CN106008848A - Comb type macromolecular dispersant and preparation method thereof - Google Patents

Abstract

A kind of comb type macromolecule dispersant is characterized in that molecular formula structure is as follows: Wherein, m is an integer ranging from 10 to 20, R ₁ , R ₃ , and R ₄ are H or methyl, R ₂ is a C ₄ -C ₁₂ alkyl group, and a, b, and c are integers greater than zero. The invention has the advantages of bright green color, energy saving, moderate water solubility and high solid content.

Description

A comb-shaped polymer dispersant and preparation method thereof

technical field

The invention belongs to the technical field of additives in the detergent industry, and mainly relates to a comb-shaped polymer dispersant that can be used to disperse solid particles and a preparation method thereof.

Background technique

Surfactants are the main components of decontamination in detergents. Generally, anionic surfactants such as linear alkyl sodium sulfonate (LAS), fatty alcohol polyoxyethylene ether sodium sulfate (AES) and fatty alcohol polyethylene oxide Compounded with non-ionic surfactants such as ether (AEO). During the washing process, some anionic surfactants, such as LAS, will combine with a large amount of Ca ²⁺ and Mg ²⁺ in water to precipitate and deposit on the surface of the fabric. These deposited grains will enter the fiber network structure of the clothes, not only causing clothing It will also reduce the cleaning effect due to the deactivation of surfactants. The polymer surfactant can inhibit the formation of CaCO ₃ crystals or form smaller crystals that can be suspended in water, reduce the deposition of crystals on the fiber surface, and improve the anti-compacting ability.

Patent CN104327203A describes the preparation of a sodium polyacrylate dispersant by using acrylic acid as a polymerization monomer, using water as a solvent, and using an oxidation-reduction initiator. It is characterized in that the product has excellent dispersibility compared with sodium polyacrylate on the market, a large amount of chain transfer agent is not used in the production process, and the process of distilling the low-carbon alcohol chain transfer agent is omitted. However, the mass concentration of the monomers used in the polymerization process is low, the equipment utilization rate is not high, and the charge density of the polymerization product is relatively low, and the dispersion effect is average in high hardness water.

In JP-A-56-55407 (Japanese Open Patent Gazette), the preparation method of acrylate series low-molecular polymers is announced. Due to the introduction of sulfo groups in the molecule, the charge density and charge intensity of the product increase significantly, making the dispersion of the product Both sex and chelating ability are greatly improved. However, the monomer used in this method is a solution system of acrylate. When the concentration of the reaction system is too high, the viscosity will obviously increase, and the reaction is difficult to control. Therefore, the monomer concentration is required to be low, and the production efficiency is relatively low.

Patent CN1367200A describes a kind of silicic acid, sodium silicate, acrylic acid-maleic anhydride copolymer with surface active silyl group formed by polymerizing acrylic acid maleic acid (anhydride) polymer and sodium silicate in aqueous solution (or acrylic acid homopolymer) sodium salt complex. The product has strong adsorption capacity, good dispersibility, good exchange capacity for calcium and magnesium ions and anti-reprecipitation performance. Although the performance of the product is better, similar to the above two kinds of polymerization products, the water content of the polymerization product is relatively large, and the subsequent distillation treatment still needs to consume a lot of energy.

Compared with sodium polyacrylate, a commonly used detergent and dispersant, the presence of carboxylic acid chains in comb polymers ensures that the polymers can be better adsorbed on the surface of solid particles; the introduction of groups such as longer ethoxy chains in branched chains, The degree of branching of the polymer is improved, and after the polymer is adsorbed on the solid surface, the ethoxy chain enhances the steric hindrance, which can improve the dispersion stability of the product; and the introduction of some hydrophobic groups has many advantages: first, the hydrophobic group The introduction makes the product have a certain surface activity, the degree of branching of the product is improved, and the polymerization product is endowed with a certain dispersion performance; secondly, the introduction of an appropriate amount of hydrophobic group can play a certain role in regulating the water solubility of the product. , can increase the solid content of the product; in addition, adding this kind of hydrophobic comb polymer to the super-concentrated detergent, the hydrophobic group is inserted between the surfactants of the spherical lamellar liquid crystal, while the hydrophilic group is On the outside of the lamellar liquid crystal, the hydrophilic group not only has a penetrating effect, but also has a steric hindrance effect, making the detergent system more stable. By controlling the reaction conditions, regulating the molecular weight and monomer ratio of the comb polymerization, a suitable polymerization product can be obtained. It can be predicted that this kind of comb polymer can have a good dispersion effect when added to detergent.

