent to the first monomer and second comonomer gross weight is washed in step 4
It washs, then with 2-4 times of the solvent dispersion for being equivalent to the first monomer and second comonomer gross weight.
In the preparation method of above-mentioned medical acrylic acid class thickener, the unsaturated carboxylic acid monomer be acrylic acid,
One of methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or a variety of combinations.
In the preparation method of above-mentioned medical acrylic acid class thickener, step 1, solvent is independently selected described in 3
From in one of benzene, toluene, hexamethylene, ethyl acetate, methylene chloride, dichloroethanes or multiple combinations, the step 1
Solvent usage is 5-8 times of the first monomer and second comonomer gross weight.
In the preparation method of above-mentioned medical acrylic acid class thickener, initiator is benzoyl peroxide, the peroxidating moon
Osmanthus acyl, acetyl peroxide cyclohexylsulfonyl, peroxidating neodecanoic acid α-isopropyl phenyl ester, peroxidating neodecanoic acid -1,1- dimethyl -3- hydroxyl
Base butyl ester, dicetyl peroxydicarbonate two (3- methoxybutyl), di-isopropyl peroxydicarbonate, two (2- of dicetyl peroxydicarbonate
Ethylhexyl), the new enanthic acid α-isopropyl phenyl ester of peroxidating, peroxy dicarbonate di-n-propyl ester, in new peroxide tert-butyl caprate
One or more kinds of combinations, the weight of the initiator be equivalent to the first monomer and second comonomer gross weight 0.1%~
0.8%.
In the preparation method of above-mentioned medical acrylic acid class thickener, the dispersing agent is sorbitan fatty
Acid esters, polyglyceryl fatty acid ester, sucrose fatty ester, alkylbenzene sulfonate, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether
One or more combinations of sulfonate weight, the dispersant weight are equivalent to the 0.3- of the first monomer and second comonomer gross weight
1.0%.
In the preparation method of above-mentioned medical acrylic acid class thickener, two or three described polymerizable olefinics are not
The polyalkenyl ether for being saturated double bond is pentaerythritol diallyl ether, pentaerythritol triallyl ether, trimethylolpropane diene
One of propyl ether, trimethylolpropane tris allyl ether or a variety of mixing.
The sucrose base allyl ether series crosslinking agent is sucrose diallyl ether, sucrose triallyl ether.
Meanwhile the invention also discloses a kind of medical acrylic acid class thickener, it is prepared by such as above-mentioned method.
The beneficial effects of the present invention are:
The present invention uses partial monosomy to carry out pre-polymerization first, and the crosslinking agent which uses is the friendship of sucrose base allyl ether series
Join agent, sucrose base allyl ether series crosslinking agent, due to its architectural characteristic, can make the crosslinking of its stratum nucleare equal in the preparation process of stratum nucleare
Even property is improved, in the case where certain dosage, conducive to the particulate porous gap structure in later period decompression spray process
It is formed, improves the degree of volatility of solvent and monomer, specifically, sucrose base allyl ether series crosslinking agent is due to being with disaccharides structure
Based on its there is five yuan, hexa-atomic oxygen heterocycle, in the case where same amount its crosslink density be lower than other crosslinking agents, when by
When environmental pressure is plummeted to low pressure by high pressure, the hole formation of the network structure of stratum nucleare is advantageous.The crosslinking agent of shell can
To carry out the selection of diversification, it is preferred that being the crosslinking agent and trimethylolpropane class crosslinking agent of Pentaerythritols, the type
Crosslinking agent the intensity of shell is advantageous, prevent when environmental pressure is plummeted to low pressure by high pressure, polymer molecule knot
The deterioration of viscosity and light transmittance caused by structure destroys.
The contribution that above-mentioned polymer removes residual monomer is, poly- in particle when carrying out unexpected decompression operation
Polymeric network can uniform diastole, conducive to the quick evolution of solvent in particle, and then take away remaining in the solvent quickly to volatilize
Monomer significantly reduces the monomer residue of product to ppm rank.
Specific embodiment
With reference to embodiment, technical solution of the present invention is described in further detail, but do not constituted pair
Any restrictions of the invention.
