CN104448107A - Alkaline-soluble acrylate polymer composition and preparation method thereof - Google Patents
Alkaline-soluble acrylate polymer composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an alkaline-soluble acrylate polymer composition, which is prepared from the raw material formula by emulsion polymerization. The alkaline-soluble acrylate polymer composition comprises the following components in percentage by weight: 8wt%-15wt% of an unsaturated carboxylic acid monomer as a monomer phase, 19wt%-28wt% of at least one C1-C10 alkyl ester of acrylic acid or methacrylic acid, 60wt%-70wt% of deionized water as a water phase, 1wt%-3wt% of a prepolymerized linear polymer, 0wt%-3wt% of protective colloid, 0.05wt%-1.0wt% of an emulsifier, 0.05wt%-0.2wt% of a cross-linking agent and 0.05wt%-0.5wt% of an initiator, wherein the number-average molecular weight is 10,000-100,000; and the cross-linking agent is added to a reaction system after 28%-58% of monomer phase is consumed. The invention aims at providing the alkaline-soluble acrylate polymer composition which is small in amount in the formula, good in suspending power in a low pH condition, high in thickening capacity, and good in transparency; and meanwhile, a preparation method of the alkaline-soluble acrylate polymer composition is also provided.
Description
Technical field
The invention belongs to Polymer Synthesizing field, particularly there is an excellent thickening suspension property, even if also can play within the scope of low pH that transparency is high, thickening suspension property good, alkali-soluble acrylate's polymer composition of good rheological property and the preparation method of said composition.
Background technology
The class I liquid I thickening material being usually used in thickening surfactivity aqueous systems is caustic solubility/alkali swelling type emulsion polymer (ASE).It is in not carrying out with alkali and front water-fast, only has the effect its pH value being adjusted to more than 6.5 its rheology control agents of competence exertion.Its stream become thickening mechanism into: along with pH value increases and the neutralization of carboxylic group, polymer molecule carries out hydrated, and its molecular chain is expanded under the anionic charge central electrostatic repulsion repulsion effect of carboxyl.Molecular chain expansion causes the hydrodynamic size of polymkeric substance to increase, and this increases tangling and resistance to flow of molecule again conversely.This process is called as hydromeehanics thickening.Although containing in the aqueous systems of tensio-active agent under pH >=6.5 can provide good viscosity, suspend and transparency, in acid range under (pH≤6.0), can become muddy, cause clarity and the rheological property of difference.
Food preservation additive is due to anti-microbial effect, mild and do not produce the advantages such as safety problem and cause increasing concern gradually, and cosmetic formulations teacher also tends to use this kind of sanitas and replaces the traditional preservatives likely forming health threat that contacts with human skin, scalp and hair.The organic acid such as citric acid, phenylformic acid is applied more in food preservatives, and during along with pH rising (pH≤6), this kind of sanitas is sent out protogenic to dissociate, and forms acid salt, just has antimicrobial acivity.
A kind of performance alkali swelling type thickening material and preparation method thereof is disclosed in patent CN103204968A, polymkeric substance cannot dissolve at low ph values, could can only dissolve behind pH >=7, higher viscosity and transparency can be provided in the formula of transparent exfoliating shower gel, but suspension property is not good, particle only can suspend 20d at (40 ± 1) DEG C.
In patent CN1312828A, disclose a kind of hydrophobic association type alkali soluble latex thickeners, this polymkeric substance can dissolve when pH value is about 4.5 ~ 6.0, be particularly useful for make-up composition, but the shortcomings such as there is pH narrow range, the viscosity provided is higher, and rheological property is not good.
In patent CN103068865A, disclose the acrylate copolymer thickening material of a kind of structurizing (straight chain core/crosslinked shell), can provide that the stream of expectation becomes in containing aqueous tenside compounds, clarity and aesthetic property, particularly at a low ph.But this polymkeric substance exists consumption in formula, and greatly, thickening capabilities is limited, the problem that turbidity is high, therefore develops one consumption in formula little, the polymer emulsion that thickening capabilities significantly also improves turbidity of filling a prescription simultaneously very has market outlook.
Summary of the invention
An object of the present invention is to provide a kind of alkali-soluble acrylate's copolymer compositions that consumption little, low pH condition low suspension ability is good in formula, thickening capabilities strong, the transparency is good.
In addition, another object of the present invention is to provide the preparation method of above-mentioned alkali-soluble acrylate's copolymer compositions.
Technical scheme provided by the invention is: described composition obtains with letex polymerization by following composition of raw materials, and described composition of raw materials comprises following component:
The unsaturated carboxylic acid monomer of monomer phase: 8wt% ~ 15wt%;
The alkyl ester of at least one C1 ~ C10 of the acrylic or methacrylic acid of 19wt% ~ 28wt%;
The deionized water of aqueous phase: 60wt% ~ 70wt%;
1wt% ~ 3wt% through prepolymerized linear polymer, its number-average molecular weight is 10000 ~ 100000;
The protective colloid of 0wt% ~ 3wt%;
The emulsifying agent of 0.05wt% ~ 1.0wt%;
And the linking agent of 0.05wt% ~ 0.2wt% and the initiator of 0.05wt% ~ 0.5wt%;
Wherein, monomer phase and initiator add in aqueous phase and are polymerized, and linking agent joins in reaction system after monomer consumes 28% ~ 58% mutually.
