CN103497272B - A kind of polymer emulsion and preparation method thereof - Google Patents
A kind of polymer emulsion and preparation method thereof Download PDFInfo
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- CN103497272B CN103497272B CN201310455204.XA CN201310455204A CN103497272B CN 103497272 B CN103497272 B CN 103497272B CN 201310455204 A CN201310455204 A CN 201310455204A CN 103497272 B CN103497272 B CN 103497272B
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Abstract
The invention discloses a kind of polymer emulsion and preparation method thereof, comprise the following steps: (1) adopts RAFT polymerization to prepare the amphipathic nature block polymer of compound with regular structure, the mass fraction of each component of this copolymer is as follows: hydrophilic unsaturated monomer 8～15 parts, hydrophobicity unsaturated monomer 25～40 parts, RAFT reagent 0.3～0.8 part, oil-soluble initiator 0.1～0.2 part, mixed solvent 30～45 parts, nertralizer 3～6 parts, 15～25 parts of water；(2) using this amphipathic nature block polymer as macromole emulsifying agent, carry out emulsion polymerization, prepare purpose emulsion.The emulsion that the present invention prepares has excellent adhesive attraction on not pretreated polyolefin substrate；In drying varniss process, macromole emulsifying agent not easily migrates to coating surface, thus improving the water resistance of paint film.
Description
Technical field
A kind of method that the present invention relates to polymer emulsion prepared and there is excellent adhesive attraction on untreated polyolefin.
Background technology
One of significant challenge of plastic paint industry is the adhesive force obtaining excellence on plastics (such as not pretreated PP, PE) base material that hydrophobicity is very strong.Polyolefin can be low because of surface, and hydrophobicity is strong, it does not have being available for the active group of reaction, conventional coating especially water paint is difficult to obtain good adhesive force on its surface.At present, the Technology obtaining excellent adhesive attraction on not preprocessed polyolefin substrate is mainly surface treatment and uses adhesion promoter.Surface treatment method is labour intensive not only, and treatment effect is often uneven.In car paint industry, chloridized polyolefin (CPOs) adhesion promoter is widely used on polyolefin substrate to obtain the adhesive force of excellence.CPOs energy effective wetting base material, also has certain compatibility with other resin, can improve coating adhesive force on polyolefin substrate, but still suffer from many deficiencies.In CPOs, chlorine atom is reactive group, meets high temperature or is easily come off by long-term illumination chlorine atom, coating toughness and poor durability, and CPOs price is higher.In recent years, scholars have developed the novel aqueous adhesion promoter of polyolefin without chlorine, but its price is higher than CPOs, and effect is poor.Therefore, invent a kind of polymer emulsion on not preprocessed polyolefin substrate with excellent adhesive attraction to be significant.
Improve the mechanism of adhesive force according to CPOs, the structure of untreated polyolefin adhesion promoter should be on the main chain of polarity with more non-polar functional group.7,7-dimethyl norbornane groups are the nonpolar bicyclic alkyls similar to molecular polyolefin structure, have strong intermolecular force with molecular polyolefin, have raising paint film performance of adhesive force on polyolefin substrate.When 7,7-more dimethyl norbornane groups are in close contact with polyolefin substrate with emulsion particle divergent shape shell structurre, paint film can be made to obtain excellent adhesive attraction on unprocessed polyolefin substrate.But, owing to 7,7-dimethyl norbornane groups are huge nonpolar bicyclic alkyls, by containing this group mono-olefinic compounds be polymerized gained polymer fragility big, hydrophobicity is strong.
