CN104448107B - A kind of alkali-soluble acrylate's polymer composition and preparation method thereof - Google Patents
A kind of alkali-soluble acrylate's polymer composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of alkali-soluble acrylate's polymer composition, described composition is obtained with emulsion polymerization by following composition of raw materials, and described composition of raw materials includes following component：Single phase：The unsaturated carboxylic acid monomer of 8wt%～15wt%；The Arrcostab of at least one C1～C10 of the acrylic or methacrylic acid of 19wt%～28wt%；Water phase：The deionized water of 60wt%～70wt%；1wt%～3wt% through prepolymerized linear polymer, its number-average molecular weight be 10000～100000；The protecting colloid of 0wt%～3wt%；The emulsifying agent of 0.05wt%～1.0wt%；And the crosslinking agent of 0.05wt%～0.2wt% and the initiator of 0.05wt%～0.5wt%, crosslinking agent is added in reaction system after single phase consumes 28%～58%.The present invention is intended to provide a kind of alkali-soluble acrylate's copolymer compositions that consumption is little in formula, low ph condition low suspension ability is good, thickening capabilities strong, the transparency is good, while also providing the preparation method of alkali-soluble acrylate's copolymer compositions.
Description
Technical field
The invention belongs to Polymer Synthesizing field, particularly a kind of with excellent thickening suspendability, even if in low pH
In the range of can also play that transparency is high, thickening suspendability is good, alkali-soluble acrylate's combination of polymers of good rheological property
Thing and the preparation method of said composition.
Background technology
The class I liquid I thickener for being usually used in thickening surface-active aqueous systems is alkali solubility/alkali swelling type emulsion polymer
(ASE).It is insoluble in water with alkali before not being neutralized, only by its pH value be adjusted to more than 6.5 competence exertions its
The effect of rheology control agent.Its rheology thickening mechanism is：As pH value increases the neutralization with carboxylic group, polymer molecule is carried out
Hydrated, its strand are expanded under the anionic charge central electrostatic repulsion repulsion effect of carboxyl.Strand expansion causes to gather
The hydrodynamic size of compound increases, and this increases tangling and flow resistance for molecule in turn again.This process is referred to as fluid
Mechanics thickening.Although good viscosity can be provided in the aqueous systems containing surfactant under pH >=6.5, suspend and saturating
Lightness, but in acid range under (pH≤6.0), can become muddy, cause poor clarity and rheological property.
Food preservation additive is gradually caused more due to anti-microbial effect, mild and the advantages of not producing safety problem
Carry out more concerns, cosmetic formulations teacher also tends to using this kind of preservative and replaces and human skin, scalp and hair phase
The traditional preservatives for being possible to composition health threat of contact.The organic acids such as citric acid, benzoic acid are applied in food preservative
More, when raising (pH≤6) with pH, dissociation sent out protogenic by this kind of preservative, forms acid salt, just has antimicrobial work
Property.
A kind of performance alkali swelling type thickener and preparation method thereof, polymer is disclosed in patent CN103204968A
Cannot dissolve at low ph values, can only could dissolve behind pH >=7, can provide relatively in the formula of transparent exfoliating shower curry
High viscosity and transparency, but suspendability is not good, particle are only capable of suspension 20d at (40 ± 1) DEG C.
In patent CN1312828A, a kind of hydrophobic association type alkali soluble latex thickeners are disclosed, the polymer is in pH
Value can be dissolved when being for about 4.5～6.0, be particularly suited for cosmetic composition, but be there is pH narrow range, and the viscosity for providing is relatively
Height, the shortcomings of rheological property is not good.
In patent CN103068865A, a kind of acrylate copolymer of structuring (straight chain core/crosslinking shell) is disclosed
Thickener, can provide desired rheology, clarity and aesthetic property, particularly low in containing aqueous tenside compounds
Under pH.But the polymer has consumption in formula, and greatly, thickening capabilities are limited, the high problem of turbidity, therefore develop one kind
In formula, consumption is little, and thickening capabilities are notable and while the polymer emulsion for improving formula turbidity has market prospects very much.
Content of the invention
It is an object of the present invention to provide one kind consumption in formula is little, low ph condition low suspension ability is good, thickening energy
Alkali-soluble acrylate's copolymer compositions that power is strong, the transparency is good.
Additionally, another object of the present invention is the preparation of the alkali-soluble acrylate's copolymer compositions for providing above-mentioned
Method.
