CN107936812A - A kind of preparation method of Hydroxylated acrylic resin coating - Google Patents
A kind of preparation method of Hydroxylated acrylic resin coating Download PDFInfo
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- CN107936812A CN107936812A CN201711331648.7A CN201711331648A CN107936812A CN 107936812 A CN107936812 A CN 107936812A CN 201711331648 A CN201711331648 A CN 201711331648A CN 107936812 A CN107936812 A CN 107936812A
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- acrylic resin
- hydroxylated acrylic
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- mixed solvent
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- 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
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
Abstract
The preparation method of a kind of Hydroxylated acrylic resin coating of the present invention, with the sec-butyl acetate and propylene glycol methyl ether acetate mixed solvent of low toxicity.Solves the problems, such as the high poison solvent such as toluene and dimethylbenzene.The Hydroxylated acrylic resin coating of the excellent high solids content of performance is prepared, effectively reduces the discharge of harmful substance.Make mixed solvent with the larger sec-butyl acetate of saturated vapor pressure difference and propylene glycol methyl ether acetate, in elevated cure, effectively avoid single solvent rate of volatilization it is too fast it is either excessively slow caused by film turn white, bubbling or the defects of sagging, pin hole.Mixed solvent boiling point meets to polymerize at a higher temperature, and the molecular resin amount of preparation is smaller.Mixed solvent can effectively regulate and control the viscosity of Hydroxylated acrylic resin in the case where solid content is higher.The appearance of film prepared after cured is smooth, bright, and hardness is high, and pencil hardness is up to 2H, and adhesive force is good, and adhesive force is 0 grade.The solid content of the coating reaches 75%.As based finish varnish for vehicles coating.
Description
Technical field
It is main to be specifically related to use sec-butyl acetate-propane diols first the invention belongs to based finish varnish for vehicles technical field of coatings
Ether acetate has synthesized a kind of low toxicity, environment-friendly type Hydroxylated acrylic resin preparation method for coating as mixed solvent.
Background technology
With the development of national economy, it is essential heavy that car paint industry progressively develops into all fields of national economy
Want industry.From 2009, China had become the country in the automobile volume of production and marketing whole world first.In solvent based coating, develop Gao Gu
Body content coating and poisonous and hazardous solvent is replaced to have become development trend [1] with low poison solvent.Current dosage is maximum in the industry
Poisonous and harmful solvent be benzene kind solvent, such as toluene, dimethylbenzene [2].Benzene kind solvent is not only inflammable, has irritation, to sky
Compression ring border, water environment and water source etc. can all pollute.And the infringement to human body mainly to the hemopoietic system of human body and
Nervous system causes serious harm.With coating in production and use to the pay attention to day by day of environmental protection, reduce VOC and raising
Solid content becomes development trend.Meanwhile encouragement substitutes benzene kind solvent [3] with esters solvent.Select low poison solvent type high solids content
Coating becomes the development trend of this kind of coating.（Bibliography：[1] Liu Zhun, Yuan Jixian, Guo Dengfeng, Zhu Xinbao, Xu Gang, wait green
Application of the color environmentally friendly solvent in coatings industry and prospect China coating, 2011,26 (9)：6-10.
[2] Liu Guojie, Niu Changrui, Qi Xiangzhao, application brief comment China of Luwen's brightness dimethyl carbonates in coatings industry apply
Material, 2015,30 (3)
[3] Yu Yuan, Lu Qiang, Lin Hexing, Zhao Wenfei, beautiful peaceful good is a kind of to build environmentally friendly thermosetting acrylic coating and its preparation
Method, Chemical Engineering Technology and exploitation 2016,45 (7)：25-28.
The content of the invention
Existing in the prior art in order to solve the problems, such as, the present invention provides a kind of preparation side of Hydroxylated acrylic resin coating
Method.Purpose is the environment-friendly type mixed solvent for selecting low toxicity, while the comprehensive performance of coating is improved, prepares performance
Excellent height consolidates Hydroxylated acrylic resin coating, can effectively reduce the discharge of harmful substance.
