JPH03212421A - Process for producing addition compounds and dispersants containing this compound - Google Patents

Abstract

PURPOSE: To obtain an addition compd. having high gloss, extremely good transparency and high color intensity and not generating gloss loss and suitable for a dispersant, by reacting polyisocyanate with a specified hydroxy compd.

CONSTITUTION: Polyisocyanate with average functionality of 2.5-6 is reacted with a monohydroxy compd. represented by formula Y-OH [wherein Y is 8-30C (subsid.) aliphatic or alicyclic hydrocarbon] and the reaction product is reacted with a compd. containing 2-3 active hydrogen atoms in its molecule on an average, especially, organopolysiloxane having an org. functional group containing 2-3 groups capable of reacting with an isocyanate group in a molecule in total on an average and bonded through a Sic bridge and the reaction product is reacted with a compd. represented by formula Z-Q (wherein Q is OH or NH₂; and Z is a 2-10C aliphatic group containing a tertiary amino group) to obtain the objective compd.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for the preparation of addition compounds or salts thereof suitable as dispersants, obtained by reacting polyisocyanates with selected hydroxy compounds.

PRIOR ART The invention is based on the state of the art as described in EP 0 154 678.

The subject of EP 0 154 678 is the preparation of polyisocyanates, hydroxy compounds, Tzelevitinoff hydrogens and compounds containing at least one nitrogen-containing basic group and optionally amine hydrogen-containing compounds, optionally in the presence of a solvent or Addition compounds and their salts suitable as dispersants, obtained by reaction optionally in the presence of reaction catalysts, in which case these compounds can be used to react polyisocyanates with an average functionality of 2.5 to 6. a) Formula: Y-OH [wherein Y is i) 8 to 3 carbon atoms, the hydrogen atoms of which may be partially substituted with halogen and/or aryl groups;
0 aliphatic and/or alicyclic hydrocarbon groups, ii) at least one -0 and/or -C, the hydrogen atoms of which may be partially substituted by halogen;
Molecular weight 350-goo, including O-leaf group.

represents an aliphatic, alicyclic and/or aromatic group] and a monohydroxy compound of
~50%, advantageously from 20 to 40%, particularly preferably from 20 to
b) The reaction product obtained has the formula: G-(E).

[In the formula, E represents -0H1-NO3 and/or -NHR (in the formula, R represents an alkyl group having 1 to 4 carbon atoms), n
is 2 or 3, and G is the number of carbon atoms, which may contain -0-, -COO-, -CONH-1-8- and/or -8O□- groups, with a molecular weight of up to 3000. representing at least two aliphatic, cycloaliphatic and/or aromatic groups] and another 15 to 45%, preferably 20 to 40% and particularly preferably of the NCO- groups of the isocyanate initially used. reacts by 20-35%, but the sum of the NCO conversion rates in a) and b) reactions is at least 40% and at most 75%,
C) The reaction product obtained has the general formula: z-q [wherein Q is 10H1-OH]. , -NHR(
R represents an alkyl group having 1 to 4 carbon atoms) or -5H
, Z represents an aliphatic group containing at least one tertiary amino group and having 2 to 10 carbon atoms, or a heterocyclic group having at least one basic ring nitrogen atom that does not contain a hydrogen atom, The cyclic group may be bonded to the group Q via an alkylene group having 1 to 10 carbon atoms] and step a.
) and b) by reacting in such an amount that at least one molecule of compound ZQ is distributed to each remaining incyanate group that remains unreacted.

The dispersants described in EP 0 154 678 facilitate the incorporation of powdered or fibrous solid substances into liquid systems. This ease of formulation is influenced in particular by the wettability of the solid substance by the surrounding medium and by its affinity for this medium. The dispersants of EP 0 154 678 reduce the costs of dispersion. Furthermore, the reagglomeration of solid substances in the dispersion is prevented or significantly reduced.6 Problem to be Solved by the Invention The present invention overcomes the state of the art that can be predicted from EP 0 154 678. The fundamental challenge is to improve this type of dispersant.

A disadvantage of these known dispersants is that they gel when left in air. This makes its use extremely difficult. It is therefore an object of the present invention to provide dispersants which do not undergo this gelation at all or only have it to a significantly reduced extent.

