CN109468006A - A kind of preparation method of the core-shell type aqueous acrylic resin coating of antifriction - Google Patents
A kind of preparation method of the core-shell type aqueous acrylic resin coating of antifriction Download PDFInfo
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- CN109468006A CN109468006A CN201811361730.9A CN201811361730A CN109468006A CN 109468006 A CN109468006 A CN 109468006A CN 201811361730 A CN201811361730 A CN 201811361730A CN 109468006 A CN109468006 A CN 109468006A
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- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The invention discloses a kind of preparation methods of the core-shell type aqueous acrylic resin coating of antifriction, and the raw material of following weight proportion: water, emulsifier, acrylic acid is added into 500ml three-necked flask, and 30min is stirred in heating, and A monomer, emulsification is added；It is warming up to 70 DEG C and starts logical recirculation water, kept the temperature after being warming up to 80 DEG C, initiator is added dropwise, time for adding continues 1 ~ 2h, reacts 2h after dripping；Antifriction liniment A and aluminium chloride are added, 0.5h is stirred to react, obtains stratum nucleare lotion；The initiator of B monomer sum is added dropwise simultaneously into stratum nucleare lotion obtained by step (1), time for adding continues 0.5h, 75 ~ 85 DEG C, which are kept the temperature, after dripping is stirred to react 2h, 70 DEG C again, emulsifier and antifriction liniment B is added, reaction time 30min adds ammonium hydroxide tune pH value to 7 ~ 8, obtains water soluble acrylic acid esters resin coating；Gained acrylic resin coating is poured into gained mixture template, 24 ~ 48h is placed, obtains the core-shell type aqueous acrylic resin coating of antifriction, gained acrylic resin coefficient of friction is small.
Description
Technical field
The invention belongs to water soluble acrylic acid esters resin paint fields, and in particular to a kind of core-shell type aqueous propylene of antifriction
The preparation method of esters of gallic acid cold coating.
Background technique
The kind of Chinese acrylic resin comparatively perfect, but with it is external it is advanced go together compared with, production scale, technique
There is also certain gaps for the product that control and part property require.
The building coating of China ratio shared in acrylic coating is 24%, is in the medium development level in the world.At present
The annual output of China is at 500,000 tons or so, and wherein interior wall accounts for 60%, and exterior wall accounts for 25%, other account for 15%.
Although China's coating used at present, still based on low and middle-grade, the kind of Chinese acrylic coating is more complete, with
Developed country compares, gap and the kind for not lying in coating, but raw material, production equipment, production technology and production-scale
Gap.Wherein production scale is larger, the higher enterprise of technology starting point, and the product technology content of production is high, high-quality.
Substrate carry, towing etc. during can frequently encounter more serious friction, however conventional urethane coating
Surface lubrication it is poor, be easy to fall off when encountering friction, be damaged, reducing the protecting effect to substrate.
Fish scale is combined between layers relatively closely, single scale shows irregular centre in folded layered distribution
6 thin side shape shapes of thick both sides, due to its unique arrangement mode, there are exposed region and non-exposed region in fish scale surface, by upper one layer
Being covered is non-exposed region, and fish scale surface is divided into 3 areas, is embedded in skin corium and is covered and is
Push up area；Being exposed to outer is base area;Two sides are lateral areas, and the focus in 3rd area is that squama is burnt.Observed under electron microscope scale table
The part that there are concentric circles in face is that ringed line is referred to as squama ridge and discontinuous radioactive ray part i.e. squama ditch, and most of fish scale has 3
Squama ditch, squama ridge and squama ditch may play the role of reducing resistance.
The shrinkage pool on fish scale surface is copied, three-dimensional fish scale shape shrinkage pool simplified model is established, which, which has, more significantly subtracts
Effect is hindered, relative to smooth surface, although fish scale shape pit surface produces additional pressure drag, but be also greatly reduced simultaneously
Frictional resistance, finally produces drag-reduction effect.
Patent of invention 201710450821.9 is related to the invention discloses a kind of antifriction polyurethane coating, it is by weight
Than the materials A and curing agent composition for 2 ~ 3:1, by the esterification of oleic acid and trimethylolpropane, obtain having good
The ester of greasy property, while inorganic lubricant filler sufficiently being organised, be modified its dispersibility between polymer, and obtains
Lubricating ester forms effective collaboration lubricant effect, improves the antifriction performance of finished product film, disadvantage of the invention is non-aqueous
Ratio added by property, inorganic filler is big, reduce the compatibility of added material and polyurethane, while frictional property has and further decreases
Space.
Summary of the invention
The invention discloses a kind of preparation methods of the core-shell type aqueous acrylic resin coating of antifriction, using to core
It is modified that the core and shell of shell acrylic esters resin use antifriction enhancing materials respectively, and the fish-skin for being used for fish scale does mould
Plate, formed film have good antifriction coefficient.