A kind of Hydroxylated acrylic resin coating provided by the invention is made of Hydroxylated acrylic resin and mixed solvent；Hydroxyl
The preparation process and condition of acrylic resin are as follows：（1）The raw material and auxiliary material of 10wt% are added anti-with agitating device
Answer in device, be warming up to 93~105oC, rotating speed is stirred for 300r/min, when the reaction time 1~2 is small, obtains component 1；It is described
Raw material be 22wt% methyl methacrylate（MMA）, 44wt% styrene (St), the n-BMA of 30wt%
(BA), the hydroxyethyl methacrylate (HEMA) of the acrylic acid (AA) of 1wt% and 3wt%；Auxiliary material is：Initiator azo two is different
Butyronitrile（AIBN）For the 2wt% of the gross mass of raw material；Chain-transferring agent tert-dodecylmercaotan（TDM）For the gross mass of raw material
0.5wt%；The total mass ratio of mixed solvent and raw material is 1：3, mixed solvent is that mass ratio is (8.06~0.60):1 acetic acid is secondary
The mixed solvent of butyl ester and propylene glycol methyl ether acetate；
(2) remaining raw material and auxiliary material are mixed and made into mixed solution as component 2 again, component 2 is added drop-wise to component 1
In, 1~2 is added dropwise when small, and it is 93~105oC then to maintain temperature, when reaction 6 is small, obtains Hydroxylated acrylic resin；
(3) Hydroxylated acrylic resin is pressed：Curing agent hexamethylene diisocyanate trimer：Catalyst dibutyltin dilaurylate
Mass ratio be 1：0.04：0.001, room temperature is uniformly mixed, and obtains Hydroxylated acrylic resin coating.
A kind of Hydroxylated acrylic resin coating prepared by the present invention can be used as based finish varnish for vehicles coating.
Beneficial effect：The present invention provides a kind of preparation method of Hydroxylated acrylic resin coating.Employ the second of low toxicity
The secondary butyl ester of acid and propylene glycol methyl ether acetate mixed solvent.Solve tradition prepare Hydroxylated acrylic resin coating using toluene and
The problem of high poison solvent such as dimethylbenzene.While not reducing or even improving the comprehensive performance of coating, it is excellent to prepare performance
The Hydroxylated acrylic resin coating of good high solids content, can effectively reduce the discharge of harmful substance.
The single solvent that Hydroxylated acrylic resin coating uses has been prepared, rate of volatilization mistake occurs in elevated cure
The problem of fast or excessively slow.The problems such as rate of volatilization is too fast to cause film to turn white, orange peel, bubbling, rate of volatilization can cause slowly excessively
The problems such as coating flowing hanging, pin hole.The present invention selects the larger sec-butyl acetate and propylene glycol monomethyl ether acetic acid of saturated vapor pressure difference
Ester is larger as mixed solvent, the rate of volatilization difference of the two.So in elevated cure, single solvent can be effectively avoided
Paint film defect caused by rate of volatilization is too fast or excessively slow.
The mixed solvent boiling point that the present invention selects meets to polymerize at a higher temperature, and the molecular resin amount of preparation is smaller.
The mixed solvent can effectively regulate and control the viscosity of Hydroxylated acrylic resin in the case where solid content is higher.It is made after cured
Standby appearance of film is smooth, bright, and hardness is high, and pencil hardness is up to 2H, and adhesive force is good, and adhesive force is 0 grade.It is prepared by the present invention
The solid content of Hydroxylated acrylic resin coating reach 75%.The hydroxy of Hydroxylated acrylic resin coating prepared by the present invention
Acid resin can be used as based finish varnish for vehicles coating.
Embodiment
A kind of Hydroxylated acrylic resin coating of embodiment 1 is made of Hydroxylated acrylic resin and mixed solvent；Hydroxy
The preparation process and condition of acid resin are as follows：（1）The raw material and auxiliary material of 10wt% are added the reactor with agitating device
In, 93oC is warming up to, rotating speed is stirred for 300r/min, when the reaction time 2 is small, obtains component 1；The raw material is methyl
Methyl acrylate（MMA）For 22wt%, 324.29g, styrene (St) are 44wt%, 648.58g, n-BMA
(BA) it is 30wt%, 442.21g, acrylic acid (AA) are 1wt%, and 14.74g and hydroxyethyl methacrylate (HEMA) are
3wt%, is 44.22g；Auxiliary material is：Initiator azodiisobutyronitrile（AIBN）For the 2wt% of the gross mass of raw material, it is
29.48g；Chain-transferring agent tert-dodecylmercaotan（TDM）It is 7.37g for the 0.5wt% of the gross mass of raw material；Mixed solvent and original
The total mass ratio of material is 1：3, mixed solvent is that mass ratio is 8.06：1 sec-butyl acetate 436.82g and propylene glycol monomethyl ether acetic acid
The mixed solvent of ester 54.18g;
（2）Remaining raw material and auxiliary material are mixed and made into mixed solution as component 2 again, using the mode of dropwise addition by component 2
Be added dropwise in component 1,1 is added dropwise when small, maintain always under 97oC reaction 6 it is small when, obtain Hydroxylated acrylic resin；
（3）By Hydroxylated acrylic resin：Curing agent hexamethylene diisocyanate trimer：Catalyst dibutyltin dilaurylate
Mass ratio be 1:0.04:0.001, room temperature is uniformly mixed, and obtains Hydroxylated acrylic resin coating.
