CN103030747A - Polyquaternary amine salt with rheologic modification function and application thereof - Google Patents
Polyquaternary amine salt with rheologic modification function and application thereof Download PDFInfo
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- CN103030747A CN103030747A CN201210530696XA CN201210530696A CN103030747A CN 103030747 A CN103030747 A CN 103030747A CN 201210530696X A CN201210530696X A CN 201210530696XA CN 201210530696 A CN201210530696 A CN 201210530696A CN 103030747 A CN103030747 A CN 103030747A
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Abstract
The invention provides a synthetic cationic high-polymer polyquaternary amine salt with rheologic modification function, which is polymerized from the following components in parts by weight in a water solution environment: 7-14 parts of dimethylaminoethyl methacrylate, 3-10 parts of acrylic acid, 0.5-5 parts of allyl polyethyleneglycol, 0.3-3 parts of ammonium persulfate, 1-7 parts of hydrochloric acid, 0.1-6 parts of 10% sodium sulfite water solution and 53-88 parts of deionized water. On the premise of not losing cationic polyquaternary amine salt characteristics, the polyquaternary amine salt provided by the invention has favorable rheologic modification function, and can be used as a conditioner in liquid washing products, such as shampoo, body wash, liquid soap and the like. Due to the properties, the polyquaternary amine salt can enable the liquid washing product to have stable rheological properties in both high and low temperature environments, and is especially suitable for improving the rheological properties under low temperature conditions, thereby enhancing the service convenience of the product.
Description
Technical field
The present invention relates to a kind of polyquaternium, relate in particular to a kind of polyquaternium that can improve the liquid product rheological property, more specifically relate to a kind of synthetic cationoid polyphosphazene polymer quaternary ammonium salt with rheology rhetorical function.The invention still further relates to the application of this polyquaternium in cleaning product.
Background technology
The positively charged ion polyquaternium can be divided into the macromolecule modified cationoid polymkeric substance of plant, cellulose modified cationoid polymkeric substance, synthetic cationoid polyphosphazene polymer quaternary ammonium salt, wherein the macromolecule modified cationoid polymkeric substance of plant, cellulose modified cationoid polymkeric substance have cationic functional and to the thickening function of system, belong to multi-functional cation opsonizing agent, and the cation high molecular polyquaternium function ratio of synthetic is more single, but can have more specific aim.Polyquaternium is owing to there being good solubility property in water, have wide spectrum, efficient sterilization algae removal ability, the disinfectant of Ceng Zuowei water treatment uses, but because on the high side, be eliminated gradually, find that afterwards the cationic properties of polyquaternium uniqueness has different purposes: a. for hair conditioner in cleaning product, can greatly improve modifiability and the conditioning property of hair, can make hair glossy after the hair washing, submissive easy comb; B. be used for skin-protection product, have well smooth and lubrication; C. be used for foaming agent, can produce rapidly foam abundant, dense, longer duration, make skin smooth and without any oil film; Thereby how polyquaternium uses as the amendment in the cleaning product now.
The liquid cleaning products such as shampoo, body wash, Liquid soap are under high temperature and the environment at low temperature, and rheology viscosity has larger variation, namely can be thinning in the viscosity of product in high-temperature environment, flowability is very good, and under low temperature environment, it is very large that the viscosity of product can become, mobile non-constant.This huge rheological property difference that under high and low temperature environment, occurs of liquid cleaning product, bring very large inconvenience to the user, such as the summer in sweltering heat, accidentally will make the liquid body in the bottle leak or extrude too many, and in colder winter, the phenomenon that at all can't extrude appears sometimes.Along with producer is more and more stricter to the control of product cost, how can be in the situation that do not change existing prescription, by increasing the function of amendment, make liquid cleaning product under high and low temperature environment, have more stably rheological, be the problem that the expectation of existing cleaning product manufacturing enterprise solves.
Summary of the invention
For solving the problem of above existence, the purpose of this invention is to provide a kind of polyquaternium with rheology rhetorical function, this polyquaternium is on the basis that keeps original cationic properties, can also make liquid cleaning product under high and low temperature environment, have more stably rheological, thereby improve the accessibility that product uses.
