CN104592439A - Interpenetrating network emulsion having high adhesive force to metal substrate material and synthetic method of interpenetrating network latex - Google Patents

Abstract

The invention discloses an interpenetrating network emulsion with high adhesion to metal substrates and a synthesis method thereof. The interpenetrating network emulsion is an interpenetrating network polymer with a core-shell structure and has a solid content of 30-45%. The core of the interpenetrating network polymer with a core-shell structure is formed by polymerization of the core layer monomer and the crosslinking monomer under the action of an initiator; the shell of the interpenetrating network polymer with a core-shell structure is a shell Layer monomers and phosphate functional monomers are polymerized under the action of an initiator. The emulsion synthesized by the method of the invention has the following advantages: (1) good adhesion to metal substrates; (2) high damping factor, the maximum value of which is as high as 1.3; (3) the emulsion has a core-shell structure of an interpenetrating network.

Description

A kind of interpenetrating network emulsion with high adhesion to metal substrate and its synthesis method

technical field

The invention relates to an interpenetrating network emulsion and a preparation method thereof, in particular to an interpenetrating network emulsion with high adhesion to metal substrates and a synthesis method thereof.

Background technique

Interpenetrating network (IPN) polymers are a class of polymer materials with good comprehensive properties developed in recent years. It is formed by cross-linking the cross-linked polymer A and cross-linked polymer B. The network obtained by cross-linking each other is continuously interspersed with each other, and has a special spatial topology. At least one polymer is network-like, and the other polymers are Can exist in linear form. Due to the cross-penetration and mechanical entanglement between the polymer networks, it plays the role of forced mutual compatibility and synergistic effect, which provides an effective method for improving the performance of polymers. Due to the two effects of thermodynamic incompatibility and forced compatibility of physical entanglement, a microphase separation structure is formed. By properly adjusting the degree of microphase separation, there is a damping material with good performance.

Interpenetrating network polymer emulsion (LIPN) is a kind of damping material with high damping performance. Based on the concept of particle design, the glass transition temperature (Tg) value can be designed to meet the requirements of different practical applications on the damping temperature response. Require. At present, researchers have reported many application fields of interpenetrating network polymer emulsions, but there are few reports on marine applications, because the base resin suitable for preparing marine damping coatings not only requires high damping in a specific temperature range The factor must also meet the requirements of environmental protection. In addition, because the damping paint is directly applied to the polished deck in its actual application conditions, it needs strong adhesion and anti-rust ability. However, there is no report on an excellent emulsion possessing these properties at the same time. For example, patent CN 100560626 discloses a self-crosslinking interpenetrating network polymer antirust emulsion and its preparation method, which solves the problems of weather resistance, water resistance and salt spray resistance of the existing antirust emulsion, but does not It has not been reported to have good damping properties. Another example is the patent CN 102731731 B, which discloses a preparation method of hyperbranched polyurethane/polyacrylate damping material. First, the partially blocked water-based polyurethane prepolymer is synthesized by traditional methods; React with isocyanate groups, graft to water-based polyurethane prepolymer to obtain hyperbranched water-based polyurethane prepolymer; then add triethylamine and some vinyl monomers for ionization, and add water to disperse under high-speed stirring to obtain polyurethane/ Vinyl monomer dispersion; finally, raise the temperature of the above dispersion to 65~80°C, start to add the remaining vinyl monomer, initiator and crosslinking agent dropwise, continue the heat preservation reaction for 2~6 hours, and cool down to obtain hyperbranched polyurethane/polymer Acrylate emulsion, the material after the coating film is cured has relatively good damping performance and heat resistance performance, but it has not been reported that it has excellent antirust performance.

Contents of the invention

One of the objects of the present invention is to provide an interpenetrating network emulsion with high adhesion to metal substrates.

The second object of the present invention is to provide a method for synthesizing the interpenetrating network emulsion.