In order to which more clearly the present invention will be described, embodiment is listed below to illustrate superiority of the invention.
Embodiment 1
Step 1: under nitrogen protection, the first monomer of 25g, 500g ethyl acetate and hexamethylene being added into four-hole boiling flask
(mass ratio of ethyl acetate and hexamethylene is 4:1), 0.5g sorbitan fatty ester, stir and are warming up to 65 DEG C；Institute
The first monomer stated is made of acrylic acid and 0.28g sucrose diallyl ether；
Step 2: the peroxidating for accounting for initiator total amount 16wt% is added in a manner of dropwise addition respectively into the reactor of step 1
The neodecanoic acid tert-butyl ester (gross weight of used initiator is 0.5g in this step 2), time for adding is 0.5 hour；Then with drop
75g second comonomer and remaining new peroxide tert-butyl caprate is added in the mode added, and time for adding is 6 hours；Described second
Monomer is made of acrylic acid and 0.38g pentaerythritol diallyl ether；Reaction temperature in this step is 60 DEG C.
Step 3: filtering after reaction, and (mass ratio of ethyl acetate and hexamethylene is with ethyl acetate and hexamethylene
It 4:1) washs 3 times, each cleaning solvent dosage is 40g, collects filter residue；
Step 4: be added into filter residue 400g ethyl acetate and hexamethylene (mass ratio of ethyl acetate and hexamethylene is 4:
1) it, stirs 2 hours；
Step 5: being dried in the form of spray drying after the mixture of step 4 is stirred, the dust after collecting drying
To obtain the final product；The equipment of spray drying is the small spraying drying instrument B-290 of Switzerland BUCHI Laboratory Instruments company, and charging rate is
20ml/min, inlet air temperature are 125 DEG C；Leaving air temp is 80 DEG C, and atomizing pressure 0.7Mpa, carrier gas is inert gas.
Embodiment 2
Step 1: under nitrogen protection, the first monomer of 20g, 700g ethyl acetate and hexamethylene being added into four-hole boiling flask
(mass ratio of ethyl acetate and hexamethylene is 1:2), 1g sucrose fatty ester, stir and are warming up to 80 DEG C；Described first is single
Body is made of acrylic acid and 0.24g sucrose triallyl ether；
Step 2: the two (3- of dicetyl peroxydicarbonate of 20wt% is added in a manner of dropwise addition respectively into the reactor of step 1
Methoxybutyl) (gross weight of used initiator is 0.8g in this step 2), time for adding is 1 hour；Then with dropwise addition
80g second comonomer and remaining dicetyl peroxydicarbonate two (3- methoxybutyl) is added in mode, and time for adding is 4 hours；It is described
Second comonomer be made of acrylic acid and 0.32g trimethylolpropane allyl ether；Reaction temperature in this step is 80 DEG C.
Step 3: filtering after reaction, and (mass ratio of ethyl acetate and hexamethylene is with ethyl acetate and hexamethylene
It 1:2) washs 3 times, each cleaning solvent dosage is 60g, collects filter residue；
Step 4: be added into filter residue 200g ethyl acetate and hexamethylene (mass ratio of ethyl acetate and hexamethylene is 1:
2) it, stirs 2 hours；
Step 5: being dried in the form of spray drying after the mixture of step 4 is stirred, the dust after collecting drying
To obtain the final product；The equipment of spray drying is the SD-06 Laboratary type spray-dried instrument of Britain Labplant company, and charging rate is
10ml/min, the inlet air temperature of spray drying are 120 DEG C, and leaving air temp is 60 DEG C；Atomizing pressure is 0.4Mpa.
Embodiment 3
Step 1: under nitrogen protection, the first monomer of 22g, 600g benzene, 0.8g polyoxyethylene rouge being added into four-hole boiling flask
Fat acid esters stirs and is warming up to 70 DEG C；First monomer is made of acrylic acid and 0.22g sucrose triallyl ether；
Step 2: the dicetyl peroxydicarbonate two positive third of 18wt% is added in a manner of dropwise addition respectively into the reactor of step 1
Ester (gross weight of used initiator is 0.4g in this step 2), time for adding is 1 hour；Then it is added in a manner of dropwise addition
78g second comonomer and remaining peroxy dicarbonate di-n-propyl ester, time for adding are 5 hours；The second comonomer is by propylene
Acid and 0.62g pentaerythritol triallyl ether composition；Reaction temperature in this step is 70 DEG C.
