CN110511325A - A kind of preparation method of high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization object - Google Patents
A kind of preparation method of high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization object Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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- C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
The present invention discloses a kind of preparation method of high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization object.The preparation method is using sulfonic acid base class monomer and alkyls monomer as raw material, using surfactant- free emulsion polymerization, make a kind of soap-free polymerization object by oneself, the soap-free polymerization object is reacted with other raw materials again and synthesizes a kind of polymer emulsion, this preparation method is eliminated by emulsifier bring ill effect, it joined graphene oxide in synthesis process, improve film forming and film strength, with sulfonic group, alkyl monomer is raw material, the polymer molecular weight moderate range generated in the environment of pH value 9-9.5, the hydrophobic group on main chain can be made to be easy to form a film in surface enrichment so that waterproof performance is excellent, entanglement effect between polymer molecule backbone can be made significant again, the resistance of motion increases, so that the cohesive force of itself and basal plane, tensile elasticity and durability are all very good.
Description
Technical field
The invention belongs to architectural waterproof material technical field, specifically a kind of high-weatherability sulfonic group alkyls soap-free emulsion
The preparation method of polymer.
Background technique
Construction material be in construction projects applied by a variety of materials.Construction material is many kinds of, is roughly divided into: (1)
Inorganic material, it includes metal material (including ferrous material and nonferrous materials) and nonmetallic materials (such as natural stone
Material, earth burning product, cement, concrete and silicate product etc.).(2) organic material, it includes plant material, synthesis high score
Sub- material (including plastics, coating, adhesive) and asphalt material.(3) composite material, it includes bituminous concrete, and polymer is mixed
Solidifying soil etc., is generally combined by inorganic non-metallic material and organic material.And the coating in organic material refers to coated in quilt
Protection or the body surface decorated, and the continuous film of firm attachment can be formed with coated article, usually with resin or oil,
OrLotionBased on, pigment, filler are added or do not added, corresponding additive, the viscous fluid being formulated with organic solvent or water are added
Body.And what water-repellent paint referred to naturally is exactly the coating for playing waterproof action.
Nowadays water-repellent paint majority in the market is polymer waterproof coating material, but water-repellent paint at this stage has some disadvantages
End, so that its requirement for being unable to satisfy people, for example, temperature must be higher than 5 degree when execution conditions strict construction, rainy weather or base
Layer has and should not construct when bright water；And the flexible polymer that is compounded by a variety of organic-inorganics of waterproof material and rigid cement advantage
Complementation achievees the purpose that waterproof.But the problems such as it is poor with bond matrix power to exist, and is easy to fall off, and durability is poor.The present invention uses nothing
Soap emulsion polymerization, with sulfonic acid base class hydrophilic monomer, alkyls hydrophobic monomer and initiator are raw material, with no soap sulfonic group list
Body, the polymer that no soap alkyl monomer synthesizes solve the problems, such as conventional emulsifier as emulsifier, simultaneously participate in polymerization
In reaction, a kind of Polymeric water repellent material is prepared, this preparation method also introduces new functional group, substantially increases product
Various performances.
Patent CN201710468129.9 discloses a kind of waterproof heat-resisting coating, and the waterproof heat-resisting coating is by following
Composition composition: 15-30 parts of mica, 2-10 parts of aluminium powder, 2-7 parts of zinc powder, 20-55 parts of magnesia, 1-6 parts of talcum powder.The technology
The scheme technical solution simple production process, at low cost, the good waterproof effect and long service life time is long, adds in the technical solution
Talcum powder can increase tensile strength, shear strength, high temperature resistance, reduce deformation, extension rate, thermal expansion coefficient, epigranular,
It is dispersed strong, the waterproof and corrosion resistance of paint film are greatly improved, is promoted and applied convenient for further.
Patent CN201510720349.7 discloses a kind of method of producing waterproof coating material, including following material liquid material and powder
Material, liquid material includes lotion 80-120kg, dispersing agent 0.4-0.6kg, defoaming agent 0.6-1.0kg, wetting agent 0.05-0.12kg, powder
Material includes cement 400-600kg, 200 mesh silica flour 180-240kg, 120 mesh silica flour 80-140kg, coarse whiting 180-220kg, subtracts
Aqua 0-8kg；This kind of water-repellent paint, as water penetration enters in the hole and gap of concrete structure.Concrete micropore,
It is transmitted in slit and capillary, is full, hydration occurs again for the ingredient of the particle and incomplete aquation that are catalyzed in concrete,
And form insoluble complicated and confused shape crystallization and be combined into entirety with concrete, prevent water and harmful substance from all directions.
Patent CN201810668080.6 discloses a kind of corrosion-resistant macromolecule composite water-proof paint, constituent are as follows::
Acrylic emulsion 5-15 parts by weight, waterproofing agent of organosilicon 1-5 parts by weight, silica 0.5-3 parts by weight, pigments and fillers 20-40 weight
Measure part, sterilization antiseptic 0-0.5 parts by weight, age resister 0-1 parts by weight, dispersing agent 0.2-0.8 parts by weight, defoaming agent 0.4-1
Parts by weight, coalescing agent 0.5-2 parts by weight, hydroxyethyl cellulose 0.6-3 parts by weight, ammonium metavanadate 0.3-1 parts by weight, water 10-
30 parts by weight.The invention has excellent high resiliency and excellent waterproof performance.Product is nontoxic, tasteless, safety and environmental protection.Film is resistance to
Aqueous, alkali resistance, anti-uv-ray are strong, fracture elongation with higher, tensile strength and are automatically repaired function.