To achieve the above object, the present invention adopts the following technical solutions:

An interpenetrating network emulsion with adhesion to a metal substrate is characterized in that the emulsion is formed by emulsification of an interpenetrating network polymer with a core-shell structure, and its solid content is 30 to 45%; The core of the interpenetrating network polymer emulsion with a shell structure is formed by polymerizing the core layer monomer and the cross-linking monomer under the action of an initiator. The preparation process uses a new type of emulsifier. The core layer monomer and cross-linking monomer The mass ratio to the initiator is: 100:0.1~5:0.1~1.0, and the core layer monomer is composed of a hard monomer and a soft monomer in a mass ratio of 50~70:30~50; The shell of the interpenetrating network polymer of the core-shell structure is formed by polymerization of the shell monomer and the phosphate functional monomer under the action of the initiator, and the mass ratio of the shell monomer, the phosphate functional monomer and the initiator is 100:1~8:0.1~1.0, the shell monomer is composed of hard monomer and soft monomer in a mass ratio of 20~40:60~80; the hard monomer is: methacrylic acid Methyl ester, styrene, acrylonitrile or vinyl acetate, described soft monomer is n-butyl acrylate, ethyl acrylate, isooctyl acrylate; The mass ratio of described shell monomer and core layer monomer is 1:1~2; the cross-linking agent is at least one of ethylene glycol dimethacrylate, dipropylene glycol diacrylate, polyethylene glycol dimethacrylate and divinylbenzene; the The emulsifier used in the emulsification is a reactive emulsifier and an ionic emulsifier compounded at a mass ratio of 0.1 to 1:1, and its dosage is 1 to 8% of the mass of the core layer monomer. .

The above-mentioned reactive emulsifier is: allyl-containing special alcohol ether sulfate or allyloxypropyl alkyl alcohol polyether nonionic emulsifier.

The above-mentioned ionic emulsifiers are: tridecyl alcohol polyoxyethylene ether sulfate sodium salt, branched chain alkyl alcohol polyoxyethylene ether phosphate monoester or N-(1,2-dicarboxyethyl)-N-octadecyl Alkyl succinic acid tetrasodium salt.

The above-mentioned phosphate ester functional monomer is at least one of polyethylene glycol methacrylate phosphate and alkyl acrylate phosphate.

The above initiators are: potassium persulfate, ammonium persulfate, potassium persulfate-sodium bisulfite or ammonium persulfate-sodium bisulfite.

A synthetic method for preparing the above-mentioned interpenetrating network emulsion with adhesion to metal substrates, characterized in that the specific steps of the method are:

(1) Preparation of nuclear pre-emulsion: Slowly add the core layer monomer and cross-linking monomer to the emulsifier, water and initiator, and stir at high speed for 10-30 minutes for pre-emulsion to obtain the nuclear pre-emulsion; the emulsifier The dosage is 50~70% of the total emulsifier dosage;

(2) Preparation of seed emulsion: under the protection of an inert atmosphere, add 5-20% of the nuclear pre-emulsion obtained in step (1) to the remaining emulsifier and deionized water, heat to 60-85°C to initiate polymerization, and wait for the blue light to appear After half an hour of heat preservation, the seed emulsion was prepared;

(3) Preparation of nuclear emulsion: at a stirring speed of 200-350 rpm, at 60-85°C, evenly add the remaining nuclear pre-emulsion to the seed emulsion obtained in step (2) within 1-2 hours , after the dropwise addition, keep warm for 1 to 2 hours to obtain the nuclear emulsion;

(4) Evenly add the shell monomer, phosphate functional monomer and initiator water to the core emulsion obtained in step (3), ensuring that the shell monomer is added dropwise within 1-2 hours, and then keep warm for 1-2 hours. 2 hours;

(5) Add formaldehyde sodium bisulfite-tert-butyl hydroperoxide to the emulsion obtained in step (4) to eliminate the initiator, keep it warm for 0.5-1 hour, adjust the pH value to 7-8, cool down to room temperature, and filter out material, that is, an interpenetrating network emulsion with adhesion to the metal substrate is obtained.

The present invention prepares the interpenetrating network emulsion by introducing a crosslinking agent, and for the first time introduces the functional phosphate ester monomer into the interpenetrating network emulsion with a core-shell structure, by using a reactive emulsifier and an ionic emulsifier to compound , the excellent performance emulsion with good adhesion, high damping factor, and its maximum value as high as 1.3 is prepared, and the emulsion is very suitable as a matrix resin for marine damping paint.