The present invention provide technical scheme be：Described composition is obtained with emulsion polymerization by following composition of raw materials, described
Composition of raw materials include following component：
Single phase：The unsaturated carboxylic acid monomer of 8wt%～15wt%；
The Arrcostab of at least one C1～C10 of the acrylic or methacrylic acid of 19wt%～28wt%；
Water phase：The deionized water of 60wt%～70wt%；
1wt%～3wt% through prepolymerized linear polymer, its number-average molecular weight be 10000～100000；
The protecting colloid of 0wt%～3wt%；
The emulsifying agent of 0.05wt%～1.0wt%；
And the crosslinking agent of 0.05wt%～0.2wt% and the initiator of 0.05wt%～0.5wt%；
Wherein, single phase and initiator are added and are polymerized in water phase, and crosslinking agent consumes 28%～58% in single phase
After be added in reaction system.
It should be noted that in the present invention, wt% be equivalent to the percentage of raw material gross weight.
Preferably, described alkali-soluble acrylate's polymer composition, composition of raw materials include following component：
Single phase：The unsaturated carboxylic acid monomer of 9wt%～14wt%,
The Arrcostab of at least one C1～C10 of the acrylic or methacrylic acid of 20wt%～25wt%；
Water phase：The deionized water of 62wt%～68wt%；
1.5wt%～2.5wt% through prepolymerized linear polymer, its number-average molecular weight be 10000～100000；
The protecting colloid of 1wt%～3wt%；
The emulsifying agent of 0.5wt%～0.9wt%；
And the crosslinking agent of 0.1wt%～0.15wt% and the initiator of 0.08wt%～0.22wt%；
Wherein, described unsaturated carboxylic acid monomer is acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, crow
At least one in head acid, maleic acid；
Described composition is prepared by emulsion polymerisation process, and wherein, single phase and initiator are added and entered in water phase
Row polymerization, crosslinking agent are added in reaction system after single phase consumes 30%～48%.
Wherein, the Arrcostab of at least one C1～C10 of acrylic or methacrylic acid includes but is not limited to following chemical combination
Thing：Methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid n-pentyl ester, isoamyl acrylate, methyl methacrylate
Ester, EMA, n-BMA, n-amylmethacrylate, isopentyl methacrylate, metering system
The just own ester of acid, 2-Ethylhexyl Methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, decyl-octyl methacrylate.Acrylic or methacrylic
The Arrcostab of at least one C1～C10 of acid can be chosen as the Arrcostab of C1～C5, the preferably Arrcostab of C1～C5 and C6
The mixing of～C10 Arrcostab, wherein, the part by weight of the Arrcostab of C1～C5 and C6～C10 Arrcostab is 10～20:1.
Emulsifying agent can be chosen as anionic, non-ionic, amphoteric and cationic surface active agent, and it
Mixture.Preferably, using anion and nonionic surface active agent, and their mixture.
In above-mentioned alkali-soluble acrylate's polymer composition, described linear polymer is by unsaturated carboxylic acid monomer
Carry out being polymerized obtaining with acrylic ester monomer, described acrylic ester monomer is monomer A, acrylic compounds fluoroalkyl,
One or more in acrylic compounds polyoxy vinethene Arrcostab；
The formula of described monomer A is：Wherein n=0～4, R1For hydroxyl or H,
R2For methyl or H.
Wherein, described acrylic compounds fluoroalkyl be preferably hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate,
Methacrylic acid 2,2,2- trifluoro ethyl ester, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, methacrylic acid 13
One kind in fluorine monooctyl ester, perluorooctyl acrylate.
Wherein, described acrylic compounds polyoxy vinethene Arrcostab is preferably Steareth methacrylic acid
Ester, eicosyl polyethenoxy ether metacrylic acid ester, beheneth methacrylate, octadecyl gather
In oxygen vinethene acrylate, eicosyl APEO acrylate, beheneth acrylate
A kind of.
Wherein, the unsaturated carboxylic acid monomer for obtaining linear polymer for polymerization is preferably acrylic acid, methacrylic acid, clothing
Health acid, fumaric acid, crotonic acid, aconitic acid, at least one in maleic acid.
Preferably, described linear polymer can select the mixture of methacrylic acid and methyl methacrylate, its
The part by weight of middle methacrylic acid and methyl methacrylate is 10:8～12.
Preferably, described linear polymer is by acrylic compounds polyoxy vinethene Arrcostab and acrylic acid and metering system
Sour methyl esters carries out copolymerization and obtains, described linear polymer can select beheneth methacrylate,
Methacrylic acid and methyl methacrylate, beheneth methacrylate, methacrylic acid and methyl
The part by weight of methyl acrylate is：12：8～12：8～12.
Preferably, described linear polymer is by acrylic compounds fluoroalkyl and acrylic acid and hydroxyethyl methacrylate second
Ester carries out copolymerization and obtains.Wherein, the mass ratio of acrylic compounds fluoroalkyl, acrylic acid and hydroxyethyl methacrylate is 2
～4:1～1.5:1～1.5.