It should be noted that, in the present invention, wt% is the per-cent being equivalent to raw material gross weight.
Preferably, described alkali-soluble acrylate's polymer composition, composition of raw materials comprises following component:
The unsaturated carboxylic acid monomer of monomer phase: 9wt% ~ 14wt%,
The alkyl ester of at least one C1 ~ C10 of the acrylic or methacrylic acid of 20wt% ~ 25wt%;
The deionized water of aqueous phase: 62wt% ~ 68wt%;
1.5wt% ~ 2.5wt% through prepolymerized linear polymer, its number-average molecular weight is 10000 ~ 100000;
The protective colloid of 1wt% ~ 3wt%;
The emulsifying agent of 0.5wt% ~ 0.9wt%;
And the linking agent of 0.1wt% ~ 0.15wt% and the initiator of 0.08wt% ~ 0.22wt%;
Wherein, described unsaturated carboxylic acid monomer is at least one in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, β-crotonic acid, equisetic acid, toxilic acid;
Described composition is prepared by emulsion polymerisation process, and wherein, monomer phase and initiator add in aqueous phase and be polymerized, and linking agent joins in reaction system after monomer consumes 30% ~ 48% mutually.
Wherein, the alkyl ester of at least one C1 ~ C10 of acrylic or methacrylic acid includes but not limited to following compound: the just own ester of methyl acrylate, ethyl propenoate, n-butyl acrylate, vinylformic acid n-pentyl ester, isoamyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, n-amylmethacrylate, isopentyl methacrylate, methacrylic acid, 2-Ethylhexyl Methacrylate, Octyl methacrylate, decyl-octyl methacrylate.The alkyl ester of at least one C1 ~ C10 of acrylic or methacrylic acid can be chosen as the alkyl ester of C1 ~ C5, be preferably the alkyl ester of C1 ~ C5 and the mixing of C6 ~ C10 alkyl ester, wherein, the alkyl ester of C1 ~ C5 and the part by weight of C6 ~ C10 alkyl ester are 10 ~ 20:1.
Emulsifying agent can be chosen as anionic, non-ionic type, amphoteric and cationic surfactant, and their mixture.Preferably, use negatively charged ion and nonionic surface active agent, and their mixture.
In above-mentioned alkali-soluble acrylate's polymer composition, described linear polymer is undertaken being polymerized obtaining by unsaturated carboxylic acid monomer and acrylic ester monomer, and described acrylic ester monomer is one or more in monomer A, acrylic acid or the like fluoroalkyl, acrylic acid or the like polyoxy Vinyl Ether alkyl ester;
The general formula of described monomer A is:
wherein n=0 ~ 4, R
1for hydroxyl or H, R
2for methyl or H.
Wherein, described acrylic acid or the like fluoroalkyl is preferably vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, methacrylic acid 2, one in 2,2-trifluoro ethyl ester, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, methacrylic acid ten trifluoro monooctyl ester, vinylformic acid ten trifluoro monooctyl ester.
Wherein, described acrylic acid or the like polyoxy Vinyl Ether alkyl ester is preferably the one in Steareth methacrylic ester, eicosyl polyethenoxy ether metacrylic acid ester, beheneth methacrylic ester, Steareth acrylate, eicosyl Soxylat A 25-7 acrylate, beheneth acrylate.
Wherein, at least one in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, β-crotonic acid, equisetic acid, toxilic acid is preferably for being polymerized the unsaturated carboxylic acid monomer obtaining linear polymer.
Preferably, described linear polymer can select the mixture of methacrylic acid and methyl methacrylate, and wherein the part by weight of methacrylic acid and methyl methacrylate is 10:8 ~ 12.
Preferably, described linear polymer carries out copolymerization by acrylic acid or the like polyoxy Vinyl Ether alkyl ester and vinylformic acid and methyl methacrylate and obtains, described linear polymer can select beheneth methacrylic ester, methacrylic acid and methyl methacrylate, and the part by weight of beheneth methacrylic ester, methacrylic acid and methyl methacrylate is: 12:8 ~ 12:8 ~ 12.
Preferably, described linear polymer carries out copolymerization by acrylic acid or the like fluoroalkyl and vinylformic acid and hydroxyethyl methylacrylate and obtains.Wherein, the mass ratio of acrylic acid or the like fluoroalkyl, vinylformic acid and hydroxyethyl methylacrylate is 2 ~ 4:1 ~ 1.5:1 ~ 1.5.