A kind of preparation method of the core-shell type aqueous acrylic resin coating of antifriction, it is characterised in that: (1) to
It is added the raw material of following weight proportion in 500ml three-necked flask: 40 ~ 60 g of water, 0.6 ~ 14g of emulsifier, acrylic acid 0.4 ~
2.0 parts, 40 ~ 55 DEG C are warming up to, stirs 30min, A monomer is added, emulsifies 30 ~ 60min；70 DEG C are warming up to open
Begin logical recirculation water, and 1h is kept the temperature after being warming up to 80 DEG C, 0.2 ~ 0.5g of initiator is added dropwise, and time for adding continues 1 ~ 2h, anti-after dripping
Answer 2h；1 ~ 2 g of antifriction liniment A and aluminium chloride 1.2g are added, 80 DEG C are stirred to react 0.5h, obtain stratum nucleare lotion；
The A monomer be by: 1 ~ 2g of hydroxy-ethyl acrylate, 6 ~ 8 g of butyl acrylate, 2 ~ 6 g of methyl methacrylate,
2.5 ~ 3.5 g of ethyl acrylate is mixed；
(2) B monomer and the initiator of 0.2 ~ 0.4g is added dropwise simultaneously into stratum nucleare lotion obtained by step (1), time for adding is lasting
0.5h keeps the temperature 75 ~ 85 DEG C after dripping and is stirred to react 2h, then 0 DEG C, be added 0.2 g of emulsifier and antifriction liniment B0.4 ~
0.7g, reaction time 30min add ammonium hydroxide tune pH value to 7 ~ 8, obtain water soluble acrylic acid esters resin coating；
The B monomer be by: 3 ~ 4g of butyl acrylate, 3 ~ 5 g of methyl methacrylate, ethyl acrylate 3.5 ~
4.5g, 0 ~ 1.5 g of styrene mixing composition；
(3) the fish-skin 20g with fish scale is peeled, being sequentially placed into mass concentration is 30%, 50%, 70%, 90%, 100%
It is dehydrated in graded ethanol, is then placed in the baking oven that temperature is 40 ~ 50 DEG C and dries, obtain the dry fish-skin with fish scale；It will
The ratio that dimethyl silicone polymer, curing agent, substance A and cure boosters are 10: 2:1:0.2 according to mass ratio
Example is mixed to get mixture, then falls mixture on the fish-skin obtained above with fish scale one side, in vacuum tank
It is transferred to after vacuumizing in the baking oven that temperature is 110 ~ 120 DEG C and solidifies 2 ~ 4h；By dimethyl silicone polymer, solidification
Agent, the mixture of substance A and cure boosters and fish-skin are removed, and mixture template is obtained；
(4) acrylic resin coating 30g ~ 50g obtained by step (2) is poured into mixture template obtained by step (3), places 24
~ 48h obtains the core-shell type aqueous acrylic resin coating of antifriction.
Emulsifier is the mixture that neopelex is mixed with fatty alcohol polyoxyethylene ether by weight 3:1；
Initiator is potassium peroxydisulfate, ammonium persulfate, azo diisobutyl amidine hydrochloride (AIBA, V-50 initiator), azo diisopropyl
Any one in imidazoline (abbreviation AIP, VA-061 initiator)；Antifriction liniment A is octamethylcy-clotetrasiloxane, γ-chlorine third
Any one of ethyl triethoxy silicane alkane, 5,7- dihydroxy -4'- methoxy isoflavone, trihydroxy-isoflavone；Antifriction liniment B is
One triethanolamine salt of 2-pyrrolidone-5-carboxylic acid, carboxymethyl chitosan, 3,3,4,5- tetrachlorosalicylanilide, CyclopropanecarboxylAcid Acid Isopropyl Ester
Any one；The curing agent is divinylbenzene, N,N methylene bis acrylamide, trimethylolpropane, dimethyl propylene
Any one of olefin(e) acid glycol ester；The cure boosters are the preparation method comprises the following steps: by 54g trimethylolpropane and phosphorus oxychloride
51g mixing, 0.5 ~ 2h of temperature rising reflux are washed to neutrality, are dried under reduced pressure to get intermediate A is arrived；Again by intermediate A, phosphorous acid two
32 ~ 48g of methyl esters is added in solvent acetone 78g, is heated up 70 ~ 80 DEG C, is reacted 1h, is added methyl propanediol 12g and sodium methoxide
1.6g, reacts 1 ~ 2h at 75 ~ 95 DEG C, and vacuum distillation removes solvent and residual methanol, obtains cure boosters；The substance A
Are as follows: 35g acetone will be added in o-ethoxyphenol 17g, 2 2- dihydromethyl propionic acid 38.6g, acetylacetone,2,4-pentanedione epoxy titanium 0.24g,
It is stirred to react 1 ~ 2h at 75 ~ 80 DEG C, adds aluminum sulfate 4.5g and water 3.6g, 1h is stirred to react at 75 ~ 90 DEG C, decompression is steamed
Acetone is fallen in distillation, obtains substance A.