Specifically, the water of the described linear polymer containing unsaturated carboxylic acid is mutually prepared by the following method：
In water phase, under conditions of inert gas shielding and initiator are present, add above-mentioned monomer water-soluble to emulsifying agent
Cause polymerase 10 .1h～0.5h in liquid, above-mentioned water phase is obtained, wherein, the consumption of initiator is 0.005～0.02wt%, polymerization temperature
Spend for 80～90 DEG C, the mixture obtained by preparing after terminating mutually continues to be reacted with single phase as water, substantially exists
The sandwich layer part of polymer adds the copolymer of a kind of homopolymers of above-mentioned monomer or two or more monomer, its number
Average molecular weight is 10000～100000.
Preferably, described protecting colloid is polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, cellulose derivative
In one kind.The degree of polymerization of polyethylene glycol is preferably 5～30.
In the present invention, crosslinking agent multiselect is selected as how unsaturated monomer, such as diallyl phthalate, trihydroxy methyl third
Alkane three (methyl) acrylate, triethylene glycol two (methyl) acrylate, dipentaerythritol six (methyl) acrylate, divinyl
Base glycol, divinylbenzene, tetramethylol methane four (methyl) acrylate, diallyl itaconate, diallyl maleate,
Trimethylolpropane dialkylene propyl ether, trimethylolpropane tris allyl ether, divinyl glycol, divinylbenzene, methylene
Base diacrylamine etc..
Initiator can be chosen as：Water-soluble inorganic persulfate compound, peroxide, peroxy acid, oil soluble free love
Base initiator, it is preferable that water-soluble inorganic persulfate compound is particularly well-suited to the reaction system of the present invention, which can select
For the one kind in ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate.Peroxide can be chosen as organic peroxide and inorganic mistake
Oxide, such as lauryl peroxide, hydrogen peroxide etc., oleosoluble radical initiators such as 2,2 '-azodiisobutyronitrile etc..
The present invention also provides the preparation method of above-mentioned alkali-soluble acrylate's polymer composition, comprises the following steps：
Step 1：Water is added in reaction vessel, under the protection of inert gas, 80 DEG C～90 DEG C of constant temperature, list will be accounted for
The monomer of the 28%～58% of body phase total amount is added to stirring reaction 1h in reaction vessel～2h under conditions of initiator presence；
Step 2：By residual monomer in single phase and crosslinking agent under initiator existence condition, it is added in reaction vessel,
80 DEG C～90 DEG C of constant temperature, reacts 1h～3h, terminates reaction and obtains alkali-soluble acrylate's polymer composition；
Wherein, described single phase includes the unsaturated carboxylic acid monomer of 8wt%～15wt%, the third of 19wt%～28wt%
The Arrcostab of at least one C1～C10 of olefin(e) acid or methacrylic acid；Described unsaturated carboxylic acid monomer is acrylic acid, methyl-prop
At least one in olefin(e) acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid, maleic acid；
Described water mutually includes the deionized water of 60wt%～70wt%；1wt%～3wt% through prepolymerized linear
Polymer, its number-average molecular weight are 10000～100000；The protecting colloid of 0wt%～3wt%；0.05wt%～1.0wt%'s
Emulsifying agent；
In step 1 and step 2, the total amount of initiator is 0.05wt%～0.5wt%, and in step 2, the amount of crosslinking 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 is by unsaturated carboxylic acid monomer
Obtain with being polymerized for one or more in monomer A, acrylic compounds fluoroalkyl, acrylic compounds polyoxy vinethene Arrcostab；
The formula of described monomer A is：Wherein n=0～4, R1For hydroxyl or H,
R2For methyl or H.
Wherein, described acrylic compounds fluoroalkyl be preferably hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate,
Methacrylic acid 2,2,2- trifluoro ethyl ester, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, methacrylic acid 13
One kind in fluorine monooctyl ester, perluorooctyl acrylate.
Wherein, described acrylic compounds polyoxy vinethene Arrcostab is preferably Steareth methacrylic acid
Ester, eicosyl polyethenoxy ether metacrylic acid ester, beheneth methacrylate, octadecyl gather
In oxygen vinethene acrylate, eicosyl APEO acrylate, beheneth acrylate
A kind of.
Wherein, the unsaturated carboxylic acid monomer for obtaining linear polymer for polymerization is preferably acrylic acid, methacrylic acid, clothing
Health acid, fumaric acid, crotonic acid, aconitic acid, at least one in maleic acid.
Preferably, described linear polymer can select the mixture of methacrylic acid and methyl methacrylate, its
The part by weight of middle methacrylic acid and methyl methacrylate is 10:8～12.
