CN110283268A - A kind of compatibility is good, the hydroxy acryl acid resin that stability is high and preparation method thereof - Google Patents
A kind of compatibility is good, the hydroxy acryl acid resin that stability is high and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
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- 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
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- 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
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- C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
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- 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
- C09D133/062—Copolymers with monomers not covered by C09D133/06
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Abstract
The present invention relates to aqueous paint technology fields,, hydroxy acryl acid resin that stability high good more particularly to a kind of compatibility and preparation method thereof, is made of following components in percentage by weight: 12~80 parts of acrylate, 1~2 part of initiator, 1~4 part of chain-transferring agent, 2~25 parts hydroxyl of acrylate, 40~50 parts of 0.5~5 part of 3~5 parts of 5~10 parts of acrylate, neutralizer, response type anion emulsifier, the water with carboxylic acid；The resin has the advantages that capacitive is good, stability is high, which can produce the preparation method for the hydroxy acryl acid resin having the above advantages.
Description
Technical field
The present invention relates to aqueous paint technology fields, and in particular to the hydroxyl propylene that a kind of compatibility is good, stability is high
Acid resin and preparation method thereof.
Background technique
Water based acrylic resin is not only more conducive to ring than solvent type Hydroxylated acrylic resin using water as decentralized medium
It protects, and lower than aqueous polyurethane preparation cost and be easier to adjustment and control system stickiness, therefore, water-based hydroxyl than aqueous polyurethane
Acrylic resin is more welcomed by the people.
In practical application, water based acrylic resin more payes attention to the dispersion of resin particle than common acrylic resin
Property, thus need to add the problem of dispersing agent is reunited to avoid water based acrylic resin, but dispersing agent is easy to lead
It causes the water resistance of the aqueous woodware paint paint film of property of water-bearing Hydroxylated acrylic resin to be deteriorated bad with brokenly bubble, affects the product of paint film
Matter.Therefore, the prior art promotes the dispersion stabilization of dispersing agent by addition emulsifier, it is intended to improve water-based hydroxyl acrylic acid
The stability of resin, and the monomer in water based acrylic resin is promoted to polymerize by micella basis mechanism, to guarantee the poly- of monomer
Rate, the numbers of particles for guaranteeing monomer are closed, guarantee monomer particle particle size and guarantees the degree of distribution of monomer particle.
However, the stability of water based acrylic resin is mainly improved using ionic emulsifying agent now, but now
Although used ionic emulsifying agent can improve the stability of water based acrylic resin, another problem is brought,
Since ionic emulsifying agent is only coated on the emulsion particle surface of water based acrylic resin, when environment occurs mobile, cream
Ionic emulsifying agent on micelle will dissociate, to will lead to following problems: (1) ionic emulsifying agent occurs free,
Water based acrylic resin can generate the hydration layer of migration, so that in the painting paint formula containing water based acrylic resin
Curing agent, coalescing agent etc. cannot be preferably compatible with water based acrylic resin, reduce water based acrylic resin
The compatibility of system；(2) ionic emulsifying agent occurs free, and under high shear, water based acrylic resin is easy
The group's of generation wadding；(3) ionic emulsifying agent occurs free, when hydrotropism's Hydroxylated acrylic resin adds oiliness auxiliary agent, ionic cream
Among the monomer particle and oiliness auxiliary agent of resin competitive Adsorption can occur for agent, affect water based acrylic resin system
Stability；(3) ionic emulsifying agent occurs free, and ionic emulsifying agent when film forming is caused to be transferred to the outermost layer of paint film,
Influence gloss, physical property and the compactness of paint film；(4) remaining ionic emulsifying agent also will cause under the rate of film build of paint vehicle
Drop, reduces the water resistance of film.
Summary of the invention
For the prior art there are above-mentioned technical problem, the present invention provides the hydroxyl that a kind of compatibility is good, stability is high
Acrylic resin and, the preparation method for the hydroxy acryl acid resin having the above advantages can be produced.