The dispersant must be compatible with other, eg anionic, dispersants. For example, it is known to disperse titanium oxide pigments in white lac with ionic auxiliaries. In this case the white lacquer must be able to be mixed with a pigmented paint containing an improved dispersant without loss of gloss.

A further object of the present invention is to reduce the viscosity of the dispersant to such an extent that the dispersant containing a large amount of solid can be dissolved in an organic solvent. If it is possible to produce a concentrated solution of the dispersant, its use in a refill system is greatly facilitated.

Finally, the solubility of the dispersant in organic solvents, especially lac systems, should be improved.

Means for Solving the Problems These problems of the present invention are unexpectedly solved by European Patent No. 015
A solution can be achieved by using selected organo-modified polysiloxanes in the second reaction step when producing dispersants such as those described in No. 4678.

Accordingly, the present invention provides that, in preparing the initially described dispersant,
The reaction in step b) is carried out using organopolysiloxanes with organofunctional groups bonded via SiC bridges, which contain in their average molecule a total of 2 or 3 groups capable of reacting with incyanate groups. Characterized by implementation.

Examples of groups capable of reacting with isocyanate groups are hydroxy groups and amino groups. Particular preference is given to organopolysiloxanes with hydroxyl-containing organic functional groups bonded via SiC bridges. In this case, two or three groups capable of reacting with incyanate groups should be present in the average molecule. This ensures the insertion of the organo-modified polysiloxane into the backbone of the dispersant. Organic functional groups having groups capable of reacting with isocyanate groups are bonded to the organopolysiloxane via SiC bridges. This SiC-
Bonds are particularly preferred because of their stability.

Step b) is carried out with -up to: [wherein the radicals R1 are the same or different and represent a methyl group or a phenyl group, at least 90% of the radicals R1 are methyl groups and the radicals R2 are the same or different and the group R1, (CH2)-OH1(CH2CH2)so)qH
selected from the group consisting of, R3 represents an alkyl group having 1 to 4 carbon atoms, x = 1 to 8, y = 2 to 8, Z = 2 to 8
, n=2 or 3, p=1-100 and q=5-100, two or three of the groups R2 are groups having active hydrogen, a=1-100 and b=o-3, Particularly advantageous are the dispersants obtained by carrying out the procedure using organopolysiloxanes of the following.

Each of the groups R1 may be the same or different in the polymer molecule; at least 90% of the groups R1 are methyl groups. Up to 10% of the radicals R1 may be phenyl groups.

Each group R2 may also be the same or different, and the following two R1 groups (CI(2)XOH1(CH2
), NHR', (CHz)zo(CnHz,,0)pH
and (CH2), 0(1 C(CH2)50)QH.

When selecting the group R2 from the above group, it is necessary to satisfy the condition that two or three of the groups R2 have active hydrogen. A group having active hydrogen is OH-
group or a group having an NHR'- group. In this case R3 is an alkyl group having 1 to 4 carbon atoms, preferably a straight-chain alkyl group, in particular a methyl, ethyl, propyl or butyl group. The index X has a value of 1 to 8, and y has a value of 2 to 8.2. n has a value of 2 or 3. In this case n in the polymer molecule can assume various values, for example 2 or 3, so that the value n in the average molecule can be a fraction.

p is the number of oxyalkylene units and has a value of 1-100. 9 has a value of 5-100.

This group is -C2H2OH1-C3H60H, -CaHs
OH, CaH1□OH, -CH2Cl(CH3)CH2
CH20H, -C11Hz□0H2CH・CH2H20
Particular preference is given to H.

As the group having a secondary amine group, the group (Ctlz)sN
HR3 is advantageous.

A good polyether group has the formula: (CH2)30(C,t
h. 0)-1, in which case n in the average numerator has a value of 2 and p has a value of 20.

1 groups (C11□hO(C(C)h)50)-I+ are preferred as polyester groups.

The index a indicates the number of difunctional siloxy units, from 1 to 100
, advantageously has a value of 1 to 50.

The index indicates the number of trifunctional siloxy units and has a value of 0 to 3. Preference is given to compounds in which b=0.

Examples of organopolysiloxanes that can be used in process step 1)) are: R2=HO CH2 CH2 H-CH2 CI.

