CN107841183A - Associative thickener preparation - Google Patents

Abstract

The associative thickener preparation that a kind of solution viscosity is less than 25000mPas is disclosed, including：(a) combination of at least one structural viscosity type associative thickeners (A) and at least one newton-type associative thickeners (B)；And/or (b) at least one structural viscosity type associative thickeners (A), the combination of at least one newton-type associative thickeners (B) and at least one diluent (C)；And/or (c) at least one structural viscosity type associative thickeners (A), the combination of at least one newton-type associative thickeners (B) and at least one wetting agent；And/or (d) at least one structural viscosity type associative thickeners (A), the combination of at least one newton-type associative thickeners (B) and at least one solvent；And/or (e) at least one structural viscosity type associative thickeners (A), at least one newton-type associative thickeners (B), the combination of at least one solvent and at least one wetting agent；And/or the combination of (f) at least one structural viscosity type thickener (A) and at least one diluent (C)；And/or the combination of (g) at least one newton-type thickener (B) and at least one diluent (C).

Description

Associative thickener preparation

Technical field

Associative thickeners be it is a kind of have been known for many years, the thickener for Aquo System.They are especially used In the scattered water-based paint (Farben) and coating (Lacken) combined, and other Aquo Systems, such as cleaning agent, cosmetic Product, pickle, aqueous pigment paste, automobile coating, industrial coating, printing-ink, lubricating grease, whitewash paint and wall paint, textile coating, Pharmaceutical formulation, crop protection preparation, filler dispersion, adhesive, scale remover, wax dispenser, polishing agent, three-level oil Exploitation adjuvant etc. is also to adjust rheological characteristic with this thickener.

Background technology

The typical effect mode of these thickeners is determined by their chemical composition.Generally, associative thickeners contains There is a water miscible hydrophily major part, i.e. polyethylene glycol is contained in a kind of water miscible polymer chain, the part mostly Either containing cellulose derivative, acrylate chains, polyether chain or polyester chain, wherein it is connected to dredge on these polymer chains Water-based group.This two parts is mutually connected to each other by a kind of very wide covalent bond of Type Range.Connection mentioned here Such as it can be realized by urethane bond, ester bond, ehter bond, urea bond, carbonic acid ester bond or amido link.

The common preparation of associative thickeners is by realization of such as getting off, for example, difunctional alcohol (is usually poly- second two Alcohol) and the reactant (be usually diisocyanate) of difunctionality reacted to each other in sudden reaction, it is and anti-by adding simple function Thing (monofunctional alcohol, such as nonyl phenol ethoxy compound) is answered to terminate the addition reaction.Formed required for association interacts Hydrophobic group is bonded on water-soluble polymer chain as end group.

In application system, hydrophilic parts are remained dissolved in aqueous phase.However, hydrophobic group accumulates in hydrophobicity Surface, such as accumulate in above the organic bond for being disperseed or being emulsified, accumulate in aqueous coating, such as emulsion paint On the hydrophobic surface of filler, pigment etc., etc..Due to thickener polymers generally have two it is (or multiple attached in end Add) hydrophobic parts, it can be connected with multiple dispersed particles simultaneously.They are mutually interconnected with the help of hydrophily base chain It is connected together.As a result thickening effect is just generated, the effect is built upon in the Aquo System hydrophobic parts or less water On the association of insoluble portion, and the basis established by the 3 D stereo network structure of Van der Waals interaction.Thus claim Be associative thickeners.

However, this mechanism is it is axiomatic that hydrophobic parts are not only associated with hydrophobicity part, example Such as in paint.In the case where dispersion or other hydrophobicity parts are not present, hydrophobic group also can be formed mutually Close and form such as micella.This also results in thickening ground effect.This thickening can also occur in only thickener polymers list In the case of being solely dissolved in water.Because the common supply form of polymer is the aqueous solution, it is evident that excessive increasing herein Thick is undesirable.Because this complicates processing and processing, or makes maximum of the soluble thickener polymers in water Concentration is confined to several percentages.

By the selection and/or the regulation of molecular weight to hydrophobic ending group, the rheological effect of thickener can be adjusted Section, to form newton-type associative thickeners (B) or relatively obvious structural viscosity type associative thickeners (A).For rear Person, due to the influence of intermolecular interaction, individually thicken in water and be also especially apparent, and reduce the necessity of viscosity especially Greatly, because can also provide herein in the acceptable polymer concentration that can handle form.

In order to suppress structural viscosity type associative thickeners (A) individually high viscosity in water, and then make thickener more hold Easily handled or can be provided with higher concentration, the scheme that may largely implement has been formulated out, and very Also it has been put to implement for many years and has applied.

The usual method for reducing viscosity is addition solvent.Especially glycols, such as propane diols, butyl glycol, butyl Diethylene glycol (DEG) and butyltriglycol are for this purpose.However, these products are can be discharged into the typical solvent gone in environment.Cause This, in nearest paint formulations for example in terms of the ecology due to be no longer desire to use them.Dilution effect substantially base On the fact that：These solvents have a typical end with a ready water-solubility similar to surfactant in itself Hold the structure of (alcohol/glycol) and non-water-soluble fractions (butyl etc.).By the way that hydrophobic alkyl is added into associative thickeners The hydrophobic grouping of molecule, its polarity will invert, and the strong interaction between thickener molecule will be inhibited Or weaken.This point also can obtain Partial Proof by following phenomenon：After adding water, the thickening of fluid is tuned into this way Agent solution initially becomes thicker, and this is due to that the solvent of ready water-solubility is diluted and makes the reason of decreased effectiveness.

