阅读说明：本技术 一种超支化聚合物水性分散剂的制备方法及应用 (Preparation method and application of hyperbranched polymer water-based dispersant ) 是由 许钧强 于 2021-07-23 设计创作，主要内容包括：本发明涉及一种超支化聚合物水性分散剂的制备方法及其在水性色浆中的应用,为聚(苯乙烯-co-马来酸酐)-g-(聚乙二醇单甲醚+EO-PO-EO+NR-(3)),可生物降解、不含烷基酚；本发明提供一种超支化聚合物水性分散剂的制备方法,具有阴非离子-多支链梳状结构,分子结构中含有芳环、羧基、羟基、胺基及聚醚等多个颜料吸附基团,利用空间位阻防止颜料颗粒絮凝沉降,优异的降粘分散性,提高着色力,防止浮色和发花,可制备无树脂/树脂体系的高固低粘颜料浓缩浆分散体,如机红、黄、紫色颜料、无机颜料、消光粉,也可用于有机颜料、防锈颜料及填料的混合分散,适用于水性色浆、水性工业涂料、水性油墨、水性防腐防锈底漆等水性体系。(The invention relates to a preparation method of a hyperbranched polymer aqueous dispersant and application of the hyperbranched polymer aqueous dispersant in aqueous color paste, wherein the hyperbranched polymer aqueous dispersant is poly (styrene-co-maleic anhydride) -g- (polyethylene glycol monomethyl ether + EO-PO-EO + NR) 3 ) Biodegradable, alkylphenol-free; the invention provides a preparation method of a hyperbranched polymer aqueous dispersant, which has negative non-ionsThe multi-branched comb-shaped structure contains a plurality of pigment adsorption groups such as aromatic rings, carboxyl, hydroxyl, amino, polyether and the like in a molecular structure, prevents pigment particles from flocculating and settling by utilizing steric hindrance, has excellent viscosity reduction and dispersibility, improves tinting strength, prevents flooding and floating, can prepare high-solid low-viscosity pigment concentrated slurry dispersoids without resin/resin systems, such as organic red, yellow and purple pigments, inorganic pigments and matting powder, can also be used for mixed dispersion of organic pigments, anti-rust pigments and fillers, and is suitable for aqueous systems such as aqueous color paste, aqueous industrial coating, aqueous ink, aqueous anticorrosive and anti-rust primer and the like.)

1. The hyperbranched polymer water-based dispersant is characterized by being a hyperbranched comb-shaped anionic or nonionic type, and the components are SMA-g-MPEG + EO-PO-EO + NR₃The molecular structural formula is shown as follows:

wherein x and y in the molecular formula are 1: 1-2: 1; z is 8-10;

r is-CH₂CH₃or-CH₂CH₂OH; r' isq＝22～28；

EO-PO-EO asm＝40～45；n＝2～5；

The hyperbranched polymer aqueous dispersant has the number average molecular weight of 20000-22000.

2. The preparation method of the hyperbranched polymer aqueous dispersant of claim 1, which comprises the following steps:

weighing styrene-maleic anhydride copolymer, polyethylene glycol monomethyl ether and ethylene oxide-propylene oxide segmented copolymer according to the weight percentage, adding the styrene-maleic anhydride copolymer, the polyethylene glycol monomethyl ether and the ethylene oxide-propylene oxide segmented copolymer into a reaction kettle, heating to 120 ℃ to start melting, starting vacuum, and dehydrating for 1h under the control of the vacuum degree of 0.09 MPa; starting stirring after complete dissolution, continuously heating to 170-175 ℃, controlling the vacuum degree to be 0.07-0.08 MPa, reacting for 3-4 hours, sampling every 0.5 hour to detect the acid value, and stopping the reaction when the acid value reaches a specified value; cooling to 120 ℃, and closing N₂Adding tertiary amine and deionized water under stirring, cooling to 60 ℃ when the pH value is 7.0-8.5, filtering and packaging,obtaining the hyperbranched polymer water-based dispersant;

the material comprises the following raw materials in percentage by weight:

the ethylene oxide-propylene oxide block copolymer has a number average molecular weight of 2000-2200, and the EO content accounts for 8.0-10.0%.

