CN104592439B - A kind of interpenetrating networks emulsion and its synthetic method to metal base with high adhesion force - Google Patents
A kind of interpenetrating networks emulsion and its synthetic method to metal base with high adhesion force Download PDFInfo
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- CN104592439B CN104592439B CN201510010659.XA CN201510010659A CN104592439B CN 104592439 B CN104592439 B CN 104592439B CN 201510010659 A CN201510010659 A CN 201510010659A CN 104592439 B CN104592439 B CN 104592439B
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Abstract
The invention discloses a kind of interpenetrating networks emulsion and its synthetic method to metal base with high adhesion force, the interpenetrating networks emulsion is the interpenetrating net polymer with nucleocapsid structure, and solid content is 30 ~ 45%；The core of the described interpenetrating net polymer with nucleocapsid structure is that nuclear layer monomer is polymerized under initiator effect with cross-linking monomer；The shell of the described interpenetrating net polymer with nucleocapsid structure is that shell monomers and phosphate ester function monomer are polymerized under initiator effect.The emulsion synthesized using the inventive method, with advantages below：(1) it is good to metal base adhesive force；(2) damping factor is high, and its maximum is up to 1.3；(3) emulsion has the nucleocapsid structure of interpenetrating networks.
Description
Technical field
The present invention relates to a kind of interpenetrating networks emulsion and preparation method thereof, particularly a kind of to have high attachment to metal base
The interpenetrating networks emulsion of power and its synthetic method.
Background technology
Interpenetrating networks (IPN) polymer is the good macromolecular material of a class combination property that developed recently gets up.It is
Continuously mutually interted by the network of gained after cross linked polymer A and each self-crosslinkings of cross linked polymer B, with special
Space expanding, wherein at least one polymer is netted, and other polymer can be in the form of line style.Due to each
Cross one another between polymer network infiltration, mechanical interlocking, plays and forces mutual tolerance and cooperative effect effect, is to improve polymer
Performance provides a kind of effective ways.As thermodynamic (al) incompatible and physical entanglement compatible both effects that force form micro-
Phase separation structure, by the appropriate degree for adjusting microphase-separated, just has a kind of damping material of good performance.
Interpenetrating network polymer emulsion（LIPN）It is a kind of damping material of high damping properties, particle design can be based on
Theory, by designing glass transition temperature (Tg) value, meet different practical applications to damping temperature-responsive
Require.At present, researchers report the application of many interpenetrating network polymer emulsions, but which is in marine vessel applications occasion
Report is little, because the binder resin suitable for preparing damping paint peculiar to vessel does not require nothing more than specific range of temperatures interval with high
Damping factor will also meet environmental requirement, additionally due to being that damping paint is directly coated on Jing polishings in its practical application operating mode
Deck on, therefore and need very strong adhesive force and antirust ability.But have no that report is provided simultaneously with these performances at present
Excellent emulsion.Such as patent CN 100560626 discloses a kind of self-crosslinked interpenetrating net type polymer antirust emulsion and its system
Preparation Method, it solves the problems, such as the coating weatherability of existing antirust emulsion, resistance to water, salt fog resistance, but does not report its tool
There is good damping capacity.A kind of super branched polyurethane/polyacrylate resistance is disclosed in 102731731 B of patent CN and for example
The preparation method of damping material, the Waterborne Polyurethane Prepolymer for first being blocked with traditional method composite part；Again by the homemade hydroxyl containing end
Base super branched polyurethane, by being reacted with NCO, is grafted on Waterborne Polyurethane Prepolymer, obtains hyperbranched aqueous poly-
Urethane performed polymer；Being subsequently adding triethylamine and part vinyl monomer carries out ionizing, and under high velocity agitation, adds water and disperse
To polyurethane/vinyl monomer dispersion liquid；Above-mentioned dispersion liquid is warming up to into 65 ~ 80 DEG C finally, starts Deca residual ethylene base list
Body, initiator and cross-linking agent, continue insulation reaction 2 ~ 6 hours, and cooling obtains super branched polyurethane/polyacrylate dispersion, applies
Material after film solidification has more excellent damping capacity and heat resistance, but which possesses excellent rust-preventing characteristic to have no report
Energy.
