Patent Application
20180319911
The invention relates to a new type of thickening polymer with special properties which is free from associative monomers and/or whose chain contains no such associative monomers.
Unless stated otherwise, all quantitative data are percentages by mass based on the total mass of the preparation.
Within the context of the present specification, associative monomers are monomers of the type U-S-L, where U contains an ethylenically unsaturated group such as methacrylate, acrylate, allyl or vinyl groups, S is a spacer from a polyoxyalkylene chain having 2 to 300 alkyleneoxy units such as polyethylene glycol, polypropylene glycol or polybutylene glycol, and L is a hydrophobic group such as an alkyl and/or aryl group, which has at least 4, preferably at least 8 carbon atoms, for example a lauryl group.
Within the context of the present specification, tan δ value means the quotient of the loss modulus and the storage modulus, in each case measured at 40° C. The measuring device used here is not important. The values given in this specification were determined using the Malvern Gemini HR nano.
In general, thickening polymers serve to thicken water or water-containing preparations. In this connection, the water allows the polymers to swell to gels in order, in so doing, to influence viscosity and flow behavior. Thickening polymers are of importance in the manufacture of body cleansing compositions, creams, cleaning compositions, finishes, printing inks, coatings, emulsion paints and other coating materials, adhesives, paper, foods and so on.
Known from EP 1465932 B1 were alkali-swellable and alkali-soluble associative multipurpose polymers which is the polymerization product of a monomer mixture of
Such polymers are prepared by emulsion polymerization. For this, firstly the monomer mixture is emulsified or suspended with a surfactant in water in the form of micelles. The actual reactor is charged with the initiator in aqueous solution or suspension, and the monomer suspension is slowly added. The rate at which the monomer is added is controlled so as to avoid a considerable increase in the reaction temperature as a result of the Trommsdorff effect (gel effect). The gel effect arises in the event of too great an increase in the conversion and leads to the rate of the polymerization increasing as a result of diffusion of the polymer radicals being hindered, and the polymerization in itself is accelerated. Attempts are made to prevent this for reasons of safety and to obtain a narrow molar mass distribution. If the gel effect does arise, then a bimodal molar mass distribution is obtained. Further prior art can be found in EP 1272159, WO03062288, WO03061615, WO03062288, WO2007090759, U.S. Pat. No. 6,242,531.
Thickening polymers with which it is possible to thicken aqueous preparations such that gels which are as clear as possible are formed are desirable.
Thickening polymers with which tan δ values which are as low as possible can be achieved in aqueous solution are also desirable.
Thickening polymers with a considerably extended storage stability are likewise desirable.
The prior art lacked thickening polymers which make it possible to produce clear gels coupled with simultaneously low tan δ values.
Surprisingly and unforeseeably to the person skilled in the art, it has now been found that a polymer obtainable by free-radical emulsion polymerization of
(A) at least one acidic vinyl monomer or salt thereof,
(B) at least one nonionic vinyl monomer, particularly preferably a hydrophobic nonionic vinyl monomer,
(C) at least one monomer containing an unsaturated end group and a polyoxyalkylene portion,
(D) at least one crosslinking monomer,
(E) optionally a protective colloid, characterized in that the polymerization is controlled such that at least at times the gel effect arises, achieved by the fact that the monomer addition (dosing time) takes place over the course of 40 minutes, particularly preferably over the course of 30 minutes, overcomes the defects of the prior art. In the case of such a polymerization utilizing the Trommsdorff effect, i.e. with the constant addition of the monomers and simultaneously high addition rate of the monomers, a monomer excess is formed which leads to an autoacceleration of the polymerization (Trommsdorff effect). The result is an increase in the molecular weights coupled with simultaneously advantageous morphology of the polymers. In this connection, it is particularly preferred if (F) associative monomers are not present or have at most a concentration of 15% by weight, preferably 10% by weight, particularly preferably 5% by weight, very particularly preferably 2.5% by weight, very extraordinarily preferably 1% by weight, very particularly extraordinarily preferably 0.1% by weight. It is particularly preferred if the acidic vinyl monomer (A) is selected from vinyl monomers with carboxyl groups, particularly preferably acrylic acid or methacrylic acid or alkali metal, alkaline earth metal, ammonium or alkylammonium salts thereof, very particularly preferably methacrylic acid or alkali metal, alkaline earth metal, ammonium or alkylammonium salts thereof. It is particularly preferred if the nonionic vinyl monomer (B) is selected from C1-C22-alkyl (meth)acrylates and mixtures thereof. As a result, good flow properties and thus an advantageous rheological profile are achieved.