To achieve the above object, the present invention the following technical schemes are provided:
The hydroxy acryl acid resin that a kind of compatibility is good, stability is high is provided, is made of the raw material of following parts by weight:
12~80 parts of acrylate
1~2 part of initiator
1~4 part of chain-transferring agent
2~25 parts of hydroxyl acrylate
5~10 parts of acrylate with carboxylic acid
3~5 parts of neutralizer
0.5~5 part of response type anion emulsifier
40~50 parts of water；
The acrylate contains the first acrylate and the second acrylate；
First acrylate by high glass transition temperature 5~30 parts of acrylate and low glass transition temperature third
2~15 parts of olefin(e) acid ester compositions, the high glass transition temperature is 105~150 DEG C, and the low glass transition temperature is -55~10
℃。
5~10 parts of groups of acrylate of second acrylate by 2~25 parts hydroxyl of acrylate and with carboxylic acid
At.
Wherein, the high glass transition temperature acrylate is one or both of methyl methacrylate or styrene
Mixture.
Wherein, the low glass transition temperature acrylate is n-butyl acrylate, Isooctyl acrylate monomer, methacrylic acid
One of butyl ester, lauryl methacrylate or any two or more mixture.
Wherein, the hydroxyl acrylate is acrylic acid -2- hydroxyl ethyl ester, 2-hydroxyethyl methacry-late, acrylic acid
One of hydroxypropyl acrylate or hydroxy propyl methacrylate or any two or more mixture.
Wherein, the acrylate with carboxylic acid is one in acrylic acid, methacrylic acid, itaconic acid or itaconic acid n-butyl
Kind or any two or more mixture.
Wherein, the initiator is the mixing of one or more of dibenzoyl peroxide or azodiisobutyronitrile
Object.
Wherein, the chain-transferring agent be lauryl mercaptan, tert-dodecylmercaotan, 3- mercaptopropionic acid ethyl hexyl alcohol ester,
One of α-methylstyrene, the own ester of 3- thioacetic acid -2- methyl or any two or more mixture.
Wherein, the neutralizer is one of ammonium hydroxide, triethanolamine or dimethylethanolamine or any two or more
Mixture.
Wherein, the response type anion emulsifier is allyl ether series sulfonate, acrylamido sulfonate, maleic acid
One of derivative or sodium allyl sulfosuccinic alkyl ester or any two or more mixture.
To achieve the above object two, the present invention provides following technical scheme
A kind of preparation method for the hydroxy acryl acid resin that compatibility is good, stability is high is provided, comprising the following steps:
Step 1: weighing material
The response type anion emulsifier for weighing formula ratio, be classified as response type anion emulsifier A, response type yin from
Sub- emulsifier B, response type anion emulsifier C；
The water for weighing formula ratio is classified as water A, water B and water C；
The initiator for weighing formula ratio, is classified as initiator A and initiator B；
Wherein, ionic emulsifying agent A, response type anion emulsifier B, response type anion emulsifier C, this three is according to reality
Border service condition sets up weight ratio separately, is not required to the weight ratio being strict between its three；
Water A, water B and water C, this three set up weight ratio separately according to actual use situation, be not required to be strict with thirdly
Weight ratio between person；
Initiator A and initiator B, both sets up weight ratio separately according to actual use situation, is not required to be strict with
Weight ratio between the two.
Step 2: preparing hydroxy acryl acid resin
(1) the response type anion emulsifier A and water A for weighing formula ratio respectively, put into first reactor for the two
In, it stirs and heats the first reactor so that material is warming up to 60~80 DEG C, heat preservation for standby use；
(2) the high glass transition temperature acrylate, response type anion emulsifier B and water B of formula ratio are weighed respectively, it will
Its three puts into second reactor, and mixed at high speed stirs 40~60min, obtains mixture；
(3) initiator A for weighing formula ratio takes 7~10% above-mentioned (2) obtained mixtures, feeds the mixture into
In the material of one reactor, to the material stirring in first reactor, after stirring 5~7min, initiator A is added, is stirred to react
After 30~40min, then the remainder of above-mentioned (2) obtained mixture is slowly added dropwise in first reactor, after dripping,
Insulated and stirred reacts 50~60min；
(4) initiator B for weighing formula ratio adds it in first reaction, and keeping temperature is 68~75 DEG C, after
It is continuous to be stirred to react 50~60min, 80~85 DEG C are then warming up to, 50~60min is kept the temperature, hydroxyl propylene is made in cooling discharge
Acid resin.