Owing to the Nomenclature Composition and Structure of Complexes of polymer chain is controlled very limited by current industrial polymerisation course of reaction, so a kind of novel polymeric method should be adopted to prepare the amphipathic nature block polymer of compound with regular structure.In recent years, controllable/active free radical polymerization method reversible addion-fragmentation chain transfer radical polymerization (RAFT) polymerization, because of advantages such as its reaction condition are gentle, suitable monomers is in extensive range, becomes most probable and realizes industrialized controllable/active free radical polymerization method.Available RAFT polymerization prepares this amphipathic nature block polymer so that it is have regular structure.But the RAFT polymerization reported at present is prepared amphipathic nature block polymer and is two-step method, complex technical process, and Chang Yinwei RAFT reagent selects inappropriate, cause that the system that the polymerization single polymerization monomer with larger space steric group is participated in reaction controls effect relatively low, it is difficult to prepare the amphipathic nature block polymer of compound with regular structure.
The patent of application number WO2009/121911A1 adopt RAFT polymerization be prepared for the amphipathic nature block polymer containing 7,7-dimethyl norbornane groups.Used by it, RAFT reagent is xanthic acid esters, and chain transfer constant is relatively low, and the control of polymerization process is poor, and the amphipathic nature block polymer structural regularity prepared is poor, causes that it is self-assembled into the character of micelle in water poor.Therefore with the amphipathic nature block polymer of gained as in the emulsion polymerization of macromole emulsifying agent, it is necessary to add a certain amount of small-molecular emulsifier and assisted, stable product could be prepared.And its polymerization adopted is two-step method, and operating process is complex.
Summary of the invention
An object of the present invention is to prepare a kind of polymer emulsion that may be directly applied on not preprocessed polyolefin substrate, and structure is as shown in Figure 1.Emulsifying agent used by this polymer emulsion is the macromole amphipathic nature block polymer containing 7,7-dimethyl norbornane group.7,7-dimethyl norbornane groups are huge nonpolar bicyclic alkyls, utilize the structural similarity of its polymer chain and molecular polyolefin, make paint film obtain excellent adhesive attraction on polyolefinic plastic substrate.
The two of the purpose of the present invention are in that the preparation method providing described emulsion.
The purpose of the present invention is achieved through the following technical solutions:
The preparation method of a kind of polymer emulsion, comprises the following steps:
(1) adopting RAFT polymerization to prepare the amphipathic nature block polymer of compound with regular structure, the mass fraction of each component of this copolymer is as follows:
(2) using this amphipathic nature block polymer as macromole emulsifying agent, carry out emulsion polymerization, prepare purpose emulsion.
Described hydrophilic unsaturated monomer is the mono-olefinic compounds with carboxyl, hydroxyl or sulfonic group hydrophilic radical；Hydrophobicity unsaturated monomer is the mono-olefinic compounds with 7,7-dimethyl norbornane groups.
Described hydrophilic unsaturated monomer be in acrylic acid, α-methacrylic acid, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, styrene sulfonic acid, sodium vinyl sulfonate any one or two or more；Described hydrophobicity unsaturated monomer is any one or two kinds in isobornyl acrylate, isobornyl methacrylate.
Described RAFT reagent has high chain transfer constant; preferred 2-carbethoxyl group propane-2-dithio Benzene potassium acid ester (EPDTB), 2-{ [(dodecyl sulfenyl) thioformyl] sulfanyl } succinic acid (DCTSS), s, s-two (alpha-alpha-dimethyl acetic acid hydroxyl ethyl ester) trithiocarbonate, O-ethyl group-S-(1-carbomethoxy) in ethyl group dithiocarbonates any one or two or more.
Described oil-soluble initiator be in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), 4 ' 4-azos double; two (cyanopentanoic acid), benzoyl peroxide, the benzoyl peroxide tert-butyl ester any one or two or more；Described mixed solvent be in dehydrated alcohol, butanone, toluene, ethyl acetate, dimethyl phthalate any two or more；Described nertralizer is any one or two kinds in triethylamine, ammonia.