Preferably, described linear polymer is by acrylic compounds polyoxy vinethene Arrcostab and acrylic acid and metering system
Sour methyl esters carries out copolymerization and obtains, described linear polymer can select beheneth methacrylate,
Methacrylic acid and methyl methacrylate, beheneth methacrylate, methacrylic acid and methyl
The part by weight of methyl acrylate is：12：8～12：8～12.
Preferably, described linear polymer is by acrylic compounds fluoroalkyl and acrylic acid and hydroxyethyl methacrylate second
Ester carries out copolymerization and obtains.Wherein, the mass ratio of acrylic compounds fluoroalkyl, acrylic acid and hydroxyethyl methacrylate is 2
～4:1～1.5:1～1.5.
In the preparation method of above-mentioned alkali-soluble acrylate's polymer composition, protecting colloid is polyethylene glycol, gathers
One kind in vinyl alcohol, polyvinylpyrrolidone, cellulose derivative.
In the preparation method of above-mentioned alkali-soluble acrylate's polymer composition, in step 1, single phase is to drip
Mode be added in reactor, time of dropping is 1h～2h；
In step 2, single phase and crosslinking agent are added in reactor in the way of dripping, time of dropping be 1h～
3h.
The present invention is polymerized by emulsion polymerization, and water phase and single phase are completely separable, is reduced polymerization and is started
Stage monomer concentration, it is ensured that the relatively low degree of polymerization of linear polymerization reaction, is conducive to increasing its transparency, in reaction after
Phase, increase crosslinking agent and reaction system is entered, improve viscosity and the suspendability of product, it is even more important that the present invention enters one
Step improves the addition by linear pre-polymer with optional various of monomer as raw material, further increases the viscosity, thoroughly of product
Suspending stabilized and thickening property under bright property and suspendability, particularly low ph condition.
Specific embodiment
With reference to specific embodiment, technical scheme is described in further detail, but do not constitute right
Any restriction of the present invention.
Specific embodiment 1：
Equipped with nitrogen device, magnetic stirring apparatus and peristaltic pump 2L four-hole boiling flask in add 166g acrylic acid,
324g methyl methacrylate, forms single phase.
The ammonium persulfate solution 68g containing 1.12g ammonium persulfate is prepared, is labeled as initiator.
In five mouthfuls of flasks of the 2L equipped with nitrogen device, condenser pipe, mixer, thermometer and peristaltic pump, add 894g to go
Ionized water and 13g lauryl sodium sulfate, 10g methyl methacrylate, stirring added 10g methacrylic acid after 10 minutes, opened
Open stirring and lead to nitrogen, make system that 86 DEG C are warming up to, start initiator (0.28mL/min) is dripped, 20min is dripped, form water phase.
Continue initiator to be dripped with the speed of 0.28mL/min, and start to drip single phase to five mouthfuls of flasks, dropping speed
Spend for 2.29mL/min, stopping dropping after single phase and initiator dropping 1.5h, addition 1g phthalic acid two in five mouthfuls of bottles
Allyl ester, is then incubated 20min, 85 ± 1 DEG C of temperature control.
Residual monomer phase 120min is at the uniform velocity dripped with the rate of addition of 2.1mL/min after being incubated and with rate of addition be
The rate of addition of 0.28mL/min at the uniform velocity drips remaining initiator 130min, continues to be incubated 60min at 85 ± 1 DEG C after adding,
Resulting polymers emulsion product is cooled to normal temperature, is packed by 400 mesh filter clothes.
Specific embodiment 2：
Equipped with nitrogen device, magnetic stirring apparatus and peristaltic pump 2L four-hole boiling flask in add 166g acrylic acid,
324g EMA, forms single phase.
The ammonium persulfate solution 68g containing 1.12g ammonium persulfate is prepared, is labeled as initiator.
In five mouthfuls of flasks of the 2L equipped with nitrogen device, condenser pipe, mixer, thermometer and peristaltic pump, add 894g to go
Ionized water and 13g lauryl sodium sulfate, 10g methyl methacrylate, stirring added 10g methacrylic acid after 10 minutes, opened
Open stirring and lead to nitrogen, make system that 82 DEG C are warming up to, start initiator (0.28mL/min) is dripped, 20min is dripped, form water phase.
Continue initiator to be dripped with the speed of 0.28mL/min, and start to drip single phase to five mouthfuls of flasks, dropping speed
Spend for 2.29mL/min, temperature control stops dropping after single phase and initiator dropping 1.5h, in five mouthfuls of bottles at 82 ± 1 DEG C
1g diallyl phthalate is added, is then incubated 20min, 84-86 DEG C of temperature control.