Beneficial effects of the present invention:
(1) hydroxy acryl acid resin that a kind of compatibility of the invention is good, stability is high, by high glass transition temperature
Acrylate, the acrylate of low glass transition temperature, initiator, chain-transferring agent, hydroxyl acrylate, with carboxylic acid
Acrylate, neutralizer, response type anion emulsifier and water, since its component includes the acrylate of high glass transition temperature
With the acrylate of low glass transition temperature, the gamma transition time of hydroxy acryl acid resin can be effectively extended, is conducive to promote
Into the movement of raw molecule, thus be conducive to improve the uniformity of resin reaction, and the longer glass of hydroxy acryl acid resin turns
Shifting state, conducive to the anti-deformation nature for improving hydroxy acryl acid resin；And due to hydroxyl acrylate and with carboxylic acid
Condensation reaction can occur for acrylate, therefore can promote the reaction between resin, improve the quality of resin.
(2) hydroxy acryl acid resin that a kind of compatibility of the invention is good, stability is high, emulsifier are response type yin
Ionic emulsifying agent, the active monomer in the surface of response type anion emulsifier, the activated monomer and hydroxy acryl acid resin
The surface of latex particle generates covalent bond, and covalent bond not only can avoid reaction with the firm combination in the surface of resin emulsion particle
Type anion emulsifier is free so that resin material, which is led to the problem of, is hydrated layer, and due to covalent bond neutral, resin
Material will not cause to occur to reunite between resin emulsion grain mobile and and response type anion emulsifier also will not be with
Other additive competitive Adsorptions improve the stability and compatibility of hydroxy acryl acid resin in resin emulsion particles；And
And since response type ionic emulsifying agent of the invention can be steadily evenly dispersed in water phase, water phase not residual emulsifying agents,
It is avoidable in this way to lead to the excessive problem of mechanical bubble of painting due to residual emulsifying agents, while also accelerating japanning film forming speed, subtract
The time required to few painted surface is dry, the physical property conducive to raising japanning water resistance and initial stage of painting shows speed；Further, since
Response type anion emulsifier be not present free state, corresponding to japanning film forming when, can avoid emulsifier sent out in japanning
The problem of raw interfacial migration phenomenon, to improve the mechanics of japanning, glossiness and the ground of japanning followability.
(3) preparation method for the hydroxy acryl acid resin that a kind of compatibility of the invention is good, stability is high has and is easy to
Operation is suitable for the advantages of large-scale production and application.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
The hydroxy acryl acid resin that a kind of compatibility of the present embodiment is good, stability is high, by the original of following parts by weight
Material composition: 12 parts of acrylate, 1 part of initiator, 1 part of chain-transferring agent, 2 parts hydroxyl of acrylate, the acrylic acid with carboxylic acid
50 parts of ester, 3 parts of neutralizer, 0.5 part of response type anion emulsifier and 40 parts of water；
The acrylate contains the first acrylate and the second acrylate, and first acrylate is turned by high glass
Change 5 parts of the acrylate of temperature and 2 parts of acrylate compositions of low glass transition temperature, the high glass transition temperature is 105
~150 DEG C, the low glass transition temperature is -55~10 DEG C.
Second acrylate is made of 2 parts hydroxyl of acrylate and 5 parts of acrylate with carboxylic acid.
In the present embodiment, the high glass transition temperature acrylate is the mixing in methyl methacrylate and styrene
Object.
In the present embodiment, the low glass transition temperature acrylate is n-butyl acrylate, Isooctyl acrylate monomer, methyl
The mixture of butyl acrylate, lauryl methacrylate.
In the present embodiment, the hydroxyl acrylate be acrylic acid -2- hydroxyl ethyl ester, 2-hydroxyethyl methacry-late,
Mixture in hydroxypropyl acrylate or hydroxy propyl methacrylate.
In the present embodiment, the acrylate with carboxylic acid, acrylic acid, methacrylic acid, itaconic acid or itaconic acid n-butyl
Mixture.
In the present embodiment, the initiator is the mixture of dibenzoyl peroxide or azodiisobutyronitrile.
In the present embodiment, the chain-transferring agent is lauryl mercaptan, tert-dodecylmercaotan, 3- mercaptopropionic acid ethyl hexyl
Alcohol ester, α-methylstyrene, the own ester of 3- thioacetic acid -2- methyl mixture.
In the present embodiment, the neutralizer is the mixture of ammonium hydroxide, triethanolamine or dimethylethanolamine.
In the present embodiment, the response type anion emulsifier be allyl ether series sulfonate, acrylamido sulfonate,
The mixture of maleic acid derivatives or sodium allyl sulfosuccinic alkyl ester.