For realizing above purpose, polyquaternium with rheology rhetorical function of the present invention is by comprising that components by weight percent is that dimethylaminoethyl methacrylate 7-14 part, vinylformic acid 3-10 part, allyl polyglycol 0.5-5 part, ammonium persulphate 0.3-3 part, hydrochloric acid 1-7 part, sodium sulfite aqueous solution 0.1-6 part and deionized water 53-88 part of 10% obtain with following method:
(1) add 70% of deionized water total amount in reactor, be heated to 95 ± 5 ℃, add ammonium persulphate, stirring and dissolving is even;
(2) add dimethylaminoethyl methacrylate and hydrochloric acid, stir, maintain the temperature at 95 ± 5 ℃;
(3) 17% of vinylformic acid and deionized water total amount mixed, and the control temperature obtains acrylic acid solution at 58-60 ℃;
(4) acrylic acid solution is slowly joined in the reactor, maintain the temperature at 93 ± 5 ℃ of reactions 1 hour;
(5) allyl polyglycol and the dissolving of remaining deionized water and stirring is even, add in the reactor, after stirring, cool to 60 ± 1 ℃;
(6) continuation adds 10% sodium sulfite aqueous solution, stirs, and filters blowing with 200 order filtering nets after 10 minutes.
For the speed of better control monomer polymerization, in the aforesaid method, preferred 0.1 Kilograms Per Second of feed rate when step (4) acrylic acid solution adds reactor.
In order to prolong the quality guaranteed period of product, in the aforesaid method, when adding 10% sodium sulfite aqueous solution, step (6) adds 0.01-1 part Kathon CG.
Above-mentioned polyquaternium with rheology rhetorical function, each feed composition preferable methyl vinylformic acid dimethylamino ethyl ester 10-12 part, vinylformic acid 5-8 part, allyl polyglycol-2500 2-4 part, ammonium persulphate 1-2 part, hydrochloric acid 3-6 part, sodium sulfite aqueous solution 2-4 part and deionized water 55-75 part of 10%.
Above-mentioned allyl polyglycol preferred allyl polyglycol-2500.
The preferred 0.08-0.2 part of the add-on of above-mentioned Kathon CG.
Above-mentioned polyquaternium with rheology rhetorical function in the liquid cleaning products such as shampoo, body wash, Liquid soap as conditioner application.
Polyquaternium with rheology rhetorical function of the present invention, adopt dimethylaminoethyl methacrylate, vinylformic acid and have fine water miscible allyl polyglycol (2500) as monomer, take ammonium persulphate as initiator, be 2-3 by the pH value that adds a certain amount of hydrochloric acid control reaction system, and the pre-molten method of employing, after first monomer being dissolved fully with deionized water, again monomer solution is divided order to add to control the molecular structure of polymkeric substance, thereby the shape of molecule micella in the change washing system, so that surfactant micelle forms layered liquid crystal, finally reach the rheological property that changes washing system, and stop proceeding of polyreaction by the speed of control vinylformic acid adding with a certain amount of S-WAT, can control on the one hand the speed of monomer polymerization, also make on the other hand the molecular weight of product controlled.Polyquaternium of the present invention is not in the situation that lose positively charged ion polyquaternium primary characteristic, has good rheology rhetorical function, in the liquid cleaning products such as shampoo, body wash, Liquid soap, use as amendment, its performance that has can make liquid cleaning product have more stably rheological under high and low temperature environment, be specially adapted to the improvement of rheological property under the cold condition, thereby improve the accessibility that product uses.In addition, polyquaternium of the present invention has overcome the more single shortcoming of cation high molecular polyquaternium function ratio of synthetic, is the larger space of its application extension.
Description of drawings
Fig. 1 is in without the Liquid soap system of adding adhesion agent, has added the front and back viscograph comparison diagram of polyquaternium of the present invention.
Fig. 2 is in the Liquid soap system of adding adhesion agent, has added the front and back viscograph comparison diagram of polyquaternium of the present invention.