Residual monomer phase 120min is at the uniform velocity dripped with the rate of addition of 2.1mL/min after being incubated and with rate of addition be
The rate of addition of 0.28mL/min at the uniform velocity drips remaining initiator 130min, continues to be incubated 60min at 84-86 DEG C after adding,
Resulting polymers emulsion product is cooled to normal temperature, is packed by 400 mesh filter clothes.
Specific embodiment 3：
It is substantially the same with embodiment 1, is where difference, crosslinking agent during the course of the reaction is crosslinking agent itaconic acid two
Allyl ester 1g, initiator are potassium peroxydisulfate 1.2g.
Specific embodiment 4：
Be substantially the same with embodiment 1, be where difference, add in the four-hole boiling flask of 2L 166g methacrylic acid and
324g methyl methacrylate.
Specific embodiment 5：
Be substantially the same with embodiment 4, difference where be, in the four-hole boiling flask of 2L add 166g methacrylic acid,
294g EMA and the positive heptyl ester of 30g methacrylic acid.
Specific embodiment 6：
Be substantially the same with embodiment 1, difference where be, sequentially add in five mouthfuls of flasks of 2L 894g deionized water and
13g lauryl sodium sulfate, 12g beheneth methacrylate, 10g methyl methacrylate, stirring
10g methacrylic acid is added after 10 minutes, make system that 86 DEG C are warming up to, start to drip initiator (0.28mL/min), dropping
20min, forms water phase.
Specific embodiment 7：
The ammonium persulfate solution 68g containing 1.12g ammonium persulfate is prepared, is labeled as initiator.
Sequentially add in five mouthfuls of flasks of the 2L equipped with nitrogen device, condenser pipe, mixer, thermometer and peristaltic pump
893.78g deionized water and 12.68g lauryl sodium sulfate, 5.12g Hexafluorobutyl mathacrylate, 5.12g methacrylic acid
Hydroxyl ethyl ester, stirring added 10g methacrylic acid after 10 minutes, and stirring under nitrogen protection is warming up to 85 ± 1 DEG C.
166.64g methyl-prop is added in the four-hole boiling flask of the 2L equipped with nitrogen device, magnetic stirring apparatus and peristaltic pump
Olefin(e) acid, 324.1g ethyl acrylate, open stirring and lead to nitrogen.
After five mouthfuls of flasks reach 86 DEG C of reaction temperature, start initiator (0.28mL/min) is dripped, after dropping 20min, open
Dropping single phase begin to five mouthfuls of flasks, rate of addition is 2.29mL/min, stops dropping after single phase dropping 1.5h, at five mouthfuls
1.024g diallyl phthalate is added in bottle, is then incubated 20min, 85 ± 1 DEG C of temperature control.
Residual monomer phase 120min is at the uniform velocity dripped with the rate of addition of 2.1mL/min after being incubated and with rate of addition be
The rate of addition of 0.28mL/min at the uniform velocity drips remaining initiator 130min, continues to be incubated 60min at 84-86 DEG C after adding,
Resulting polymers emulsion product is cooled to normal temperature, is packed by 400 mesh filter clothes.
Specific embodiment 8
It is substantially the same with embodiment 1, is where difference, in the four-hole boiling flask of 2L, adds 207g acrylic acid and 356g first
Base ethyl acrylate.
Specific embodiment 9
Equipped with nitrogen device, magnetic stirring apparatus and peristaltic pump 2L four-hole boiling flask in add 166g acrylic acid,
324g methyl methacrylate, forms single phase.
The ammonium persulfate solution 68g containing 1.12g ammonium persulfate is prepared, is labeled as initiator.
In five mouthfuls of flasks of the 2L equipped with nitrogen device, condenser pipe, mixer, thermometer and peristaltic pump, add 894g to go
Ionized water and 13g lauryl sodium sulfate, 10g methyl methacrylate, stirring added 10g methacrylic acid after 10 minutes, opened
Open stirring and lead to nitrogen, make system that 86 DEG C are warming up to, start initiator (0.28mL/min) is dripped, 20min is dripped, form water phase.
Continue initiator to be dripped with the speed of 0.28mL/min, and start to drip single phase to five mouthfuls of flasks, dropping speed
Spend for 2.29mL/min, stopping dropping after single phase and initiator dropping 1.2h, addition 1g phthalic acid two in five mouthfuls of bottles
Allyl ester, is then incubated 20min, 86 ± 2 DEG C of temperature control.
Residual monomer phase 148min is at the uniform velocity dripped with the rate of addition of 2.14mL/min after being incubated and with rate of addition be
The rate of addition of 0.25mL/min at the uniform velocity drips remaining initiator 150min, continues to be incubated 60min at 86 ± 2 DEG C after adding,
Resulting polymers emulsion product is cooled to normal temperature, is packed by 400 mesh filter clothes.