The disadvantage that the generally existing molecule chain rigidity of water-repellent paint is small in the prior art, glass transition temperature is low, glutinous stream temperature is low,
Product shows the not high problem of heat resistance and tensile strength.
Summary of the invention
In order to solve the above technical problem, the present invention provides a kind of high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization objects
Preparation method.
The present invention uses emulsifier-free emulsion polymerization method, containing sulfonic function monomer and will have strong hydrophobic ability and contain
The unsaturated monomer of alkyl causes polymerization under the action of initiator and prepares a kind of high molecular material containing sulfonic group alkyl, point
Son amount moderate range can make the hydrophobic group on main chain be easy to form a film in surface enrichment so that waterproof performance is excellent and make
Entanglement effect is significant between polymer molecule backbone, and the resistance of motion increases, so that its cohesive force with basal plane, tensile elasticity and resistance to
Long property is all very good.The present invention is added to suitable polyethers in the synthesis process, and the waterproof effect for not only increasing film is also sent out
Waved good defoaming effect, make polymer reaction more sufficiently, film is more smooth, coating waterproofing effect is more excellent.Synthesis process
In joined graphene oxide, improve film forming and film strength.The netted combination of the crosslinking agent of addition strengthens painting
The consistency and hardness for expecting film forming enhance the caking property between coating and building surface and coating and coating, improve and apply
The waterproof ability and weatherability of layer.
Technical solution provided by the invention is as follows:
A kind of preparation method of high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization object, which is characterized in that including following
Step:
1) by 200 parts of water, 4-8 parts without soap sulfonic acid base class hydrophilic monomer, 6-14 parts without soap alkyls hydrophobic monomer, 0.32-
0.62 part of initiator a, 0.38-0.86 parts of chain-transferring agent be added directly into the three-necked flask with agitating device, stir evenly
Afterwards, control temperature is reacted 2.5-4.2 hours at 66-85 DEG C, then keeps the temperature 1.0-3.0 hours, obtains soap-free polymerization object；
Described is sodium styrene sulfonate without soap sulfonic acid base class hydrophilic monomer, in 2- acrylamide-2-methyl propane sulfonic
It is one or more of；Preferably one or both of sodium styrene sulfonate, 2- acrylamide-2-methyl propane sulfonic form；It is more excellent
Sodium styrene sulfonate and 2- acrylamide-2-methyl propane sulfonic mass ratio are selected as the composition of 1:3；
Described is one of N- octadecyl acrylamide, octadecyl vinyl ether without soap alkyls hydrophobic monomer
Or two kinds；Preferably N- octadecyl acrylamide；
2) by 220-290 parts of alkyls hydrophobic monomer, 5-10 parts of sulfonic acid base class hydrophilic monomer, 2.5-5.9 parts of pH adjusting agent,
0.3-1.0 parts of graphene oxide function monomer, 7-18 parts of polyethers be configured to A liquid；2.8-6.2 parts of initiator b and 60 parts of water are matched
B liquid is made；
The alkyls hydrophobic monomer is N- dodecylacrylamide；
3) soap-free polymerization object is cooled to 38-64 DEG C, A liquid and B liquid is slowly dropped in three-necked flask simultaneously, A drop
4.2-6.2 hour between added-time, B liquid time for adding ratio A liquid is 1 hour long, stirs soap-free polymerization object when being added dropwise, starts in stirring
Crosslinking agent 5.2-9.5 parts is added after half an hour；
4) after completion of dropwise addition, by heat preservation, neutralizer 7-20 parts, and moisturizing is added in curing after solution is cooled to room temperature
To 1000 parts, it is about 30% polymer waterproof coating material that mass fraction can be obtained after mixing evenly；
The number is mass parts.
Specifically,
The sulfonic acid base class hydrophilic monomer is sodium vinyl sulfonate, in acrylic sodium sulfonate, methylpropene sodium sulfonate
It is one or more of.Preferably one or more of sodium vinyl sulfonate, acrylic sodium sulfonate form；More preferably vinyl sulphur
The composition that sour sodium and acrylic sodium sulfonate mass ratio are 1:2.
Specifically, the crosslinking agent is equal benzene dianhydride dimethacrylate hydroxyl ethyl ester, two (methylacryoyloxyethyls)
Equal benzene dianhydride ester, ethylene glycol dimethacrylate, polyethyleneglycol diacrylate (n=5), polyethyleneglycol diacrylate (n
=9), three (2- ethoxy) isocyanuric acid triacrylates, ethylene glycol dimethacrylate, 1,4-butanediol dimethyl allene
One or more of acid esters.Preferably equal benzene dianhydride dimethacrylate hydroxyl ethyl ester, two (methylacryoyloxyethyl) equal benzene
One or more of dianhydride ester, ethylene glycol dimethacrylate composition；More preferably equal benzene dianhydride dimethacrylate hydroxyl
The composition that ethyl ester and ethylene glycol dimethacrylate mass ratio are 1:4.
