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

Interpenetrating network emulsion having high adhesive force to metal substrate material and synthetic method of interpenetrating network latex Download PDF

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Publication number
CN104592439A
CN104592439A CN201510010659.XA CN201510010659A CN104592439A CN 104592439 A CN104592439 A CN 104592439A CN 201510010659 A CN201510010659 A CN 201510010659A CN 104592439 A CN104592439 A CN 104592439A
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emulsion
monomer
interpenetrating
polymer
core
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CN104592439B (en
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俞成丙
陈赛赛
伍芳芳
胡季华
石小龙
王琪
董一然
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The invention discloses an interpenetrating network emulsion having high adhesive force to a metal substrate material and a synthetic method of the interpenetrating network emulsion. 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 the core shell structure is formed by virtue of polymerization between a nuclear layer monomer and a crosslinking monomer under the action of an initiator; and the shell of the interpenetrating network polymer with the core shell structure is formed by virtue of polymerization between a shell layer monomer and a phosphate functional monomer under the action of an initiator. The emulsion synthesized by the method disclosed by the invention has the following advantages: (1) the adhesive force to the metal substrate material is good; (2) the damping factor is high and can reach a maximum value of 1.3; and (3) the emulsion has a core shell structure of an interpenetrating network.

Description

A kind of interpenetrating(polymer)networks emulsion and synthetic method thereof metal base to high adhesive force
Technical field
The present invention relates to a kind of interpenetrating(polymer)networks emulsion and preparation method thereof, particularly a kind of interpenetrating(polymer)networks emulsion and synthetic method thereof metal base to high adhesive force.
Background technology
Interpenetrating(polymer)networks (IPN) polymkeric substance is the good macromolecular material of a class over-all properties that developed recently gets up.It is by the network of gained after cross-linked polymer A and each self-crosslinking of cross-linked polymer B continuously mutually intert, have special Space expanding, wherein at least one polymkeric substance is netted, other polymkeric substance can line style form exist.Due to cross one another between each polymer network infiltration, mechanical interlocking, play and force mutual tolerance and synergistic effect effect, for the performance improving polymkeric substance provides a kind of effective ways.Because thermodynamic (al) compatible these the two kinds effects that force that are incompatible and physical entanglement form micro phase separation structure, by suitably regulating the degree of microphase-separated, just there is a kind of damping material of good performance.
Interpenetrating network polymer emulsion (LIPN) be a kind of high damping properties damping material, can based on the theory of particle design, by design second-order transition temperature (Tg) value, meet the requirement of different practical application to damping temperature response.At present, investigators report the Application Areas of a lot of interpenetrating network polymer emulsion, but it is little at the report of marine vessel applications occasion, because the binder resin being applicable to prepare damping paint peculiar to vessel not only requires that specific range of temperatures interval has high damping factor and also will meet environmental requirement, in addition owing to being directly be coated on by damping paint on the deck of polishing in its practical application operating mode, therefore very strong sticking power and antirust ability is needed again.But have no the excellent emulsion that report possesses these performances simultaneously at present.Such as patent CN 100560626 discloses a kind of self-crosslinked interpenetrating net type polymkeric substance antirust emulsion and preparation method thereof, it solve the coating weatherability of existing antirust emulsion, water tolerance, salt fog resistance problem, but do not report it there is good damping capacity.And for example disclose the preparation method of a kind of super branched polyurethane/polyacrylic ester damping material in patent CN 102731731 B, first use the Waterborne Polyurethane Prepolymer of traditional method composite part end-blocking; Again by homemade containing superbrnaching end-hydroxy urethane, by with isocyanic ester radical reaction, be grafted on Waterborne Polyurethane Prepolymer, obtain hyperbranched aqueous polyurethane performed polymer; Then add triethylamine and part vinyl monomer carries out ionization, and under high velocity agitation, add water-dispersion and obtain polyurethane/vinyl monomer dispersion liquid; Finally above-mentioned dispersion liquid is warming up to 65 ~ 80 DEG C, start to drip residual ethylene base monomer, initiator and linking agent, continue insulation reaction 2 ~ 6 hours, cooling obtains super branched polyurethane/polyacrylate dispersion, material after curing of coating has more excellent damping capacity and resistance toheat, but it possesses excellent rustless property to have no report.