1 -O(C(CH2)50)19H For the implementation of the entire treatment of the compounds that can be used in steps a) and C) and for the amounts to be used of each reactant, see EP 0 154 678. is shown. Without repeating the entire content of EP 0154678, the following points will be pointed out.

As monohydroxy compounds of Y-OH, aliphatic, cycloaliphatic and/or araliphatic compounds each having 8 to 30 carbon atoms can be used; mixtures of these compounds can also be used. . It is also possible to use straight-chain and branched aliphatic or araliphatic compounds. These compounds may be saturated or unsaturated. Preference is given to saturated compounds. The hydrogen atoms may be partially replaced by halogens, advantageously fluorine and/or chlorine,
When using compounds substituted in this way, preference is given to aliphatic monoalcohols. Examples of special fluorinated alcohols are hetadecafluorodecanol or C6F, CH2
It is CH20H.

Monohydroxy compounds of the formula Y-OH include Kano and/
Alternatively, it is also possible to use compounds of this type containing at least an IWA group. This compound is polyether,
Polyester or mixed polyether-polyester.

This compound of the formula Y--OH is reacted with a polyisocyanate of average functionality 2.5-6 in amounts such that 15-50% of the NCO- groups are reacted.

Examples of suitable polyisocyanates are those which can be obtained by adding diisocyanates to polyols or from diisocyanates by Billet reaction.

In a first process step, the reaction product obtained is then reacted in a manner known per se with the organopolysiloxanes which can be used according to the invention and which have reactive organofunctional groups. .

The NCO of the polyisocyanate initially used in this reaction
- The other 15-45% of the groups react.

Subsequently, the product obtained in process step b) is reacted in a third process step with one maximum Z-Q compound in an amount such that for each incyanate group still remaining there is at least one molecule of compound Z-Q. let It is advantageous to use a slight excess in order to avoid undesirable reticulation. Generally about 1
An excess of 0 mol %, preferably 5 mol %, is sufficient. Q
is advantageously a NO3 group. Z is preferably a mono- or di-nuclear heterocyclic group, of which one ring nitrogen atom is preferably bonded to the group Q via an alkylene group having 2 to 5 carbon atoms. Preferred heterocycles are triazole, pyrimidine, imidazole, lysine, morpholine, pyrrolidone, piperazine, benzimidazole, benzothiazole and/or triazine. These heterocycles contain substituents, for example 1 to 6 carbon atoms, preferably 1
-4 alkyl and/or alkoxy groups (methoxy groups are preferred in this case), amine groups (which on reaction with isocyanates give rise to polyfunctional compounds), 3
It may have up to 1, preferably 1 substituent. The above heterocycle may be directly bonded to the group Q. However, the compounds can also be bonded via groups customary in this field, such as alkylene groups having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, or polyether groups having the same number of carbon atoms.

The products according to the invention have the properties mentioned at the outset. That is, when this dispersant is dissolved in a solvent, this solution can be left in the air without the risk of gelation.1 The viscosity of the dispersant and the viscosity of the solvent containing the dispersant are higher than those of products of the prior art. Solutions with lower viscosity and thus containing higher amounts of solids can be produced. At the same time, the solubility of the dispersant in organic solvents and especially in lac systems, and thus its compatibility, is improved.

EXAMPLES In the following examples, we first detail the preparation of the dispersants according to the invention and also compare the technical properties of use of the dispersants according to the invention with dispersants of the prior art according to EP 0 154 678. and show.

In each example, all "parts" represent "parts by weight" unless otherwise specified.

Preparation Example 1 (Reference Example) A dispersant was prepared in accordance with Example 6 of EP 0 154 678 in a Desm module under a protective gas atmosphere.

19.4 parts of DUR)L (67% in ethylene glycol acetate/Kijirol 1:1) are diluted with 30 parts of Ode Lengericol Acetate/Kijilol (1:1). Dissolved in 15 parts of pheasant roll, average molecular weight 7so
g 1 mol of commercially available methoxypolyethylene glycol 13
．． 3 parts and 1 to 0.003 parts of dibutyltin dilaure were added and heated to 50°C.