The preparation method of the amphipathic nature block polymer of described compound with regular structure comprises the steps:
(1) add RAFT reagent and 24～36 parts of mixed solvents in a kettle., pass into N2, warming-in-water is to 75 DEG C；Join in reactor together with 0.8～1.5 part of hydrophilic unsaturated monomer after 0.03～0.09 part of oil-soluble initiator is dissolved in 3～4.5 parts of mixed solvents, after being incubated 15 minutes, cool the temperature to 70 DEG C；Dripping remaining hydrophilic unsaturated monomer again, time for adding is 2.5～3 hours, after dropwising, is incubated 3 hours；
(2) parallel with hydrophobicity unsaturated monomer after remaining oil soluble initiator being dissolved in 3～4.5 parts of mixed solvents being added drop-wise in reactor, time for adding is 2.5～3 hours, after dropwising, is incubated 3 hours, is cooled to 40 DEG C with down sampling；
(3) under 1000r/min mixing speed, with nertralizer, reactant liquor is carried out ionizing；Then, under 7000r/min mixing speed, reactant liquor is scattered in water；Finally, stir 30 minutes under the mixing speed of 4000r/min, obtain the amphipathic nature block polymer aqueous dispersion of compound with regular structure.
The mass fraction that described emulsion is polymerized each component is as follows:
Described soft monomer is homopolymer vitrification point between the rare keyed unsaturated monomer of list of-20 DEG C～-70 DEG C；Described hard monomer is the rare keyed unsaturated monomer of the homopolymer vitrification point list more than 0 DEG C.
Described soft monomer be in the just own ester of butyl acrylate, ethyl acrylate, Isooctyl acrylate monomer, n-propyl, n-butyl acrylate, acrylic acid any one or two or more；Described hard monomer be in methyl methacrylate, isopropyl methacrylate, n-BMA, 2-Propenoic acid, 2-methyl-, isooctyl ester, methacrylic acid-β-hydroxypropyl acrylate any one or two or more；Described water soluble starter be potassium peroxydisulfate, Ammonium persulfate., sodium peroxydisulfate, special (uncle) butyl of hydroperoxidation, cumene hydroperoxide, hydroperoxidation in Meng alkane any one or two or more.
The preparation method of described purpose emulsion comprises the following steps:
(1) add amphipathic nature block polymer aqueous dispersion and 37.5～50 parts of aqueous solutions, stirring in a kettle., pass into N2, warming-in-water is to 65 DEG C；Add 1～2.5 part of soft monomer, 1～2.5 part of hard monomer, be incubated 20 minutes；Add after 0.03～0.08 part of water soluble starter is dissolved in 3.75～5 parts of aqueous solutions in reactor again, after being warming up to 80 DEG C, be incubated 10 minutes；
(2) residue water soluble starter being dissolved in 3.75～5 parts of aqueous solutions, hard monomer soft with remaining is parallel to be added drop-wise in reactor, and time for adding is 3 hours；It is incubated 1 hour after dropwising, then cools the temperature to after below 40 DEG C, filter discharging, obtain purpose emulsion.
The principle of the invention: 1) emulsifying agent used by Inventive polymers emulsion is the macromole amphipathic nature block polymer containing 7,7-dimethyl norbornane group.Due to containing 7, the polymer fragility of list rare keyed compound polymerization gained of 7-dimethyl norbornane group is big, hydrophobicity is strong, in order to allow it obtain certain pliability and water dispersible, good to itself and pliability hydrophilic section being combined, formation has the amphipathic nature block polymer on the main chain of polarity with more non-polar functional group's structure.The amphipathic nature block polymer of recycling compound with regular structure self-assembly property in selective solvent, it can be used as the macromole emulsifying agent in emulsion polymerization, and preparation has the polymer emulsion of excellent adhesive attraction on not preprocessed polyolefin substrate.In film forming procedure, on the one hand, this group is enriched in emulsion particle shell structurre, it is in close contact with polyolefin substrate, utilizes intermolecular force strong between the two, improve paint film adhesive force on polyolefin substrate；On the other hand, macromole emulsifying agent not easily migrates to coating surface, can improve the water resistance of paint film.2) the dihydrogen thiocarbonate. esters chain-transferring agent that employing chain transfer constant is high is as RAFT reagent, can prepare the amphipathic nature block polymer of compound with regular structure.Utilize amphipathic nature block polymer self-assembly property in selecting solvent, the emulsifying agent in emulsion polymerization can be it can be used as.7,7-dimethyl norbornane groups are contained in the hydrophobic side of this emulsifying agent, in film forming procedure, this group is enriched in emulsion particle shell structurre, it is in close contact with polyolefin substrate, utilizes intermolecular force strong between the two, improve paint film adhesive force on polyolefin substrate.3) during RAFT polymerization synthesizing amphipathic block copolymer, adopting the mixed solvent that can fully dissolve monomer and RAFT reagent, enable the technical process of synthesizing amphipathic block copolymer to continuously perform, technique is simpler, more convenient operation.