The content of the invention
An object of the present invention is to provide a kind of interpenetrating networks emulsion to metal base with high adhesion force.
The second object of the present invention is to provide a kind of synthetic method of the interpenetrating networks emulsion.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
It is a kind of to have cohesive interpenetrating networks emulsion to metal base, it is characterised in that the emulsion is by tying with nucleocapsid
The interpenetrating net polymer Jing emulsifyings of structure are formed, and its solid content is 30 ~ 45%；The described interpenetrating networks with nucleocapsid structure gather
The core of compound emulsion is that nuclear layer monomer is polymerized under initiator effect with cross-linking monomer, and preparation process employs novel emulsion
Agent, the mass ratio of described nuclear layer monomer, cross-linking monomer and initiator is：100：0.1~5：0.1 ~ 1.0, described nuclear layer monomer
50 ~ 70 are pressed by hard monomer and soft monomer：30 ~ 50 mass ratio composition；The described interpenetrating net polymer with nucleocapsid structure
Shell be that shell monomers, phosphate ester function monomer are polymerized under initiator effect, described shell monomers, phosphoric acid ester function
Monomer is 100 with the mass ratio of initiator：1~8：0.1 ~ 1.0, described shell monomers press 20 ~ 40 by hard monomer and soft monomer：
60 ~ 80 mass ratio composition；Described hard monomer is：Methyl methacrylate, styrene, acrylonitrile or vinylacetate, institute
The soft monomer stated is n-butyl acrylate, ethyl acrylate, Isooctyl acrylate monomer；The matter of described shell monomers and nuclear layer monomer
Amount is than being 1:1~2；Described cross-linking agent is ethylene glycol dimethacrylate, propylene glycol diacrylate, Polyethylene Glycol two
At least one in methacrylate and divinylbenzene；Emulsifying agent used by described emulsifying be reactive emulsifier with
Ionic emulsifying agent presses 0.1 ~ 1：1 mass ratio compounding is formed, its consumption for nuclear layer monomer quality 1 ~ 8%..
Above-mentioned reactive emulsifier is：Extraordinary ether alcohol sulfate containing pi-allyl or allyloxy propyl alkyl alcohol polyethers
Type nonionic emulsifier.
Above-mentioned ionic emulsifying agent is：13 carbon polyoxyethylenated alcohol sodium sulfate salts, branched alkyl polyoxyethylenated alcohol
Phosphate monoester or N- (bis- carboxyethyls of 1,2-)-N- octadecylsuccinic acid sulfonic acid tetrasodium salts.
Above-mentioned phosphate ester function monomer is：In Polyethylene Glycol methacrylic acid phosphoric acid ester, alkyl acrylate phosphate ester
At least one.
Above-mentioned initiator is：Potassium peroxydisulfate, Ammonium persulfate., potassium peroxydisulfate-bisulfite are received or Ammonium persulfate .-sulfurous acid
Hydrogen sodium.