After 34% of the NCO- groups have reacted, 6 tng KOH/g of LO dissolved in 30 parts of Quizilol, prepared from 1,4-butanediol and 182.0 g of caprolactone.
9.5 parts of caprolactone ester having an OH value of (the preparation of this caprolactone ester is described in Preparation Example H of EP 0 154 678) are added. The reaction is terminated as soon as 68% of the NCO groups have reacted.

To add to the remaining NCO groups, 2.3 parts of 2-(2-hydroxyethyl)pyridine in 31 parts of Quizilol are added. Increase temperature to 70°C. The reaction was terminated after 2 hours.

The product is colorless and slightly viscous. The solid matter content is 25.3%.

Preparation Example 2 (Reference Example) A dispersant was prepared in accordance with Example 1 of EP 0 154 678 under a protective gas atmosphere.

10.8 parts of N (75% in ethylene glycol acetate/Kizilol 1:1) were combined with 15 parts of ethylene glycol acetate and 14.0 parts of n-octatool.
29 mg KOH/g O dissolved in 30 parts of kijirole, prepared from 4 parts and 185.6 parts of caprolactone.
caprolactone polyester with H-value (the production of this caprolactone ester is described in European Patent No. 0154678)
27.2 parts (described in Preparation Example C of the specification) are homogenized, 0.008 parts of dibutyltin dilaurate are added, and the mixture is stirred at 60 DEG C. until the OH groups have completely reacted.

For the binding reaction, 1.2 parts of 12-diaminododecane (diluted with 15 parts of quijirole and dissolved in 15 parts of N-methylpyrrolidone) was added all at once.

After 66% of the initially used NCO groups have reacted, 2.9 g of N,N-diallylmelamine diluted with 198 parts of quidylol and dissolved in 15 parts of N-methylpyrrolidone are added. Warm to 70°C and stir at this temperature for 1 hour.

The final product has an average viscosity and is clear and colorless. The solid matter content is 29.6%.

Production example 3 (according to the present invention) Desm.

19.4 parts of NCO-L are reacted with 13.3 parts of methoxypolyethylene glycol having an average molecular weight of 750 g 1 mol and 0.003 parts of dibutyltin dilaurate at 50°C. After 34% of the NCO- groups have reacted, 30 parts of Kizylol are reacted. 9.5 g of linear α,ω-hydroxypropyl-polydimethylsiloxane (a=5.5, b=0) with an OH value of 106 mg KOH,/g, dissolved
Add. The reaction is terminated as soon as 68% of the NCO groups have reacted.

To add to the remaining NCO groups, 2.3 parts of 2-(2-hydroxyethyl)pyridine in 31 parts of Quizilol are added. Increase temperature to 70°C. After a further 2 hours, the reaction is terminated.

The product is colorless and rather viscous. The solid matter content is 25.3%.

Preparation Example 4 (According to the Invention) Preparation Example 3 (According to the Invention) is repeated, but the modified polysiloxane is of the following average formula: The OH-value of the modified siloxane is □lll1 g KOH/g
It is.

The product obtained is colorless and slightly viscous, with a solids content of 28.6%.

Preparation Example 5 (According to the Invention) Preparation Example 2 (Reference Example) is repeated, but a linear α,ω-aminopropyl-polydimethyl is prepared by dissolving 1.2 parts of 1.12 diaminododecane in 44.3 parts of Quijirole. Replaced with 8.5 parts of siloxane (a-9, b-O).

The product obtained has an average viscosity and is colorless and transparent. The solid matter content is 29.6%.

Preparation Example 6 (According to the Invention) Corresponding to Preparation Example 3 (According to the Invention) 15.5 g of Desmodur N (75% in ethyl glycol acetate/Kizilol 1:1) are mixed with 20 parts of ethyl glycol acetate. Dilute with 76 mg KOH/g O dissolved in 15 parts of pheasant
Methoxypolyethylene glycol with H value 15,1
1 part and 0.008 parts of dibutyltin dilaurate were added, and the mixture was reacted at 50°C.

After 34% of the NCO groups have reacted, 75.6 parts of an average caprolactone ester of formula: % formula % dissolved in 80 parts of quizyrole are added.