Contents of the invention

The purpose of the present invention is to overcome the existing technical defects and provide a green, energy-saving, moderately water-soluble, high-solid-content comb-shaped polymer dispersant and a preparation method.

The synthetic route of the present invention is as follows:

Wherein, m is an integer ranging from 10 to 20, R ₁ , R ₃ , and R ₄ are H or methyl, R ₂ is a C ₄ -C ₁₂ alkyl group, and a, b, and c are integers greater than zero.

Described comb type macromolecule dispersant is prepared according to the following steps:

(1) Mix 1/3 volume of mixed monomers, emulsifiers, chain transfer agents, initiators, and distilled water, stir, and heat up to 65-80°C. After reacting for about 1 hour, start to add the remaining mixed monomers, 40min- After 60 minutes of dripping, continue to keep warm for 4-6 hours;

(2) Stop heating, cool to room temperature, remove the upper water layer to obtain a comb-shaped polymer dispersant.

As mentioned above, the mass composition of each material is: mixed monomer 10%-40%, emulsifier 0.4%-2%, initiator 1%-3%, chain transfer agent 2%-4%, distilled water 51%-85% , the polymerization temperature is 65-80°C, the reaction is easy to control, and implosion is not easy to occur.

_The mixed monomer is composed _of A1, A2 and A3, wherein A1 accounts for ₂₀ %-50 _% of the mass fraction _of the mixed monomer, A2 accounts for 20-50% _of the mass fraction of the mixed monomer, and A3 accounts for the mass fraction of the mixed monomer. The monomer mass fraction is 20%-40%.

The structure composed of A ₁ , A ₂ and A ₃ is as follows:

The emulsifier is an anionic surfactant and nonionic surfactant compound emulsifier, wherein the mass ratio of anionic surfactant and nonionic surfactant is 1:4-5:1, preferably 1:2-2 :1. One or more of alkyl sodium sulfate, alkylbenzene sodium sulfonate, and fatty acid methyl ester sulfonate (MES) in anionic surfactants, and nonionic surfactants are sugar-based amide-modified polysiloxane, One or more of acetylene glycol ethoxylate polyether co-modified siloxanes.

The initiator is one or more of persulfate and water-soluble azo initiators. The persulfate is sodium persulfate, ammonium persulfate, etc.; the water-soluble azo initiator is azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, etc.

The chain transfer agent is one or more of isopropanol, mercapto alcohol, bisulfite.

In the synthesis of the comb-shaped polymer dispersant of the present invention, the proportion of monomers, the amount of initiator and chain transfer agent can be selected according to actual needs.

According to the method provided by the invention, the comb-shaped polymer dispersant obtained by free radical polymerization has the advantages of not being prone to sudden aggregation, easy separation of products and high solid content.

The comb-shaped polymer dispersant provided by the invention has high dispersibility for solid particles. Using it as a detergent dispersant can suspend the crystal grains in water, reduce the deposition of crystals on the fiber surface, and improve the anti-hardening ability, so it has potential application value in the detergent industry.

Compared with existing synthetic methods, the present invention has the following advantages:

(1) The present invention uses water as a solvent, the synthesis method is simple and easy, and the process is greener;

(2) The polymer emulsion obtained by emulsion polymerization in the present invention has moderate water solubility, can be naturally separated from water, has high solid content, saves complicated and energy-consuming water removal processes, and is more energy-saving;

(3) The comb-shaped polymer dispersant obtained in the present invention has a large dispersion amount of solid particles and good dispersion stability.