Additional long-chain alkyl acrylates (C12 and C18) are particularly preferred because they increase the viscosity that can be achieved. It is particularly preferred if the monomer (C) containing an unsaturated end group and a polyoxyalkylene portion is selected from vinylpolyalkylene glycols or polymerizable surfactants or mixtures thereof, is particularly preferably selected from R307, RAL307, A11/1800, R1100, A111R, AB25-8. It is particularly preferred if the crosslinking monomer (D) is selected from polyol (meth)acrylates with at least two (meth)acrylate groups and the mixed esters of polyols with acrylic acid and/or methacrylic acid. It is further particularly preferred if the monomers (A) are present in contents of from 10 to 75%, preferably 30 to 50%, particularly preferably 35 to 49%, (B) are present in contents of from 10 to 90%, preferably 30 to 80%, particularly preferably 47 to 60%, (C) are present in contents of from 0.5 to 40%, preferably 1 to 10%, particularly preferably 2 to 6%, (D) are present in contents of up to 1%, preferably 0.05 to 0.5%, particularly preferably 0.1 to 0.35%. It is very particularly preferred if the monomers (A):(B) are present in mass ratios of from 1:2 to 2:1. It is very particularly preferred if the polymer is selected from example 22, 24, 25, 28, 35, 37, 40 or 52. The invention also encompasses a thickened preparation comprising a polymer as claimed in any one of the preceding claims. It is particularly preferred if the use concentration of the polymer for thickening aqueous, preferably surfactant-containing aqueous, preparations is 2 to 3%. As a result, the preparation becomes transparent at pH values <6.5 and has a viscosity of at least 3000 mPa·s, which means that added suspended substances do not settle out, possible suspended substances being beads, pigments or air bubbles. It is particularly preferred if the preparations according to the invention are a health product, cleaning product, household product, shower gel, paint, inks, dispersant, antisettling agent, concrete and cement additive, coatings, medicinal product, cosmetic product or dermatological product. The invention also encompasses the use of a polymer according to the invention as thickener, emulsifier, dispersant or consistency regulator.
The preparations—if they are gel-like preparations with yield point—are advantageously designed such that they have a yield point of 0.5-20 Pa, preferably 1-6 Pa.
The yield point is considered to be the critical shear stress of the flow curve. It can be ascertained according to the invention as follows:
The flow curve is measured on a shear-stress-controlled rheometer at 25° C.±1° C. with 20 mm plate/plate geometry with a gap between 0.8 mm and 1.2 mm, with charging being carried out in a structure-preserving manner. A suitable constant shear stress gradient is pregiven and, before the test, a corresponding structure recovery time is observed and the critical shear stress at the maximum of the flow curve is given.
Advantageously, the preparations are designed such that they have a tan δ of 0.05-0.6, preferably 0.1-0.5.
According to the invention, tan δ is understood as meaning the quotient of the loss modulus and the storage modulus. The tan δ is ascertained as follows:
Loss and storage moduli are measured by a dynamic frequency test on a shear-stress-controlled rheometer at 40° C.±1° C. with 20 mm plate/plate geometry with a gap between 0.8 mm and 1.2 mm, charging being carried out in a structure-preserving manner. The frequency test is carried out according to the prior art with an appropriate structure recovery time before the test, and the tan δ in the frequency range between 0.05 rad/s and 3.0 rad/s is quoted, preferably between 0.08 rad/s and 1.0 rad/s.
The preparations are advantageously designed such that, at pH<6.2, they have a turbidity value of NTU (Nephelometric Turbidity Unit)<20. The turbidity value is measured using a turbidity measuring device, with distilled water having a value of NTU=0 serving as standard.
It is also in accordance with the invention if not water, but other polar liquids are thickened by polymers according to the invention. In particular, alcohols, glycols, polyols, amines and organic acids such as for example acrylic acid can be thickened.
The use of polymers according to the invention as emulsifier is also in accordance with the invention. In this way, creams and lotions can be provided.