Specific embodiment 10
It is substantially the same with specific embodiment 2, is where difference, also added with 23g polyethylene glycol in five mouthfuls of flasks of 2L,
The degree of polymerization of wherein polyethylene glycol is 25.
Application Example 1
Table 1：(the application formula of transparent bath foam)
| Component | Consumption (wt%) | Function | |
| 1 | Deionized water | Supply 100 | Solvent |
| 2 | Disodium ethylene diamine tetraacetate | 0.05 | Chelating agent |
| 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 surfactant |
| 7 | Sodium Benzoate | 0.1 | Preservative |
| 8 | Citric acid (50%) | Supply pH | PH adjusting agent |
| 9 | The colored bead of Puensomes greenl 24/30 | 1 | Test suspendability |
The composition of embodiment 1～7 is configured to transparent bath foam according to above-mentioned formula, formula solution begins in process for preparation
Become stirring eventually, each component (1,2,3) is sequentially added in stainless steel under agitation, then use NaOH (component 4)
Formula pH is tuned into about 6.5, adds component 5, component 6, be eventually adding citric acid (component 7) pH value is tuned into 5.5,5,4.5,
4.The 200g clear formula for preparing under each pH value is transferred in the transparent plastic drug package of 150g PET, is carried out centrifugation and is eliminated gas
Bubble, tested viscosity, yield value and turbidity after constant temperature 24h at 25 DEG C
The method of testing of viscosity is as follows：
The viscosity of product is determined using Brook field RVT viscosimeter, and from No. 4 rotors, test rotating speed is 5rpm, treats
After stable reading, reading is multiplied by parameter and obtains viscosity.
The method of testing of yield value is as follows：
(1) sample is put in centrifuge, starts to be centrifuged under 2000r/m speed, stop centrifugation after 13min, go degasification
Bubble.
(2) sample is placed in 20h～24h in 25 DEG C of insulating boxs.
(3) viscosity of product is determined using Brook field RVT viscosimeter, from No. 5 rotors, is tested rotating speed and is respectively
0.5rpm and 1rpm, computing formula is：
Note：η is the viscosity (unit under subscript rotating speed：Cps), yield value (unit：Pa)
The method of testing of turbidity is as follows：
(1) start preheating transmissometer 30min, and correct transmissometer.
(2) it is encased in turbidity bottle with stainless steel medicine bale-out sample.
(3) 10min is centrifuged under centrifuge 1200r/m, eliminate bubble.
(4) the turbidity bottle after being centrifuged equipped with sample is placed in transmissometer test position, directly reads reading.
Suspendability method of testing is as follows：
(1) by formulation samples down in 60mL transparent sample bottle.
(2) add particle in sample bottle, stirred with spoon and be uniformly distributed to the particle of sample, bubble.
(3) result is observed after placing sample bottle 30 days in 40 DEG C and 48 DEG C of baking ovens：1) if particle suspend decline 0%～
5% remember 4 points, decline 5%～30% be designated as 3 points, decline 30%～60% be designated as 2 points, decline be designated as 1 point more than 60%.
Test result such as table 2 below and table 3 below：
Table 2 (performance of transparent bath foam formula under each pH value)：
Table 3 (suspendability of transparent bath foam formula under each pH value)：
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), deionization
Water (complements to 100%wt), and wherein POLYQUAT is the cationic cellulose of Guangzhou Tianci Advanced Materials Co., Ltd,
TC-SHD is the amphoteric surfactant of Guangzhou Tianci Advanced Materials Co., Ltd, and TC-3560 is bestowed by heaven high green wood for Guangzhou
The silicone emulsion of material limited company, TC-5075 are to be bestowed by heaven the silicone emulsion of new high-tech material limited company, TC-DMDMH
For the preservative of the new high-tech material limited company that is bestowed by heaven, the composition of embodiment 7 formulated become scalp care hair shampoo formula after,
Viscosity 7200mPa.s that tests after 24h, tested viscosity 7800mPa.s after 1 month, shampoo outward appearance for milky white, and at 48 DEG C
Lower not stratified after 1 one months.
Application Example 3
Mildy wash is filled a prescription：EDTA 2Na (0.1%wt), 32% composition (4%wt), AES (100%, 2EO) (15%
Wt), NaOH (18%wt) adjusts 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), wherein lemon acid for adjusting pH to 5.5, TC-SHD are Guangzhou day
The amphoteric surfactant of new high-tech material limited company is grant, TC-MAB40LD is bestowed by heaven the limited public affairs of new high-tech material share for Guangzhou
The amphoteric surfactant of department, TC-DMDMH are the preservative of Guangzhou Tianci Advanced Materials Co., Ltd, the group of embodiment 7
Compound formulated become mildy wash formula after, tested viscosity be 18500mPa.s, at 48 DEG C after one month, mildy wash regardless of
Layer.