Description of drawings

Fig. 1 is the infrared spectrogram of the synthetic product 1# of embodiment 1 of the present invention;

Fig. ₂ is four embodiments of the present invention, and the obtained synthetic product is to CaCO Dispersion particle size and distribution figure thereof;

Fig. 3 is a transmission electron micrograph of the dispersed CaCO ₃ of the synthesized product obtained in Example 1 of the present invention.

Fig. 4 is a transmission electron microscopic image of CaCO ₃ dispersed in the synthesized product obtained in Example 2 of the present invention.

Fig. 5 is a transmission electron microscopic image of CaCO ₃ dispersed in the synthesized product obtained in Example 3 of the present invention.

Fig. 6 is a transmission electron microscopic image of CaCO ₃ dispersed in the synthesized product obtained in Example 4 of the present invention.

detailed description

The following specific examples are given to describe the patent of the present invention, but the present invention is not limited to the following examples.

The method for testing the dispersion performance of the comb-type polymer dispersant obtained in the embodiments of the present invention is mainly by measuring the amount _of dispersion and its stability of CaCO3, and the measurement method is as follows:

Weigh 1g of the polymer salt product, dissolve it in a 100ml stoppered measuring cylinder, weigh 2g _of CaCO3 powder, shake it up and down vigorously 100 times, let it stand at room temperature for 30min, pipette 20mL of the dispersion into a conical flask at 50mL, add 65mL water, 10mL 1moL/L HCl solution, titrate with 0.5mol/L NaOH standard solution.

Dispersion amount = 100.09C(V ₀ -V ₁ )/(2m×20%)

In the formula, C—the standard solution concentration of NaOH;

m - the mass of the polymer sample;

V ₀ - volume of standard solution consumed for titration blank (mL);

V ₁ - the volume of the standard solution consumed for titrating the sample (mL).

The calculated unit is mg/g, and the larger the result, the greater the dispersion of the polymer to the particles.

CaCO ₃ dispersion particle size and distribution measurement: Use a particle size analyzer to test the particle size and distribution of the dispersed system after three days of stability.

Morphology of CaCO ₃ dispersed particle size distribution: The morphology of the dispersion system after three days of stability was observed by transmission electron microscope TEM.

Example 1

The monomers used are A ₁ : acrylic acid, A ₂ : isooctyl acrylate, A ₃ : polyethylene glycol methyl ether methacrylate with a degree of polymerization of 20, wherein A ₁ : A ₂ : A ₃ =3:1: 6. The amount of other substances, reaction conditions and preparation process are as follows:

12g of acrylic acid, 4g of isooctyl acrylate, 24g of polyethylene glycol methyl ether methacrylate with a degree of polymerization of 20, 2g of isopropanol, 1.6g of sodium azobisisobutylamidine hydrochloride, and 0.2g of dodecylsulfuric acid Sodium, 0.4g of glucosamide-modified aminoethylaminopropylpolysiloxane were mixed, and finally 100g of water was added, and stirred and emulsified without delamination. Add 1/3 volume of mixed monomer emulsion into a four-necked flask equipped with a stirrer, reflux tube, and thermometer, stir, and raise the temperature to 70°C. After reacting for 1 hour, start to add the remaining monomer emulsion dropwise, and the dripping is completed in about 53 minutes. Continue the insulation reaction for 4 hours, stop the reaction, and remove the water layer to obtain a comb-shaped polymer dispersant (1#) with a solid content of 50.94%.