Specifically, the aqueous phase of the described linear polymer containing unsaturated carboxylic acid is prepared by the following method:
In aqueous phase; under protection of inert gas and initiator existent condition; add initiated polymerization 0.1h ~ 0.5h in above-mentioned monomer to emulsifier aqueous solution; obtain above-mentioned aqueous phase; wherein; the consumption of initiator is 0.005 ~ 0.02wt%; polymerization temperature is 80 ~ 90 DEG C; preparation terminates rear obtained mixture and continues to react mutually with monomer as aqueous phase; be in fact add a kind of homopolymer of above-mentioned monomer or the multipolymer of two or more monomer in the sandwich layer part of polymkeric substance, its number-average molecular weight is 10000 ~ 100000.
Preferably, described protective colloid is the one in polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, derivatived cellulose.The polymerization degree of polyoxyethylene glycol is preferably 5 ~ 30.
In the present invention, linking agent multiselect is selected as many unsaturated monomers, as Phthalic acid, diallyl ester, trimethylolpropane tris (methyl) acrylate, triethylene glycol two (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, divinyl glycol, Vinylstyrene, tetramethylol methane four (methyl) acrylate, diallyl itaconate, diallyl maleate, TriMethylolPropane(TMP) dialkylene propyl ether, trimethylolpropane tris allyl ethers, divinyl glycol, Vinylstyrene, methylene diacrylamine etc.
Initiator can be chosen as: water-soluble inorganic persulfate compound, superoxide, peroxy acid, oleosoluble radical initiators, preferably, water-soluble inorganic persulfate compound is specially adapted to reaction system of the present invention, and it can be chosen as the one in ammonium persulphate, Potassium Persulphate and Sodium Persulfate.Superoxide can be chosen as organo-peroxide and inorganic peroxide, and as lauryl peroxide, hydrogen peroxide etc., oleosoluble radical initiators is as 2,2 '-Diisopropyl azodicarboxylate etc.
The present invention also provides the preparation method of above-mentioned alkali-soluble acrylate's polymer composition, comprises the following steps:
Step 1: aqueous phase is joined in reaction vessel, under the protection of rare gas element, constant temperature 80 DEG C ~ 90 DEG C, joins stirring reaction 1h ~ 2h in reaction vessel by the monomer of account for monomer phase total amount 28% ~ 58% under initiator existent condition;
Step 2: by monomer mutually in residual monomer and linking agent under initiator existence condition, join in reaction vessel, constant temperature 80 DEG C ~ 90 DEG C, reaction 1h ~ 3h, terminate to be obtained by reacting alkali-soluble acrylate's polymer composition;
Wherein, described monomer comprises the unsaturated carboxylic acid monomer of 8wt% ~ 15wt% mutually, the alkyl ester of at least one C1 ~ C10 of the acrylic or methacrylic acid of 19wt% ~ 28wt%; Described unsaturated carboxylic acid monomer is at least one in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, β-crotonic acid, equisetic acid, toxilic acid;
Described aqueous phase comprises the deionized water of 60wt% ~ 70wt%; 1wt% ~ 3wt% through prepolymerized linear polymer, its number-average molecular weight is 10000 ~ 100000; The protective colloid of 0wt% ~ 3wt%; The emulsifying agent of 0.05wt% ~ 1.0wt%;
In step 1 and step 2, the total amount of initiator is 0.05wt% ~ 0.5wt%, and in step 2, the amount of linking agent is 0.05wt% ~ 0.2wt%.
In the preparation method of above-mentioned alkali-soluble acrylate's polymer composition,
In above-mentioned alkali-soluble acrylate's polymer composition, described linear polymer to be polymerized with one or more in monomer A, acrylic acid or the like fluoroalkyl, acrylic acid or the like polyoxy Vinyl Ether alkyl ester by unsaturated carboxylic acid monomer and to obtain;
The general formula of described monomer A is:
wherein n=0 ~ 4, R
1for hydroxyl or H, R
2for methyl or H.
Wherein, described acrylic acid or the like fluoroalkyl is preferably vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, methacrylic acid 2, one in 2,2-trifluoro ethyl ester, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, methacrylic acid ten trifluoro monooctyl ester, vinylformic acid ten trifluoro monooctyl ester.
Wherein, described acrylic acid or the like polyoxy Vinyl Ether alkyl ester is preferably the one in Steareth methacrylic ester, eicosyl polyethenoxy ether metacrylic acid ester, beheneth methacrylic ester, Steareth acrylate, eicosyl Soxylat A 25-7 acrylate, beheneth acrylate.
Wherein, at least one in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, β-crotonic acid, equisetic acid, toxilic acid is preferably for being polymerized the unsaturated carboxylic acid monomer obtaining linear polymer.
Preferably, described linear polymer can select the mixture of methacrylic acid and methyl methacrylate, and wherein the part by weight of methacrylic acid and methyl methacrylate is 10:8 ~ 12.