Present invention has an advantage that
(1) shrinkage pool for copying fish scale surface, establishes three-dimensional fish scale shape shrinkage pool simplified model, which has more apparent drag reduction
Effect, relative to smooth surface, although fish scale shape pit surface produces additional pressure drag, but also significantly reduce simultaneously
Frictional resistance finally produces drag-reduction effect.
(2) preparation method of the core-shell type aqueous acrylic resin coating of a kind of antifriction, using to hud typed propylene
It is modified that the core and shell of acid esters resinoid use antifriction enhancing materials respectively, and the fish-skin for being used for fish scale does template, formed
Film has good antifriction coefficient.
(3) octamethylcy-clotetrasiloxane, γ-chloropropyl triethoxysilane, 5,7- dihydroxy -4'- methoxy isoflavone,
Trihydroxy-isoflavone, one triethanolamine salt of 2-pyrrolidone-5-carboxylic acid, carboxymethyl chitosan, 3,3,4,5- tetrachlorosalicylanilide, ring
Propane isopropyl formate is used as the material of antifriction coefficient.
(4) aluminium chloride is hydrolyzed under the action of certain water, and friction reducing material A is fixed.
(5) acetylacetone,2,4-pentanedione epoxy titanium is used as the catalyst for preparing of substance A, and the effect of substance A is to increase fish scale surface
Antifriction coefficient.
(6) part, parts by weight are equal to g.
Specific embodiment
Embodiment 1
A kind of preparation method of the core-shell type aqueous acrylic resin coating of antifriction, it is characterised in that: (1) to 500ml tri-
The raw material of following weight proportion: 40 g of water, emulsifier 0.6g (all emulsifier proportions are identical), propylene is added in mouth flask
0.4 g of acid is warming up to 40 DEG C, stirs 30min, and A monomer is added, and emulsifies 30min；70 DEG C are warming up to start to lead to
Recirculation water keeps the temperature 1h after being warming up to 80 DEG C, potassium peroxydisulfate 0.2g(5g water is added dropwise and dissolves), time for adding continues 1h, drips
After react 2h；1 g of octamethylcy-clotetrasiloxane and aluminium chloride 1.2g are added, 80 DEG C are stirred to react 0.5h, obtain stratum nucleare cream
Liquid；
The A monomer is by hydroxy-ethyl acrylate 1g, butyl acrylate 6g, methyl methacrylate 2g, acrylic acid second
Ester 2.5g is mixed；
(2) B monomer and the potassium peroxydisulfate (being dissolved with 5g water) of 0.2g, drop is added dropwise simultaneously into stratum nucleare lotion obtained by step (1)
Continue 0.5h between added-time, 75 DEG C are kept the temperature after dripping and is stirred to react 2h, then 70 DEG C, 0.2 g of emulsifier and pyrrolidones is added
Carboxylic acid one triethanolamine salt 0.4g, reaction time 30min, add ammonium hydroxide tune pH value to 7 ~ 8, obtain water soluble acrylic acid esters resin
Coating；
The B monomer is made of: butyl acrylate 3g, methyl methacrylate 3g, ethyl acrylate 3.5g mixing；
(3) the fish-skin 20g with fish scale is peeled, being sequentially placed into mass concentration is 30%, 50%, 70%, 90%, 100%
It is dehydrated in graded ethanol, is then placed in the baking oven that temperature is 40 DEG C and dries, obtain the dry fish-skin with fish scale；It will gather
The ratio that dimethyl siloxane, divinylbenzene, substance A and cure boosters are 10: 2:1:0.2 according to mass ratio
Example is mixed to get mixture (total weight 2.1g), then falls mixture on the fish-skin obtained above with fish scale one side,
It is transferred to after being vacuumized in vacuum tank in the baking oven that temperature is 110 DEG C and solidifies 2h；By dimethyl silicone polymer,
Divinylbenzene, the mixture of substance A and cure boosters and fish-skin are removed, and mixture template is obtained；
(4) acrylic resin coating 30g obtained by step (2) is poured into mixture template obtained by step (3), places for 24 hours, obtains
To the core-shell type aqueous acrylic resin coating of antifriction.