Step 3: filtering, and washed 3 times with benzene after reaction, each cleaning solvent dosage is 50g, collects filter residue；
Step 4: 300g benzene being added into filter residue, stirs 4 hours；
Step 5: being dried in the form of spray drying after the mixture of step 4 is stirred, the dust after collecting drying
To obtain the final product；The equipment of spray drying is the SD-06 Laboratary type spray-dried instrument of Britain Labplant company, and charging rate is
15ml/min, the inlet air temperature of spray drying are 100 DEG C, and leaving air temp is 70 DEG C；Atomizing pressure is 0.6Mpa.
Embodiment 4
Step 1: under nitrogen protection, the first monomer of 21g, 500g ethyl acetate and hexamethylene being added into four-hole boiling flask
(mass ratio of ethyl acetate and hexamethylene is 1:4), 0.8g polyoxyethylene fatty acid ester, stir and are warming up to 70 DEG C；Described
First monomer is made of acrylic acid and 0.22g sucrose diallyl ether；
Step 2: the dicetyl peroxydicarbonate two positive third of 18wt% is added in a manner of dropwise addition respectively into the reactor of step 1
Ester (gross weight of used initiator is 0.4g in this step 2), time for adding is 1 hour；Then it is added in a manner of dropwise addition
78g second comonomer and remaining peroxy dicarbonate di-n-propyl ester, time for adding are 5 hours；The second comonomer is by propylene
Acid and 0.62g pentaerythritol triallyl ether composition；
Step 3: filtering, and washed 3 times with benzene after reaction, each cleaning solvent dosage is 50g, collects filter residue；
Step 4: 300g benzene being added into filter residue, stirs 4 hours；
Step 5: being dried in the form of spray drying after the mixture of step 4 is stirred, the dust after collecting drying
To obtain the final product；The equipment of spray drying is the SD-06 Laboratary type spray-dried instrument of Britain Labplant company, and charging rate is
15ml/min, the inlet air temperature of spray drying are 95 DEG C, and leaving air temp is 70 DEG C；Atomizing pressure is 0.6Mpa.
Embodiment 5
Step 1: under nitrogen protection, the first monomer of 21g, 500g ethyl acetate and hexamethylene being added into four-hole boiling flask
(mass ratio of ethyl acetate and hexamethylene is 1:4), 0.8g polyoxyethylene fatty acid ester, stir and are warming up to 70 DEG C；Described
First monomer is made of acrylic acid and 0.22g sucrose diallyl ether；
Step 2: the dicetyl peroxydicarbonate two positive third of 18wt% is added in a manner of dropwise addition respectively into the reactor of step 1
Ester (gross weight of used initiator is 0.4g in this step 2), time for adding is 1 hour；Then it is added in a manner of dropwise addition
78g second comonomer and remaining peroxy dicarbonate di-n-propyl ester, time for adding are 5 hours；The second comonomer is by propylene
Acid and 0.62g sucrose triallyl ether composition；
Step 3: filtering, and washed 3 times with benzene after reaction, each cleaning solvent dosage is 50g, collects filter residue；
Step 4: 300g benzene being added into filter residue, stirs 4 hours；
Step 5: being dried in the form of spray drying after the mixture of step 4 is stirred, the dust after collecting drying
To obtain the final product；The equipment of spray drying is the small spraying drying instrument B-290 of Switzerland BUCHI Laboratory Instruments company, and charging rate is
15ml/min, the inlet air temperature of spray drying are 90 DEG C, and leaving air temp is 70 DEG C；Atomizing pressure is 0.6Mpa.
Comparative example 1:
10 parts of commercially available cross-linking type agent for polyacrylic acid thickening.
Comparative example 2:
It is substantially the same with embodiment 1, different places is, the first monomer is by acrylic acid and 0.28g trimethylolpropane
Triallyl ether composition.