Compared with prior art, the invention have the advantages that
A) in the present invention, emulsion particle shell is the amphipathic nature block polymer with 7,7-dimethyl norbornane groups, and in film forming procedure, 7,7-dimethyl norbornane groups are in close contact with polyolefin substrate.Owing to having strong molecular force between the two, coating has the adhesive force of excellence on non-pretreatment polyolefin substrate.
B) in the present invention, RAFT reagent used has high chain transfer constant, is more suitable for the polymerization single polymerization monomer with larger space steric group and participates in the system of reaction.With dithio esters, xanthic acid esters geometric ratio relatively, it is readily synthesized, purifies；There is better heat stability and hydrolytic stability；By its less appearance inhibition phenomenon of polyreaction as RAFT reagent, than other RAFT reagent more advantage.
C) in the present invention, a step completes the process that RAFT polymerization prepares the amphipathic nature block polymer of compound with regular structure, it is selected to fully dissolve the mixed solvent of RAFT reagent and monomer, a same reactor is sequentially completed the synthesis of two blocks, it is not necessary to through the discharging of intermediate product, purification.Compared with current reported RAFT two-step method polymerization process, technical process is simpler, and the response time is shorter.
D) in conventional emulsion polymerizations, emulsifying agent great majority used are small-molecular emulsifier, and in film forming procedure, small-molecular emulsifier easily migrates to coating surface, owing to its hydrophilic is relatively strong, reduce the water resistance of paint film to a certain extent.The present invention adopts the amphipathic nature block polymer that can be self-assembly of micelle in aqueous as macromole emulsifying agent, the problems referred to above can be avoided, improve the water resistance of paint film.
Accompanying drawing explanation
Fig. 1 is emulsion particle structural representation.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is more specifically described in detail, but embodiments of the present invention are not limited to this, for the technological parameter not indicated especially, can refer to routine techniques and carry out.
Embodiment 1
1) RAFT polymerization prepares the amphipathic nature block polymer of compound with regular structure
Set of monomers becomes acrylic acid, isobornyl acrylate; RAFT reagent set becomes 2-{ [(dodecyl sulfenyl) thioformyl] sulfanyl } succinic acid (DCTSS); initiator consists of 4 ' 4-azos double; two (cyanopentanoic acid); mixed solvent consists of dehydrated alcohol, butanone; nertralizer consists of triethylamine, and its component formula is as follows:
Acrylic acid and isobornyl acrylate mass ratio are 1:3, acrylic acid and 2-{ [(dodecyl sulfenyl) thioformyl] sulfanyl } succinic acid (DCTSS) mol ratio is 80:1.