3. The hyperbranched polymeric aqueous dispersant of claim 2, wherein the styrene-maleic anhydride copolymer has a number average molecular weight of 1000 to 2000; the molar ratio of the styrene to the maleic anhydride is 1: 1-2: 1.

4. The hyperbranched polymer aqueous dispersant of claim 2, wherein the polyethylene glycol monomethyl ether has a number average molecular weight of 1000 to 1200.

5. The hyperbranched polymeric aqueous dispersant of claim 2, wherein said tertiary amine is one of triethylamine or triethanolamine.

6. The application of the hyperbranched polymer aqueous dispersant of claim 2 in aqueous color paste, wherein the aqueous color paste comprises the following components in percentage by weight as shown in tables 1 and 2:

table 1: aqueous color paste composition

Table 2: aqueous color paste composition

Technical Field

The invention relates to an aqueous dispersant, in particular to a preparation method and application of a hyperbranched polymer aqueous dispersant, belonging to the technical field of polymer dispersants.

Background

In the production of paint and ink, pigment dispersion is a crucial link, a proper dispersant is selected to easily obtain a paint with uniform pigment dispersion and stable storage, although the traditional dispersant shows an effective dispersion stabilizing effect in an aqueous dispersion medium, the traditional dispersant is not firmly adsorbed on the surface of pigment particles and is easily desorbed from the surface of the particles to cause re-aggregation or precipitation of the dispersed particles, the long-term stability of the system is poor, and the properties of paint film appearance, hardness, aging resistance and the like are also adversely affected, especially the characteristic of strong pertinence of the dispersant is that the same dispersant cannot be widely applied to the dispersion of different organic pigments, so that the production cost of a user is increased.

The dispersant is a surfactant which has two opposite properties of lipophilicity and hydrophilcity in a molecule, can uniformly disperse solid particles of inorganic and organic pigments which are difficult to dissolve in liquid, and simultaneously prevents the solid particles from settling and agglomerating. With the improvement of the requirements of people on health and environmental protection, the water-based environment-friendly paint becomes a new favorite in the field of architectural decoration, in the paint manufacturing process, the pigment is uniformly dispersed in the paint material in the form of tiny particles under the grinding and shearing force, and as the polarity of the surface of the pigment particles is low, but the surface tension of water is much greater than that of an organic solvent, some auxiliary agents are required to be added to reduce the surface tension of water and enhance the wetting effect on the pigment particles, so that the problem of dispersion stability is difficult to solve when preparing the water-based paint ink, and the application range of the water-based paint ink is narrowed; therefore, the surface of the pigment must be modified to cover the surface of the pigment particles with a dispersant, thereby improving the application properties of the pigment.

The molecular chain of the styrene-maleic anhydride copolymer (SMA) contains a hydrophobic styrene chain segment and a hydrophilic maleic anhydride chain segment, and a hydrolysate of the styrene-maleic anhydride copolymer (SMA) is a common high-molecular dispersant; meanwhile, the anhydride unit in the SMA molecular chain can be subjected to modification such as amidation, esterification and cationization, and the benzene ring unit can be subjected to modification such as sulfonation, so that the high-molecular dispersing agent with excellent performance is obtained. Such a polymeric dispersant has a good dispersion stabilizing effect on ultrafine solid particles (e.g., pigments, inorganic particles, etc.) having an extremely large surface area and a high specific surface energy, and is therefore called a styrene-maleic acid-based hyperdispersant. Styrene-maleic acid hyperdispersants are widely used in the fields of pigments, dyes, coatings, printing, paper making, construction, etc. at home and abroad.

Zhang.l et al synthesized a styrene-maleic anhydride copolymer using reversible addition-fragmentation chain transfer (RAFT) to control polymerization, investigated the dispersing ability of its hydrolyzed copolymer, and found that it has good dispersing properties for an organic phthalocyanine blue pigment. Xu Y, Liu j, etc. synthesized a hyperbranched styrene-maleic anhydride copolymer (BPSMA) and applied the product to carbon black dispersion in aqueous systems, the results showed that BPSMA had smaller particle size, narrower particle size distribution and higher stability to carbon black pigment dispersions than linear styrene-maleic anhydride copolymer (LPSMA).