Specifically, the graphene oxide function monomer is graphene oxide.
Specifically, the initiator a is azodiisobutyronitrile, dilauroyl peroxide, the peroxidating trimethylacetic acid tert-butyl ester, mistake
Aoxidize one or more of dibenzoyl.Preferably one of dilauroyl peroxide, peroxidating trimethylacetic acid tert-butyl ester or two
Kind composition；The composition that more preferable dilauroyl peroxide and peroxidating trimethylacetic acid tert-butyl ester mass ratio are 5:7.
Specifically, the initiator b is azobisisoheptonitrile, di-isopropyl peroxydicarbonate, dicetyl peroxydicarbonate
One or more of dicyclohexyl maleate.Preferably di-cyclohexylperoxy di-carbonate, one in two cyclopropyl ester of dicetyl peroxydicarbonate
Kind or two kinds；The composition that more preferable two cyclopropyl ester of dicetyl peroxydicarbonate and di-cyclohexylperoxy di-carbonate mass ratio are 1:2.
The initiator b activity is less than initiator a.
Specifically,
The pH adjusting agent is sodium methoxide, in sodium ethoxide, ethanol amine, diethanol amine, triethanolamine, triisopropanolamine
It is one or more of.Preferably one or more of sodium methoxide, sodium ethoxide, ethanol amine form；More preferably sodium methoxide and ethyl alcohol
Sodium mass ratio is the composition of 3:2.
The neutralizer is sodium hydroxide solution, potassium hydroxide, sodium carbonate, sodium bicarbonate, the potassium carbonate of 30% solubility
One or more of.Preferably one or more of sodium carbonate, sodium bicarbonate, potassium carbonate form；More preferably sodium carbonate
The composition for being 3:2 with sodium bicarbonate mass ratio.
Specifically, the polyethers is ethylene oxide and propylene oxide mass ratio is 1:2 copolyether, ethylene oxide and ring
Copolyether, ethylene oxide and the propylene oxide mass ratio that Ethylene Oxide mass ratio is 2:1 are one or more of copolyether of 3:2
Composition.Preferably ethylene oxide and propylene oxide mass ratio be 2:1 copolyether.
Specifically, the chain-transferring agent is methylpropene sodium sulfonate.
Another object of the present invention is to provide the high-weatherability sulfonic group alkyls using above method preparation without soap cream
Liquid polymer.
Raw material needed for preparing above-mentioned high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization object, with gross mass part 1000
Part meter, including following content of component:
Sulfonic acid base class hydrophilic monomer: 5-10 parts
Without soap sulfonic acid base class hydrophilic monomer: 4-8 parts
Chain-transferring agent: 0.38-0.86 parts
A:0.32-0.62 parts of initiator
B:2.8-6.2 parts of initiator
Without soap alkyls hydrophobic monomer: 6-14 parts
Alkyls hydrophobic monomer: 220-290 parts
Crosslinking agent: 5.2-9.5 parts
Polyethers: 7-18 parts
PH adjusting agent: 2.5-5.9 parts
Neutralizer: 7-20 parts
Graphene oxide function monomer: 0.3-1.0 parts
Surplus is water.
Beneficial effects of the present invention:
Waterproof material of the invention uses emulsifier-free emulsion polymerization mode, synthesizes a kind of sulfonic acid base class hydrophilic radical, alkyls
The high molecular polymer of hydrophobic grouping cross arrangement without soap sulfonic acid base class hydrophilic radical and no soap alkyls hydrophobic grouping and will draw
Agent is sent out, a kind of soap-free polymerization object is made in reaction, then this soap-free polymerization object is reacted with other raw materials to obtain a kind of polymer and is prevented
Water paint, preparation method reaction step is few, reacts very reliable, and reaction efficiency is high, environmental pollution is small, reaction condition is mild,
It is insensitive.Using the strong sulfonic group monomer of polarity as raw material, the molecule chain rigidity synthesized is big, and glass transition temperature is high, sticks stream temperature
Height, the product heat resistance synthesized is high, and tensile strength is big.In addition to this, there are also following effects by the present invention:
1. the surfactant- free emulsion polymerization that the present invention uses, will be without soap sulfonic acid base class hydrophilic monomer, no hydrophobic list of soap alkyls
Body and initiator a reaction synthesize a kind of soap-free polymerization object, and this soap-free polymerization object is with the effect of emulsifier and synthesis material and its
He synthesizes a kind of polymer waterproof coating material at raw material reaction, this preparation method not only overcomes in conventional emulsion polymerizations due to emulsifier
Have the defects that and cause polymer electrical property, optical property, surface property and in terms of, while also as not
With addition emulsifier, and cost is greatly saved.
2. using sulfonic group, alkyl monomer as raw material, the polymer molecular weight range that is generated in the environment of pH value 9-9.5
It is moderate, the hydrophobic group on main chain can be made to be easy to form a film in surface enrichment so that waterproof performance is excellent and make polymer point
Entanglement effect is significant between sub- main chain, and the resistance of motion increases, so that it is all non-with the cohesive force, tensile elasticity and durability of basal plane
Chang Hao.