The preparation method of the hydroxy acryl acid resin, comprising the following steps:
Step 1: weighing material
The response type anion emulsifier for weighing formula ratio, be classified as response type anion emulsifier A, response type yin from
Sub- emulsifier B, response type anion emulsifier C；
The water for weighing formula ratio is classified as water A, water B and water C；
The initiator for weighing formula ratio, is classified as initiator A and initiator B；
Wherein, the weight of response type anion emulsifier A, response type anion emulsifier B, response type anion emulsifier C
The ratio between amount is 1:1:1；The weight ratio of water A, water B and water C three are 1:3:2；The weight ratio of initiator A and initiator B is
1:0.5。
Step 2: preparing hydroxy acryl acid resin
(1) the response type anion emulsifier A and water A for weighing formula ratio respectively, put into first reactor for the two
In, it stirs and heats the first reactor so that material is warming up to 60 DEG C, heat preservation for standby use；
(2) the high glass transition temperature acrylate, response type anion emulsifier B and water B of formula ratio are weighed respectively, it will
Its three puts into second reactor, and mixed at high speed stirs 40min, obtains mixture；
(3) initiator A for weighing formula ratio takes 7% above-mentioned (2) obtained mixture, and it is anti-to feed the mixture into first
It answers in the material of device, to the material stirring in first reactor, after stirring 5min, initiator A is added, is stirred to react 30min
Afterwards, then by the remainder of above-mentioned (2) obtained mixture it is slowly added dropwise in first reactor, after dripping, insulated and stirred
React 50min；
(4) initiator B for weighing formula ratio adds it in first reaction, and keeping temperature is 68 DEG C, continues to stir
Reaction 50min is mixed, is then warming up to 80 DEG C, keeps the temperature 50min, hydroxy acryl acid resin is made in cooling discharge.
Embodiment 2.
The hydroxy acryl acid resin that a kind of compatibility of the present embodiment is good, stability is high, by the original of following parts by weight
Material composition: 80 parts of acrylate, 2 parts of initiator, 4 parts of chain-transferring agent, 25 parts hydroxyl of acrylate, the acrylic acid with carboxylic acid
10 parts of ester, 5 parts of neutralizer, 5 parts of response type anion emulsifier and 50 parts of water；
The acrylate contains the first acrylate and the second acrylate, and first acrylate is turned by high glass
Change 30 parts of the acrylate of temperature and 15 parts of acrylate compositions of low glass transition temperature, the high glass transition temperature is
105~150 DEG C, the low glass transition temperature is -55~10 DEG C.
Second acrylate is made of 25 parts hydroxyl of acrylate and 10 parts of acrylate with carboxylic acid.
In the present embodiment, the high glass transition temperature acrylate is one of methyl methacrylate or styrene
Or two kinds of mixture.
In the present embodiment, the low glass transition temperature acrylate is n-butyl acrylate, Isooctyl acrylate monomer, methyl
One of butyl acrylate, lauryl methacrylate or any two or more mixture.
In the present embodiment, the hydroxyl acrylate be acrylic acid -2- hydroxyl ethyl ester, 2-hydroxyethyl methacry-late,
One of hydroxypropyl acrylate or hydroxy propyl methacrylate or any two or more mixture.
In the present embodiment, the acrylate with carboxylic acid is acrylic acid, methacrylic acid, itaconic acid or itaconic acid n-butyl
One of or any two or more mixture.
In the present embodiment, the initiator is one or more of dibenzoyl peroxide or azodiisobutyronitrile
Mixture.
In the present embodiment, the chain-transferring agent is lauryl mercaptan, tert-dodecylmercaotan, 3- mercaptopropionic acid ethyl hexyl
One of alcohol ester, α-methylstyrene, the own ester of 3- thioacetic acid -2- methyl or any two or more mixture.
In the present embodiment, the neutralizer is one of ammonium hydroxide, triethanolamine or dimethylethanolamine or two kinds any
Above mixture.
In the present embodiment, the response type anion emulsifier be allyl ether series sulfonate, acrylamido sulfonate,
One of maleic acid derivatives or sodium allyl sulfosuccinic alkyl ester or any two or more mixture.