Summary of the invention
An object of the present invention is to provide a kind of interpenetrating(polymer)networks emulsion metal base to high adhesive force.
Two of object of the present invention is the synthetic method providing this interpenetrating(polymer)networks emulsion a kind of.
For achieving the above object, the present invention adopts following technical scheme:
A kind of 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.。
Above-mentioned reactive emulsifier is: containing allylic extraordinary ether alcohol sulfate or allyloxy propyl alkyl alcohol polyether-type nonionic emulsifying agent.
Above-mentioned 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.
Above-mentioned phosphoric acid ester function monomer is: at least one in polyoxyethylene glycol methacrylic acid phosphoric acid ester, alkyl acrylate phosphoric acid ester.
Above-mentioned initiator is: Potassium Persulphate, ammonium persulphate, Potassium Persulphate-bisulfite are received or ammonium persulfate-sodium bisulfite.
Prepare the above-mentioned synthetic method to the hesive interpenetrating(polymer)networks emulsion of metal base tool, 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.
The present invention has prepared interpenetrating(polymer)networks emulsion by introducing linking agent, and first functional phosphate ester monomer is introduced and have in the interpenetrating(polymer)networks emulsion of nucleocapsid structure, by adopt reactive emulsifier and ionic emulsifying agent composite, prepare and have that sticking power is good, damping factor is high, its maximum value up to 1.3 excellent property emulsion, this emulsion is highly suitable for the matrix resin as a kind of damping paint peculiar to vessel.
Embodiment
Embodiment 1: each raw material is constructed as follows by mass fraction:
Stratum nucleare:
Methyl methacrylate 13.84 parts
N-butyl acrylate 7.16 parts
Ethylene glycol dimethacrylate 0.21 part
Propylene glycol diacrylate 0.21 part
Ammonium persulphate 0.0945 part
12.877 parts, water
13 carbon polyoxyethylenated alcohol sodium sulfate salts 0.252 part
Containing allylic extraordinary ether alcohol sulfate 0.504 part
Shell:
Methyl methacrylate 6.72 parts
Butyl acrylate 14.28 parts
Polyoxyethylene glycol methacrylic acid phosphoric acid ester 0.42 part
Ammonium persulphate 0.0945 part
20.23 parts, water
End liquid:
22.50 parts, water
13 carbon polyoxyethylenated alcohol sodium sulfate salts 0.504 part
Sodium bicarbonate 0.06 part
The preparation process of the nucleocapsid structure interpenetrating(polymer)networks emulsion of embodiment 1 is as follows:
(1) preparation of core pre-emulsion
According to above-mentioned formula, core mix monomer, cross-linking monomer ethylene glycol dimethacrylate (EGDMA) are slowly joined in the container that emulsifying agent, water and initiator are housed, within 30 minutes, carry out pre-emulsification to prepare core pre-emulsion 800 revs/min of high-speed stirring.20% pre-emulsion is got as seed pre-emulsion from core pre-emulsion.
(2) preparation of seed emulsion
Being equipped with partial emulsifier and deionized water and in the reactor of protection of inert gas, adding 20% core pre-emulsion, be heated to 82 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 250 revs/min, under 82 DEG C of conditions, adopt semi-continuous process to be evenly added drop-wise in seed emulsion in 2 hours by core pre-emulsion, dropwise rear insulation and obtain core emulsion in 1 hour.
(4) preparation of shell emulsion
On the basis preparing core emulsion, shell monomers in above-mentioned formula, functional phosphate ester monomer PAM-100 and initiator solution are added drop-wise in core emulsion simultaneously equably, ensure that shell monomer dropwised at 2 hours, be warming up to 87 DEG C, then continue reaction and namely obtain nucleocapsid structure interpenetrating(polymer)networks emulsion in 2 hours.
(2) last handling process
In reactor, add the aqueous solution of rear elimination initiator, be incubated 1 hour, adjust ph to 7 ~ 8, be down to room temperature, filter discharging, namely obtain inierpeneirating network structure emulsion, the monomer wherein preparing nuclear emulsion particle accounts for 50% of total mass, and secondary outer monomer accounts for 50% of monomer total mass.
Detect sticking power carry out according to national standard " cross cut test of paint and varnish paint film " GB/T 9286-1998 and adopt its damping capacity of dynamic thermomechanometry, its result is: the sticking power of latex film reaches 2 grades, damping peak value can reach 1.2, and the effective damping temperature range (tan σ >0.3) between-40 ~ 80 DEG C is about 60 DEG C.
Embodiment 2: each raw material is constructed as follows by mass fraction:
Stratum nucleare:
Methyl methacrylate 13.84 parts
N-butyl acrylate 7.16 parts
Ethylene glycol dimethacrylate 0.21 part
Ammonium persulphate 0.0945 part
12.877 parts, water
13 carbon polyoxyethylenated alcohol sodium sulfate salts 0.252 part
Containing allylic extraordinary ether alcohol sulfate 0.504 part