First, acrylic acid synthesizing Macromolecular chain transfer agent (PAA-RAFT).1.65 grams of DCTSS are dissolved in 80 grams of mixed solvents, join in the reactor equipped with thermometer, agitator, temperature control heating device and condensation reflux unit, stir and be warming up to 75 DEG C, pass into N simultaneously230 minutes.Being dissolved in 10 grams of mixed solvents by 0.195 gram of 4 ' 4-azo double; two (cyanopentanoic acid), then itself and 2.5g acrylic acid are joined in reactor by one batch, react 15 minutes.Cool the temperature to 70 DEG C again, drip remaining acrylic acid, continue completion of dropwise addition in 2.5～3 hours, be incubated 3 hours.
Then, acrylic acid synthesizing, isobornyl acrylate amphipathic nature block polymer (PAA-b-PiBOA).Double; two for remaining 0.195 gram of 4 ' 4-azo (cyanopentanoic acid) is dissolved in 10 grams of mixed solvents, then it parallel with isobornyl acrylate is added drop-wise in reactor, persistently completion of dropwise addition in 2.5～3 hours, it is incubated 3 hours.After completion of the reaction, it is cooled to 40 DEG C and following, discharging, sampling.Recycling high-speed stirred dispersion machine, 13 grams of triethylamines are added under 1000r/min mixing speed, after stirring 10 minutes, while mixing speed is increased to 7000r/min, while adding 50 grams of water, stir 10 minutes, then stir 30 minutes under the mixing speed of 4000r/min, obtain PAA-b-PiBOA aqueous dispersion.Finally, Rotary Evaporators is utilized to reclaim mixed solvent.
2) PAA-b-PiBOA is prepared emulsion as macromole emulsifying agent
Set of monomers becomes methyl methacrylate, n-butyl acrylate, and emulsifying agent consists of 1) gained PAA-b-PiBOA, initiator consists of potassium peroxydisulfate, and its component formula is as follows:
First, PAA-b-PiBOA is dissolved in 100 grams of water, joins in the reactor equipped with thermometer, agitator, temperature control heating device and condensation reflux unit, stir and be warming up to 65 DEG C, pass into N simultaneously230 minutes.Again 10 weight % mix monomers (4.2g n-butyl acrylate/5.8g methyl methacrylate) are joined in reactor, be incubated 20 minutes.Then join in reactor after 0.1 gram of potassium peroxydisulfate being dissolved in 10 grams of water, be warming up to 80 DEG C simultaneously, react 10 minutes.Finally, 0.2 gram of potassium peroxydisulfate is dissolved in 10 grams of water, more parallel with remaining mix monomer (n-butyl acrylate/methyl methacrylate) is added drop-wise in reactor, continue to dropwise for 3 hours, it is cooled to less than 40 DEG C after being incubated 1 hour, filters discharging, obtain product.
Embodiment 2
1) RAFT polymerization prepares the amphipathic nature block polymer of compound with regular structure
Set of monomers becomes acrylic acid, isobornyl acrylate; RAFT reagent set becomes 2-{ [(dodecyl sulfenyl) thioformyl] sulfanyl } succinic acid (DCTSS); initiator consists of 4 ' 4-azos double; two (cyanopentanoic acid); mixed solvent consists of dehydrated alcohol, butanone; nertralizer consists of triethylamine, and its component formula is as follows:
Acrylic acid and isobornyl acrylate mass ratio are 1:4, acrylic acid and 2-{ [(dodecyl sulfenyl) thioformyl] sulfanyl } succinic acid (DCTSS) mol ratio is 80:1.
First, acrylic acid synthesizing Macromolecular chain transfer agent (PAA-RAFT).1.65 grams of DCTSS are dissolved in 80 grams of mixed solvents, join in the reactor equipped with thermometer, agitator, temperature control heating device and condensation reflux unit, stir and be warming up to 75 DEG C, pass into N simultaneously230 minutes.Being dissolved in 10 grams of mixed solvents by 0.195 gram of 4 ' 4-azo double; two (cyanopentanoic acid), then itself and 10 weight % acrylic acid (2.5g) are joined in reactor by one batch, react 15 minutes.Cool the temperature to 70 DEG C again, drip remaining acrylic acid, continue completion of dropwise addition in 2.5～3 hours, be incubated 3 hours.