Preferably, described linear polymer carries out copolymerization by acrylic acid or the like polyoxy Vinyl Ether alkyl ester and vinylformic acid and methyl methacrylate and obtains, described linear polymer can select beheneth methacrylic ester, methacrylic acid and methyl methacrylate, and the part by weight of beheneth methacrylic ester, methacrylic acid and methyl methacrylate is: 12:8 ~ 12:8 ~ 12.
Preferably, described linear polymer carries out copolymerization by acrylic acid or the like fluoroalkyl and vinylformic acid and hydroxyethyl methylacrylate and obtains.Wherein, the mass ratio of acrylic acid or the like fluoroalkyl, vinylformic acid and hydroxyethyl methylacrylate is 2 ~ 4:1 ~ 1.5:1 ~ 1.5.
In the preparation method of above-mentioned alkali-soluble acrylate's polymer composition, protective colloid is the one in polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, derivatived cellulose.
In the preparation method of above-mentioned alkali-soluble acrylate's polymer composition, in step 1, monomer joins in reactor in the mode dripped, and the time of dropping is 1h ~ 2h;
In step 2, monomer phase and linking agent join in reactor in the mode dripped, and the time of dropping is 1h ~ 3h.
The present invention is polymerized by emulsion polymerization, aqueous phase and monomer separate mutually completely, reduce polymerization initial stage monomer concentration, ensure that the lower polymerization degree that linear polymerization reacts, be conducive to increasing its transparency, in the middle and later periods of reaction, increase linking agent and enter reaction system, improve viscosity and the suspension property of product, what is more important, the present invention improves adding by the linear pre-polymer that is raw material with optional various of monomer further, further increase the viscosity of product, the transparency and suspension property, suspending stabilized and thickening property particularly under low pH condition.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described in further detail, but does not form any limitation of the invention.
Specific embodiment 1:
In the four-hole boiling flask of 2L that nitrogen device, magnetic stirring apparatus and peristaltic pump are housed, add 166g vinylformic acid, 324g methyl methacrylate, form monomer phase.
The ammonium persulfate solution 68g of preparation containing 1.12g ammonium persulphate, is labeled as initiator.
894g deionized water and 13g sodium lauryl sulphate is added in five mouthfuls of flasks of 2L that nitrogen device, prolong, stirrer, thermometer and peristaltic pump are housed, 10g methyl methacrylate, stir and add 10g methacrylic acid after 10 minutes, open and stir logical nitrogen, system is made to be warming up to 86 DEG C, start to drip initiator (0.28mL/min), drip 20min, form aqueous phase.
Continue to drip initiator with the speed of 0.28mL/min, and start to drip in monomer to five mouthful flask, rate of addition is 2.29mL/min, monomer phase and initiator stop dripping after dripping 1.5h, in five mouthfuls of bottles, add 1g Phthalic acid, diallyl ester, be then incubated 20min, temperature control 85 ± 1 DEG C.
At the uniform velocity drip residual monomer phase 120min with the rate of addition of 2.1mL/min after being incubated and be that the rate of addition of 0.28mL/min at the uniform velocity drips remaining initiator 130min with rate of addition, add rear continuation at 85 ± 1 DEG C of insulation 60min, resulting polymers emulsion product, through being cooled to normal temperature, is packed by 400 order filter clothes.
Specific embodiment 2:
In the four-hole boiling flask of 2L that nitrogen device, magnetic stirring apparatus and peristaltic pump are housed, add 166g vinylformic acid, 324g β-dimethyl-aminoethylmethacrylate, form monomer phase.
The ammonium persulfate solution 68g of preparation containing 1.12g ammonium persulphate, is labeled as initiator.
894g deionized water and 13g sodium lauryl sulphate is added in five mouthfuls of flasks of 2L that nitrogen device, prolong, stirrer, thermometer and peristaltic pump are housed, 10g methyl methacrylate, stir and add 10g methacrylic acid after 10 minutes, open and stir logical nitrogen, system is made to be warming up to 82 DEG C, start to drip initiator (0.28mL/min), drip 20min, form aqueous phase.
Continue to drip initiator with the speed of 0.28mL/min, and start to drip in monomer to five mouthful flask, rate of addition is 2.29mL/min, temperature controls at 82 ± 1 DEG C, monomer phase and initiator stop dripping after dripping 1.5h, in five mouthfuls of bottles, add 1g Phthalic acid, diallyl ester, be then incubated 20min, temperature control 84-86 DEG C.
At the uniform velocity drip residual monomer phase 120min with the rate of addition of 2.1mL/min after being incubated and be that the rate of addition of 0.28mL/min at the uniform velocity drips remaining initiator 130min with rate of addition, add rear continuation at 84-86 DEG C of insulation 60min, resulting polymers emulsion product, through being cooled to normal temperature, is packed by 400 order filter clothes.