Comparative example 3:
Step 1: under nitrogen protection, the first monomer of 20g, 700g ethyl acetate and hexamethylene being added into four-hole boiling flask
(mass ratio of ethyl acetate and hexamethylene is 1:2), 1g sucrose fatty ester, stir and are warming up to 80 DEG C；Described first is single
Body is made of acrylic acid and 0.24g sucrose diallyl ether；
Step 2: the two (3- of dicetyl peroxydicarbonate of 20wt% is added in a manner of dropwise addition respectively into the reactor of step 1
Methoxybutyl) (gross weight of used initiator is 0.8g in this step 2), time for adding is 1 hour；Then with dropwise addition
80g second comonomer and remaining dicetyl peroxydicarbonate two (3- methoxybutyl) is added in mode, and time for adding is 4 hours；It is described
Second comonomer be made of acrylic acid and 0.32g trimethylolpropane allyl ether；
Step 3: it filters after reaction, and dry in vacuum oven under conditions of 70 DEG C, in vacuum oven-
0.095Mpa。
Performance test and analysis
Test method:
1,1% gel viscosity measurement method:
200g deionized water is weighed in the beaker of 500mL, be added product 2g, by beaker be placed under electric blender in
1000rpm is stirred until homogeneous；Then it uses 18wt% sodium hydroxide solution while stirring under the speed of 300rpm, adjusts pH value
Are as follows: 6.8~7.3, it stirs evenly, centrifugation defoaming measures viscosity.
2, the measurement of light transmittance
Partial gel will be fitted into 1cm cuvette after 25 DEG C of gel constant temperature one hour of above-mentioned centrifugation, is then placed in bottom
Portion is lined with paper handkerchief and (works as a buffer) in plastic centrifuge tube with centrifuge centrifugation defoaming.Centrifugal rotational speed 3500rmp, time 30min.
With ultraviolet specrophotometer at 420nm, its light transmittance is surveyed.
3, monomer residue test method:
Range
The measurement of residual acrylic acid level of this standard suitable for acrylic thickener.
Normative reference
The preparation of GB/T602-2002 chemical reagent impurity determination standard solution
Principle
This method is to measure residual acrylic acid in polymer emulsion sample and establish.Polymer samples are in alcoholic solution
1.5h~2.0h is extracted, extract liquor is diluted with water after being centrifuged, filtering, and uses efficient liquid phase chromatographic analysis.The peak area of acquisition
Content is relatively obtained with standard curve.
Measurement
Instrument
3.1.1Agilent high performance liquid chromatograph, VWD detector, Ezchrom chromatographic work station；
3.1.2C185um(150mm*4.6mm)；
3.1.40.45um water system, organic solvent filter membrane；
3.1.50.45um water system sample filter；
3.1.6 ultrasonic cleaner；
3.1.7pH it counts: scale division value 0.01pH；
3.1.8 electronic balance: scale division value 0.0001g；
3.1.9 magnetic stirring apparatus；
3.1.10 vacuum apparatus；
Routine Test Lab glassware.
3.2 reagents and solution
3.2.1 acrylic acid: AR, mass fraction are greater than 98.0%；
3.2.3 methanol: chromatographically pure is used and preceding is filtered with 0.45um organic system filter membrane；
3.2.4 potassium dihydrogen phosphate: AR；
3.2.5 phosphoric acid: AR；
3.2.6 potassium dihydrogen phosphate buffer solution (0.01mol/L): the biphosphate of 0.54g (being accurate to 0.001g) is weighed
Potassium adds 800mL water stirring and dissolving uniform in 1000mL beaker, aqueous with band 0.45um with concentrated phosphoric acid tune pH value to 3 ± 0.1
The vacuum apparatus of filter membrane filters.
3.2.71000mg/L the preparation of Standard Stock solutions:
Precision weighs the acrylic acid standard sample of (0.1 ± 0.001) g (being accurate to 0.0001g) to the volumetric flask of 100mL
In, scale constant volume is slowly diluted to water, concentration is the Standard Stock solutions of 1000mg/L.
3.2.8100mg/L the preparation of standard solution:
1000mg/L Standard Stock solutions 10mL is pipetted in the volumetric flask of 100mL, is diluted with water to scale constant volume, concentration
For the Standard Stock solutions of 100mg/L.