Example 2

The monomers used are A ₁ : methacrylic acid, A ₂ : hexyl methacrylate, A ₃ : polyethylene glycol methyl ether acrylate with a degree of polymerization of 19, where A ₁ : A ₂ : A ₃ =3:4 : 3, other material consumption, reaction conditions and preparation process are as follows:

12g methacrylic acid, 16g hexyl methacrylate, 12g polyethylene glycol methyl ether acrylate with a polymerization degree of 19, 3.2g sodium bisulfite, 1.2g potassium persulfate, 1g sodium dodecylbenzenesulfonate , 1g of butynediol monoethoxy ether polyether modified siloxane, and finally make up 100g with water, stir and emulsify without delamination. Add 1/3 volume of mixed monomer emulsion into a four-necked flask equipped with a stirrer, reflux tube, and thermometer, stir, and raise the temperature to 80°C. After reacting for 1 hour, start to add the remaining monomer emulsion dropwise, and finish dropping in about 40 minutes. Continue the insulation reaction for 6 hours, stop the reaction, and remove the water layer to obtain a comb-shaped polymer dispersant (2#) with a solid content of 61.25%.

Example 3

The monomers used are A ₁ : acrylic acid, A ₂ : butyl methacrylate, A ₃ : polyethylene glycol methyl ether methacrylate with a degree of polymerization of 16, where A ₁ : A ₂ : A ₃ =3:3: 4. The amount of other substances, reaction conditions and preparation process are as follows:

9g of acrylic acid, 9g of butyl methacrylate, 12g of polyethylene glycol methyl ether methacrylate with a degree of polymerization of 16, 3.2g of 2-mercaptoethanol, 1.2g of ammonium persulfate solution, 0.5g of dodecylbenzenesulfonate Sodium diol dipropoxy ether polyether co-modified siloxane mixed with 1g of butynediol dipropoxy ether polyether, and finally make up 100g with water, stirred and emulsified without delamination. Add 1/3 volume of mixed monomer emulsion into a four-necked flask equipped with a stirrer, reflux tube, and thermometer, stir, and raise the temperature to 80°C. After 1 hour of reaction, start to add the remaining monomer emulsion dropwise, and the drop will be completed after about 1 hour. Continue the insulation reaction for 5 hours, stop the reaction, and remove the water layer to obtain a comb-shaped polymer dispersant (3#) with a solid content of 44.69%.

Example 4

The monomers used are A1: methacrylic acid, A2: hexyl methacrylate, A3: polyethylene glycol methyl ether acrylate with a degree of polymerization of 12, where A1: A2: A3 = 3:1:6, and the amount of other substances , reaction conditions and preparation process are as follows:

12g of methacrylic acid, 4g of hexyl methacrylate, 24g of polyethylene glycol methyl ether acrylate with a degree of polymerization of 12, 1.6g of isopropanol and mercapto alcohol, 1.2g of potassium persulfate, 0.5g of dodecane Sodium phenyl sulfonate, 1g of butynediol monoethoxy ether polyether modified siloxane, and finally make up 100g with water, stir and emulsify without delamination. Add 1/3 volume of mixed monomer emulsion into a four-necked flask equipped with a stirrer, reflux tube, and thermometer, stir, and raise the temperature to 75°C. After reacting for about 1 hour, start adding the remaining monomer emulsion dropwise, and finish dropping in about 50 minutes. , continue the insulation reaction for 6 hours, stop the reaction, and remove the water layer to obtain a comb-shaped polymer dispersant (4#) with a solid content of 57.25%.

Polymer product structure characterization and performance evaluation results provided by the present invention are as follows:

(1) Fig. 1 is the infrared spectrogram of gained product 1# in embodiment 1, and wherein 3419cm ^-1 is carboxylate absorption peak, and 2931cm ^-1 is _CH The absorption peak, 1710cm- ¹ is the characteristic absorption peak of C=O , there is no absorption peak at 1650cm ^-1 , indicating that the monomer has basically reacted completely.

(2) The dispersions measured by titration are 1633.52mg/g, 1397.07mg/g and 1382.25mg/g respectively, and 1189.26mg/g corresponds to the dispersed particle diameter of CaCO3, which are respectively ₁ #- The particle size distribution of 4# can be seen to be mainly concentrated in the vicinity of 1um, and the distribution is relatively narrow, indicating that the synthesized comb polymer has good dispersion effect and dispersion stability on solid particles of CaCO ₃ .