3. the present invention is using the strong sulfonic group monomer of polarity as raw material, the molecule chain rigidity synthesized is big, and glass transition temperature is high,
Glutinous stream temperature is high, and the product heat resistance synthesized is high, and tensile strength is big.
4. the present invention is added to suitable polyethers in the synthesis process, the waterproof effect for not only increasing film is also played
Good defoaming effect, make polymer reaction more sufficiently, film is more smooth, coating waterproofing effect is more excellent.
5. joined graphene oxide in synthesis process, mechanical property is obviously improved, and improves film forming and film strength,
Water resistance open country obtains a degree of promotion, and simultaneous oxidation graphene oxygen-containing functional group abundant can improve hydrolysis product of cement
Tensile strength and toughness, therefore the present invention is mixed with cement also good effect.
6. the netted combination of crosslinking agent strengthens the consistency and hardness of coating film forming, coating and building are enhanced
Caking property between surface and coating and coating improves the waterproof ability and weatherability of coating.
7. two different initiators that the present invention uses at different temperature more agree with required for two polymerization reactions
Activity so that two polymerization reactions synthesis polymer effect it is more preferable.
8. after synthesizing soap-free polymerization object, heat preservation makes this soap-free polymerization object remain most highly active, then by this no soap
Polymer is reacted with other raw materials, so that the activity of this soap-free polymerization object is fully utilized.
Specific embodiment
The present invention is further described combined with specific embodiments below, and the contents of the present invention are completely without being limited thereto.
Example 1
Raw material needed for preparing high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization object, in terms of 1000 parts of gross mass part,
Component including following mass parts:
The composition that sodium styrene sulfonate and 2- acrylamide-2-methyl propane sulfonic mass ratio are 2:5: 4 parts
Acrylic sodium sulfonate: 5 parts
Methylpropene sodium sulfonate: 0.47 part
The composition that dilauroyl peroxide and peroxidating trimethylacetic acid tert-butyl ester mass ratio are 5:7: 0.35 part
The composition that azobisisoheptonitrile and di-cyclohexylperoxy di-carbonate mass ratio are 3:8: 4.4 parts
Octadecyl vinyl ether: 6 parts
N- dodecylacrylamide: 250 parts
The composition that equal benzene dianhydride dimethacrylate hydroxyl ethyl ester and ethylene glycol dimethacrylate mass ratio are 1:4:
7.6 part
The copolyether that oxidative ethane and propylene oxide mass ratio are 2:1: 7 parts
The composition that ethanol amine and diethanol amine mass ratio are 4:5: 2.5 parts
The composition that potassium hydroxide and sodium carbonate mass ratio are 4:3: 10 parts
Graphene oxide: 0.6 part
Surplus is water.
The preparation method is as follows:
It 1) is the composition 4 of 2:5 by 200 parts of water, sodium styrene sulfonate and 2- acrylamide-2-methyl propane sulfonic mass ratio
Part, 0.47 part of methylpropene sodium sulfonate, the composition that dilauroyl peroxide and peroxidating trimethylacetic acid tert-butyl ester mass ratio are 5:7
0.35 part, 6 parts of octadecyl vinyl ether are added directly into the three-necked flask with agitating device, after mixing evenly, control
Temperature is reacted 2.8 hours at 75 DEG C, then keeps the temperature 1.6 hours, obtains soap-free polymerization object.
2) by 250 parts of N- dodecylacrylamide, 5 parts of acrylic sodium sulfonate, ethanol amine and diethanol amine mass ratio are
2.5 parts of the composition of 4:5,0.6 part of graphene oxide, oxidative ethane and propylene oxide mass ratio are that 7 parts of copolyether of 2:1 are configured to
A liquid, for use；Azobisisoheptonitrile is matched with 4.4 parts and 60 parts water of composition that di-cyclohexylperoxy di-carbonate mass ratio is 3:8
B liquid is made, for use.
3) soap-free polymerization object is cooled to 56 DEG C, A liquid and B liquid is slowly dropped in three-necked flask simultaneously, the A drop added-time
Between 5.6 hours, B liquid time for adding be 6.6 hours, while be added dropwise while stir soap-free polymerization object, stirring beginning half an hour
Equal benzene dianhydride dimethacrylate hydroxyl ethyl ester and ethylene glycol dimethacrylate mass ratio is added afterwards as the composition 7.6 of 1:4
Part.
Example 2
Raw material needed for preparing high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization object, in terms of 1000 parts of gross mass part,
Component including following mass parts:
Sodium styrene sulfonate: 4 parts
Sodium vinyl sulfonate: 6 parts
Methylpropene sodium sulfonate: 0.54 part
Azodiisobutyronitrile: 0.42 part
Azobisisoheptonitrile: 3.8 parts
Octadecyl vinyl ether: 8 parts
N- dodecylacrylamide: 241 parts
Polyethyleneglycol diacrylate (n=9): 6.3 parts
The copolyether that ethylene oxide and propylene oxide mass ratio are 1:2: 7 parts
Diethanol amine: 5.2 parts
Potassium hydroxide: 8 parts
Graphene oxide: 0.9 part
Surplus is water.