Detailed ways

Embodiment 1: each raw material constitutes as follows by mass parts:

Nuclear layer:

Methyl methacrylate 13.84 parts

n-butyl acrylate 7.16 parts

Ethylene glycol dimethacrylate 0.21 parts

Dipropylene glycol diacrylate 0.21 parts

Ammonium persulfate 0.0945 parts

Water 12.877 parts

Tridecyl alcohol polyoxyethylene ether sulfate sodium salt 0.252 parts

Allyl-containing special alcohol ether sulfate 0.504 parts

Shell:

Methyl methacrylate 6.72 parts

Butyl acrylate 14.28 parts

Polyethylene glycol phosphate methacrylate 0.42 parts

Ammonium persulfate 0.0945 parts

Water 20.23 parts

Bottom fluid:

Water 22.50 parts

Tridecyl alcohol polyoxyethylene ether sulfate sodium salt 0.504 parts

Sodium bicarbonate 0.06 parts

The preparation steps of the core-shell interpenetrating network emulsion of Example 1 are as follows:

(1) Preparation of nuclear pre-emulsion

According to the above formula, slowly add the core mixed monomer and cross-linking monomer ethylene glycol dimethacrylate (EGDMA) into the container with emulsifier, water and initiator, and stir at 800 rpm for 30 minutes Pre-emulsification was performed to prepare a nuclear pre-emulsion. Take 20% pre-emulsion from the nuclear pre-emulsion as the seed pre-emulsion.

(2) Preparation of seed emulsion

Add 20% nuclear pre-emulsion to a reaction kettle with part of emulsifier and deionized water and inert gas protection, heat to 82°C to initiate polymerization, and keep warm for half an hour after the blue light appears to prepare the seed emulsion.

(3) Preparation of nuclear emulsion

At a stirring speed of 250 rpm and at 82°C, the nuclear pre-emulsion was evenly added dropwise to the seed emulsion within 2 hours by using a semi-continuous method.

(4) Preparation of shell emulsion

On the basis of preparing the core emulsion, the shell monomer, functional phosphate monomer PAM-100 and initiator aqueous solution in the above formula are uniformly added dropwise to the core emulsion at the same time to ensure that the shell monomer drops within 2 hours. After the addition, the temperature was raised to 87° C., and the reaction was continued for 2 hours to obtain the core-shell interpenetrating network emulsion.

(2) Post-processing process

Add the aqueous solution to eliminate the initiator in the reaction kettle, keep it warm for 1 hour, adjust the pH value to 7~8, drop to room temperature, filter and discharge the material, and then obtain the interpenetrating network structure emulsion, wherein the monomers for preparing nuclear latex particles account for the total 50% of the mass, and the sub-outer monomer accounts for 50% of the total mass of the monomer.

The detection of adhesion is carried out according to the national standard "Cross-cut test of paint and varnish paint film" GB/T 9286-1998, and its damping performance is analyzed by dynamic thermomechanical. The result is: the adhesion of latex film reaches level 2, and the damping The peak value can reach 1.2, and the effective damping temperature range (tanσ>0.3) between -40 and 80°C is about 60°C.

Embodiment 2: each raw material constitutes as follows by mass parts:

Nuclear layer:

Methyl methacrylate 13.84 parts

n-butyl acrylate 7.16 parts

Ethylene glycol dimethacrylate 0.21 parts

Ammonium persulfate 0.0945 parts

Water 12.877 parts

Tridecyl alcohol polyoxyethylene ether sulfate sodium salt 0.252 parts

Allyl-containing special alcohol ether sulfate 0.504 parts

Shell:

Methyl methacrylate 6.72 parts

Butyl acrylate 14.28 parts

Polyethylene glycol phosphate methacrylate 0.42 parts

Alkyl acrylate phosphate 0.42 parts

Ammonium persulfate 0.0945 parts

Water 20 parts

Bottom fluid:

Water 22.26 parts

Tridecyl alcohol polyoxyethylene ether sulfate sodium salt 0.504 parts

Sodium bicarbonate 0.1 parts

Example 2 Synthesis steps are the same as Example 1.

The detection of adhesion is carried out according to the national standard "Cross-cut test of paint and varnish paint film" GB/T 9286-1998, and its damping performance is analyzed by dynamic thermomechanical. The result is: the adhesion of latex film reaches level 1, and the damping The peak value can reach 1.3, and the effective damping temperature range (tanσ>0.3) between -40 and 80°C is about 70°C.