Specific embodiment 3:
Substantially identical with embodiment 1, different places is, the linking agent in reaction process is linking agent diallyl itaconate 1g, and initiator is Potassium Persulphate 1.2g.
Specific embodiment 4:
Substantially identical with embodiment 1, different places is, adds 166g methacrylic acid and 324g methyl methacrylate in the four-hole boiling flask of 2L.
Specific embodiment 5:
Substantially identical with embodiment 4, different places is, adds 166g methacrylic acid, 294g β-dimethyl-aminoethylmethacrylate and the positive heptyl ester of 30g methacrylic acid in the four-hole boiling flask of 2L.
Specific embodiment 6:
Substantially identical with embodiment 1, different places is, 894g deionized water and 13g sodium lauryl sulphate is added successively in five mouthfuls of flasks of 2L, 12g beheneth methacrylic ester, 10g methyl methacrylate, stirs and adds 10g methacrylic acid after 10 minutes, system is made to be warming up to 86 DEG C, start to drip initiator (0.28mL/min), drip 20min, form aqueous phase.
Specific embodiment 7:
The ammonium persulfate solution 68g of preparation containing 1.12g ammonium persulphate, is labeled as initiator.
893.78g deionized water and 12.68g sodium lauryl sulphate is added successively in five mouthfuls of flasks of 2L that nitrogen device, prolong, stirrer, thermometer and peristaltic pump are housed; 5.12g Hexafluorobutyl mathacrylate; 5.12g hydroxyethyl methylacrylate; stir and add 10g methacrylic acid after 10 minutes, stir under nitrogen protection and be warming up to 85 ± 1 DEG C.
In the four-hole boiling flask of 2L that nitrogen device, magnetic stirring apparatus and peristaltic pump are housed, add 166.64g methacrylic acid, 324.1g ethyl propenoate, open and stir logical nitrogen.
After five mouthfuls of flasks reach temperature of reaction 86 DEG C, start to drip initiator (0.28mL/min), after dripping 20min, start to drip in monomer to five mouthful flask, rate of addition is 2.29mL/min, and monomer stops dripping after dripping 1.5h mutually, adds 1.024g Phthalic acid, diallyl ester in five mouthfuls of bottles, then 20min is incubated, temperature control 85 ± 1 DEG C.
At the uniform velocity drip residual monomer phase 120min with the rate of addition of 2.1mL/min after being incubated and be that the rate of addition of 0.28mL/min at the uniform velocity drips remaining initiator 130min with rate of addition, add rear continuation at 84-86 DEG C of insulation 60min, resulting polymers emulsion product, through being cooled to normal temperature, is packed by 400 order filter clothes.
Specific embodiment 8
Substantially identical with embodiment 1, different places is, adds 207g vinylformic acid and 356g β-dimethyl-aminoethylmethacrylate in the four-hole boiling flask of 2L.
Specific embodiment 9
In the four-hole boiling flask of 2L that nitrogen device, magnetic stirring apparatus and peristaltic pump are housed, add 166g vinylformic acid, 324g methyl methacrylate, form monomer phase.
The ammonium persulfate solution 68g of preparation containing 1.12g ammonium persulphate, is labeled as initiator.
894g deionized water and 13g sodium lauryl sulphate is added in five mouthfuls of flasks of 2L that nitrogen device, prolong, stirrer, thermometer and peristaltic pump are housed, 10g methyl methacrylate, stir and add 10g methacrylic acid after 10 minutes, open and stir logical nitrogen, system is made to be warming up to 86 DEG C, start to drip initiator (0.28mL/min), drip 20min, form aqueous phase.
Continue to drip initiator with the speed of 0.28mL/min, and start to drip in monomer to five mouthful flask, rate of addition is 2.29mL/min, monomer phase and initiator stop dripping after dripping 1.2h, in five mouthfuls of bottles, add 1g Phthalic acid, diallyl ester, be then incubated 20min, temperature control 86 ± 2 DEG C.
At the uniform velocity drip residual monomer phase 148min with the rate of addition of 2.14mL/min after being incubated and be that the rate of addition of 0.25mL/min at the uniform velocity drips remaining initiator 150min with rate of addition, add rear continuation at 86 ± 2 DEG C of insulation 60min, resulting polymers emulsion product, through being cooled to normal temperature, is packed by 400 order filter clothes.
Specific embodiment 10
Substantially identical with specific embodiment 2, different places is, be also added with 23g polyoxyethylene glycol in five mouthfuls of flasks of 2L, wherein the polymerization degree of polyoxyethylene glycol is 25.