Emulsifier is the mixture that neopelex is mixed with fatty alcohol polyoxyethylene ether by weight 3:1
(according to the ratio, following instance is identical for step 1 and all emulsifier of step 2)
The cure boosters the preparation method comprises the following steps: 54g trimethylolpropane and phosphorus oxychloride 51g are mixed, temperature rising reflux 0.5h,
It is washed to neutrality, is dried under reduced pressure to get intermediate A is arrived；Intermediate A, dimethylphosphite 32g are added to solvent acetone again
It in 78g, heats up 70 DEG C, reacts 1h, add methyl propanediol 12g and sodium methoxide 1.6g, 1h is reacted at 75 DEG C, decompression is steamed
It evaporates, removes solvent and residual methanol, obtain cure boosters；
The substance A are as follows: by o-ethoxyphenol 17g, 2 2- dihydromethyl propionic acid 38.6g, acetylacetone,2,4-pentanedione epoxy titanium 0.24g
Middle addition 35g acetone, is stirred to react 1h at 75 DEG C, adds aluminum sulfate 4.5g and water 3.6g, be stirred to react 1h at 75 DEG C,
Acetone is removed in vacuum distillation, obtains substance A.
Embodiment 2
A kind of preparation method of the core-shell type aqueous acrylic resin coating of antifriction, it is characterised in that: (1) to 500ml tri-
The raw material of following weight proportion is added in mouth flask: 60 g of water, emulsifier 1.4g, 2.0 g of acrylic acid are warming up to 55 DEG C,
30min is stirred, A monomer is added, emulsifies 60min；It is warming up to 70 DEG C and starts logical recirculation water, kept the temperature after being warming up to 80 DEG C
1h is added dropwise ammonium persulfate 0.5g(5g water and dissolves), time for adding continues 2h, reacts 2h after dripping；Add γ-chlorine third
2 g of ethyl triethoxy silicane alkane and aluminium chloride 1.2g, 80 DEG C are stirred to react 0.5h, obtain stratum nucleare lotion；
The A monomer is by hydroxy-ethyl acrylate 2g, 8 g of butyl acrylate, 6 g of methyl methacrylate, acrylic acid second
3.5 g of ester is mixed；
(2) B monomer and the ammonium persulfate (being dissolved with 5g water) of 0.4g, drop is added dropwise simultaneously into stratum nucleare lotion obtained by step (1)
Continue 0.5h between added-time, keeps the temperature 85 DEG C after dripping and be stirred to react 2h, then 70 DEG C of 0.2 g of addition emulsifier and carboxymethyl chitosan
Sugared 0.7g, reaction time 30min add ammonium hydroxide tune pH value to 7 ~ 8, obtain water soluble acrylic acid esters resin coating；
The B monomer is by butyl acrylate 4g, 5 g of methyl methacrylate, ethyl acrylate 4.5g, styrene 1.5
G mixing composition；
(3) the fish-skin 20g with fish scale is peeled, being sequentially placed into mass concentration is 30%, 50%, 70%, 90%, 100%
It is dehydrated in graded ethanol, is then placed in the baking oven that temperature is 50 DEG C and dries, obtain the dry fish-skin with fish scale；It will gather
Dimethyl siloxane, N,N methylene bis acrylamide, substance A and cure boosters according to mass ratio be 10:
The ratio of 2:1:0.2 is mixed to get mixture (total weight 2.1g), then falls mixture and has fish scale in obtained above
On fish-skin on one side, it is transferred to after being vacuumized in vacuum tank in the baking oven that temperature is 120 DEG C and solidifies 4h；By poly- diformazan
Radical siloxane, N, N- methylene-bisacrylamide, the mixture of substance A and cure boosters and fish-skin are removed, are mixed
Close object template；
(4) acrylic resin coating 50g obtained by step (2) is poured into mixture template obtained by step (3), places 48h, obtains
To the core-shell type aqueous acrylic resin coating of antifriction.
Emulsifier is the mixture that neopelex is mixed with fatty alcohol polyoxyethylene ether by weight 3:1；
The cure boosters are the preparation method comprises the following steps: 54g trimethylolpropane and phosphorus oxychloride 51g are mixed, temperature rising reflux 2h, water
It is washed till neutrality, is dried under reduced pressure to get intermediate A is arrived；Intermediate A, dimethylphosphite 48g are added to solvent acetone 78g again
In, it heats up 80 DEG C, reacts 1h, add methyl propanediol 12g and sodium methoxide 1.6g, 2h is reacted at 95 DEG C, be evaporated under reduced pressure,
Solvent and residual methanol are removed, cure boosters are obtained；
The substance A are as follows: by o-ethoxyphenol 17g, 2 2- dihydromethyl propionic acid 38.6g, acetylacetone,2,4-pentanedione epoxy titanium 0.24g
Middle addition 35g acetone, is stirred to react 2h at 80 DEG C, adds aluminum sulfate 4.5g and water 3.6g, be stirred to react 1h at 90 DEG C,
Acetone is removed in vacuum distillation, obtains substance A.