(3) From the TEM images in Figure 3-6, it can be seen that the particle size of CaCO ₃ is relatively small, mainly concentrated at 100 nanometers, and the distribution is uniform.

Claims (15)

1. a combed macromolecule dispersing agent, it is characterised in that structural formula is as follows:

Wherein, m is the integer of 10 to 20, R₁、R₃、R₄For H or methyl, R₂For C₄-C₁₂Alkyl, a, b, c are the integer more than zero.

The preparation method of a kind of combed macromolecule dispersing agent the most as claimed in claim 1, it is characterised in that comprise the steps:

(1) by the mix monomer of 1/3 volume, emulsifying agent, chain-transferring agent, initiator, distilled water mixes, and stirs, is warming up to 65-80 DEG C, starting after reacting about 1h to drip remaining mix monomer, 40-60min drips off, and continues insulation reaction 4-6 hour；

(2) stop heating, be cooled to room temperature, remove upper aqueous layer, obtain combed macromolecule dispersing agent.

The preparation method of a kind of combed macromolecule dispersing agent the most as claimed in claim 2, it is characterised in that each quality of material group Become: mix monomer 10%-40%, emulsifying agent 0.4%-2%, initiator 1%-3%, chain-transferring agent 2%-4%, distilled water 51%-85%.

The preparation method of a kind of combed macromolecule dispersing agent the most as claimed in claim 2, it is characterised in that described mix monomer By A₁、A₂And A₃Composition, wherein A₁Accounting for mix monomer mass fraction is 20%-50%, A₂Accounting for mix monomer mass fraction is 20- 50%, A₃Accounting for mix monomer mass fraction is 20%-40%.

The preparation method of a kind of combed macromolecule dispersing agent the most as claimed in claim 4, it is characterised in that described A₁Structure such as Under:

The preparation method of a kind of combed macromolecule dispersing agent the most as claimed in claim 4, it is characterised in that described A₂Structure such as Under:

The preparation method of a kind of combed macromolecule dispersing agent the most as claimed in claim 4, it is characterised in that described A₃Structure such as Under:

The preparation method of a kind of combed macromolecule dispersing agent the most as claimed in claim 2, it is characterised in that described emulsifying agent is The Compositional type emulsifying agent of anion surfactant and nonionic surfactant, wherein anion surfactant and nonionic Surfactant qualities is than for 1:4-5:1.

The preparation method of a kind of combed macromolecule dispersing agent the most as claimed in claim 8, it is characterised in that described anion table Face activating agent and nonionic surfactant ratio are 1:2-2:1.

The preparation method of a kind of combed macromolecule dispersing agent the most as claimed in claim 8, it is characterised in that anionic surface is lived Property agent is one or more in alkyl sodium sulfate, sodium alkyl benzene sulfonate, MES.

The preparation method of 11. a kind of combed macromolecule dispersing agents as claimed in claim 8, it is characterised in that non-ionic surface is lived Property agent be one or more in glycosyl amide modified polysiloxane, acetylenic glycols b-oxide polyethers altogether modified siloxane.

The preparation method of 12. a kind of combed macromolecule dispersing agents as claimed in claim 2, it is characterised in that described initiator is Persulfate, one or more in water-soluble azo initiator.

The preparation method of 13. a kind of combed macromolecule dispersing agents as claimed in claim 12, it is characterised in that described persulfuric acid Salt is sodium peroxydisulfate or Ammonium persulfate..

The preparation method of 14. a kind of combed macromolecule dispersing agents as claimed in claim 12, it is characterised in that described water solublity Azo initiator is azo-bis-isobutyrate hydrochloride or azo two isobutyl imidazoline hydrochloride.

The preparation method of 15. a kind of combed macromolecule dispersing agents as claimed in claim 2, it is characterised in that described chain-transferring agent For isopropanol, mercaptoalcohol, bisulfites one or more.