It is a kind of to prepare the above-mentioned synthetic method for having cohesive interpenetrating networks emulsion to metal base, it is characterised in that
The method is concretely comprised the following steps：
（1）The preparation of core pre-emulsion：Nuclear layer monomer, cross-linking monomer are slowly added in emulsifying agent, water and initiator,
High-speed stirred carries out pre-emulsification in 10 ~ 30 minutes, obtains core pre-emulsion；The consumption of wherein emulsifying agent is the 50 of whole emulsifiers
~70%；
（2）The preparation of seed emulsion：Under inert atmosphere protection, step is added in residual emulsifier and deionized water
(1) the core pre-emulsion 5 ~ 20% obtained by, is heated to 60 ~ 85 DEG C and causes polymerization, and half an hour i.e. prepared seed is incubated after blue light occurs
Emulsion；
（3）The preparation of core emulsion：In 200 ~ 350 revs/min of mixing speed, under the conditions of 60 ~ 85 DEG C, will be remaining core pre-
Emulsion was uniformly added drop-wise in seed emulsion obtained by step (2) in 1 ~ 2 hour, and insulation after completion of dropping obtains core breast for 1 ~ 2 hour
Liquid；
（4）Shell monomers, phosphate ester function monomer and initiator water are equably added drop-wise to into core emulsion obtained by step (3)
In, it is ensured that then shell monomers are incubated 1 ~ 2 hour in 1 ~ 2 hour completion of dropping；
（5）Formaldehyde sodium bisulfite-tert-butyl hydroperoxide is added in emulsion obtained by step (4) to eliminate initiation
Agent, is incubated 0.5 ~ 1 hour, adjusts pH value to 7 ~ 8, is down to room temperature, and filtering and discharging obtains having cohesive to metal base
Interpenetrating networks emulsion.
The present invention has prepared interpenetrating networks emulsion by introducing crosslinked agent, and draws feature phosphate ester monomer first
Enter in the interpenetrating networks emulsion with nucleocapsid structure, by being compounded with ionic emulsifying agent using reactive emulsifier, prepared
Obtain with adhesive force is good, damping factor is high, the function admirable emulsion of its maximum up to 1.3, the emulsion are highly suitable for making
For a kind of matrix resin of damping paint peculiar to vessel.
Specific embodiment
Embodiment 1：It is as follows that each raw material presses mass fraction composition：
Stratum nucleare：
13.84 parts of methyl methacrylate
7.16 parts of n-butyl acrylate
0.21 part of ethylene glycol dimethacrylate
0.21 part of propylene glycol diacrylate
0.0945 part of Ammonium persulfate.
12.877 parts of water
13 0.252 part of carbon polyoxyethylenated alcohol sodium sulfate salts
0.504 part of extraordinary ether alcohol sulfate containing pi-allyl
Shell：
6.72 parts of methyl methacrylate
14.28 parts of butyl acrylate
0.42 part of Polyethylene Glycol methacrylic acid phosphoric acid ester
0.0945 part of Ammonium persulfate.
20.23 parts of water
Bottom liquid：
22.50 parts of water
13 0.504 part of carbon polyoxyethylenated alcohol sodium sulfate salts
0.06 part of sodium bicarbonate
The preparation process of the nucleocapsid structure interpenetrating networks emulsion of embodiment 1 is as follows：
（1）The preparation of core pre-emulsion
According to above-mentioned formula, by core mix monomer, cross-linking monomer ethylene glycol dimethacrylate（EGDMA）It is slowly added to
To in the container equipped with emulsifying agent, water and initiator, carry out pre-emulsification to prepare within 30 minutes in 800 revs/min of high-speed stirred
Core pre-emulsion.20% pre-emulsion is taken from core pre-emulsion as seed pre-emulsion.
(2) preparation of seed emulsion
In the reactor equipped with partial emulsifier and deionized water and inert gas shielding, 20% core pre-emulsification is added
Liquid, is heated to 82 DEG C and causes polymerization, and half an hour i.e. prepared seed emulsion is incubated after blue light occurs.
(3) preparation of core emulsion
It is in 250 revs/min of mixing speed, core pre-emulsion is uniform in 2 hours using semi-continuous process under the conditions of 82 DEG C
It is added drop-wise in seed emulsion, insulation after completion of dropping obtains core emulsion in 1 hour.
(4) preparation of shell emulsion
On the basis of core emulsion is prepared, by the shell monomers in above-mentioned formula, feature phosphate ester monomer PAM-
100 and initiator solution be simultaneously equably added drop-wise in core emulsion, it is ensured that shell monomer is warming up in 2 hours completion of dropping
87 DEG C, then proceed to reaction 2 hours and nucleocapsid structure interpenetrating networks emulsion is obtained.
（2）Last handling process
The aqueous solution of initiator is eliminated after adding in reactor, 1 hour is incubated, and pH value is adjusted to 7 ~ 8, is down to room temperature,
Filtering and discharging, that is, obtain inierpeneirating network structure emulsion, wherein the monomer for preparing nuclear emulsion particle accounts for the 50% of gross mass, secondary outer layer
Monomer accounts for the 50% of monomer gross mass.