Shell:
Methyl methacrylate 6.72 parts
Butyl acrylate 14.28 parts
Polyoxyethylene glycol methacrylic acid phosphoric acid ester 0.42 part
Alkyl acrylate phosphoesterase 30 .42 part
Ammonium persulphate 0.0945 part
20 parts, water
End liquid:
22.26 parts, water
13 carbon polyoxyethylenated alcohol sodium sulfate salts 0.504 part
Sodium bicarbonate 0.1 part
The 2-in-1 one-tenth step of embodiment is with embodiment 1.
Detect sticking power carry out according to national standard " cross cut test of paint and varnish paint film " GB/T 9286-1998 and adopt its damping capacity of dynamic thermomechanometry, its result is: the sticking power of latex film reaches 1 grade, damping peak value can reach 1.3, and the effective damping temperature range (tan σ >0.3) between-40 ~ 80 DEG C is about 70 DEG C.
Embodiment 3: each raw material is constructed as follows by mass fraction:
Stratum nucleare:
Methyl methacrylate 13.84 parts
N-butyl acrylate 7.16 parts
Ethylene glycol dimethacrylate 0.63 part
Ammonium persulphate 0.0945 part
12.657 parts, water
13 carbon polyoxyethylenated alcohol sodium sulfate salts 0.504 part
Allyloxy propyl alkyl alcohol polyether-type nonionic emulsifying agent 0.252 part
Shell:
Methyl methacrylate 6.72 parts
Butyl acrylate 14.28 parts
Polyoxyethylene glycol methacrylic acid phosphoric acid ester 0.42 part
Alkyl acrylate phosphoesterase 30 .63 part
Ammonium persulphate 0.0945 part
20 parts, water
End liquid:
22 parts, water
13 carbon polyoxyethylenated alcohol sodium sulfate salts 0.504 part
Sodium bicarbonate 0.2 part
Embodiment 3 synthesis step is with embodiment 1.
Detect sticking power carry out according to national standard " cross cut test of paint and varnish paint film " GB/T 9286-1998 and adopt its damping capacity of dynamic thermomechanometry, its result is: the sticking power of latex film reaches 1 grade, damping peak value can reach 1.19, and the effective damping temperature range (tan σ >0.3) between-40 ~ 80 DEG C is about 66 DEG C.
Embodiment 4: each raw material is constructed as follows by mass fraction:
Stratum nucleare:
Methyl methacrylate 10.5 parts
N-butyl acrylate 3.57 parts
Ethyl propenoate 6.93 parts
Ethylene glycol dimethacrylate 0.9 part
Potassium Persulphate 0.0945 part
12.25 parts, water
Branched-chain alkyl polyoxyethylenated alcohol phosphate monoester 0.504 part
Allyloxy propyl alkyl alcohol polyether-type nonionic emulsifying agent 0.252 part
Shell:
Methyl methacrylate 8.61 parts
Butyl acrylate 11.55 parts
Ethyl propenoate 0.84 part
Polyoxyethylene glycol methacrylic acid phosphoric acid ester 0.42 part
Potassium Persulphate 0.0945 part
20.48 parts, water
End liquid:
22.49 parts, water
Branched-chain alkyl polyoxyethylenated alcohol phosphate monoester 0.504 part
Sodium bicarbonate 0.15 part
Embodiment 4 synthesis step is with embodiment 1.
Detect sticking power carry out according to national standard " cross cut test of paint and varnish paint film " GB/T 9286-1998 and adopt its damping capacity of dynamic thermomechanometry, its result is: the sticking power of latex film reaches 1 grade, damping peak value can reach 0.85, and the effective damping temperature range (tan σ >0.3) between-40 ~ 80 DEG C is about 50 DEG C.
Embodiment 5: each raw material is constructed as follows by mass fraction:
Stratum nucleare:
Methyl methacrylate 10.5 parts
N-butyl acrylate 3.57 parts
Ethyl propenoate 6.93 parts
Ethylene glycol dimethacrylate 0.3 part
Potassium Persulphate 0.0945 part
12.85 parts, water
Branched-chain alkyl polyoxyethylenated alcohol phosphate monoester 0.504 part
Allyloxy propyl alkyl alcohol polyether-type nonionic emulsifying agent 0.252 part
Shell:
Methyl methacrylate 8.61 parts
Butyl acrylate 11.55 parts
Ethyl propenoate 0.84 part
Polyoxyethylene glycol methacrylic acid phosphoric acid ester 0.42 part
Alkyl acrylate phosphoesterase 30 .42 part
Potassium Persulphate 0.0945 part
20.48 parts, water
End liquid:
22.49 parts, water
Branched-chain alkyl polyoxyethylenated alcohol phosphate monoester 0.504 part
Sodium bicarbonate 0.2 part
Embodiment 4 synthesis step is with embodiment 1.
Detect sticking power carry out according to national standard " cross cut test of paint and varnish paint film " GB/T 9286-1998 and adopt its damping capacity of dynamic thermomechanometry, its result is: the sticking power of latex film reaches 1 grade, damping peak value can reach 1.24, and the effective damping temperature range (tan σ >0.3) between-40 ~ 80 DEG C is about 63 DEG 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.
CN201510010659.XA 2015-01-09 2015-01-09 A kind of interpenetrating networks emulsion and its synthetic method to metal base with high adhesion force Expired - Fee Related CN104592439B (en)

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CN108203488A (en) * 2016-12-20 2018-06-26 中国制浆造纸研究院有限公司 Fibre seal material acrylic emulsion and its synthetic method
CN108250877A (en) * 2017-12-19 2018-07-06 吉力水性新材料科技(珠海)有限公司 A kind of phosphate modified acrylic acid aqueous industrial coating

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CN108203488A (en) * 2016-12-20 2018-06-26 中国制浆造纸研究院有限公司 Fibre seal material acrylic emulsion and its synthetic method
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