3.2.9 the preparation of standard solution:
Standard Stock solutions that 1mL, 5mL, 10mL, 25mL, 50mL concentration are 100mg/L are drawn respectively to 5 100mL's
In volumetric flask, scale is added water to, is shaken up, is made into the acrylic acid standard of 1mg/L, 5mg/L, 10mg/L, 25mg/L, 50mg/L respectively
Solution.
3.3 liquid phase chromatogram condition
3.3.1 mobile phase: Jia Chun ︰ potassium dihydrogen phosphate buffer solution=2 ︰ 8；
3.3.2 flow velocity: 1.0mL/min；
3.3.3 sample volume: 20uL；
3.3.4 chromatographic column: C184.6*150mm；
3.3.5 detector wavelength: 200nm；
Before experiment starts, high performance liquid chromatograph is started with conditions above, leads to mobile phase until obtaining stable baseline, so
Sample introduction afterwards.
3.4 analytical procedure
3.4.1 the formulation of standard curve
The acrylic acid standard solution of 1mg/L, 5mg/L, 10mg/L, 25mg/L, 50mg/L are subjected to liquid chromatogram point respectively
Analysis, measures acrylic acid peak area (the secondary parallel sample introduction of standard specimen), obtains the standard curve at acrylic acid peak.
If curve crosses origin, it is also possible to which single-point method is tested.
3.4.2 the preparation of sample
(0.2 ± 0.1) g (being accurate to 0.0001g) sample is accurately weighed into the polyethylene bottle with cover of 60mL, is added
50.00mL methanol is added magnet rotor, screws bottle cap, be put on magnetic stirring apparatus and stir 2h.10min is stood, supernatant liquor is turned
Enter in 10mL centrifuge tube, sealed with preservative film, at 3500r/min, is centrifugated 40min.
3.4.3 measurement
The supernatant liquor of 2.00mL is pipetted into 10mL volumetric flask, with water constant volume, is shaken up, and with 0.45 μm of water system sample
Filter filtering.Take this filtrate, after ultrasound (1-2) min, sample introduction carries out liquid-phase chromatographic analysis, obtains the chromatography of residual acrylic acid
Peak area.And its concentration c is found from standard curve.
3.5 calculate:
The mass fraction w1 of residual acrylic acid, numerical value are indicated with %, are calculated by following equation (1):
In formula:
C --- the concentration checked on standard curve, mg/L；
M --- sample quality, g.
3.6 points for attention
3.6.1 the degree of fitting of standard curve needs >=0.9995 or more, because degree of fitting is higher, accuracy is higher, therefore such as
Can reach four it is 9 best.
3.6.2 standard curve can be primary to do within one month, but because standard sample standing time it is longer after, result can be relatively low,
And standing time longer result is smaller.So needing to carry out single point correction using the solution now prepared daily.Single point correction is mainly anticipated
Whether justice is to reflect the state of instrument as state when doing standard curve.If error very little (≤0.1mg/L), can see
Make instrument state not change；If difference teaches big (> 0.1mg/L), please first confirm whether pillar cleans up, instrument setting and
The method of use whether with it is consistent in the past, such as inconsistent, then instrument to the response signal of same concentration and draws standard song at this time
It has had any different when line, standard curve need to be repainted.
3.6.3 the validity period of acrylic acid Standard Stock solutions is one month.
Test result is as follows table 1:
The viscosity and monomer residue test result of table 1 embodiment 1-3 and comparative example 1-3
Can be seen that the present processes by above-mentioned test can effectively improve the monomer in spray-drying process
Eradicating efficacy significantly reduces the monomer residue in product.
Stratum nucleare crosslinking agent is that sucrose base allyl ether series crosslinking agent can reduce monomer residue, and shell monomers are preferably season penta
Tetrol diallyl ether, pentaerythritol triallyl ether, trimethylolpropane allyl ether, trimethylolpropane tris allyl
One of ether or a variety of mixing improve conducive to the intensity of shell, prevent from causing viscosity loss and thoroughly in spray-drying process
The loss of light rate.