Detection adhesive force is according to national standard《The cross cut test of paint and varnish paint film》GB/T 9286-1998 carry out,
And its damping capacity is analyzed using dynamic thermomechanical, its result is：The adhesive force of latex film reaches 2 grades, and damping peak value is reachable
1.2, the effective damping temperature range between -40 ~ 80 DEG C（tanσ>0.3）About 60 DEG C.
Embodiment 2：It is as follows that each raw material presses mass fraction composition：
Stratum nucleare：
13.84 parts of methyl methacrylate
7.16 parts of n-butyl acrylate
0.21 part of ethylene glycol dimethacrylate
0.0945 part of Ammonium persulfate.
12.877 parts of water
13 0.252 part of carbon polyoxyethylenated alcohol sodium sulfate salts
0.504 part of extraordinary ether alcohol sulfate containing pi-allyl
Shell：
6.72 parts of methyl methacrylate
14.28 parts of butyl acrylate
0.42 part of Polyethylene Glycol methacrylic acid phosphoric acid ester
Alkyl acrylate phosphoesterase 30 .42 parts
0.0945 part of Ammonium persulfate.
20 parts of water
Bottom liquid：
22.26 parts of water
13 0.504 part of carbon polyoxyethylenated alcohol sodium sulfate salts
0.1 part of sodium bicarbonate
Embodiment it is 2-in-1 into step with embodiment 1.
Detection adhesive force is according to national standard《The cross cut test of paint and varnish paint film》GB/T 9286-1998 carry out,
And its damping capacity is analyzed using dynamic thermomechanical, its result is：The adhesive force of latex film reaches 1 grade, and damping peak value is reachable
1.3, the effective damping temperature range between -40 ~ 80 DEG C（tanσ>0.3）About 70 DEG C.
Embodiment 3：It is as follows that each raw material presses mass fraction composition：
Stratum nucleare：
13.84 parts of methyl methacrylate
7.16 parts of n-butyl acrylate
0.63 part of ethylene glycol dimethacrylate
0.0945 part of Ammonium persulfate.
12.657 parts of water
13 0.504 part of carbon polyoxyethylenated alcohol sodium sulfate salts
0.252 part of allyloxy propyl alkyl alcohol polyether-type nonionic emulsifying agent
Shell：
6.72 parts of methyl methacrylate
14.28 parts of butyl acrylate
0.42 part of Polyethylene Glycol methacrylic acid phosphoric acid ester
Alkyl acrylate phosphoesterase 30 .63 parts
0.0945 part of Ammonium persulfate.
20 parts of water
Bottom liquid：
22 parts of water
13 0.504 part of carbon polyoxyethylenated alcohol sodium sulfate salts
0.2 part of sodium bicarbonate
3 synthesis step of embodiment is with embodiment 1.
Detection adhesive force is according to national standard《The cross cut test of paint and varnish paint film》GB/T 9286-1998 carry out,
And its damping capacity is analyzed using dynamic thermomechanical, its result is：The adhesive force of latex film reaches 1 grade, and damping peak value is reachable
1.19, the effective damping temperature range between -40 ~ 80 DEG C（tanσ>0.3）About 66 DEG C.