The polymers are also suitable as dispersants and antisettling agents.
Synthesis of the Copolymers
The examples below aim to illustrate the present invention without limiting it. The preparation of the examples takes place in accordance with the method described below, the type and amounts of the monomers, chain-transfer agents and protective colloids each used as starting components being summarized in Table 2. Parts and percentages refer to the weight.
The reaction vessel, which is equipped with stirrer, reflux condenser, nitrogen feed, dosing device and internal thermometer, is charged with 173.146 parts of water and 0.300 parts of sodium lauryl sulfate. The mixture is heated to 82° C. with stirring and under a nitrogen atmosphere.
The monomer mixture is prepared in a second stirred vessel which is equipped with stirrer and nitrogen feed. For this purpose, the monomer phase with 37.000 parts methacrylic acid, 51.800 parts ethyl acrylate, 5.000 parts octadecyl acrylate, 6.000 parts Emulsogen R307 and 0.300 parts trimethylpropane triacrylate is introduced, and into this is mixed the water phase with 33.060 parts water and 0.984 parts sodium lauryl sulfate with stirring and under a nitrogen atmosphere.
As soon as a temperature of 82° C. is reached in the reaction vessel, an initiator phase A, consisting of 0.069 parts ammonium persulfate and 1.911 parts of water, is added and the monomer mixture is metered in uniformly at 85-88° C. over the course of 30 minutes. Then, an initiator phase B, consisting of 0.021 parts ammonium persulfate and 2.909 parts water, is added and then the reaction mixture is post-polymerized for a further 4 hours at 90° C. before being cooled to <40° C.
The examples below (Table 1) are prepared analogously to Example 1. In most examples, sodium lauryl sulfate was used as emulsifier. In a departure from this, Examples 5 and 11 were prepared from a combination of sodium lauryl sulfate and ethoxylated isotridecyl alcohol (Genapol X1005, Clamant), and Example 10 was prepared with isotridecyl alcohol (Genapol X1005, Clamant).
The preparation below is intended to illustrate the present invention without limiting it. Unless stated otherwise, all quantitative data, fractions and percentages are based on the weight and the total amount or on the total weight of the preparation.
The polymer according to the invention is diluted with some of the water phase and added to the surfactant phase with stirring. The other formulation constituents apart from NaOH and the suspended bodies are then added with stirring. After the pH has been adjusted, the suspended bodies are stirred into the finished gel base with as little shear as possible.
The viscosity of the preparations is measured on a rheometer at 25° C.±1° C. with 40 mm cone/plate geometry (1° cone angle) with a gap of 0.03 mm, charging being carried out in a structure-preserving manner. A suitable constant shear rate time ramp is pregiven and a corresponding structure recovery time is observed before the test. The viscosity is given for a shear rate of 10 s−1.
It has surprisingly been found that the morphology of the polymers produced by a rapid dosing of the monomer mixture is advantageous within the context of the present invention. Table 4 shows the various properties of two polymers when the dosing time is varied. The dosing time is preferably 40 minutes and particularly preferably 30 minutes.
The polymers according to the invention must have adequate storage stability. For this purpose, a shower gel according to Example 53 was produced again after one year from Examples 1, 22, 24, 25 and 28. It is found that the polymers according to the invention are also advantageous after prolonged storage at room temperature.
Compared to other polymers, the polymers according to the invention overcome deficiencies in the prior art compared to other polymers.
In order to illustrate this, a shower gel according to Example 53 was prepared in each case from Examples 24, 37 and Carbopol® AQUA SF-1 (Lubrizol).
At a lower pH than AQUA SF-1, the polymers according to the invention have a better tan δ and a lower turbidity. Turbidity values of <10 are comparable with spring water. Upon adjusting a preparation containing AQUA SF-1 to a lower pH value, e.g.: 6.20, the preparation is distinctly perceptibly turbid (NTU=58).
| Number | Date | Country | Kind |
|---|---|---|---|
| 102010022063.9 | May 2010 | DE | national |
The present application is a continuation of application Ser. No. 13/700,406, which is a National Stage of International Application PCT/EP2011/054247, filed Mar. 21, 2011; the entire disclosures of both applications are expressly incorporated by reference herein.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13700406 | Apr 2013 | US |
| Child | 16033394 | US |