Application Example 1
The application formula of table 1:(transparent bath foam)
| Component | Consumption (wt%) | Function | |
| 1 | Deionized water | Supply 100 | Solvent |
| 2 | Disodium ethylene diamine tetraacetate | 0.05 | Sequestrant |
| 3 | Composition (32%) | 4 | Rheology modifier |
| 4 | AES(20％) | 62 | Primary surfactant |
| 5 | NaOH(18％) | Supply pH | PH adjusting agent |
| 6 | CAB(35％) | 7.4 | Auxiliary tensio-active agent |
| 7 | Sodium Benzoate | 0.1 | Sanitas |
| 8 | Citric acid (50%) | Supply pH | PH adjusting agent |
| 9 | The colored bead of Puensomes greenl 24/30 | 1 | Test suspension performance |
The composition of embodiment 1 ~ 7 is become transparent bath foam according to above-mentioned formulated, in process for preparation, formula solution becomes whipped state all the time, each component (1,2,3) be sequentially added under agitation in mixing vessel, then use NaOH (component 4) will to fill a prescription pH furnishing about 6.5, add component 5, component 6, finally adds citric acid (component 7) by pH value furnishing 5.5,5,4.5,4.The 200g clear formula prepared under each pH value is transferred in the transparent plastic drug package of 150g PET, carries out centrifugal elimination bubble, tested viscosity, yield value and turbidity after constant temperature 24h at 25 DEG C
The testing method of viscosity is as follows:
Use the viscosity of Brook field RVT viscometer determining product, select No. 4 rotors, test rotating speed is 5rpm, after stable reading, reading is multiplied by parameter and obtains viscosity.
The testing method of yield value is as follows:
(1) sample is put into whizzer, start under 2000r/m speed centrifugal, stop centrifugal after 13min, remove bubble.
(2) sample is placed in 25 DEG C of thermostat container 20h ~ 24h.
(3) use the viscosity of Brook field RVT viscometer determining product, select No. 5 rotors, test rotating speed is respectively 0.5rpm and 1rpm, and calculation formula is:
Note: η is the viscosity (unit: cps) under subscript rotating speed, yield value (unit: Pa)
The testing method of turbidity is as follows:
(1) start shooting preheating turbidimeter 30min, and correct turbidimeter.
(2) be encased in turbidity bottle with stainless steel medicine bale-out sample.
(3) centrifugal 10min under whizzer 1200r/m, eliminates bubble.
(4) by centrifugal complete after sample is housed turbidity bottle be placed at turbidimeter test position, directly read reading.
Suspension property testing method is as follows:
(1) by formulation samples down in 60mL transparent sample bottle.
(2) add particle in sample bottle, with spoon be stirred to the particle of sample, bubble is uniformly distributed.
(3) sample bottle to be placed in 40 DEG C and 48 DEG C of baking ovens observations after 30 days: 1) if particle suspension decline 0% ~ 5%, remembers 4 points, decline 5% ~ 30% be designated as 3 points, decline 30% ~ 60% be designated as 2 points, declining is greater than 60% and is designated as 1 point.
Test result is as following table 2 and following table 3:
Table 2 (performance that under each pH value, transparent bath foam is filled a prescription):
Table 3 (suspension property that under each pH value, transparent bath foam is filled a prescription):
Application Example 2
Scalp care hair shampoo is filled a prescription: EDTA 2Na (0.1%wt), 32% composition (4%wt), AES (20%, 3EO) (56%wt), POLYQUAT 400 (0.3%wt), CMEA (0.5%wt), pearlescent flake (1%wt), cetostearyl alcohol (0.5%wt), TC-SHD (5%wt), TC-3560 (2.5%wt), TC-5075 (2.5%wt), TC-DMDMH (0.3%wt), deionized water (complementing to 100%wt), wherein POLYQUAT is the cationic cellulose of Guangzhou Tianci Advanced Materials Co., Ltd, TC-SHD is the amphoterics of Guangzhou Tianci Advanced Materials Co., Ltd, TC-3560 is the silicone emulsion of Guangzhou Tianci Advanced Materials Co., Ltd, TC-5075 is the silicone emulsion of new high-tech material limited-liability company of being bestowed by heaven, TC-DMDMH is the sanitas of new high-tech material limited-liability company of being bestowed by heaven, the composition of embodiment 7 is after being mixed with scalp care hair shampoo formula, the viscosity 7200mPa.s tested after 24h, tested viscosity 7800mPa.s after 1 month, shampoo outward appearance is milky white, and it is not stratified after 1 one months at 48 DEG C.
Application Example 3
Face cleaning milk is filled a prescription: EDTA 2Na (0.1%wt), 32% composition (4%wt), AES (100%, 2EO) (15%wt), NaOH (18%wt) regulates pH to 6.5 ~ 7.0, pearlescent flake (1.5%wt), TC-SHD (30%) (6%wt), TC-MAB40LD (40%wt) (3%wt), TC-DMDMH (0.3%wt), lemon acid for adjusting pH to 5.5, wherein TC-SHD is the amphoterics of Guangzhou Tianci Advanced Materials Co., Ltd, TC-MAB40LD is the amphoterics of Guangzhou Tianci Advanced Materials Co., Ltd, TC-DMDMH is the sanitas of Guangzhou Tianci Advanced Materials Co., Ltd, the composition of embodiment 7 is after being mixed with face cleaning milk formula, tested viscosity is 18500mPa.s, at 48 DEG C after one month, face cleaning milk is not stratified.