Embodiment 3
A kind of preparation method of the core-shell type aqueous acrylic resin coating of antifriction, it is characterised in that: (1) to 500ml tri-
The raw material of following weight proportion is added in mouth flask: 50 g of water, emulsifier 1.0g, 1.2 g of acrylic acid are warming up to 48
DEG C, 30min is stirred, A monomer is added, emulsifies 45min；It is warming up to 70 DEG C and starts logical recirculation water, protected after being warming up to 80 DEG C
Azo diisobutyl amidine hydrochloride (AIBA, V-50 initiator) 0.35g (being dissolved with 5g water) is added dropwise in warm 1h, and time for adding is lasting
1.5h reacts 2h after dripping；Add 1.5 g of Biochanin A and aluminium chloride 1.2g, 80 DEG C
It is stirred to react 0.5h, obtains stratum nucleare lotion；
The A monomer is by hydroxy-ethyl acrylate 1.5g, 7 g of butyl acrylate, 4 g of methyl methacrylate, propylene
Acetoacetic ester 3g is mixed；
(2) B monomer and the azo diisobutyl amidine hydrochloride of 0.3g is added dropwise simultaneously into stratum nucleare lotion obtained by step (1)
(AIBA, V-50 initiator) (is dissolved) with 5g water, and time for adding continues 0.5h, is kept the temperature 80 DEG C after dripping and is stirred to react 2h,
70 DEG C of addition emulsifiers 0.2 g and 3,3,4,5- tetrachlorosalicylanilide 0.55g, reaction time 30min add ammonium hydroxide tune again
PH value obtains water soluble acrylic acid esters resin coating to 7 ~ 8；
The B monomer is by butyl acrylate 3.5g, 4 g of methyl methacrylate, ethyl acrylate 4g, styrene
0.75g mixing composition；
(3) the fish-skin 20g(20g with fish scale practical is peeled) peel, be sequentially placed into mass concentration be 30%, 50%, 70%,
90%, it is dehydrated in 100% graded ethanol, being then placed in temperature is to dry in 45 DEG C of baking oven, is obtained dry with fish scale
Fish-skin；It is according to mass ratio by dimethyl silicone polymer, trimethylolpropane, substance A and cure boosters
10: 2:1:0.2 ratio is mixed to get mixture (total weight 2.1g), then falls mixture and has in obtained above
On the fish-skin of fish scale one side, it is transferred to after being vacuumized in vacuum tank in the baking oven that temperature is 115 DEG C and solidifies 3h；It will gather
Mixture and the fish-skin removing of dimethyl siloxane, trimethylolpropane, substance A and cure boosters, are mixed
Object template；
(4) acrylic resin coating 40g obtained by step (2) is poured into mixture template obtained by step (3), places 36h, obtains
To the core-shell type aqueous acrylic resin coating of antifriction.
Emulsifier is the mixture that neopelex is mixed with fatty alcohol polyoxyethylene ether by weight 3:1；
The cure boosters are the preparation method comprises the following steps: 54g trimethylolpropane and phosphorus oxychloride 51g are mixed, temperature rising reflux 1h, water
It is washed till neutrality, is dried under reduced pressure to get intermediate A is arrived；Intermediate A, dimethylphosphite 40g are added to solvent acetone 78g again
In, it heats up 75 DEG C, reacts 1h, add methyl propanediol 12g and sodium methoxide 1.6g, 1.5h is reacted at 85 DEG C, decompression is steamed
It evaporates, removes solvent and residual methanol, obtain cure boosters；
The substance A are as follows: by o-ethoxyphenol 17g, 2 2- dihydromethyl propionic acid 38.6g, acetylacetone,2,4-pentanedione epoxy titanium 0.24g
Middle addition 35g acetone, is stirred to react 1.5h at 75 DEG C, adds aluminum sulfate 4.5g and water 3.6g, be stirred to react at 80 DEG C
1h, vacuum distillation remove acetone, obtain substance A.