Then, acrylic acid synthesizing, isobornyl acrylate amphipathic nature block polymer (PAA-b-PiBOA).Double; two for remaining 0.195 gram of 4 ' 4-azo (cyanopentanoic acid) is dissolved in 10 grams of mixed solvents, then it parallel with isobornyl acrylate is added drop-wise in reactor, persistently completion of dropwise addition in 2.5～3 hours, it is incubated 3 hours.After completion of the reaction, it is cooled to less than 40 DEG C, discharging, sampling.Recycling high-speed stirred dispersion machine, 13 grams of triethylamines are added under 1000r/min mixing speed, after stirring 10 minutes, while mixing speed is increased to 7000r/min, while adding 50 grams of water, stir 10 minutes, then stir 30 minutes under the mixing speed of 4000r/min, obtain PAA-b-iBOA aqueous dispersion.Finally, Rotary Evaporators is utilized to reclaim mixed solvent.
2) PAA-b-PiBOA is prepared emulsion as macromole emulsifying agent
Set of monomers becomes methyl methacrylate, n-butyl acrylate, and emulsifying agent consists of 1) gained PAA-b-PiBOA, initiator consists of potassium peroxydisulfate, and its component formula is as follows:
First, PAA-b-PiBOA is dissolved in 100 grams of water, joins in the reactor equipped with thermometer, agitator, temperature control heating device and condensation reflux unit, stir and be warming up to 65 DEG C, pass into N simultaneously230 minutes.Again 10 weight % mix monomers (4.2g n-butyl acrylate/5.8g methyl methacrylate) are joined in reactor, be incubated 20 minutes.Then join in reactor after 0.1 gram of potassium peroxydisulfate being dissolved in 10 grams of water, be warming up to 80 DEG C simultaneously, react 10 minutes.Finally, 0.2 gram of potassium peroxydisulfate is dissolved in 10 grams of water, more parallel with remaining mix monomer (n-butyl acrylate/methyl methacrylate) is added drop-wise in reactor, continue to dropwise for 3 hours, it is cooled to less than 40 DEG C after being incubated 1 hour, filters discharging, obtain product.
Embodiment 3
1) RAFT polymerization prepares the amphipathic nature block polymer of compound with regular structure
Set of monomers becomes acrylic acid, isobornyl acrylate; RAFT reagent set becomes 2-{ [(dodecyl sulfenyl) thioformyl] sulfanyl } succinic acid (DCTSS); initiator consists of 4 ' 4-azos double; two (cyanopentanoic acid); mixed solvent consists of dehydrated alcohol, butanone; nertralizer consists of triethylamine, and its component formula is as follows:
Acrylic acid and isobornyl acrylate mass ratio are 1:5, acrylic acid and 2-{ [(dodecyl sulfenyl) thioformyl] sulfanyl } succinic acid (DCTSS) mol ratio is 80:1.
First, acrylic acid synthesizing Macromolecular chain transfer agent (PAA-RAFT).1.65 grams of DCTSS are dissolved in 80 grams of mixed solvents, join in the reactor equipped with thermometer, agitator, temperature control heating device and condensation reflux unit, stir and be warming up to 75 DEG C, pass into N simultaneously230 minutes.Being dissolved in 10 grams of mixed solvents by 0.195 gram of 4 ' 4-azo double; two (cyanopentanoic acid), then itself and 10 weight % acrylic acid (2.5g) are joined in reactor by one batch, react 15 minutes.Cool the temperature to 70 DEG C again, drip remaining acrylic acid, continue completion of dropwise addition in 2.5～3 hours, be incubated 3 hours.