Embodiment 3: each raw material constitutes as follows by mass parts:

Nuclear layer:

Methyl methacrylate 13.84 parts

n-butyl acrylate 7.16 parts

Ethylene glycol dimethacrylate 0.63 parts

Ammonium persulfate 0.0945 parts

Water 12.657 parts

Tridecyl alcohol polyoxyethylene ether sulfate sodium salt 0.504 parts

Allyloxypropyl alkyl alcohol polyether nonionic emulsifier 0.252 parts

Shell:

Methyl methacrylate 6.72 parts

Butyl acrylate 14.28 parts

Polyethylene glycol phosphate methacrylate 0.42 parts

Alkyl acrylate phosphate 0.63 parts

Ammonium persulfate 0.0945 parts

Water 20 parts

Bottom fluid:

Water 22 parts

Tridecyl alcohol polyoxyethylene ether sulfate sodium salt 0.504 parts

Sodium bicarbonate 0.2 parts

Embodiment 3 synthesis steps are the same as embodiment 1.

The detection of adhesion is carried out according to the national standard "Cross-cut test of paint and varnish paint film" GB/T 9286-1998, and its damping performance is analyzed by dynamic thermomechanical. The result is: the adhesion of latex film reaches level 1, and the damping The peak value can reach 1.19, and the effective damping temperature range (tanσ>0.3) between -40 and 80°C is about 66°C.

Embodiment 4: each raw material constitutes as follows by mass parts:

Nuclear layer:

Methyl methacrylate 10.5 parts

n-butyl acrylate 3.57 parts

Ethyl acrylate 6.93 parts

Ethylene glycol dimethacrylate 0.9 parts

Potassium persulfate 0.0945 parts

Water 12.25 parts

Branched-chain alkyl alcohol polyoxyethylene ether phosphate monoester 0.504 parts

Allyloxypropyl alkyl alcohol polyether nonionic emulsifier 0.252 parts

Shell:

Methyl methacrylate 8.61 parts

Butyl acrylate 11.55 parts

Ethyl acrylate 0.84 parts

Polyethylene glycol phosphate methacrylate 0.42 parts

Potassium persulfate 0.0945 parts

Water 20.48 parts

Bottom fluid:

Water 22.49 parts

Branched-chain alkyl alcohol polyoxyethylene ether phosphate monoester 0.504 parts

Sodium bicarbonate 0.15 parts

The synthetic steps of embodiment 4 are the same as that of embodiment 1.

The detection of adhesion is carried out according to the national standard "Cross-cut test of paint and varnish paint film" GB/T 9286-1998, and its damping performance is analyzed by dynamic thermomechanical. The result is: the adhesion of latex film reaches level 1, and the damping The peak value can reach 0.85, and the effective damping temperature range (tanσ>0.3) between -40 and 80°C is about 50°C.

Embodiment 5: each raw material constitutes as follows by mass parts:

Nuclear layer:

Methyl methacrylate 10.5 parts

n-butyl acrylate 3.57 parts

Ethyl acrylate 6.93 parts

Ethylene glycol dimethacrylate 0.3 parts

Potassium persulfate 0.0945 parts

Water 12.85 parts

Branched-chain alkyl alcohol polyoxyethylene ether phosphate monoester 0.504 parts

Allyloxypropyl alkyl alcohol polyether nonionic emulsifier 0.252 parts

Shell:

Methyl methacrylate 8.61 parts

Butyl acrylate 11.55 parts

Ethyl acrylate 0.84 parts

Polyethylene glycol phosphate methacrylate 0.42 parts

Alkyl acrylate phosphate 0.42 parts

Potassium persulfate 0.0945 parts

Water 20.48 parts

Bottom fluid:

Water 22.49 parts

Branched-chain alkyl alcohol polyoxyethylene ether phosphate monoester 0.504 parts

Sodium bicarbonate 0.2 parts

The synthetic steps of embodiment 4 are the same as that of embodiment 1.

The detection of adhesion is carried out according to the national standard "Cross-cut test of paint and varnish paint film" GB/T 9286-1998, and its damping performance is analyzed by dynamic thermomechanical. The result is: the adhesion of latex film reaches level 1, and the damping The peak value can reach 1.24, and the effective damping temperature range (tanσ>0.3) between -40 and 80°C is about 63°C.