The preparation method is as follows:
1) by 200 parts of water, 4 parts of sodium styrene sulfonate, 0.54 part of methylpropene sodium sulfonate, 0.42 part of azodiisobutyronitrile,
8 parts of octadecyl vinyl ether are added directly into the three-necked flask with agitating device, after mixing evenly, control temperature 66
It is reacted 3.2 hours at DEG C, then keeps the temperature 2.7 hours, obtain soap-free polymerization object.
2) by 241 parts of N- dodecylacrylamide, 6 parts of sodium vinyl sulfonate, 5.2 parts of diethanol amine, graphene oxide
0.9 part, ethylene oxide and propylene oxide mass ratio are that 7 parts of copolyether of 1:2 are configured to A liquid, for use；Azobisisoheptonitrile 3.8
Part and 60 parts of water are configured to B liquid, for use.
3) soap-free polymerization object is cooled to 46 DEG C, A liquid and B liquid is slowly dropped in three-necked flask simultaneously, the A drop added-time
Between 5.3 hours, B liquid time for adding be 6.3 hours, while be added dropwise while stir soap-free polymerization object, stirring beginning half an hour
6.3 parts of addition polyethyleneglycol diacrylate (n=9) afterwards.
4) after completion of dropwise addition, by heat preservation, curing is added 8 parts of potassium hydroxide after solution is cooled to room temperature, and moisturizing is arrived
1000 parts, it is about 30% polymer waterproof coating material that mass fraction can be obtained after mixing evenly.
Example 3
Raw material needed for preparing high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization object, in terms of 1000 parts of gross mass part,
Component including following mass parts:
Sodium styrene sulfonate: 9 parts
The composition that sodium vinyl sulfonate and acrylic sodium sulfonate mass ratio are 1:2: 7 parts
Methylpropene sodium sulfonate: 0.84 part
Dibenzoyl peroxide: 0.61 part
The composition that two cyclopropyl ester of dicetyl peroxydicarbonate and di-cyclohexylperoxy di-carbonate mass ratio are 1:2: 3.8 parts
Octadecyl vinyl ether: 14 parts
N- dodecylacrylamide: 231 parts
The composition that equal benzene dianhydride dimethacrylate hydroxyl ethyl ester and ethylene glycol dimethacrylate mass ratio are 1:4:
6.5 part
The copolyether that ethylene oxide and propylene oxide mass ratio are 2:1: 7 parts
The composition that ethanol amine and diethanol amine mass ratio are 4:5: 5.1 parts
Sodium bicarbonate: 12 parts
Graphene oxide: 0.9 part
Surplus is water.
The preparation method is as follows:
1) by 200 parts of water, 9 parts of sodium styrene sulfonate, 0.84 part of methylpropene sodium sulfonate, dibenzoyl peroxide 0.61
Part, 14 parts of octadecyl vinyl ether are added directly into the three-necked flask with agitating device, after mixing evenly, control temperature
It is reacted 3.9 hours at 79 DEG C, then keeps the temperature 2.2 hours, obtain soap-free polymerization object.
2) by 231 parts of N- dodecylacrylamide, the group that sodium vinyl sulfonate and acrylic sodium sulfonate mass ratio are 1:2
Close 7 parts of object, 5.1 parts of composition that ethanol amine and diethanol amine mass ratio are 4:5,0.9 part of graphene oxide, ethylene oxide and ring
Ethylene Oxide mass ratio is that 7 parts of copolyether of 2:1 are configured to A liquid, for use；Two cyclopropyl ester of dicetyl peroxydicarbonate and dicetyl peroxydicarbonate
Dicyclohexyl maleate mass ratio is that 3.8 parts and 60 parts water of composition of 1:2 are configured to B liquid, for use.
3) soap-free polymerization object is cooled to 43 DEG C, A liquid and B liquid is slowly dropped in three-necked flask simultaneously, the A drop added-time
Between 6.2 hours, B liquid time for adding be 7.2 hours, while be added dropwise while stir soap-free polymerization object, stirring beginning half an hour
Equal benzene dianhydride dimethacrylate hydroxyl ethyl ester and ethylene glycol dimethacrylate mass ratio is added afterwards as the composition 6.5 of 1:4
Part.
4) after completion of dropwise addition, by heat preservation, 12 parts of sodium bicarbonate, and moisturizing is added in curing after solution is cooled to room temperature
To 1000 parts, it is about 30% polymer waterproof coating material that mass fraction can be obtained after mixing evenly.