When 68% of the NCO- groups have reacted, add 2 parts of 1-(2-aminoethyl)piperazine in 5 parts of ethyl glycol acetate to add the remaining NCO- groups to terminate the reaction.
, 6 parts and increase the temperature to 70°C. The reaction is terminated after 2 hours.

The product is viscous and colorless. Solid substance content is 45.
It is 9%.

Preparation Example 7 (According to the Invention) Preparation Example 6 (According to the Invention) is repeated, but using as modified polysiloxane the following average formula: % formula %) parts dissolved in 30 parts of Quizylol.

The product obtained has an average viscosity and is transparent.

Use of the dispersant according to the invention in comparison with the dispersant according to EP 0 154 678 Technical characteristics test Use examples The products Log obtained in Preparation Examples 1 to 7 are each poured into a glass dish (diameter 10 CI 11); exposed to air at room temperature 2
Dry for 4 hours. Thereafter, an experiment was conducted in which the resulting residue was absorbed with Kijiroll. Products not according to the invention gel and are therefore insoluble, whereas products according to the invention can be dissolved again.

In a 250 mQ glass flask, add 37.5 parts of a 50% solution of hydroxyacrylate fat, 9 parts of Kijirole,
Solvesso 150
7. To 5 parts of Chang 1, add X parts of a dispersant or a comparative product according to the prior art according to the company, homogenize, and add Y parts of pigments. (1st
table). Parts by weight of dispersant were calculated assuming 100% solids.

300% by weight of washed glass beads (based on the batch of crushed material) are added to the crushed material and dispersed by shaking the glass flask on a vibrator for 60 minutes.

After basic dispersion treatment, hydroxyacrylate (50%) 79
．． A coating rack material prepared from 5 parts and 1.65 parts of pheasant roll is added to the grind.

The resulting rack is shaken again in the vibrator for 5 minutes in order to homogenize it. Next, pass the glass beads through the sieve. This basic rack is left for 12-15 hours before further processing.

A portion of the basic rack thus produced is further processed as described below. The other part was stored at 50°C for 14 days and then further processed in the same way.Basic rack 1 for hardening.
00 parts, add 30 parts of a curing agent (Desmodur N) containing 75%) liisocyanate and mix.

Continue to adjust the viscosity of the rack to 16” DIN 4/2 with butyl acetate.
Adjust to 3. After about an hour, the rack adjusted in this way was
Pour into polyester seedling soil fixed to a glass plate with an angle of 80°.

After the rack film is deeply cured, evaluate the gloss, color strength and clarity of the film, as well as its degree of cohesion under a microscope. Evaluation is performed using a numerical index of 0 to 3. In this case 0 = high gloss, very good transparency, no agglomeration and high color strength 1 = high gloss, good transparency, no agglomeration and slight color strength 2 - light loss of gloss and transparency, slight agglomeration 3 = no gloss , no transparency, meaning obvious agglomeration.

The results are summarized in Table 2.

This index was chosen because in the rack industry only non-agglomerated wood is considered usable.

To further measure the degree of agglomeration, the basic racks (Racks I, ■, ■ in Table 1) were mixed with white racks (Racks ■ in Table 1) in a ratio of 1:4, homogenized, and 16” DIN4/
Adjust the viscosity to 23.

Pour the resulting mixed rack into polyester seedling soil as previously described, allow the rack to dry for approximately 5 minutes, then rub the sample with your fingers until the color is consistent (kneading test = R
ub-out-test).

After the film has completely cured, the color intensity of the abraded sample as well as the sample without this treatment is measured. Therefore, indexes O to 3 were selected again.

in this case 0 = No floating high color intensity 1 = No slight color intensity floating 2 = light floating 3 = Significant floating represents.

The results are summarized in Table 3.

To test the miscibility with white lacs made with ionic dispersants, white lacs (Table 1, Pigment ■, but made with ionic dispersants) were mixed with colored lacs (Table 1, Pigments I to ■)
) mixed with The results are shown in Table 4. Gloss was measured using a gloss measuring device (angle 60°) on a surface without abrasion treatment. Noazo-arylamide derivatives such as Novoperm Orange HL 70 ■■ 4.5 4.5 4.5 5.0 5.0 5.0 Example Example Example Example Example 0.67 0.67 0.67 0 .5 0.5 0.5 Anthraquinone a derivatives such as Chro-5,0 5,0 Example 1.0 1.0 Titanium dioxide 5 Example 0.75 IVb 25 Example 0.75 c 25 0.75 a, b = according to the invention C = not according to the invention.