Can be found out by above-mentioned Application Example, adopt this programme can obtain excellent suspension effect and thickening properties, particularly stratum nucleare add in advance easier alkali molten there is rheological monomer, after the hydrophobic monomer of the especially fluoroalkyl of vinylformic acid or methacrylic acid, viscosity and properties of transparency be improved significantly.And in other formulas, also there is good thickening properties and stability.
Find after in the test that embodiment 10 is applied to transparent bath foam formula, after interpolation polyoxyethylene glycol, test after 1 month in the environment of 48 degrees Celsius, during pH=5.5 ~ 4.5, suspension stability becomes 4 points, and decreasing ratio is in the scope of 3% ~ 5%.
Above-describedly be only preferred embodiment of the present invention, all do within the scope of the spirit and principles in the present invention any amendment, equivalently to replace and improvement etc., all should be included within protection scope of the present invention.
Claims (21)
1. alkali-soluble acrylate's polymer composition, is characterized in that, described composition obtains with letex polymerization by following composition of raw materials, and described composition of raw materials comprises following component:
The unsaturated carboxylic acid monomer of monomer phase: 8wt% ~ 15wt%;
The alkyl ester of at least one C1 ~ C10 of the acrylic or methacrylic acid of 19wt% ~ 28wt%;
The deionized water of aqueous phase: 60wt% ~ 70wt%;
1wt% ~ 3wt% through prepolymerized linear polymer, its number-average molecular weight is 10000 ~ 100000;
The protective colloid of 0wt% ~ 3wt%;
The emulsifying agent of 0.05wt% ~ 1.0wt%;
And the linking agent of 0.05wt% ~ 0.2wt% and the initiator of 0.05wt% ~ 0.5wt%;
Wherein, monomer phase and initiator add in aqueous phase and are polymerized, and linking agent joins in reaction system after monomer consumes 28% ~ 58% mutually.
2. alkali-soluble acrylate's polymer composition according to claim 1, is characterized in that, described unsaturated carboxylic acid monomer is at least one in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, β-crotonic acid, equisetic acid, toxilic acid.
3. alkali-soluble acrylate's polymer composition according to claim 1, it is characterized in that, the alkyl ester of at least one C1 ~ C10 of described acrylic or methacrylic acid is methyl acrylate, ethyl propenoate, n-butyl acrylate, vinylformic acid n-pentyl ester, isoamyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, n-amylmethacrylate, isopentyl methacrylate, the just own ester of methacrylic acid, 2-Ethylhexyl Methacrylate, Octyl methacrylate, one or more in decyl-octyl methacrylate.
4. alkali-soluble acrylate's polymer composition according to claim 1, it is characterized in that, described linear polymer is undertaken being polymerized obtaining by unsaturated carboxylic acid monomer and acrylic ester monomer, and described acrylic ester monomer is one or more in monomer A, acrylic acid or the like fluoroalkyl, acrylic acid or the like polyoxy Vinyl Ether alkyl ester;
The general formula of described monomer A is:
wherein n=0 ~ 4, R
1for hydroxyl or H, R
2for methyl or H.
5. alkali-soluble acrylate's polymer composition according to claim 4, it is characterized in that, described acrylic acid or the like fluoroalkyl is vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, methacrylic acid 2, one in 2,2-trifluoro ethyl ester, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, methacrylic acid ten trifluoro monooctyl ester, vinylformic acid ten trifluoro monooctyl ester.
6. alkali-soluble acrylate's polymer composition according to claim 4, it is characterized in that, described acrylic acid or the like polyoxy Vinyl Ether alkyl ester is the one in Steareth methacrylic ester, eicosyl polyethenoxy ether metacrylic acid ester, beheneth methacrylic ester, Steareth acrylate, eicosyl Soxylat A 25-7 acrylate, beheneth acrylate.
7. according to the arbitrary described alkali-soluble acrylate's polymer composition of claim 4 ~ 6, it is characterized in that, be at least one in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, β-crotonic acid, equisetic acid, toxilic acid for being polymerized the unsaturated carboxylic acid monomer obtaining linear polymer.
8. alkali-soluble acrylate's polymer composition according to claim 1, is characterized in that, described protective colloid is the one in polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, derivatived cellulose.
9. alkali-soluble acrylate's polymer composition according to claim 1, it is characterized in that, described emulsifying agent is one or more in aniorfic surfactant, nonionic surface active agent, amphoteric surfactant, cationic surfactant.
10. alkali-soluble acrylate's polymer composition according to claim 1, it is characterized in that, described linking agent is Phthalic acid, diallyl ester, trimethylolpropane tris (methyl) acrylate, triethylene glycol two (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, divinyl glycol, Vinylstyrene, tetramethylol methane four (methyl) acrylate, diallyl itaconate, diallyl maleate, TriMethylolPropane(TMP) dialkylene propyl ether, trimethylolpropane tris allyl ethers, divinyl glycol, Vinylstyrene, one or more in methylene diacrylamine.