The preparation method of the hydroxy acryl acid resin, comprising the following steps:
Step 1: weighing material
The response type anion emulsifier for weighing formula ratio, be classified as response type anion emulsifier A, response type yin from
Sub- emulsifier B, response type anion emulsifier C；
The water for weighing formula ratio is classified as water A, water B and water C；
The initiator for weighing formula ratio, is classified as initiator A and initiator B；
Wherein, the weight of response type anion emulsifier A, response type anion emulsifier B, response type anion emulsifier C
The ratio between amount is 1:2:1；The weight ratio of water A, water B and water C three are 1:2:2；The weight ratio of initiator A and initiator B is
1:1。
Step 2: preparing hydroxy acryl acid resin
(1) the response type anion emulsifier A and water A for weighing formula ratio respectively, put into first reactor for the two
In, it stirs and heats the first reactor so that material is warming up to 80 DEG C, heat preservation for standby use；
(2) the high glass transition temperature acrylate, response type anion emulsifier B and water B of formula ratio are weighed respectively, it will
Its three puts into second reactor, and mixed at high speed stirs 60min, obtains mixture；
(3) initiator A for weighing formula ratio takes 10% above-mentioned (2) obtained mixture, and it is anti-to feed the mixture into first
It answers in the material of device, to the material stirring in first reactor, after stirring 5~7min, initiator A is added, is stirred to react 40min
Afterwards, then by the remainder of above-mentioned (2) obtained mixture it is slowly added dropwise in first reactor, after dripping, insulated and stirred
React 60min；
(4) initiator B for weighing formula ratio adds it in first reaction, and keeping temperature is 75 DEG C, continues to stir
Reaction 60min is mixed, is then warming up to 85 DEG C, keeps the temperature 60min, hydroxy acryl acid resin is made in cooling discharge.
Embodiment 3.
The hydroxy acryl acid resin that a kind of compatibility of the present embodiment is good, stability is high, by the original of following parts by weight
Material composition: 60 parts of acrylate, 1.5 parts of initiator, 3 parts of chain-transferring agent, 20 parts hydroxyl of acrylate, the propylene with carboxylic acid
7 parts of acid esters, 4 parts of neutralizer, 4 parts of response type anion emulsifier and 45 parts of water；
The acrylate contains the first acrylate and the second acrylate, and first acrylate is turned by high glass
Change 15 parts of the acrylate of temperature and 10 parts of acrylate compositions of low glass transition temperature, the high glass transition temperature is
105~150 DEG C, the low glass transition temperature is -55~10 DEG C.Second acrylate is by hydroxyl acrylate 20
Part and 7 parts of acrylate with carboxylic acid compositions.
In the present embodiment, the high glass transition temperature acrylate is one of methyl methacrylate or styrene
Or two kinds of mixture.
In the present embodiment, the low glass transition temperature acrylate is n-butyl acrylate, Isooctyl acrylate monomer, methyl
One of butyl acrylate, lauryl methacrylate or any two or more mixture.
In the present embodiment, the hydroxyl acrylate be acrylic acid -2- hydroxyl ethyl ester, 2-hydroxyethyl methacry-late,
One of hydroxypropyl acrylate or hydroxy propyl methacrylate or any two or more mixture.
In the present embodiment, the acrylate with carboxylic acid is acrylic acid, methacrylic acid, itaconic acid or itaconic acid n-butyl
One of or any two or more mixture.
In the present embodiment, the initiator is one or more of dibenzoyl peroxide or azodiisobutyronitrile
Mixture.
In the present embodiment, the chain-transferring agent is lauryl mercaptan, tert-dodecylmercaotan, 3- mercaptopropionic acid ethyl hexyl
One of alcohol ester, α-methylstyrene, the own ester of 3- thioacetic acid -2- methyl or any two or more mixture.
In the present embodiment, the neutralizer is one of ammonium hydroxide, triethanolamine or dimethylethanolamine or two kinds any
Above mixture.
In the present embodiment, the response type anion emulsifier be allyl ether series sulfonate, acrylamido sulfonate,
One of maleic acid derivatives or sodium allyl sulfosuccinic alkyl ester or any two or more mixture.