Example 4
Raw material needed for preparing high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization object, in terms of 1000 parts of gross mass part,
Component including following mass parts:
The composition that sodium styrene sulfonate and 2- acrylamide-2-methyl propane sulfonic mass ratio are 1:3: 10 parts
The composition that sodium vinyl sulfonate and acrylic sodium sulfonate mass ratio are 1:2: 8 parts
Methylpropene sodium sulfonate: 0.69 part
The composition that dilauroyl peroxide and peroxidating trimethylacetic acid tert-butyl ester mass ratio are 5:7: 0.34 part
The composition that two cyclopropyl ester of dicetyl peroxydicarbonate and di-cyclohexylperoxy di-carbonate mass ratio are 1:2: 4.2 parts
N- octadecyl acrylamide: 7 parts
N- dodecylacrylamide: 225 parts
The composition that equal benzene dianhydride dimethacrylate hydroxyl ethyl ester and ethylene glycol dimethacrylate mass ratio are 1:4:
7.5 part
The copolyether that ethylene oxide and propylene oxide mass ratio are 2:1: 6 parts
The composition that sodium methoxide and sodium ethoxide mass ratio are 3:2: 5.4 parts
The composition that sodium carbonate and sodium bicarbonate mass ratio are 3:2: 12 parts
Graphene oxide: 0.8 part
Surplus is water.
The preparation method is as follows:
It 1) is the composition of 1:3 by 200 parts of water, sodium styrene sulfonate and 2- acrylamide-2-methyl propane sulfonic mass ratio
10 parts, 0.69 part of methylpropene sodium sulfonate, the composition that dilauroyl peroxide and peroxidating trimethylacetic acid tert-butyl ester mass ratio are 5:7
0.34 part, 7 parts of N- octadecyl acrylamide are added directly into the three-necked flask with agitating device, after mixing evenly, control
Temperature processed is reacted 3.2 hours at 73 DEG C, then keeps the temperature 1.9 hours, obtains soap-free polymerization object.
2) by 225 parts of N- dodecylacrylamide, the group that sodium vinyl sulfonate and acrylic sodium sulfonate mass ratio are 1:2
8 parts of object are closed, 0.8 part of graphene oxide, sodium methoxide is 5.4 parts of composition of 3:2 with sodium ethoxide mass ratio, ethylene oxide and epoxy
Propane mass ratio is that 6 parts of copolyether of 2:1 are configured to A liquid, for use；Two cyclopropyl ester of dicetyl peroxydicarbonate and dicetyl peroxydicarbonate two
Cyclohexyl mass ratio is that 4.2 parts and 60 parts water of composition of 1:2 are configured to B liquid, for use.
3) soap-free polymerization object is cooled to 52 DEG C, A liquid and B liquid is slowly dropped in three-necked flask simultaneously, the A drop added-time
Between 5.1 hours, B liquid time for adding be 6.1 hours, while be added dropwise while stir soap-free polymerization object, stirring beginning half an hour
Equal benzene dianhydride dimethacrylate hydroxyl ethyl ester and ethylene glycol dimethacrylate mass ratio is added afterwards as the composition 7.5 of 1:4
Part.
4) after completion of dropwise addition, by heat preservation, sodium carbonate and sodium bicarbonate quality is added in curing after solution is cooled to room temperature
Than 12 parts of composition for 3:2, and moisturizing, to 1000 parts, it is about that 30% polymer is anti-that mass fraction can be obtained after mixing evenly
Water paint.
Example 5
Raw material needed for preparing high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization object, in terms of 1000 parts of gross mass part,
Component including following mass parts:
The composition that sodium styrene sulfonate and 2- acrylamide-2-methyl propane sulfonic mass ratio are 1:3: 6 parts
Sodium vinyl sulfonate: 7 parts
Methylpropene sodium sulfonate: 0.53 part
Dibenzoyl peroxide: 0.38 part
The composition that azobisisoheptonitrile and di-cyclohexylperoxy di-carbonate mass ratio are 3:8: 3.9 parts
N- octadecyl acrylamide: 7 parts
N- dodecylacrylamide: 237 parts
Equal benzene dianhydride dimethacrylate hydroxyl ethyl ester: 8.5 parts
The copolyether that ethylene oxide and propylene oxide mass ratio are 3:2: 8 parts
The composition that ethanol amine and diethanol amine mass ratio are 4:5: 4.6 parts
The composition that sodium carbonate and sodium bicarbonate mass ratio are 3:2: 14 parts
Graphene oxide: 1.0 parts
Surplus is water.
The preparation method is as follows:
It 1) is the composition 6 of 1:3 by 200 parts of water, sodium styrene sulfonate and 2- acrylamide-2-methyl propane sulfonic mass ratio
Part, 0.53 part of methylpropene sodium sulfonate, 0.38 part of dibenzoyl peroxide, 7 parts of N- octadecyl acrylamide are added directly into
In three-necked flask with agitating device, after mixing evenly, control temperature is reacted 3.2 hours at 72 DEG C, then to keep the temperature 2.2 small
When, obtain soap-free polymerization object.
2) by 237 parts of N- dodecylacrylamide, 7 parts of sodium vinyl sulfonate, ethanol amine and diethanol amine mass ratio are
4.6 parts of the composition of 4:5,1.0 parts of graphene oxide, 8 parts of the copolyether preparations that ethylene oxide and propylene oxide mass ratio are 3:2
At A liquid, for use；3.9 parts and 60 parts water of composition that azobisisoheptonitrile and di-cyclohexylperoxy di-carbonate mass ratio are 3:8
It is configured to B liquid, for use.