The solid content of the Hydroxylated acrylic resin coating of preparation is 75%.
Sample preparation：By Hydroxylated acrylic resin 5g, curing agent hexamethylene diisocyanate trimer 0.20g：Catalysis
0.005 g of agent dibutyl tin laurate, room temperature are uniformly mixed, and obtain Hydroxylated acrylic resin coating sample.
Sample is coated on the tinplate of cleaning, is put into the curing oven 30min of 80~120 oC, obtaining thickness is about
The film of 0.020mm~0.030mm.
Measure embodiment 1 and obtain Hydroxylated acrylic resin sample Mn=1.10×104, viscosity is 8528 mpas.It is obtained
Film coated surface is smooth, smooth, and without the problems such as turning white and is pin-free, it is suitable using solvent rate of volatilization to illustrate.By GB/T
Cross cut test method is measured in 9286-1998, and adhesive force is 0 grade.Measured using pencil hardness method, by GB/T 6739-2006
In manual method measure, pencil hardness 2H.According in GB/T1735-2009 method test paint film heat resistance, heat resistance,
Bubbling does not wrinkle.Paint film water resistance, water resistance are measured by method in GB/T 5209-1985, no blistering comes off.By ISO 2812-
Method test paint film chemical reagent performance in 1-2007, acid resistance, alkali resistance, no blistering come off.
A kind of Hydroxylated acrylic resin coating of embodiment 2 is made of Hydroxylated acrylic resin and mixed solvent；Hydroxy
The preparation process and condition of acid resin are as follows：（1）The raw material and auxiliary material of 10wt% are added the reactor with agitating device
In, 100oC is warming up to, rotating speed is stirred for 300r/min, when the reaction time 1.5 is small, obtains component 1；The raw material and
The mass percent of auxiliary material is the same as embodiment 1；The total mass ratio of mixed solvent and raw material is 1：3, mixed solvent is mass ratio
For 3.58：The mixed solvent of 1 sec-butyl acetate 383.87g and propylene glycol methyl ether acetate 107.13g;
（2）Surplus stock and auxiliary material are mixed and made into mixed solution as component 2 again, dripped component 2 using dropwise addition mode
It is added in component 1,2 are added dropwise when small, maintain 100oC always, when reaction 6 is small, obtain Hydroxylated acrylic resin；
（3）By Hydroxylated acrylic resin：Curing agent hexamethylene diisocyanate trimer：Catalyst dibutyltin dilaurylate
Mass ratio be 1：0.04：0.001, room temperature is uniformly mixed, and obtains Hydroxylated acrylic resin coating.
The solid content of Hydroxylated acrylic resin coating prepared by embodiment 2 is 75%.
Sample preparation is the same as embodiment 1.
Measure embodiment 2 and obtain the M of Hydroxylated acrylic resinn=1.13×104, viscosity is 8640 mpas.Obtained painting
Film surface is smooth, smooth, and without the problems such as turning white and is pin-free, it is suitable using solvent rate of volatilization to illustrate.By GB/T 9286-
Cross cut test method is measured in 1998, and adhesive force is 0 grade.Measured using pencil hardness method, by hand in GB/T 6739-2006
Dynamic method measure, pencil hardness 2H.According to the heat resistance of the method test paint film in GB/T1735-2009, water resistance, is not roused
Puff wrinkles.Paint film water resistance, water resistance are measured by method in GB/T 5209-1985, no blistering comes off.ISO 2812-1-2007
In method test paint film chemical reagent performance, acid resistance, alkali resistance, no blistering comes off.