Embodiment
Embodiment 1
1, prescription:
Dimethylaminoethyl methacrylate 4.28 Kg
Vinylformic acid 2.68 Kg
Allyl polyglycol-2,500 1.08 Kg
Ammonium persulphate 0.52 Kg
Hydrochloric acid 1.60 Kg
10% sodium sulfite aqueous solution 1.20 Kg
Kathon CG 0.04 Kg
Deionized water 28.00 Kg
2, preparation:
(1) add the 20Kg deionized water in reactor, be heated to 93 ℃, add ammonium persulphate, stirring and dissolving is even, and stirring velocity is controlled at 60 rev/mins;
(2) continue to add dimethylaminoethyl methacrylate and hydrochloric acid, stir, maintain the temperature at 93 ℃, stirring velocity is controlled at 60 rev/mins;
(3) vinylformic acid and 4.76Kg deionized water are mixed, and control temperature in 60 ℃, obtain acrylic acid solution, stirring velocity is controlled at 40 rev/mins;
(4) acrylic acid solution is slowly joined in the reactor, feed rate is controlled at 0.1 Kilograms Per Second, and keeps the material in reactor temperature at 91 ℃, reacts 1 hour, and stirring velocity is controlled at 90 rev/mins;
(5) allyl polyglycol-2500 and the dissolving of remaining deionized water and stirring is even, add in the reactor, after stirring, cool to 60 ℃, stirring velocity is controlled at 80 rev/mins;
(6) continuation adds 10% sodium sulfite aqueous solution and Kathon CG, stirs, and stirring velocity is controlled at 40 rev/mins, filters blowing with 200 order filtering nets after 10 minutes.
It is translucent thick that product is little yellow, and molecular weight is 5000 to 500,000.
Embodiment 2
1, prescription:
Dimethylaminoethyl methacrylate 10.70 Kg
Vinylformic acid 6.70 Kg
Allyl polyglycol-2,500 2.70 Kg
Ammonium persulphate 1.30 Kg
Hydrochloric acid 4.00 Kg
10% sodium sulfite aqueous solution 3.00 Kg
Kathon CG 0.10 Kg
Deionized water 72.00 Kg
2, preparation:
(1) add the 50Kg deionized water in reactor, be heated to 95 ℃, add ammonium persulphate, stirring and dissolving is even, and stirring velocity is controlled at 60 rev/mins;
(2) continue to add dimethylaminoethyl methacrylate and hydrochloric acid, stir, maintain the temperature at 95 ℃, stirring velocity is controlled at 60 rev/mins;
(3) vinylformic acid and 12Kg deionized water are mixed, and control temperature in 60 ℃, obtain acrylic acid solution, stirring velocity is controlled at 40 rev/mins;
(4) acrylic acid solution is slowly joined in the reactor, feed rate is controlled at 0.1 Kilograms Per Second, and the temperature that keeps material in the reactor reacted 1 hour at 93 ℃, and stirring velocity is controlled at 90 rev/mins;
(5) allyl polyglycol-2500 and the dissolving of remaining deionized water and stirring is even, add in the reactor, after stirring, cool to 59 ℃, stirring velocity is controlled at 80 rev/mins;
(6) continuation adds 10% sodium sulfite aqueous solution and Kathon CG, stirs, and stirring velocity is controlled at 40 rev/mins, filters blowing with 200 order filtering nets after 10 minutes.
It is translucent thick that product is little yellow, and molecular weight is 5000 to 500,000.
(2) Application Example
1, the product that above-described embodiment 2 is obtained adds in the Liquid soap of different systems (wherein fill a prescription 1,2 do not add the polyethylene glycol 6000 adhesion agent, prescription 3,4 has added the polyethylene glycol 6000 adhesion agent) to as amendment and to use common polyquaternium 7 to add the prescription of comparison in the Liquid soap of different systems to as amendment as follows:
Raw materials all is the commercially available prod in the prescription, and this prescription is the basic components of washing system, and the product that above-mentioned prescription obtains all has bath slippery and the mildness of higher decontamination dynamics, sterilization effect, washing slippery, appropriateness.
2, simultaneous test:
After the product of above-mentioned prescription carried out, place and carry out the viscosity test experiment after 24 hours, testing method is " viscosity of GB-T 15357-1994 tensio-active agent and washing composition rotary viscosity design determining liquid product ", and the Liquid soap system test result of not adding polyethylene glycol 6000 is as follows:
Its viscosity change curve as shown in Figure 1;
The Liquid soap system test result of adding polyethylene glycol 6000 is as follows:
Its viscosity change curve as shown in Figure 2.
Can find out by the test result that top two groups of contrast experiments fill a prescription, under high and low temperature environment, gathering ammonium salt of the present invention all plays obvious regulating effect to the kinetic viscosity that has or not the washing system that adds adhesion agent; Add the Liquid soap of polyquaternium of the present invention and compare with the Liquid soap that adds common polyquaternium, under high and low temperature environment, have more stably rheological.