In the evolution of non-volatility organic principle (VOC) or the paint and coating of divergence-free (discharge), to not The demand of associative thickeners containing these solvents is communicated to producer there.A kind of method of the thickener is obtained in EP-A- Described in 0 614 950.Here, thickened using cyclodextrin to suppress to supply the strong structure viscosity type associativity of form The solution viscosity of agent, and do not have to solvent.The hydrophobic parts of thickener are adsorbed in the hydrophobic parts of cyclodextrin, are avoided Interact.It has the drawback that cyclodextrin can be still retained in the system after associative thickeners release, than Such as say in paint.The absorption position that vacancy comes out again in cyclodextrin can adsorb the other components of formula again, such as soak Agent and dispersant etc., so as to cause them to fail.In addition to some other problems, also result in system such as oily The problem of stability in paint.Therefore, these must the addition of additive must optimize, and preparaton is adapted to increasing Thick dose, this point is undesirable.

Another method has similarly been employed many years.Here, to reduce the viscosity of associative thickeners, make use of The property of real nonionic surfactant or emulsifying agent (compared with the material of butyldiglycol and other higher molecular weights) Energy.Because their boiling point is too high, they are discharged into environment not by " evaporation ", so, they for example, in oil Paint is most of after drying to be remained in coating.However, they have the drawback that therefrom, to such as these paint Water resistance has a negative impact because they make paint film than it is water-soluble and therefore and the part of water imbibition be easier to expand With come off.In addition, they with the bubble-related issues also resulted in paint production.

Due to this reason, in addition to (reduction) solvent and surfactant, a kind of " defoaming of addition in addition Agent " (" Surfynol ") is also described in EP-B-0 682 094.

Other prior arts in the field are, such as WO 00/00539, DE-A-196 44 933, DE-A-43 10 702, DE-A-195 23 837, DE-A-196 00 467, US-A-4,079,028 and DE-A-14 44 243.

Sodium formate is stated as a kind of additive in US-A-2002/0052441.However, salt can industrial coating with And cause significant water-fast sex chromosome mosaicism in terms of decorative paint.

The design of test system is as follows：

By 2.5 grams of thickener solns equably stir into by 100 grams of Acronal 290D (cinnamic acrylic ester dispersion, BASF), in the mixture of 30 grams of deionized waters and 0.3 gram of defoamer ADDID 800 (Wacker) composition.After maturation 4 hours 23 DEG C, under conditions of shear rate 1sec-1,100sec-1,10000sec-1, with Bohlin viscosimeters, (measure system is PP 30,150 μm of gap) measure viscosity.In order to be simplified, viscosity of the thickener individually in adhesive is only determined, Because rule of thumb, its numerical value is related to the numerical value obtained in being tested in complete paint formulation.

Claims (6)

1. a kind of solution viscosity is less than 25000mPa.s associative thickener preparation, including：

(a) combination of at least one structural viscosity type associative thickeners (A) and at least one newton-type associative thickeners (B) Body；And/or

(b) at least one structural viscosity type associative thickeners (A), at least one newton-type associative thickeners (B) and at least A kind of combination of diluent (C)；And/or

(c) at least one structural viscosity type associative thickeners (A), at least one newton-type associative thickeners (B) and at least A kind of combination of wetting agent；And/or

(d) at least one structural viscosity type associative thickeners (A), at least one newton-type associative thickeners (B) and at least A kind of combination of solvent；And/or

(e) at least one structural viscosity type associative thickeners (A), at least one newton-type associative thickeners (B), at least one The combination of kind solvent and at least one wetting agent；And/or

(f) combination of at least one structural viscosity type thickener (A) and at least one diluent (C)；And/or

(g) combination of at least one newton-type thickener (B) and at least one diluent (C).

2. the associative thickener preparation as described in claim 1 (b-d), include a kind of structural viscosity type associative thickeners (A) and a kind of diluent (C), the wherein diluent (C) is a kind of hydrophilic water-soluble oligomer (D) and hydrophobic parts (E) condensation product.

3. associative thickener preparation as claimed in claim 2, it is characterised in that diluent (C) is a kind of by alternately hydrophilic Property and the hydrophobic molecule copolymer or co-oligomer that form, a kind of or ester with higher molecular weight, wherein these 250 DEG C of the boiling point ＞ of material.

4. associative thickener preparation as claimed in claim 2 or claim 3, it is characterised in that the hydrophobic combination of diluent (C) (E) it is a kind of bifunctional molecules X-R-X2, wherein R is saturation or undersaturated contains 2-30 carbon atom, preferably 2-12 carbon The aliphatic series or cycloaliphatic groups of atom and particularly preferred 3-6 carbon atom, or the aryl containing 6-12 carbon atom, or Aromatics/aliphatic mixed group, X and X2, the two can with identical or different, and can with the functional group Z of hydrophilic component (D) or Z2 (group containing active hydrogen, such as, hydroxyl, amino or acylamino-) reacts, and wherein X and X2 are from carboxylic acid, carboxylic acid anhydrides, acyl Chlorine, ester, isocyanates, epoxides group in select, or halogen ion.

5. associative thickener preparation as claimed in claim 4, it is characterised in that hydrophobic parts (E) are adipic acid, neighbour The group of phthalate anhydride or dimethyl terephthalate (DMT).

6. coagulating agent, coalescents or wetting are used as in Aquo System according to any one of claim 3-9 diluent (C) Agent and the purposes of dispersant.