Can be seen that by above-mentioned Application Example and excellent suspension effect and thickening property can be obtained using this programme
Can, particularly stratum nucleare be previously added be more easy to alkali soluble with rheological characteristic monomer, especially acrylic acid or methacrylic acid
After the hydrophobic monomer of fluoroalkyl, viscosity and transparent performance be improved significantly.And also have in other formulas good
Thickening properties and stability.
Find after by being applied to embodiment 10 in the test that transparent bath foam is filled a prescription, after polyethylene glycol is added,
After testing 1 month in 48 degrees Celsius of environment, during pH=5.5～4.5, suspension stability is changed into 4 points, decreasing ratio 3%～
In the range of 5%.
Above-described be only presently preferred embodiments of the present invention, all made in the range of the spirit and principles in the present invention appoint
What modification, equivalent and improvement etc., should be included within the scope of the present invention.
Claims (19)
1. a kind of alkali-soluble acrylate's polymer composition, it is characterised in that described composition by following composition of raw materials with
Emulsion polymerization is obtained, and described composition of raw materials includes following component：
Single phase：The unsaturated carboxylic acid monomer of 8wt%～15wt%；
The Arrcostab of at least one C1～C10 of the acrylic or methacrylic acid of 19wt%～28wt%；
Water phase：The deionized water of 60wt%～70wt%；
1wt%～3wt% through prepolymerized linear polymer, its number-average molecular weight be 10000～100000；
The protecting colloid of 0wt%～3wt%；
The emulsifying agent of 0.05wt%～1.0wt%；
And the crosslinking agent of 0.05wt%～0.2wt% and the initiator of 0.05wt%～0.5wt%；
Wherein, single phase and initiator are added and are polymerized in water phase, and crosslinking agent adds after single phase consumes 28%～58%
Enter in reaction system；
Described linear polymer is carried out being polymerized obtaining by unsaturated carboxylic acid monomer and acrylic ester monomer, described acrylic acid
Esters monomer is monomer A, acrylic compounds fluoroalkyl, one or more in acrylic compounds polyoxy vinethene Arrcostab；
The formula of described monomer A is：Wherein n=0～4, R1For hydroxyl or H, R2For
Methyl or H.
2. alkali-soluble acrylate's polymer composition according to claim 1, it is characterised in that in described single phase
Unsaturated carboxylic acid monomer be acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid, in maleic acid extremely
Few one kind.
3. alkali-soluble acrylate's polymer composition according to claim 1, it is characterised in that described acrylic acid or
The Arrcostab of at least one C1～C10 of methacrylic acid is methyl acrylate, ethyl acrylate, n-butyl acrylate, propylene
Sour n-pentyl ester, isoamyl acrylate, methyl methacrylate, EMA, n-BMA, metering system
Sour n-pentyl ester, isopentyl methacrylate, the just own ester of methacrylic acid, 2-Ethylhexyl Methacrylate, metering system are misery
One or more in ester, decyl-octyl methacrylate.
4. alkali-soluble acrylate's polymer composition according to claim 1, it is characterised in that described acrylic compounds
Fluoroalkyl is hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, methacrylic acid 2,2,2- trifluoro ethyl ester, methyl-prop
In ten difluoro heptyl ester of olefin(e) acid, dodecafluorhe-ptylacrylate, ten trifluoro monooctyl ester of methacrylic acid, perluorooctyl acrylate one
Kind.
5. alkali-soluble acrylate's polymer composition according to claim 1, it is characterised in that described acrylic compounds
APEO Arrcostab is Steareth methacrylate, the acid of eicosyl polyethenoxy ether methyl
Ester, beheneth methacrylate, Steareth acrylate, eicosyl polyoxy second
One kind in alkene ether acrylate, beheneth acrylate.
6. the alkali-soluble acrylate's polymer composition according to claim 4 or 5, it is characterised in that for being polymerized
To linear polymer unsaturated carboxylic acid monomer be acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid,
At least one in maleic acid.
7. alkali-soluble acrylate's polymer composition according to claim 1, it is characterised in that described protecting colloid
For the one kind in polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, cellulose derivative.
8. alkali-soluble acrylate's polymer composition according to claim 1, it is characterised in that described emulsifying agent is
In anionic surfactant, nonionic surface active agent, amphoteric surfactant, cationic surface active agent
One or more.
9. alkali-soluble acrylate's polymer composition according to claim 1, it is characterised in that described crosslinking agent is
Diallyl phthalate, trimethylolpropane tris (methyl) acrylate, triethylene glycol two (methyl) acrylate, two seasons
Penta tetrol six (methyl) acrylate, divinyl glycol, divinylbenzene, tetramethylol methane four (methyl) acrylate,
Diallyl itaconate, diallyl maleate, trimethylolpropane dialkylene propyl ether, trimethylolpropane tris pi-allyl
One or more in ether, divinyl glycol, divinylbenzene, methylene diacrylamine.