3) soap-free polymerization object is cooled to 52 DEG C, A liquid and B liquid is slowly dropped in three-necked flask simultaneously, the A drop added-time
Between 4.8 hours, B liquid time for adding be 5.8 hours, while be added dropwise while stir soap-free polymerization object, stirring beginning half an hour
After be added equal 8.5 parts of benzene dianhydride dimethacrylate hydroxyl ethyl ester.
4) after completion of dropwise addition, by heat preservation, sodium carbonate and sodium bicarbonate quality is added in curing after solution is cooled to room temperature
Than 14 parts of composition for 3:2, and moisturizing, to 1000 parts, it is about that 30% polymer is anti-that mass fraction can be obtained after mixing evenly
Water paint.
Example 6
Raw material needed for preparing high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization object, in terms of 1000 parts of gross mass part,
Component including following mass parts:
The composition that sodium vinyl sulfonate and acrylic sodium sulfonate mass ratio are 1:2: 10 parts
Acrylic sulfonic acid: 4 parts
Methylpropene sodium sulfonate: 0.86 part
Dibenzoyl peroxide: 0.54 part
The composition that two cyclopropyl ester of dicetyl peroxydicarbonate and di-cyclohexylperoxy di-carbonate mass ratio are 1:2: 3.9 parts
Ethylene glycol dimethacrylate: 5.4 parts
N- dodecylacrylamide: 228 parts
N- octadecyl acrylamide: 4.7 parts
The copolyether that polyethers is ethylene oxide and propylene oxide mass ratio is 1:2: 16 parts
The composition that sodium methoxide and sodium ethoxide mass ratio are 3:2: 3.7 parts
The composition that potassium hydroxide and sodium carbonate mass ratio are 4:3: 10 parts
Graphene oxide: 0.4 part
Surplus is water.
The preparation method is as follows:
It 1) is 10 parts of composition of 1:2 by 200 parts of water, sodium vinyl sulfonate and acrylic sodium sulfonate mass ratio, methyl-prop
0.86 part of alkene sodium sulfonate, 0.54 part of dibenzoyl peroxide, 4.7 parts of N- octadecyl acrylamide are added directly into stirring
In the three-necked flask of device, after mixing evenly, control temperature is reacted 2.5 hours at 82 DEG C, then keeps the temperature 2.5 hours, obtains nothing
Soap polymer.
2) by 228 parts of N- dodecylacrylamide, 4 parts of acrylic sulfonic acid, sodium methoxide and sodium ethoxide mass ratio are 3:2's
3.7 parts of composition, 0.4 part of graphene oxide, 16 parts of the copolyether that polyethers is ethylene oxide and propylene oxide mass ratio is 1:2 is matched
A liquid is made, for use；The composition 3.9 that two cyclopropyl ester of dicetyl peroxydicarbonate and di-cyclohexylperoxy di-carbonate mass ratio are 1:2
Part and 60 parts of water are configured to B liquid, for use.
3) soap-free polymerization object is cooled to 54 DEG C, A liquid and B liquid is slowly dropped in three-necked flask simultaneously, the A drop added-time
Between 5.3 hours, B liquid time for adding be 6.3 hours, while be added dropwise while stir soap-free polymerization object, stirring beginning half an hour
5.4 parts of ethylene glycol dimethacrylate are added afterwards.
4) after completion of dropwise addition, by heat preservation, potassium hydroxide and sodium carbonate quality is added in curing after solution is cooled to room temperature
Than 10 parts of composition for 4:3, and moisturizing, to 1000 parts, it is about that 30% polymer is anti-that mass fraction can be obtained after mixing evenly
Water paint.
Each embodiment product property tests table
As can be seen from the above table, the present invention uses the sulfonic group alkyl polymer water-repellent paint of surfactant- free emulsion polymerization preparation
Conventional waterproof coating compared to same solid content in the market all has greatly improved in performance indexes, in conjunction with example 4
Can be obvious find out, the present invention compares traditional water-repellent paint in terms of tensile strength and water resistance significant enhancement, simultaneously
Water-repellent paint of the invention not only is stablized by property, can store, and low temperature flexibility is good, impermeability is strong, and tensile strength is big, film
Smooth surface can be very good to keep sag resistance energy under daily outdoor temperature.So in contrast, waterproof of the invention applies
Material is more suitable for the market demand of today.
The foregoing is only a preferred embodiment of the present invention, but the scope of protection of the invention be not limited thereto,
Any modification that anyone skilled in the art is made in the technical scope disclosed by the present invention, equivalent replacement and
Improve etc., it should be included within the protection scope of invention.