11. alkali-soluble acrylate's polymer compositions according to claim 1, is characterized in that, described initiator is the one in water-soluble inorganic persulfate compound, superoxide, oleosoluble radical initiators.
The preparation method of 12. 1 kinds of alkali-soluble acrylate's polymer compositions as claimed in claim 1, is characterized in that, comprise the following steps:
Step 1: aqueous phase is joined in reaction vessel, under the protection of rare gas element, constant temperature 80 DEG C ~ 90 DEG C, joins stirring reaction 1h ~ 2h in reaction vessel by the monomer of account for monomer phase total amount 28% ~ 58% under initiator existent condition;
Step 2: by monomer mutually in residual monomer and linking agent under initiator existence condition, join in reaction vessel, constant temperature 80 DEG C ~ 90 DEG C, reaction 1h ~ 3h, terminate to be obtained by reacting alkali-soluble acrylate's polymer composition;
Wherein, described monomer comprises the unsaturated carboxylic acid monomer of 8wt% ~ 15wt% mutually, the alkyl ester of at least one C1 ~ C10 of the acrylic or methacrylic acid of 19wt% ~ 28wt%;
Described aqueous phase comprise the deionized water of 60wt% ~ 70wt%, 1wt% ~ 3wt% through the protective colloid of prepolymerized linear polymer, 0wt% ~ 3wt% and the emulsifying agent of 0.05wt% ~ 1.0wt%, linear polymer number-average molecular weight is 10000 ~ 100000;
In step 1 and step 2, the total amount of initiator is 0.05wt% ~ 0.5wt%, and in step 2, the amount of linking agent is 0.05wt% ~ 0.2wt%.
The preparation method of 13. alkali-soluble acrylate's polymer compositions according to claim 12, is characterized in that,
In step 1, monomer joins in reactor in the mode dripped, and the time of dropping is 1h ~ 2h;
In step 2, monomer phase and linking agent join in reactor in the mode dripped, and the time of dropping is 1h ~ 3h.
14. the preparation method of alkali-soluble acrylate's polymer composition according to claim 12, it is characterized in that, described unsaturated carboxylic acid monomer is at least one in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, β-crotonic acid, equisetic acid, toxilic acid.
The preparation method of 15. alkali-soluble acrylate's polymer compositions according to claim 12, it is characterized in that, the alkyl ester of at least one C1 ~ C10 of described acrylic or methacrylic acid is methyl acrylate, ethyl propenoate, n-butyl acrylate, vinylformic acid n-pentyl ester, isoamyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, n-amylmethacrylate, isopentyl methacrylate, the just own ester of methacrylic acid, 2-Ethylhexyl Methacrylate, Octyl methacrylate, one or more in decyl-octyl methacrylate.
The preparation method of 16. alkali-soluble acrylate's polymer compositions according to claim 12, described linear polymer is undertaken being polymerized obtaining by unsaturated carboxylic acid monomer and acrylic ester monomer, and described acrylic ester monomer is one or more in monomer A, acrylic acid or the like fluoroalkyl, acrylic acid or the like polyoxy Vinyl Ether alkyl ester;
The general formula of described monomer A is:
wherein n=0 ~ 4, R
1for hydroxyl or H, R
2for methyl or H.
The preparation method of 17. alkali-soluble acrylate's polymer compositions according to claim 16, it is characterized in that, described acrylic acid or the like fluoroalkyl is vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, methacrylic acid 2, one in 2,2-trifluoro ethyl ester, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, methacrylic acid ten trifluoro monooctyl ester, vinylformic acid ten trifluoro monooctyl ester.
The preparation method of 18. alkali-soluble acrylate's polymer compositions according to claim 16, it is characterized in that, described acrylic acid or the like polyoxy Vinyl Ether alkyl ester is the one in Steareth methacrylic ester, eicosyl polyethenoxy ether metacrylic acid ester, beheneth methacrylic ester, Steareth acrylate, eicosyl Soxylat A 25-7 acrylate, beheneth acrylate.
19. according to the preparation method of the arbitrary described alkali-soluble acrylate's polymer composition of claim 16 ~ 18, it is characterized in that, be at least one in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, β-crotonic acid, equisetic acid, toxilic acid for being polymerized the unsaturated carboxylic acid monomer obtaining linear polymer.
The preparation method of 20. alkali-soluble acrylate's polymer compositions according to claim 12, is characterized in that, described protective colloid is the one in polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, derivatived cellulose.
The preparation method of 21. alkali-soluble acrylate's polymer compositions according to claim 12, is characterized in that, described initiator is the one in water-soluble inorganic persulfate compound, superoxide, oleosoluble radical initiators.
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