Above-described is only presently preferred embodiments of the present invention, all made within the scope of the spirit and principles in the present invention
What modifications, equivalent substitutions and improvements etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of medical acrylic acid class thickener, which comprises the following steps:
Step 1: under nitrogen protection, the first monomer, solvent, dispersing agent being added into reactor, stir and be warming up to 55~80
℃；First monomer is made of unsaturated carboxylic acid monomer and sucrose base allyl ether series crosslinking agent, sucrose base allyl ether
The weight of class crosslinking agent accounts for the 1.0~1.2% of the first total weight of monomer；
Step 2: the initiator of 15~20wt% is added in a manner of dropwise addition respectively into the reactor of step 1, time for adding is
0.5~1 hour；Then it is added second comonomer and remaining initiator in a manner of dropwise addition, isothermal reaction 2~6 hours；Described
Second comonomer is by unsaturated carboxylic acid monomer and the polyalkenyl ether group with two or three polymerizable ethylenical unsaturated double bonds
At；The weight of the polyalkenyl ether accounts for the 0.4~0.8% of second comonomer weight；
The weight ratio of first monomer and second comonomer is 1:3~4；
Step 3: filtering, and again disperse sediment solvent after reaction after being washed for several times with solvent；
Step 4: the mixture of step 3 being dried in the form being spray-dried, the dust after collecting drying to obtain the final product.
2. the preparation method of medical acrylic acid class thickener according to claim 1, which is characterized in that the step 4
In, the charging rate of spray drying is 10-20ml/min, and inlet air temperature is 90~125 DEG C；Leaving air temp is 50-90 DEG C, atomization
Pressure is 0.3-0.7Mpa, and carrier gas is inert gas.
3. the preparation method of medical acrylic acid class thickener according to claim 1, which is characterized in that the unsaturation
Carboxylic acid monomer is one of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or a variety of combinations.
4. the preparation method of medical acrylic acid class thickener according to claim 1, which is characterized in that step 1, institute in 3
The solvent stated is respectively and independently selected from one of benzene, toluene, hexamethylene, ethyl acetate, methylene chloride, dichloroethanes or a variety of groups
It closes, the solvent usage in the step 1 is 5-8 times of the first monomer and second comonomer gross weight.
5. the preparation method of medical acrylic acid class thickener according to claim 1, which is characterized in that initiator is peroxide
Change benzoyl, lauroyl peroxide, acetyl peroxide cyclohexylsulfonyl, peroxidating neodecanoic acid α-isopropyl phenyl ester, the peroxidating new last of the ten Heavenly stems
Acid -1,1- dimethyl -3- hydroxybutyl ester, dicetyl peroxydicarbonate two (3- methoxybutyl), di-isopropyl peroxydicarbonate,
Dicetyl peroxydicarbonate two (2- ethylhexyl), the new enanthic acid α-isopropyl phenyl ester of peroxidating, peroxy dicarbonate di-n-propyl ester, peroxidating
The combination of one or more of the neodecanoic acid tert-butyl ester, the weight of the initiator are equivalent to the first monomer and second comonomer
The 0.1%~0.8% of gross weight.
6. the preparation method of medical acrylic acid class thickener according to claim 1, which is characterized in that the dispersing agent
For sorbitan fatty ester, polyglyceryl fatty acid ester, sucrose fatty ester, alkylbenzene sulfonate, Polyoxyethylene fatty
One of acid esters, polyoxyethylene alkyl ether sulfonate or multiple combinations, the dispersant weight be equivalent to the first monomer and
The 0.3-1.0% of second comonomer gross weight.
7. the preparation method of medical acrylic acid class thickener according to claim 1, which is characterized in that described two or
The polyalkenyl ether of three polymerizable ethylenical unsaturated double bonds is pentaerythritol diallyl ether, pentaerythrite triallyl
One of ether, trimethylolpropane allyl ether, trimethylolpropane tris allyl ether or a variety of mixing.
8. the preparation method of medical acrylic acid class thickener according to claim 1, which is characterized in that the sucrose base
Allyl ether series crosslinking agent is sucrose diallyl ether, sucrose triallyl ether.
9. a kind of medical acrylic acid class thickener, which is characterized in that be prepared by method a method as claimed in any one of claims 1-8
It arrives.
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