Embodiment 4
A kind of preparation method of the core-shell type aqueous acrylic resin coating of antifriction, it is characterised in that: (1) to 500ml tri-
The raw material of following weight proportion is added in mouth flask: 45 g of water, emulsifier 0.8g, 1.3 g of acrylic acid are warming up to 48
DEG C, 30min is stirred, A monomer is added, emulsifies 45min；It is warming up to 70 DEG C and starts logical recirculation water, protected after being warming up to 80 DEG C
Ammonium persulfate 0.4g (being dissolved with 5g water) is added dropwise in warm 1h, and time for adding continues 1.5h, reacts 2h after dripping；Add three
Hydroxy-isoflavone 1.5g and aluminium chloride 1.2g, 80 DEG C are stirred to react 0.5h, obtain stratum nucleare lotion；
The A monomer is by hydroxy-ethyl acrylate 1g, butyl acrylate 7g, methyl methacrylate 4g, acrylic acid second
Ester 2.5g is mixed；
(2) B monomer and the ammonium persulfate (being dissolved with 5g water) of 0.3g, drop is added dropwise simultaneously into stratum nucleare lotion obtained by step (1)
Continue 0.5h between added-time, 80 DEG C are kept the temperature after dripping and is stirred to react 2h, then 70 DEG C, 0.2 g of emulsifier and cyclopropane first is added
Isopropyl propionate B70.7g, reaction time 30min add ammonium hydroxide tune pH value to 7 ~ 8, obtain water soluble acrylic acid esters resin coating；
The B monomer is by butyl acrylate 3.5g, 4 g of methyl methacrylate, ethyl acrylate 4g, styrene
0.75 g mixing composition；
(3) the fish-skin 20g with fish scale is peeled, being sequentially placed into mass concentration is 30%, 50%, 70%, 90%, 100%
It is dehydrated in graded ethanol, is then placed in the baking oven that temperature is 45 DEG C and dries, obtain the dry fish-skin with fish scale；It will gather
Dimethyl siloxane, ethylene glycol dimethacrylate, substance A and cure boosters are 10: 2 according to mass ratio:
The ratio of 1:0.2 is mixed to get mixture (total weight 2.1g), then falls mixture and has fish scale one in obtained above
On the fish-skin in face, it is transferred to after being vacuumized in vacuum tank in the baking oven that temperature is 115 DEG C and solidifies 3h；By poly- diformazan
Mixture and the fish-skin removing of radical siloxane, curing agent, substance A and cure boosters, obtain mixture template；
(4) acrylic resin coating 40g obtained by step (2) is poured into mixture template obtained by step (3), places 36h, obtains
To the core-shell type aqueous acrylic resin coating of antifriction.
Emulsifier is the mixture that neopelex is mixed with fatty alcohol polyoxyethylene ether by weight 3:1；
The cure boosters are the preparation method comprises the following steps: 54g trimethylolpropane and phosphorus oxychloride 51g are mixed, temperature rising reflux 1h, water
It is washed till neutrality, is dried under reduced pressure to get intermediate A is arrived；Intermediate A, dimethylphosphite 40g are added to solvent acetone 78g again
In, it heats up 75 DEG C, reacts 1h, add methyl propanediol 12g and sodium methoxide 1.6g, 1.5h is reacted at 85 DEG C, decompression is steamed
It evaporates, removes solvent and residual methanol, obtain cure boosters；
The substance A are as follows: by o-ethoxyphenol 17g, 2 2- dihydromethyl propionic acid 38.6g, acetylacetone,2,4-pentanedione epoxy titanium 0.24g
Middle addition 35g acetone, is stirred to react 1.5h at 75 DEG C, adds aluminum sulfate 4.5g and water 3.6g, be stirred to react at 80 DEG C
1h, vacuum distillation remove acetone, obtain substance A.
Embodiment 5
A kind of preparation method of the core-shell type aqueous acrylic resin coating of antifriction, it is characterised in that: (1) to 500ml tri-
The raw material of following weight proportion is added in mouth flask: water 50g, emulsifier 0.6g, acrylic acid 1.7g are warming up to 45 DEG C,
30min is stirred, A monomer is added, emulsifies 45min；It is warming up to 70 DEG C and starts logical recirculation water, kept the temperature after being warming up to 80 DEG C
Ammonium persulfate 0.2g (being dissolved with 5g water) is added dropwise in 1h, and time for adding continues 1.5h, reacts 2h after dripping；Add three hydroxyls
Base isoflavones 1.5g and aluminium chloride 1.2g, 80 DEG C are stirred to react 0.5h, obtain stratum nucleare lotion；
The A monomer is by hydroxy-ethyl acrylate 1.2g, 7 g of butyl acrylate, methyl methacrylate 4g, acrylic acid
2.5 g of ethyl ester is mixed；
(2) B monomer and the ammonium persulfate (being dissolved with 5g water) of 0.3g, drop is added dropwise simultaneously into stratum nucleare lotion obtained by step (1)
Continue 0.5h between added-time, 80 DEG C are kept the temperature after dripping and is stirred to react 2h, then 70 DEG C, 0.2 g of emulsifier and cyclopropane first is added
Isopropyl propionate 0.5g, reaction time 30min add ammonium hydroxide tune pH value to 7 ~ 8, obtain water soluble acrylic acid esters resin coating；
The B monomer is by butyl acrylate 3g, 5 g of methyl methacrylate, ethyl acrylate 4.5g, styrene
0.6 g mixing composition；
(3) the fish-skin 20g with fish scale is peeled, being sequentially placed into mass concentration is 30%, 50%, 70%, 90%, 100%
It is dehydrated in graded ethanol, is then placed in the baking oven that temperature is 45 DEG C and dries, obtain the dry fish-skin with fish scale；It will gather
Dimethyl siloxane, N,N methylene bis acrylamide, substance A and cure boosters are 10: 2 according to mass ratio:
The ratio of 1:0.2 is mixed to get mixture (total weight 2.1g), then falls mixture and has fish scale one in obtained above
On the fish-skin in face, it is transferred to after being vacuumized in vacuum tank in the baking oven that temperature is 115 DEG C and solidifies 3h；By poly- diformazan
Radical siloxane, N, N- methylene-bisacrylamide, the mixture of substance A and cure boosters and fish-skin are removed, are mixed
Close object template；
(4) acrylic resin coating 40g obtained by step (2) is poured into mixture template obtained by step (3), places for 24 hours, obtains
To the core-shell type aqueous acrylic resin coating of antifriction.