Then, acrylic acid synthesizing, isobornyl acrylate amphipathic nature block polymer (PAA-b-PiBOA).Double; two for remaining 0.195 gram of 4 ' 4-azo (cyanopentanoic acid) is dissolved in 10 grams of mixed solvents, then it parallel with isobornyl acrylate is added drop-wise in reactor, persistently completion of dropwise addition in 2.5～3 hours, it is incubated 3 hours.After completion of the reaction, it is cooled to less than 40 DEG C, discharging, sampling.Recycling high-speed stirred dispersion machine, 13 grams of triethylamines are added under 1000r/min mixing speed, after stirring 10 minutes, while mixing speed is increased to 7000r/min, while adding 50 grams of water, stir 10 minutes, then stir 30 minutes under the mixing speed of 4000r/min, obtain PAA-b-iBOA aqueous dispersion.Finally, Rotary Evaporators is utilized to reclaim mixed solvent.
2) PAA-b-PiBOA is prepared emulsion as macromole emulsifying agent
Set of monomers becomes methyl methacrylate, n-butyl acrylate, and emulsifying agent consists of 1) gained PAA-b-PiBOA, initiator consists of potassium peroxydisulfate, and its component formula is as follows:
First, PAA-b-PiBOA is dissolved in 100 grams of water, joins in the reactor equipped with thermometer, agitator, temperature control heating device and condensation reflux unit, stir and be warming up to 65 DEG C, pass into N simultaneously230 minutes.Again 10 weight % mix monomers (4.2g n-butyl acrylate/5.8g methyl methacrylate) are joined in reactor, be incubated 20 minutes.Then join in reactor after 0.1 gram of potassium peroxydisulfate being dissolved in 10 grams of water, be warming up to 80 DEG C simultaneously, react 10 minutes.Finally, 0.2 gram of potassium peroxydisulfate is dissolved in 10 grams of water, more parallel with remaining mix monomer (n-butyl acrylate/methyl methacrylate) is added drop-wise in reactor, continue to dropwise for 3 hours, it is cooled to less than 40 DEG C after being incubated 1 hour, filters discharging, obtain product.
Product test: table one acrylic acid and the impact on polymer emulsion performance of the isobornyl acrylate mass ratio
From embodiment 1～3; along with RAFT reagent 2-{ [(dodecyl sulfenyl) thioformyl] sulfanyl } reduction of succinic acid (DCTSS) mass fraction; the molecular weight polydispersity coefficient of amphipathic nature block polymer PAA-b-PiBOA is more big; this is because its mass fraction reduces, the ability of regulation and control of system radical polymerization is reduced.In embodiment 3, owing in amphipathic nature block polymer, hydrophilic monomer acrylic acid proportion is little, hydrophilic section length is too short, causes that the hydrophilic of PAA-b-PiBOA is poor, therefore is difficult in aqueous form stable micelle.Can being obtained by embodiment 1,2, paint film adhesion strengthens along with increasing of isobornyl acrylate content.
Claims (9)
1. the preparation method of a polymer emulsion, it is characterised in that comprise the following steps:
(1) adopting RAFT polymerization to prepare the amphipathic nature block polymer of compound with regular structure, the mass fraction of each component of this copolymer is as follows:
Described RAFT reagent is 2 { [(dodecyl sulfenyl) thioformyl] sulfanyl } succinic acid；
Described hydrophobicity unsaturated monomer is isobornyl acrylate；
(2) using this amphipathic nature block polymer as macromole emulsifying agent, carry out emulsion polymerization, prepare purpose emulsion.
2. preparation method according to claim 1, it is characterised in that described hydrophilic unsaturated monomer is the mono-olefinic compounds with carboxyl, hydroxyl or sulfonic group hydrophilic radical；Hydrophobicity unsaturated monomer is the mono-olefinic compounds with 7,7-dimethyl norbornane groups.
3. preparation method according to claim 2, it is characterised in that described hydrophilic unsaturated monomer be in acrylic acid, α-methacrylic acid, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, styrene sulfonic acid, sodium vinyl sulfonate any one or two or more.