The preparation method of the hydroxy acryl acid resin, comprising the following steps:
Step 1: weighing material
The response type anion emulsifier for weighing formula ratio, be classified as response type anion emulsifier A, response type yin from
Sub- emulsifier B, response type anion emulsifier C；
The water for weighing formula ratio is classified as water A, water B and water C；
The initiator for weighing formula ratio, is classified as initiator A and initiator B；
Wherein, the weight of response type anion emulsifier A, response type anion emulsifier B, response type anion emulsifier C
The ratio between amount is 2:1:1；The weight ratio of water A, water B and water C three are 4:3:2；The weight ratio of initiator A and initiator B is
1:1。
Step 2: preparing hydroxy acryl acid resin
(1) the response type anion emulsifier A and water A for weighing formula ratio respectively, put into first reactor for the two
In, it stirs and heats the first reactor so that material is warming up to 70 DEG C, heat preservation for standby use；
(2) the high glass transition temperature acrylate, response type anion emulsifier B and water B of formula ratio are weighed respectively, it will
Its three puts into second reactor, and mixed at high speed stirs 50min, obtains mixture；
(3) initiator A for weighing formula ratio takes 7~10% above-mentioned (2) obtained mixtures, feeds the mixture into
In the material of one reactor, to the material stirring in first reactor, after stirring 6min, initiator A is added, is stirred to react
After 35min, then the remainder of above-mentioned (2) obtained mixture is slowly added dropwise in first reactor, after dripping, protected
Temperature is stirred to react 55min；
(4) initiator B for weighing formula ratio adds it in first reaction, and keeping temperature is 70 DEG C, continues to stir
Reaction 50min is mixed, is then warming up to 82 DEG C, keeps the temperature 55min, hydroxy acryl acid resin is made in cooling discharge.
Properties of product test:
1, it prepares aqueous woodware paint corresponding to Examples 1 to 3: weighing hydroxyl propylene obtained by Examples 1 to 3 respectively
Each 8kg of acid resin is respectively added wetting agent 0.2kg to its three, levelling agent 0.2kg, defoaming agent 0.2kg, thickener 0.2kg, goes
Ionized water 0.8kg, coalescing agent 0.4kg, are made aqueous woodware paint corresponding to Examples 1 to 3, and the sample in corresponding table 1 is compiled
Number be 1,2,3.
2, aqueous woodware paint corresponding to comparative example 1 is prepared, the response type anion emulsifier in embodiment 1 is replaced with
Ionic anion emulsifier (lauric acid soap), other operations are same as Example 1, obtain aqueous third obtained by comparative example 1
Olefin(e) acid resin, meanwhile, hydroxy acryl acid resin 8kg obtained by comparative example 1 is weighed, wetting agent 0.2kg, levelling is added to it
Agent 0.2kg, defoaming agent 0.2kg, thickener 0.2kg, deionized water 0.8kg, coalescing agent 0.4kg are made corresponding to comparative example 1
Aqueous woodware paint, the sample number into spectrum in corresponding table 1 is 4.
Above-mentioned obtained aqueous woodware paint is observed respectively and applies standing, after standing 2 as a child, observes the outer of aqueous woodware paint
Sight state then contains and the above-mentioned obtained aqueous woodware paint painting of 100ml is taken to be placed on ultrasonic vibration 2min in ultrasound, observes water respectively
The apparent condition of property woodcare paint.
The comparison that table 1, each aqueous woodware paint apply
As above-mentioned table 1 as it can be seen that the stability and compatibility of aqueous woodware paint obtained by using Examples 1 to 3 are than comparison
The stability and compatibility of example 1 are preferable, it is seen then that hydroxy acryl acid resin of the invention is had excellent performance.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than the present invention is protected
The limitation of range is protected, although explaining in detail referring to preferred embodiment to the present invention, those skilled in the art are answered
Work as understanding, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the reality of technical solution of the present invention
Matter and range.
Claims (10)
- The hydroxy acryl acid resin that 1. a kind of compatibility is good, stability is high, it is characterized in that: by the raw material group of following parts by weight At:12~80 parts of acrylate1~2 part of initiator1~4 part of chain-transferring agent2~25 parts of hydroxyl acrylate5~10 parts of acrylate with carboxylic acid3~5 parts of neutralizer0.5~5 part of response type anion emulsifier40~50 parts of water；The acrylate contains the first acrylate and the second acrylate；First acrylate is by 5~30 parts of the acrylate of high glass transition temperature and the acrylic acid of low glass transition temperature 2~15 parts of ester compositions, the high glass transition temperature is 105~150 DEG C, and the low glass transition temperature is -55~10 DEG C.Second acrylate is made of 2~25 parts hydroxyl of acrylate and 5~10 parts of acrylate with carboxylic acid.