Wangping et al prepared ultra-fine disperse red 60 by a grinding dispersion method and studied the influence of the synergistic effect of polystyrene-maleate PSMA and fatty alcohol-polyoxyethylene ether (AE) on the dispersion stability of disperse dyes. And the like, styrene, partially esterified maleic anhydride and maleic anhydride are used as monomers to synthesize the water-soluble polymer hyperdispersant, namely the partially esterified SMA, and the influence of various process parameters on the dispersibility of the copolymer is discussed. Zhoujiada and the like utilize 2, 3-epoxypropyltrimethyl ammonium chloride to carry out cationization modification to prepare the cationic surfactant of the partially esterified grafted quaternary ammonium salt, and researches show that the polymer has better dispersion stability to pigment yellow 14.

The forest Saint Sene et al prepared 3 comb-type amphiphilic polymers, poly (styrene-co-maleic anhydride) -g- (polyethylene glycol monomethyl ether) (A), poly (styrene-co-maleic anhydride) -g-C₁₂H₂₅OH) (B) and poly (styrene-co-maleic anhydride) -co- (polyethylene glycol monomethyl ether + C₁₂H₂₅OH) (C). When 3 comb-type amphiphilic polymers are used as a dispersing agent for carbon black, under the same conditions, the dispersing performance of 3 samples on the carbon black is sequentially B & gtC & gtA.

The invention prepares a poly (styrene-co-maleic anhydride) -g- (polyethylene glycol monomethyl ether + EO-PO-EO + NR)₃) The hyperbranched water-based dispersant has good dispersion effect on red, yellow and purple organic pigments.

Disclosure of Invention

The styrene-maleic acid hyperbranched structure has a viscosity reduction effect, anchoring groups in the molecular structure of the styrene-maleic acid hyperbranched structure, such as carboxyl, carboxylate, polyol, polyamine, polyether and the like, are tightly combined on the surface of the polar ultrafine particle through ionic bond, covalent bond, hydrogen bond, van der Waals force and other interactions, and the other part of nonpolar benzene rings are wound on the outer surface of the particle. The nonpolar benzene ring or polyether chain has good compatibility with a dispersion medium, presents an extended conformation, and forms a thick protective layer on the surface of the particle. Due to steric hindrance caused by occupied space and conformation, namely steric hindrance effect, when two particles adsorbed with hyper-dispersant molecules are mutually close, repulsive force can be generated between the particles to make the solid particles flick, so that flocculation is avoided. In addition, the poly chain contains PO branched chain, which has defoaming and foam inhibiting effects.

The invention aims to provide a hyperbranched polymer aqueous dispersant and a preparation method thereof.

In order to solve the dispersion and stability performance of the aqueous dispersant in an aqueous system, the invention adopts styrene-maleic anhydride copolymer (SMA), and the molecular structural formula of the SMA is as follows:

wherein x and y in the molecular formula are 1: 1-2: 1; and z is 8-10.

The invention adopts polyethylene glycol monomethyl ether MPEG and ethylene oxide-propylene oxide block copolymer EO-PO-EO to be capped, and then uses tertiary amine to neutralize water. The hyperbranched polymer water-based dispersant has the structure of SMA-g-MPEG + EO-PO-EO + NR₃(ii) a The molecular structural formula is as follows:

wherein x and y in the molecular formula are 1: 1-2: 1; z is 8-10;

r is-CH₂CH₃or-CH₂CH₂OH; r' isq＝22～28；

EO-PO-EO asm＝40～45；n＝2～5。

The hyperbranched polymer aqueous dispersant has the number average molecular weight of 20000-22000.

In order to solve the technical problems, the invention adopts the following technical scheme: the invention relates to a hyperbranched polymer water-based dispersant which comprises the following components in percentage by weight: 12.0-18.0% of styrene-maleic anhydride copolymer, 15.0-20.0% of polyethylene glycol monomethyl ether, 5.0-10.0% of ethylene oxide-propylene oxide block copolymer, 0.2-0.5% of tertiary amine and 45.0-60.0% of deionized water.

Wherein the styrene-maleic anhydride copolymer has a number average molecular weight of 1000-2000.

The polyethylene glycol monomethyl ether has a number average molecular weight of 1000-1200.

The ethylene oxide-propylene oxide block copolymer has a number average molecular weight of 2000-2200, and the EO content accounts for 8.0-10.0%.

The tertiary amine is one of triethylamine or triethanolamine.