2nd table coloring rack I n IIIabc
abc abc After manufacture 001 011 112 Stored at 50°C 011 011 112 0 = high gloss, no AF collection, very good clarity and high color strength 1 - high gloss, no i collection, good transparency and slight color strength, 2 = slight loss of gloss and clarity, slight agglomeration; 3 = no gloss, no transparency and obvious agglomeration.

Table 3 Mixed rack I/■II/IV [1/IVabc
abc abc After manufacture 001 001 112 Stored at 50° C. 011 001 112 0 = No floating of high color intensity 1 = No floating of slight color intensity 2 = Light floating 3 = Significant floating.

Table 4: Pigments I/IV It/TV I provides improved stability to the pigment in the pigment rack.

The advantages of the dispersants according to the invention are as follows: a) The pigmented racks and mixed racks produced using the dispersants according to the invention have high gloss, very good transparency and high color strength. These racks show no tendency to agglomerate and no floating can be observed.

b) Mixing racks with white racks rubbed with ionic dispersants can be mixed without significant loss of gloss. This is not possible with prior art dispersants.

C) It is possible to produce dispersants according to the invention with an active substance content of 50% (Example 6).

d) During evaporation of the solvent used to prepare the dispersant according to the invention, no gelation occurs, unlike the dispersants of the prior art.

Claims (1)

[Scope of Claims] 1. A polyisocyanate having an average functionality of 2.5 to 6, a) having the formula: Y-OH [wherein Y is i) the hydrogen atoms thereof are partially substituted by halogen and/or aryl groups; 8 to 3 carbon atoms, which may be
0 aliphatic and/or alicyclic hydrocarbon groups, ii) at least one -O- and/or -, the hydrogen atoms of which may be partially substituted by halogen;
aliphatic with a molecular weight of 350 to 8000, containing a COO- group;
b) The reaction product of a) is reacted with a monohydroxy compound representing an alicyclic and/or aromatic group in an amount such that 15 to 50% of the NCO- groups are reacted, and b) the reaction product of a) is The other 15-45% of the NCO- groups of the isocyanate initially used react with compounds containing 2 or 3 atoms, but a
) and b) the total NCO conversion rate in the reaction is at least 40%.
c) The reaction product obtained in b) has the general formula: Z-Q [wherein Q is -OH, -NH_2, -NHR (R is 1 carbon atom] ~4 alkyl group) or -SH, Z
contains at least one tertiary amino group and has 2 to 2 carbon atoms
10 aliphatic groups or a heterocyclic group having at least one basic ring nitrogen atom that does not contain a hydrogen atom, and the heterocyclic group is connected to the group Q via an alkylene group having 1 to 10 carbon atoms.
may be bonded to] and steps a) and b)
Compound Z is added to each remaining unreacted isocyanate group.
- In producing an addition compound or a salt thereof suitable as a dispersant, obtained by reacting an amount in which at least one molecule of Q is distributed, the reaction in step b) is carried out with an isocyanate group in the average molecule. A total of 2 possible groups
A method for producing an addition compound, characterized in that it is carried out using an organopolysiloxane having 1 or 3 organic functional groups bonded via SiC bridges. 2. Process b) is carried out using the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, the groups R^1 are the same or different and represent a methyl group or a phenyl group, %
is a methyl group, the groups R^2 are the same or different, and the groups R^1, (CH_2)_xOH, (CH_2)_
yNHR^3, (CH_2)_zO(C_mH_2_m
O) _pH and ▲ Numerical formulas, chemical formulas, tables, etc. are selected from the group consisting of ▼, R^3 represents an alkyl group having 1 to 4 carbon atoms, and x
= 1 to 8, y = 2 to 8, z = 2 to 8, n = 2 or 3, p
= 1 to 100 and q = 5 to 100, and 2 of the group R^2
or 3 are groups having active hydrogen, a = 1 to 10
The method according to claim 1, which is carried out using an organopolysiloxane represented by: 3. A dispersant containing the compound obtained by the method according to claim 1 or 2.