- The hydroxy acryl acid resin that 2. a kind of compatibility according to claim 1 is good, stability is high, it is characterized in that: institute State the mixture that high glass transition temperature acrylate is one or both of methyl methacrylate or styrene.
- The hydroxy acryl acid resin that 3. a kind of compatibility according to claim 1 is good, stability is high, it is characterized in that: institute Stating low glass transition temperature acrylate is n-butyl acrylate, Isooctyl acrylate monomer, butyl methacrylate, methacrylic acid One of lauryl or any two or more mixture.
- The hydroxy acryl acid resin that 4. a kind of compatibility according to claim 1 is good, stability is high, it is characterized in that: institute Stating hydroxyl acrylate is acrylic acid -2- hydroxyl ethyl ester, 2-hydroxyethyl methacry-late, hydroxypropyl acrylate or methyl-prop One of olefin(e) acid hydroxypropyl acrylate or any two or more mixture.
- The hydroxy acryl acid resin that 5. a kind of compatibility according to claim 1 is good, stability is high, it is characterized in that: institute It is one of acrylate, acrylic acid, methacrylic acid, itaconic acid or itaconic acid n-butyl or any two or more for stating band carboxylic acid Mixture.
- The hydroxy acryl acid resin that 6. a kind of compatibility according to claim 1 is good, stability is high, it is characterized in that: institute State the mixture that initiator is one or more of dibenzoyl peroxide or azodiisobutyronitrile.
- The hydroxy acryl acid resin that 7. a kind of compatibility according to claim 1 is good, stability is high, it is characterized in that: institute Stating chain-transferring agent is lauryl mercaptan, tert-dodecylmercaotan, 3- mercaptopropionic acid ethyl hexyl alcohol ester, α-methylstyrene, 3- One of own ester of thioacetic acid -2- methyl or any two or more mixture.
- The hydroxy acryl acid resin that 8. a kind of compatibility according to claim 1 is good, stability is high, it is characterized in that: institute Stating neutralizer is one of ammonium hydroxide, triethanolamine or dimethylethanolamine or any two or more mixture.
- The hydroxy acryl acid resin that 9. a kind of compatibility according to claim 1 is good, stability is high, it is characterized in that: institute Stating response type anion emulsifier is allyl ether series sulfonate, acrylamido sulfonate, maleic acid derivatives or allyl One of succinic acid alkyl ester sulfonate sodium or any two or more mixture.
- The preparation for the hydroxy acryl acid resin that 10. a kind of compatibility according to any one of claims 1 to 9 is good, stability is high Method, it is characterized in that: the following steps are included:Step 1: weighing materialThe response type anion emulsifier for weighing formula ratio is classified as response type anion emulsifier A, response type anion cream Agent B, response type anion emulsifier C；The water for weighing formula ratio is classified as water A, water B and water C；The initiator for weighing formula ratio, is classified as initiator A and initiator B；Step 2: preparing hydroxy acryl acid resin(1) the response type anion emulsifier A and water A for weighing formula ratio respectively, the two is put into first reactor, is stirred It mixes and heats the first reactor so that material is warming up to 60~80 DEG C, heat preservation for standby use；(2) weigh the high glass transition temperature acrylate, response type anion emulsifier B and water B of formula ratio respectively, will thirdly Person puts into second reactor, and mixed at high speed stirs 40~60min, obtains mixture；(3) initiator A for weighing formula ratio takes the obtained mixture in 7~10% above-mentioned (2) and adds the mixture to first In the material of reactor, to the material stirring in first reactor, after stirring 5~7min, initiator A is added, is stirred to react 30 After~40min, then the remainder of above-mentioned (2) obtained mixture is slowly added dropwise in first reactor, after dripping, protected Temperature is stirred to react 50~60min；(4) initiator B for weighing formula ratio adds it in first reaction, and keeping temperature is 68~75 DEG C, continues to stir 50~60min of reaction is mixed, is then warming up to 80~85 DEG C, keeps the temperature 50~60min, hydroxy acryl acid tree is made in cooling discharge Rouge.
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| CN112501914A (en) * | 2020-10-30 | 2021-03-16 | 长兴华隆丝绸有限公司 | Preparation method of waterproof and oilproof fabric |
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