Emulsifier is the mixture that neopelex is mixed with fatty alcohol polyoxyethylene ether by weight 3:1；
The cure boosters are the preparation method comprises the following steps: 54g trimethylolpropane and phosphorus oxychloride 51g are mixed, temperature rising reflux 1h, water
It is washed till neutrality, is dried under reduced pressure to get intermediate A is arrived；Intermediate A, dimethylphosphite 32g are added to solvent acetone 78g again
In, it heats up 75 DEG C, reacts 1h, add methyl propanediol 12g and sodium methoxide 1.6g, 1.5h is reacted at 85 DEG C, decompression is steamed
It evaporates, removes solvent and residual methanol, obtain cure boosters；The substance A are as follows: by o-ethoxyphenol 17g, 2 2- dihydroxy first
35g acetone is added in base propionic acid 38.6g, acetylacetone,2,4-pentanedione epoxy titanium 0.24g, is stirred to react 1.5h at 75 DEG C, adds sulfuric acid
Aluminium 4.5g and water 3.6g, is stirred to react 1h at 80 DEG C, and vacuum distillation removes acetone, obtains substance A.
Performance test: as can be seen that antifriction acrylic resin coating of the invention has more high-wear resistance, to base
The protectiveness of material is good.Selected conventional acrylic esters resin coating (water soluble acrylic acid WA-360E, Jiangsu sea cowry new material
Science and Technology Ltd.)
1 antifriction acrylic resin performance of table
| Index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Conventional acrylic esters resin |
| Akron abrasion (cm3/1.61km) | 0.0165 | 0.0236 | 0.0189 | 0.0459 | 0.0338 | 0.26 |
| Abrasion resistance (2000 times) | Film does not damage | Film does not damage | Film does not damage | Film does not damage | Film does not damage | The non-partial destruction of film |
| Appearance of film | Normally | Normally | Normally | Normally | Normally | Normally |
As can be found from Table 1, the barasion coefficient of such material is small, while abrasion resistance is good, it is normal to smear appearance.
2 antifriction acrylic resin performance of table (does not carry out step 3 and step 4 processing)
| Index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Conventional acrylic esters resin |
| Akron abrasion (cm3/1.61km) | 0.1856 | 0.0875 | 0.0942 | 0.0982 | 0.0876 | 0.26 |
As can be found from Table 2, the Akron abrasion for not carrying out such material of step 3 and step 4 increases.
3 antifriction acrylic resin performance (not plus substance A) of table
| Index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Akron abrasion (cm3/1.61km) | 0.0753 | 0.0589 | 0.0498 | 0.0664 | 0.0753 |
From table 3 it can be seen that the Akron abrasion of substance A is not added to increase.
4 antifriction acrylic resin performance of table (add substance A, not plus acetylacetone,2,4-pentanedione epoxy titanium)
| Index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Akron abrasion (cm3/1.61km) | 0.0453 | 0.0345 | 0.0378 | 0.0432 | 0.0547 |
From table 4, it can be seen that plus substance A, and be not added acetylacetone,2,4-pentanedione epoxy titanium Akron abrasion increase.
5 antifriction acrylic resin performance of table (not adding and subtracting rubbing agent A or B)
As can be seen from Table 5, rubbing agent A or B(are not added and subtracted as not plus A, then plus B) Akron abrasion it is higher, illustrate that it rubs
It is higher to wipe coefficient.