Claims (6)

1., to the hesive interpenetrating(polymer)networks emulsion of metal base tool, it is characterized in that this emulsion is formed through emulsification by the interpenetrating net polymer with nucleocapsid structure, its solid content is 30 ~ 45%; The described core with the interpenetrating network polymer emulsion of nucleocapsid structure is that nuclear layer monomer and cross-linking monomer are polymerized under initiator effect, preparation process have employed New-type emulsifier, the mass ratio of described nuclear layer monomer, cross-linking monomer and initiator is: 100:0.1 ~ 5:0.1 ~ 1.0, and described nuclear layer monomer is made up of by the mass ratio of 50 ~ 70:30 ~ 50 hard monomer and soft monomer; The described shell with the interpenetrating net polymer of nucleocapsid structure is shell monomers, phosphoric acid ester function monomer is polymerized under initiator effect, the mass ratio of described shell monomers, phosphoric acid ester function monomer and initiator is 100:1 ~ 8:0.1 ~ 1.0, and described shell monomers is made up of by the mass ratio of 20 ~ 40:60 ~ 80 hard monomer and soft monomer; Described hard monomer is: methyl methacrylate, vinylbenzene, vinyl cyanide or vinyl acetate, and described soft monomer is n-butyl acrylate, ethyl propenoate, Isooctyl acrylate monomer; Described shell monomers and the mass ratio of nuclear layer monomer are 1:1 ~ 2; Described linking agent is at least one in ethylene glycol dimethacrylate, propylene glycol diacrylate, polyethylene glycol dimethacrylate and Vinylstyrene; Described emulsification emulsifying agent used is that reactive emulsifier and ionic emulsifying agent form by the mass ratio of 0.1 ~ 1:1 is composite, and its consumption is 1 ~ 8% of nuclear layer monomer quality.

2. according to claim 1 to the hesive interpenetrating(polymer)networks emulsion of metal base tool, it is characterized in that described reactive emulsifier is: containing allylic extraordinary ether alcohol sulfate or allyloxy propyl alkyl alcohol polyether-type nonionic emulsifying agent.

3. according to claim 1 to the hesive interpenetrating(polymer)networks emulsion of metal base tool, it is characterized in that described ionic emulsifying agent is: 13 carbon polyoxyethylenated alcohol sodium sulfate salts, branched-chain alkyl polyoxyethylenated alcohol phosphate monoester or N-(1,2-bis-propyloic)-N-octadecylsuccinic acid sulfonic acid tetra-na salt.

4. according to claim 1 to the hesive interpenetrating(polymer)networks emulsion of metal base tool, it is characterized in that described phosphoric acid ester function monomer is: at least one in polyoxyethylene glycol methacrylic acid phosphoric acid ester, alkyl acrylate phosphoric acid ester.

5. according to claim 1 to the hesive interpenetrating(polymer)networks emulsion of metal base tool, it is characterized in that described initiator is: Potassium Persulphate, ammonium persulphate, Potassium Persulphate-sodium bisulfite or ammonium persulfate-sodium bisulfite.

6. prepare the synthetic method to the hesive interpenetrating(polymer)networks emulsion of metal base tool according to any one of claim 1-5, it is characterized in that the concrete steps of the method are:

(1) preparation of core pre-emulsion: nuclear layer monomer, cross-linking monomer are slowly joined in emulsifying agent, water and initiator, high-speed stirring carries out pre-emulsification in 10 ~ 30 minutes, obtains core pre-emulsion; Wherein the consumption of emulsifying agent is 50 ~ 70% of whole emulsifier;

(2) preparation of seed emulsion: under inert atmosphere protection, the core pre-emulsion 5 ~ 20% of step (1) gained is added in residual emulsifier and deionized water, be heated to 60 ~ 85 DEG C of initiated polymerizations, after blue light occurs, be incubated half an hour i.e. obtained seed emulsion;

(3) preparation of core emulsion: the stirring velocity of 200 ~ 350 revs/min, under 60 ~ 85 DEG C of conditions, remaining core pre-emulsion was evenly added drop-wise in step (2) gained seed emulsion in 1 ~ 2 hour, dropwises rear insulation and obtain core emulsion in 1 ~ 2 hour;

(4) shell monomers, phosphoric acid ester function monomer and initiator water are added drop-wise to equably in step (3) gained core emulsion, ensure that shell monomers dropwised at 1 ~ 2 hour, be then incubated 1 ~ 2 hour;

(5) in step (4) gained emulsion, formaldehyde sodium bisulfite-tertbutyl peroxide is added to eliminate initiator, be incubated 0.5 ~ 1 hour, adjust ph to 7 ~ 8, are down to room temperature, filter discharging, namely obtain the hesive interpenetrating(polymer)networks emulsion of metal base tool.