The invention provides a preparation method of a hyperbranched polymer water-based dispersant, which comprises the following preparation steps:

weighing styrene-maleic anhydride copolymer, polyethylene glycol monomethyl ether and ethylene oxide-propylene oxide segmented copolymer according to the weight percentage, adding the styrene-maleic anhydride copolymer, the polyethylene glycol monomethyl ether and the ethylene oxide-propylene oxide segmented copolymer into a reaction kettle, heating to 120 ℃ to start melting, starting vacuum, and dehydrating for 1h under the control of the vacuum degree of 0.09 MPa; starting stirring after complete dissolution, continuously heating to 170-175 ℃, controlling the vacuum degree to be 0.07-0.08 MPa, reacting for 3-4 h, sampling every 0.5h to detect the acid value, and when the acid value reaches the acid valueStopping the reaction when the reaction temperature reaches a predetermined value; cooling to 120 ℃, and closing N₂Adding tertiary amine and deionized water under stirring, cooling to 60 ℃ when the pH value is 7.0-8.5, filtering and packaging to obtain the hyperbranched polymer aqueous dispersant.

The hyperbranched polymer aqueous dispersant is produced by adopting a one-pot method, has simple process, does not use hazardous raw materials, does not discharge three wastes, and belongs to a green production process.

The application of the hyperbranched polymer water-based dispersant JW prepared by the invention in water-based color paste comprises the following components in percentage by weight as shown in the following tables 1 and 2:

table 1: aqueous color paste composition

Name (R)	Iron oxide red	Iron oxide yellow	Titanium white	PY74	PY154	PY83	PY93
								Deionized water	13.9-14.9	19.2-20.2	17.9-18.9	29.3-30.3	34.2-35.2	39.0-40.0	39.2-40.2
Propylene glycol	5.0	5.0	5.0	6.0	6.0	6.0	6.0
								Bactericide	0.2	0.2	0.2	0.2	0.2	0.2	0.2
Defoaming agent	0.2	0.2	0.2	0.2	0.2	0.2	0.2
								Wetting agent	1.0	1.0	1.0	2.0	2.0	2.0	2.0
JW dispersant	6.0-7.0	5.5-6.5	4.0-5.0	11.0-12.0	11.0-12.0	11.0-12.0	11.0-12.0
								Pigment (I)	72.0	67.0	70.0	50.0	45.0	40.0	40.0
pH regulator	0.2	0.5	0.2	0.2	0.2	0.3	0.2
								Anti-settling agent	0.5	0.4	0.5	0.1	0.2	0.3	0.2

Table 2: aqueous color paste composition

The hyperbranched polymer aqueous dispersant prepared by the invention has a negative nonionic-multi-branched comb-shaped structure, contains a plurality of pigment adsorption groups such as aromatic rings, carboxyl, hydroxyl, amino, polyether and the like in a molecular structure, prevents pigment particles from flocculating and settling by utilizing steric hindrance, has excellent viscosity reduction dispersibility, improves tinting strength, prevents flocculation, flooding and floating, can prepare high-solid low-viscosity pigment concentrated slurry dispersoids without a resin/resin system, such as organic red, yellow and purple pigments, inorganic pigments and extinction powder, can also be used for mixing and dispersing organic pigments, anti-rust pigments and fillers, and is suitable for aqueous systems such as aqueous color pastes, aqueous industrial coatings, aqueous ink, aqueous anti-corrosion and anti-rust primers and the like.

Detailed Description

The present invention is further described with reference to the following examples for the preparation of hyperbranched polymeric aqueous dispersants. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.

Example 1

A hyperbranched polymer aqueous dispersant comprises the following preparation steps:

weighing 125.0 parts of SMA1200, 155.0 parts of MPEG1000 and 65.0 parts of EO-PO-EO block copolymer by weight percent, adding into a reaction kettle, heating to 120 ℃ to start melting, starting vacuum, and dehydrating for 1h under the control of the vacuum degree of 0.09 MPa; stirring after complete melting, continuously heating to 170-175 ℃, and controlling the vacuum degree to be 0.07-0.08 MPaReacting for 4 hours, sampling every 0.5 hour to detect the acid value, and stopping the reaction when the acid value reaches the specified value; cooling to 120 ℃, and closing N₂Adding 2.6 parts of triethylamine while stirring, adding 520.0 parts of deionized water, cooling to 60 ℃ when the pH value is 7.5-7.8, filtering and packaging to obtain the hyperbranched polymer aqueous dispersant with the solid content of 40.6%.