Embodiment 4：It is as follows that each raw material presses mass fraction composition：
Stratum nucleare：
10.5 parts of methyl methacrylate
3.57 parts of n-butyl acrylate
6.93 parts of ethyl acrylate
0.9 part of ethylene glycol dimethacrylate
0.0945 part of potassium peroxydisulfate
12.25 parts of water
0.504 part of branched alkyl polyoxyethylenated alcohol phosphate monoester
0.252 part of allyloxy propyl alkyl alcohol polyether-type nonionic emulsifying agent
Shell：
8.61 parts of methyl methacrylate
11.55 parts of butyl acrylate
0.84 part of ethyl acrylate
0.42 part of Polyethylene Glycol methacrylic acid phosphoric acid ester
0.0945 part of potassium peroxydisulfate
20.48 parts of water
Bottom liquid：
22.49 parts of water
0.504 part of branched alkyl polyoxyethylenated alcohol phosphate monoester
0.15 part of sodium bicarbonate
4 synthesis step of embodiment is with embodiment 1.
Detection adhesive force is according to national standard《The cross cut test of paint and varnish paint film》GB/T 9286-1998 carry out,
And its damping capacity is analyzed using dynamic thermomechanical, its result is：The adhesive force of latex film reaches 1 grade, and damping peak value is reachable
0.85, the effective damping temperature range between -40 ~ 80 DEG C（tanσ>0.3）About 50 DEG C.
Embodiment 5：It is as follows that each raw material presses mass fraction composition：
Stratum nucleare：
10.5 parts of methyl methacrylate
3.57 parts of n-butyl acrylate
6.93 parts of ethyl acrylate
0.3 part of ethylene glycol dimethacrylate
0.0945 part of potassium peroxydisulfate
12.85 parts of water
0.504 part of branched alkyl polyoxyethylenated alcohol phosphate monoester
0.252 part of allyloxy propyl alkyl alcohol polyether-type nonionic emulsifying agent
Shell：
8.61 parts of methyl methacrylate
11.55 parts of butyl acrylate
0.84 part of ethyl acrylate
0.42 part of Polyethylene Glycol methacrylic acid phosphoric acid ester
Alkyl acrylate phosphoesterase 30 .42 parts
0.0945 part of potassium peroxydisulfate
20.48 parts of water
Bottom liquid：
22.49 parts of water
0.504 part of branched alkyl polyoxyethylenated alcohol phosphate monoester
0.2 part of sodium bicarbonate
4 synthesis step of embodiment is with embodiment 1.
Detection adhesive force is according to national standard《The cross cut test of paint and varnish paint film》GB/T 9286-1998 carry out,
And its damping capacity is analyzed using dynamic thermomechanical, its result is：The adhesive force of latex film reaches 1 grade, and damping peak value is reachable
1.24, the effective damping temperature range between -40 ~ 80 DEG C（tanσ>0.3）About 63 DEG C.
Claims (5)
1. a kind of synthetic method for having cohesive interpenetrating networks emulsion to metal base, it is characterised in that the method it is concrete
Step is：
（1）The preparation of core pre-emulsion：Nuclear layer monomer, cross-linking monomer are slowly added in emulsifying agent, water and initiator, at a high speed
Stirring carries out pre-emulsification in 10 ~ 30 minutes, obtains core pre-emulsion；The consumption of wherein emulsifying agent be whole emulsifiers 50 ~
70%；
（2）The preparation of seed emulsion：Under inert atmosphere protection, step (1) is added in residual emulsifier and deionized water
The core pre-emulsion 5 ~ 20% of gained, is heated to 60 ~ 85 DEG C and causes polymerization, and after blue light occurs, insulation half an hour is obtained seed breast
Liquid；
（3）The preparation of core emulsion：In 200 ~ 350 revs/min of mixing speed, under the conditions of 60 ~ 85 DEG C, by remaining core pre- breast
Liquid was uniformly added drop-wise in seed emulsion obtained by step (2) in 1 ~ 2 hour, and insulation after completion of dropping obtains core breast for 1 ~ 2 hour
Liquid；
（4）Shell monomers, phosphate ester function monomer and initiator water are equably added drop-wise in core emulsion obtained by step (3),
Ensure that shell monomers, in 1 ~ 2 hour completion of dropping, are then incubated 1 ~ 2 hour；