Claims (10)
1. a kind of preparation method of high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization object, which is characterized in that including following step
It is rapid:
1) by 200 parts of water, 4-8 parts without soap sulfonic acid base class hydrophilic monomer, 6-14 parts without soap alkyls hydrophobic monomer, 0.32-0.62
Part initiator a, 0.38-0.86 part of chain-transferring agent be added directly into the three-necked flask with agitating device, after mixing evenly, control
Temperature processed is reacted 2.5-4.2 hours at 66-85 DEG C, then keeps the temperature 1.0-3.0 hours, obtains soap-free polymerization object；
Described is one of sodium styrene sulfonate, 2- acrylamide-2-methyl propane sulfonic without soap sulfonic acid base class hydrophilic monomer
Or two kinds；
Described without soap alkyls hydrophobic monomer is one of N- octadecyl acrylamide, octadecyl vinyl ether or several
Kind；
2) by 220-290 parts of alkyls hydrophobic monomer, 5-10 parts of sulfonic acid base class hydrophilic monomer, 2.5-5.9 parts of pH adjusting agent, oxidation
0.3-1.0 parts of graphene function monomer, 7-18 parts of polyethers be configured to A liquid；2.8-6.2 parts of initiator b and 60 parts of water are configured to B
Liquid；
The alkyls hydrophobic monomer is N- dodecylacrylamide；
3) soap-free polymerization object is cooled to 38-64 DEG C, A liquid and B liquid is slowly dropped in three-necked flask simultaneously, the A drop added-time
Between 4.2-6.2 hour, B liquid time for adding ratio A liquid is 1 hour long, while be added dropwise while stir soap-free polymerization object, stirring beginning half
Crosslinking agent 5.2-9.5 parts is added after hour；
4) after completion of dropwise addition, by heat preservation, curing is added neutralizer 7-20 parts after solution is cooled to room temperature, and moisturizing is arrived
1000 parts, it is about 30% polymer waterproof coating material that mass fraction can be obtained after mixing evenly；
The number is mass parts.
2. according to the method described in claim 1, it is characterized by: the sulfonic acid base class hydrophilic monomer is vinyl sulfonic acid
One or more of sodium, acrylic sodium sulfonate, methylpropene sodium sulfonate.
3. according to the method described in claim 1, it is characterized by: the crosslinking agent is equal benzene dianhydride dimethacrylate hydroxyl
Ethyl ester, two (methylacryoyloxyethyls) benzene dianhydride ester, ethylene glycol dimethacrylate, polyethyleneglycol diacrylate (n
=5), polyethyleneglycol diacrylate (n=9), three (2- ethoxy) isocyanuric acid triacrylates, ethylene glycol dimethyl propylene
One or more of acid esters, 1,4-butanediol dimethylacrylate.
4. according to the method described in claim 1, it is characterized by: the graphene oxide function monomer is graphite oxide
Alkene.
5. according to the method described in claim 1, it is characterized by: the initiator a is azodiisobutyronitrile, peroxidating ten
One or more of two acyls, the peroxidating trimethylacetic acid tert-butyl ester, dibenzoyl peroxide.
6. according to the method described in claim 1, it is characterized by: the initiator b is azobisisoheptonitrile, peroxidating two
One or more of diisopropyl carbonate, di-cyclohexylperoxy di-carbonate；The initiator b activity is less than initiator a.
7. according to the method described in claim 1, it is characterized by: the pH adjusting agent is sodium methoxide, sodium ethoxide, ethyl alcohol
One or more of amine, diethanol amine, triethanolamine, triisopropanolamine；The neutralizer is the hydroxide of 30% solubility
One or more of sodium solution, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate.
8. according to the method described in claim 1, it is characterized by: the polyethers is ethylene oxide and propylene oxide mass ratio
Copolyether, ethylene oxide and the propylene oxide mass ratio for being 2:1 for the copolyether of 1:2, ethylene oxide and propylene oxide mass ratio
One or more of copolyether for 3:2 composition.
9. according to the method described in claim 1, it is characterized by: the chain-transferring agent is methylpropene sodium sulfonate.
10. a kind of high-weatherability sulfonic group alkyls emulsifier-free emulsion polymerization object, it is characterised in that: using described in claim 1~9
Method preparation.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01279902A (en) * | 1987-08-12 | 1989-11-10 | Nippon Oil & Fats Co Ltd | Preparation of non-aqueous dispersion of polymer, non-aqueous dispersion of polymer and coating composition |
| CN103724520A (en) * | 2013-12-31 | 2014-04-16 | 汕头市大千高新科技研究中心有限公司 | Styrene-acrylic emulsion for building coating and preparation method of styrene-acrylic emulsion |
| CN110028617A (en) * | 2019-04-28 | 2019-07-19 | 英德市雅家涂料有限公司 | A kind of no soap self-crosslinking nanometer acrylic emulsion and its synthesis technology and application |
-
2019
- 2019-09-19 CN CN201910888271.8A patent/CN110511325A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01279902A (en) * | 1987-08-12 | 1989-11-10 | Nippon Oil & Fats Co Ltd | Preparation of non-aqueous dispersion of polymer, non-aqueous dispersion of polymer and coating composition |
| CN103724520A (en) * | 2013-12-31 | 2014-04-16 | 汕头市大千高新科技研究中心有限公司 | Styrene-acrylic emulsion for building coating and preparation method of styrene-acrylic emulsion |
| CN110028617A (en) * | 2019-04-28 | 2019-07-19 | 英德市雅家涂料有限公司 | A kind of no soap self-crosslinking nanometer acrylic emulsion and its synthesis technology and application |
Non-Patent Citations (1)
| Title |
|---|
| 梁庆丰等: "一种高光泽聚丙烯酸酯乳液的制备及性能研究", 《中国胶粘剂》 * |
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