4. preparation method according to claim 1, it is characterized in that, described oil-soluble initiator be azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), 4, in 4 '-azo double; two (cyanopentanoic acid), benzoyl peroxide, the benzoyl peroxide tert-butyl ester any one or two or more；Described mixed solvent be in dehydrated alcohol, butanone, toluene, ethyl acetate, dimethyl phthalate any two or more；Described nertralizer is any one or two kinds in triethylamine, ammonia.
5. the preparation method according to Claims 1 to 4 any one, it is characterised in that the preparation method of the amphipathic nature block polymer of described compound with regular structure comprises the steps:
(1) add RAFT reagent and 24～36 parts of mixed solvents in a kettle., pass into N2, warming-in-water is to 75 DEG C；Join in reactor together with 0.8～1.5 part of hydrophilic unsaturated monomer after 0.03～0.09 part of oil-soluble initiator is dissolved in 3～4.5 parts of mixed solvents, after being incubated 15 minutes, cool the temperature to 70 DEG C；Dripping remaining hydrophilic unsaturated monomer again, time for adding is 2.5～3 hours, after dropwising, is incubated 3 hours；
(2) parallel with hydrophobicity unsaturated monomer after remaining oil soluble initiator being dissolved in 3～4.5 parts of mixed solvents being added drop-wise in reactor, time for adding is 2.5～3 hours, after dropwising, is incubated 3 hours, is cooled to 40 DEG C with down sampling；
(3) under 1000r/min mixing speed, with nertralizer, reactant liquor is carried out ionizing；Then, under 7000r/min mixing speed, reactant liquor is scattered in water；Finally, stir 30 minutes under the mixing speed of 4000r/min, obtain the amphipathic nature block polymer aqueous dispersion of compound with regular structure.
6. the preparation method according to Claims 1 to 4 any one, it is characterised in that the mass fraction that step (2) described emulsion is polymerized each component is as follows:
Described soft monomer is homopolymer vitrification point between the Mono-olefinic unsaturated monomer of-20 DEG C～-70 DEG C；Described hard monomer is the homopolymer vitrification point Mono-olefinic unsaturated monomer more than 0 DEG C.
7. preparation method according to claim 6, it is characterised in that described soft monomer be in the just own ester of butyl acrylate, ethyl acrylate, Isooctyl acrylate monomer, n-propyl, n-butyl acrylate, acrylic acid any one or two or more；Described hard monomer be in methyl methacrylate, isopropyl methacrylate, n-BMA, 2-Propenoic acid, 2-methyl-, isooctyl ester, methacrylic acid-β-hydroxypropyl acrylate any one or two or more；Described water soluble starter be potassium peroxydisulfate, Ammonium persulfate., sodium peroxydisulfate, special (uncle) butyl of hydroperoxidation, cumene hydroperoxide, hydroperoxidation in Meng alkane any one or two or more.
8. preparation method according to claim 6, it is characterised in that the preparation method of described purpose emulsion comprises the following steps:
(1) add amphipathic nature block polymer aqueous dispersion and 37.5～50 parts of aqueous solutions, stirring in a kettle., pass into N2, warming-in-water is to 65 DEG C；Add 1～2.5 part of soft monomer, 1～2.5 part of hard monomer, be incubated 20 minutes；Add after 0.03～0.08 part of water soluble starter is dissolved in 3.75～5 parts of aqueous solutions in reactor again, after being warming up to 80 DEG C, be incubated 10 minutes；
(2) residue water soluble starter being dissolved in 3.75～5 parts of aqueous solutions, hard monomer soft with remaining is parallel to be added drop-wise in reactor, and time for adding is 3 hours；It is incubated 1 hour after dropwising, then cools the temperature to after below 40 DEG C, filter discharging, obtain purpose emulsion.
9. the polymer emulsion that prepared by claim 1～8 any one method.
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