（5）Formaldehyde sodium bisulfite-tert-butyl hydroperoxide is added in emulsion obtained by step (4) to eliminate initiator, is protected
Temperature 0.5 ~ 1 hour, adjusts pH values to 7 ~ 8, is down to room temperature, and filtering and discharging obtains cohesive to metal base tool mutual
Wear network emulsion；
The core of the described interpenetrating network polymer emulsion with nucleocapsid structure is that nuclear layer monomer is made in initiator with cross-linking monomer
It is polymerized with, the mass ratio of described nuclear layer monomer, cross-linking monomer and initiator is：100：0.1~5：0.1 ~ 1.0, it is described
Nuclear layer monomer press 50 ~ 70 by hard monomer and soft monomer：30 ~ 50 mass ratio composition；
The shell of the described interpenetrating net polymer with nucleocapsid structure is shell monomers, phosphate ester function monomer in initiator work
It is polymerized with, the mass ratio of described shell monomers, phosphate ester function monomer and initiator is 100：1~8：0.1 ~ 1.0,
Described shell monomers press 20 ~ 40 by hard monomer and soft monomer：60 ~ 80 mass ratio composition；
Described hard monomer is methyl methacrylate, styrene, acrylonitrile or vinylacetate, and described soft monomer is propylene
Sour N-butyl, ethyl acrylate, Isooctyl acrylate monomer；Described shell monomers are 1 with the mass ratio of nuclear layer monomer:1~2；
Described cross-linking agent is ethylene glycol dimethacrylate, propylene glycol diacrylate, Polyethylene Glycol dimethyl allene
At least one in acid esters and divinylbenzene；Emulsifying agent used by described emulsifying is reactive emulsifier and ion-type breast
Agent presses 0.1 ~ 1：1 mass ratio compounding is formed, its consumption for nuclear layer monomer quality 1 ~ 8%.
2. the synthetic method for having cohesive interpenetrating networks emulsion to metal base according to claim 1, which is special
Levy and be, described reactive emulsifier is the extraordinary ether alcohol sulfate containing pi-allyl or allyloxy propyl alkyl alcohol polyether-type
Nonionic emulsifier.
3. the synthetic method for having cohesive interpenetrating networks emulsion to metal base according to claim 1, its feature
It is that described ionic emulsifying agent is 13 carbon polyoxyethylenated alcohol sodium sulfate salts, branched alkyl polyoxyethylenated alcohol phosphoric acid
Monoesters or N- (bis- carboxyethyls of 1,2-)-N- octadecylsuccinic acid sulfonic acid tetrasodium salts.
4. the synthetic method for having cohesive interpenetrating networks emulsion to metal base according to claim 1, its feature
Be that described phosphate ester function monomer is Polyethylene Glycol methacrylic acid phosphoric acid ester, in alkyl acrylate phosphate ester extremely
Few one kind.
5. the synthetic method for having cohesive interpenetrating networks emulsion to metal base according to claim 1, its feature
It is that described initiator is potassium peroxydisulfate, Ammonium persulfate., potassium peroxydisulfate-sodium sulfite or Ammonium persulfate .-bisulfite
Sodium.
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| CN108203488B (en) * | 2016-12-20 | 2020-12-15 | 中国制浆造纸研究院有限公司 | Acrylic emulsion for fiber sealing material and synthetic method thereof |
| CN108250877B (en) * | 2017-12-19 | 2020-07-17 | 吉力水性新材料科技（珠海）有限公司 | Phosphate modified acrylic water-based industrial coating |
| CN111187387A (en) * | 2019-12-11 | 2020-05-22 | 广东东方一哥新材料股份有限公司 | Metal anticorrosion emulsion and preparation method thereof |
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| ES2428518T3 (en) * | 2010-08-19 | 2013-11-08 | Basf Se | Sound damping composition with an emulsion polymer and a fluorinated compound |
| CN102757523A (en) * | 2011-04-25 | 2012-10-31 | 北京化工大学 | Preparation method of core-shell acrylic acid elastic emulsion containing phosphate group |
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