10. alkali-soluble acrylate's polymer composition according to claim 1, it is characterised in that described initiator
For the one kind in water-soluble inorganic persulfate compound, peroxide, oleosoluble radical initiators.
A kind of 11. preparation methods of alkali-soluble acrylate's polymer composition as claimed in claim 1, it is characterised in that
Comprise the following steps：
Step 1：Water is added in reaction vessel, under the protection of inert gas, 80 DEG C～90 DEG C of constant temperature, single phase will be accounted for
The monomer of the 28%～58% of total amount is added to stirring reaction 1h in reaction vessel～2h under conditions of initiator presence；
Step 2：By residual monomer in single phase and crosslinking agent under initiator existence condition, it is added in reaction vessel, constant temperature
80 DEG C～90 DEG C, 1h～3h is reacted, terminate reaction and obtain alkali-soluble acrylate's polymer composition；
Wherein, described single phase includes the unsaturated carboxylic acid monomer of 8wt%～15wt%, the acrylic acid of 19wt%～28wt%
Or the Arrcostab of at least one C1～C10 of methacrylic acid；
Described water mutually comprising the deionized water of 60wt%～70wt%, 1wt%～3wt% through prepolymerized linear polymerization
The emulsifying agent of thing, the protecting colloid of 0wt%～3wt% and 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 crosslinking agent is
0.05wt%～0.2wt%；
Described linear polymer is carried out being polymerized obtaining by unsaturated carboxylic acid monomer and acrylic ester monomer, described acrylic acid
Esters monomer is monomer A, acrylic compounds fluoroalkyl, one or more in acrylic compounds polyoxy vinethene Arrcostab；
The formula of described monomer A is：Wherein n=0～4, R1For hydroxyl or H, R2For
Methyl or H.
The preparation method of 12. alkali-soluble acrylate's polymer compositions according to claim 11, it is characterised in that
In step 1, single phase is added in reactor in the way of dripping, and the time of dropping is 1h～2h；
In step 2, single phase and crosslinking agent are added in reactor in the way of dripping, and the time of dropping is 1h～3h.
The preparation method of 13. alkali-soluble acrylate's polymer compositions according to claim 11, it is characterised in that institute
Unsaturated carboxylic acid monomer in the single phase that states be acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid,
At least one in maleic acid.
The preparation method of 14. alkali-soluble acrylate's polymer compositions according to claim 11, it is characterised in that institute
The Arrcostab of at least one C1～C10 of the acrylic or methacrylic acid that states is methyl acrylate, ethyl acrylate, acrylic acid
N-butyl, acrylic acid n-pentyl ester, isoamyl acrylate, methyl methacrylate, EMA, the positive fourth of methacrylic acid
Ester, n-amylmethacrylate, isopentyl methacrylate, the just own ester of methacrylic acid, 2-Ethylhexyl Methacrylate, first
One or more in base 2-ethyl hexyl acrylate, decyl-octyl methacrylate.
The preparation method of 15. alkali-soluble acrylate's polymer compositions according to claim 11, it is characterised in that institute
The acrylic compounds fluoroalkyl that states is hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, methacrylic acid 2,2,2- tri-
Fluorine ethyl ester, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, ten trifluoro monooctyl ester of methacrylic acid, acrylic acid 13
One kind in fluorine monooctyl ester.
The preparation method of 16. alkali-soluble acrylate's polymer compositions according to claim 11, it is characterised in that institute
The acrylic compounds polyoxy vinethene Arrcostab that states is Steareth methacrylate, eicosyl polyoxyethylene
Ether metacrylic acid ester, beheneth methacrylate, Steareth acrylate, two
One kind in ten alkyl polyoxyethylene ether acrylate, beheneth acrylate.
The preparation method of the 17. alkali-soluble acrylate's polymer compositions according to claim 15 or 16, its feature exist
In the unsaturated carboxylic acid monomer for obtaining linear polymer for polymerization is acrylic acid, methacrylic acid, itaconic acid, fumaric acid, bar
Beans acid, aconitic acid, at least one in maleic acid.
The preparation method of 18. alkali-soluble acrylate's polymer compositions according to claim 11, it is characterised in that institute
The protecting colloid that states is polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, the one kind in cellulose derivative.
The preparation method of 19. alkali-soluble acrylate's polymer compositions according to claim 11, it is characterised in that institute
The initiator that states is water-soluble inorganic persulfate compound, peroxide, the one kind in oleosoluble radical initiators.
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