Claims (7)
1. polyquaternium with rheology rhetorical function is by comprising that components by weight percent is that dimethylaminoethyl methacrylate 7-14 part, vinylformic acid 3-10 part, allyl polyglycol 0.5-5 part, ammonium persulphate 0.3-3 part, hydrochloric acid 1-7 part, sodium sulfite aqueous solution 0.1-6 part and deionized water 53-88 part of 10% obtain with following method:
(1) add 70% of deionized water total amount in reactor, be heated to 95 ± 5 ℃, add ammonium persulphate, stirring and dissolving is even;
(2) continue to add dimethylaminoethyl methacrylate and hydrochloric acid, stir, maintain the temperature at 95 ± 5 ℃;
(3) 17% of vinylformic acid and deionized water total amount mixed, and the control temperature obtains acrylic acid solution at 58-60 ℃;
(4) acrylic acid solution is slowly joined in the reactor, maintain the temperature at 93 ± 5 ℃ of reactions 1 hour;
(5) allyl polyglycol and the dissolving of remaining deionized water and stirring is even, add in the reactor, after stirring, cool to 60 ± 1 ℃;
(6) continuation adds 10% sodium sulfite aqueous solution, stirs, and filters blowing with 200 order filtering nets after 10 minutes.
2. the polyquaternium with rheology rhetorical function according to claim 1 is characterized in that: in the described method, the feed rate when step (4) acrylic acid solution adds reactor is 0.1 Kilograms Per Second.
3. the polyquaternium with rheology rhetorical function according to claim 2 is characterized in that: in the described method, add 0.01-1 part Kathon CG when step (6) adds 10% sodium sulfite aqueous solution.
4. according to claim 2 or 3 described polyquaterniums with rheology rhetorical function, it is characterized in that: described polyquaternium with rheology rhetorical function, each feed composition preferable methyl vinylformic acid dimethylamino ethyl ester 10-12 part, vinylformic acid 5-8 part, allyl polyglycol 2-4 part, ammonium persulphate 1-2 part, hydrochloric acid 3-6 part, sodium sulfite aqueous solution 2-4 part and deionized water 55-75 part of 10%.
5. the polyquaternium with rheology rhetorical function according to claim 4 is characterized in that: described allyl polyglycol preferred allyl polyglycol-2500.
6. the polyquaternium with rheology rhetorical function according to claim 5, it is characterized in that: the add-on of described Kathon CG is 0.08-0.2 part.
The described polyquaternium with rheology rhetorical function of a claim 1-6 in the liquid cleaning products such as shampoo, body wash, Liquid soap as conditioner application.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109172407A (en) * | 2018-10-25 | 2019-01-11 | 汕头市大千高新科技研究中心有限公司 | A kind of purposes of macromolecule cation polymer and its skin care item of preparation |
| CN114557926A (en) * | 2022-03-28 | 2022-05-31 | 汕头市大千高新科技研究中心有限公司 | Emulsifier for improving high-temperature stability and low-temperature stability of cosmetics and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060051311A1 (en) * | 2004-09-04 | 2006-03-09 | Andrea Walter | Hair treatment composition containing a combination of at least three different polymers |
| CN101368090A (en) * | 2008-09-19 | 2009-02-18 | 宋福如 | Process for preparing silicon-fluorine high temperature resistant thinner dry powder for drilling fluids |
| CN102382270A (en) * | 2011-08-04 | 2012-03-21 | 陶梅 | Oil well cement slurry drag reducer and preparation method thereof |
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2012
- 2012-12-11 CN CN201210530696.XA patent/CN103030747B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060051311A1 (en) * | 2004-09-04 | 2006-03-09 | Andrea Walter | Hair treatment composition containing a combination of at least three different polymers |
| CN101368090A (en) * | 2008-09-19 | 2009-02-18 | 宋福如 | Process for preparing silicon-fluorine high temperature resistant thinner dry powder for drilling fluids |
| CN102382270A (en) * | 2011-08-04 | 2012-03-21 | 陶梅 | Oil well cement slurry drag reducer and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109172407A (en) * | 2018-10-25 | 2019-01-11 | 汕头市大千高新科技研究中心有限公司 | A kind of purposes of macromolecule cation polymer and its skin care item of preparation |
| CN109172407B (en) * | 2018-10-25 | 2021-05-14 | 汕头市大千高新科技研究中心有限公司 | Application of high-molecular cationic polymer and skin care product prepared from high-molecular cationic polymer |
| CN114557926A (en) * | 2022-03-28 | 2022-05-31 | 汕头市大千高新科技研究中心有限公司 | Emulsifier for improving high-temperature stability and low-temperature stability of cosmetics and application thereof |
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| CN103030747B (en) | 2014-07-09 |
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