Claims (8)
1. a kind of preparation method of the core-shell type aqueous acrylic resin coating of antifriction, it is characterised in that:
(1) raw material of following weight proportion: 40 ~ 60 g of water, 0.6 ~ 1.4g of emulsifier, third is added into 500ml three-necked flask
0.4 ~ 2.0 part of olefin(e) acid, 40 ~ 55 DEG C are warming up to, stirs 30min, A monomer is added, emulsifies 30 ~ 60min；Heating
Start logical recirculation water to 70 DEG C, 1h is kept the temperature after being warming up to 80 DEG C, 0.2 ~ 0.5g of initiator is added dropwise, time for adding continues 1 ~ 2h, drips
2h is reacted after adding；1 ~ 2 g of antifriction liniment A and aluminium chloride 1.2g are added, 80 DEG C are stirred to react 0.5h, obtain stratum nucleare lotion
；
The A monomer be by: 1 ~ 2g of hydroxy-ethyl acrylate, 6 ~ 8 g of butyl acrylate, 2 ~ 6 g of methyl methacrylate,
2.5 ~ 3.5 g of ethyl acrylate is mixed；
(2) B monomer and the initiator of 0.2 ~ 0.4g is added dropwise simultaneously into stratum nucleare lotion obtained by step (1), time for adding is lasting
0.5h keeps the temperature 75 ~ 85 DEG C after dripping and is stirred to react 2h, then 70 DEG C, be added 0.2 g of emulsifier and antifriction liniment B0.4 ~
0.7g, reaction time 30min add ammonium hydroxide tune pH value to 7 ~ 8, obtain water soluble acrylic acid esters resin coating；
The B monomer be by: 3 ~ 4g of butyl acrylate, 3 ~ 5 g of methyl methacrylate, ethyl acrylate 3.5 ~
4.5g, 0 ~ 1.5 g of styrene mixing composition；
(3) the fish-skin 20g with fish scale is peeled, being sequentially placed into mass concentration is 30%, 50%, 70%, 90%, 100%
It is dehydrated in graded ethanol, is then placed in the baking oven that temperature is 40 ~ 50 DEG C and dries, obtain the dry fish-skin with fish scale；It will
The ratio that dimethyl silicone polymer, curing agent, substance A and cure boosters are 10: 2:1:0.2 according to mass ratio
Example is mixed to get mixture, then falls mixture on the fish-skin obtained above with fish scale one side, in vacuum tank
It is transferred to after vacuumizing in the baking oven that temperature is 110 ~ 120 DEG C and solidifies 2 ~ 4h；By dimethyl silicone polymer, solidification
Agent, the mixture of substance A and cure boosters and fish-skin are removed, and mixture template is obtained；
(4) acrylic resin coating 30g ~ 50g obtained by step (2) is poured into mixture template obtained by step (3), places 24
~ 48h obtains the core-shell type aqueous acrylic resin coating of antifriction.
2. a kind of preparation method of core-shell type aqueous acrylic resin coating as described in claim 1, feature exist
In emulsifier is the mixture that neopelex is mixed with fatty alcohol polyoxyethylene ether by weight 3:1.
3. a kind of preparation method of core-shell type aqueous acrylic resin coating as described in claim 1, feature exist
In initiator is potassium peroxydisulfate, ammonium persulfate, azo diisobutyl amidine hydrochloride (AIBA, V-50 initiator), azo diisopropyl
Any one in base imidazoline (abbreviation AIP, VA-061 initiator).
4. a kind of preparation method of the core-shell type aqueous acrylic resin coating of antifriction as described in claim 1: antifriction
Liniment A is octamethylcy-clotetrasiloxane, γ-chloropropyl triethoxysilane, 5,7- dihydroxy -4'- methoxy isoflavone, three hydroxyls
Any one of base isoflavones.
5. a kind of preparation method of the core-shell type aqueous acrylic resin coating of antifriction as described in claim 1: antifriction
Liniment B is one triethanolamine salt of 2-pyrrolidone-5-carboxylic acid, carboxymethyl chitosan, 3,3,4,5- tetrachlorosalicylanilide, cyclopropane first
Any one of isopropyl propionate.
6. a kind of preparation method of the core-shell type aqueous acrylic resin coating of antifriction as described in claim 1, described
Curing agent be divinylbenzene, N,N methylene bis acrylamide, trimethylolpropane, ethylene glycol dimethacrylate appoint
It anticipates one kind.
7. a kind of preparation method of core-shell type aqueous acrylic resin coating as described in claim 1, the solidification increase
Agent is imitated the preparation method comprises the following steps: 54g trimethylolpropane and phosphorus oxychloride 51g are mixed, 0.5 ~ 2h of temperature rising reflux is washed to neutrality,
It is dried under reduced pressure to get intermediate A is arrived；Intermediate A, 32 ~ 48g of dimethylphosphite are added in solvent acetone 78g again, risen
70 ~ 80 DEG C of temperature reacts 1h, adds methyl propanediol 12g and sodium methoxide 1.6g, and 1 ~ 2h is reacted at 75 ~ 95 DEG C, and decompression is steamed
It evaporates, removes solvent and residual methanol, obtain cure boosters.
8. a kind of preparation method of core-shell type aqueous acrylic resin coating as described in claim 1, the substance A
Are as follows: 35g acetone will be added in o-ethoxyphenol 17g, 2 2- dihydromethyl propionic acid 38.6g, acetylacetone,2,4-pentanedione epoxy titanium 0.24g,
It is stirred to react 1 ~ 2h at 75 ~ 80 DEG C, adds aluminum sulfate 4.5g and water 3.6g, 1h is stirred to react at 75 ~ 90 DEG C, decompression is steamed
Acetone is fallen in distillation, obtains substance A.
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