Example 2

A hyperbranched polymer aqueous dispersant comprises the following preparation steps:

weighing 126.0 parts of SMA1000, 165.0 parts of MPEG1000 and 55.0 parts of EO-PO-EO block copolymer by weight percent, adding into a reaction kettle, heating to 120 ℃ to start melting, starting vacuum, and dehydrating for 1h under the control of the vacuum degree of 0.09 MPa; starting stirring after complete dissolution, continuously heating to 170-172 ℃, controlling the vacuum degree to be 0.07-0.08 MPa, reacting for 4 hours, sampling every 0.5 hour to detect the acid value, and stopping the reaction when the acid value reaches a specified value; cooling to 120 ℃, and closing N₂Adding 2.8 parts of triethylamine while stirring, adding 500.0 parts of deionized water, cooling to 60 ℃ when the pH value is 7.0-7.2, filtering and packaging to obtain the hyperbranched polymer aqueous dispersant with the solid content of 41.5%.

Example 3

A hyperbranched polymer aqueous dispersant comprises the following preparation steps:

weighing 125.0 parts of SMA1000, 160.0 parts of MPEG1200 and 60.0 parts of EO-PO-EO block copolymer by weight percent, adding into a reaction kettle, heating to 120 ℃ to start melting, starting vacuum, and dehydrating for 1h under the control of the vacuum degree of 0.09 MPa; starting stirring after complete dissolution, continuously heating to 170-172 ℃, controlling the vacuum degree to be 0.07-0.08 MPa, reacting for 4 hours, sampling every 0.5 hour to detect the acid value, and stopping the reaction when the acid value reaches a specified value; cooling to 120 ℃, and closing N₂Adding 3.0 parts of triethanolamine while stirring, adding 500.0 parts of deionized water, cooling to 60 ℃ when the pH value is 7.2-7.5, filtering and packaging to obtain the hyperbranched polymer aqueous dispersant with the solid content of 41.2%.

Example 4

A hyperbranched polymer aqueous dispersant comprises the following preparation steps:

weighing 125.0 parts of SMA1000, 160.0 parts of MPEG1000 and 60.0 parts of EO-PO-EO block copolymer by weight percent, adding into a reaction kettle, heating to 120 ℃ to start melting, starting vacuum, and dehydrating for 1h under the control of the vacuum degree of 0.09 MPa; starting stirring after complete dissolution, continuously heating to 170-172 ℃, controlling the vacuum degree to be 0.07-0.08 MPa, reacting for 4 hours, sampling every 0.5 hour to detect the acid value, and stopping the reaction when the acid value reaches a specified value; cooling to 120 ℃, and closing N₂Adding 3.2 parts of triethanolamine while stirring, adding 500.0 parts of deionized water, cooling to 60 ℃ when the pH value is 7.0-7.2, filtering and packaging to obtain the hyperbranched polymer aqueous dispersant with the solid content of 42.2%.

Example 5

A gray water-based acrylic acid anti-rust primer comprises the following components: 42.0 parts of water-based acrylic resin, 3.0 parts of ethylene glycol monobutyl ether, 2.5 parts of dispersing agent, 1.0 part of flash rust inhibitor, 6.0 parts of zinc phosphate, 6.0 parts of talcum powder, 3.0 parts of aluminum tripolyphosphate, 6.0 parts of mica powder, 10.0 parts of kaolin, 5.0 parts of heavy calcium powder, 2.0 parts of titanium dioxide, 0.5 part of carbon black, 0.2 part of defoaming agent, 0.1 part of flatting agent, 0.1 part of pH regulator, 2.0 parts of dipropylene glycol monomethyl ether, 1.0 part of anti-settling agent and 11.6 parts of deionized water.

Wherein the dispersant is the hyperbranched polymer aqueous dispersant in the embodiment and the comparative example BYK-190W.

The measured performance index according to the relevant standard is shown in table 3.

Table 3: technical indexes of performance of water-based acrylic acid anti-rust primer

Although the present invention has been described in detail and with reference to exemplary embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.