A kind of Hydroxylated acrylic resin coating of embodiment 3 is made of Hydroxylated acrylic resin and mixed solvent；Hydroxy
The preparation process and condition of acid resin are as follows：（1）The raw material and auxiliary material of 10wt% are added the reactor with agitating device
In, 105oC is warming up to, rotating speed is stirred for 300r/min, when the reaction time 1 is small, obtains component 1；The raw material and auxiliary
The mass percent of raw material is helped with embodiment 1；The total mass ratio of mixed solvent and raw material is 1:3, mixed solvent is that mass ratio is
0.60：The mixed solvent of 1 sec-butyl acetate 183.59g and propylene glycol methyl ether acetate 307.41g;
（2）Surplus stock and auxiliary material are mixed and made into mixed solution again, as component 2, dripped component 2 using dropwise addition mode
It is added in component 1,1 is added dropwise when small, maintains 105oC always, when reaction 6 is small, obtains Hydroxylated acrylic resin；
（3）By Hydroxylated acrylic resin：Curing agent hexamethylene diisocyanate trimer：Catalyst dibutyltin dilaurylate
Weight mass ratio be 1:0.04:0.001, room temperature is uniformly mixed, and obtains Hydroxylated acrylic resin coating.
The solid content of Hydroxylated acrylic resin coating prepared by embodiment 3 is 75%.
Sample preparation is the same as embodiment 1.
Measure embodiment 3 and obtain Mn=1.13 × 10 of Hydroxylated acrylic resin4, viscosity is 20304 mpas.It is obtained
Film coated surface is smooth, smooth, and without the problems such as turning white and is pin-free, it is suitable using solvent rate of volatilization to illustrate.Tried using lattice are drawn
Method is tested, is measured by cross cut test method in GB/T 9286-1998, adhesive force is 0 grade.Measured, pressed using pencil hardness method
Manual method measure, pencil hardness 2H in GB/T 6739-2006.According to the resistance to of the method test paint film in GB/T1735-2009
Hot property, water resistance, not bubbling corrugation.Paint film water resistance, water resistance are measured by method in GB/T 5209-1985, no blistering takes off
Fall.Method test paint film chemical reagent performance in ISO 2812-1-2007, acid resistance, alkali resistance, no blistering come off.
In order to contrast the film of the Hydroxylated acrylic resin coating of toluene solvant preparation（Prepared by (numbering 4) and the present invention
The film of Hydroxylated acrylic resin coating（Numbering 1~3）Performance, displayed such as following table one.It is hardness, attached by contrasting film
Put forth effort, is heat-resisting, acid and alkali-resistance, illustrating that the film performance for the Hydroxylated acrylic resin coating that the present invention is prepared using mixed solvent is complete
It is good, can not only reach environmental protection, low toxicity effect and can Hydroxylated acrylic resin that completely prepared by replacement toluene solvant apply
Material.
Table one
| Numbering | 1 | 2 | 3 | 4 |
| Solid content (%) | 75 | 75 | 75 | 75 |
| Hardness (the hard method of pencil) | 2H | 2H | 2H | 2H |
| Heat-resisting (90 ± 2oC, 3h) | ○ | ○ | ○ | ○ |
| Water resistance (3d) | + | + | + | + |
| Acid resistance (H2SO4,24h) | + | + | + | + |
| Alkali resistance (NaOH, 24h) | + | + | + | + |
| Salt tolerance (5%NaCl, 3d) | + | + | + | + |
| Adhesive force (level) | 0 | 0 | 0 | 0 |
Note："○" represents that bubbling does not wrinkle, and "+" indicates that no blistering comes off.
Claims (4)
1. a kind of Hydroxylated acrylic resin coating, it is characterised in that it is made of Hydroxylated acrylic resin and mixed solvent；Hydroxyl
The preparation process and condition of acrylic resin are as follows：（1）The raw material and auxiliary material of 10wt% are added anti-with agitating device
Answer in device, be warming up to 93~105oC, rotating speed is stirred for 300r/min, when the reaction time 1~2 is small, obtains component 1；It is described
Raw material be 22wt% methyl methacrylate（MMA）, 44wt% styrene (St), the n-BMA of 30wt%
(BA), the hydroxyethyl methacrylate (HEMA) of the acrylic acid (AA) of 1wt% and 3wt%；Auxiliary material is：Initiator azo two is different
Butyronitrile（AIBN）For the 2wt% of the gross mass of raw material；Chain-transferring agent tert-dodecylmercaotan（TDM）For the gross mass of raw material
0.5wt%；The total mass ratio of mixed solvent and raw material is 1：3, mixed solvent is that mass ratio is (8.06~0.60):1 acetic acid is secondary
The mixed solvent of butyl ester and propylene glycol methyl ether acetate；
(2) remaining raw material and auxiliary material are mixed and made into mixed solution as component 2 again, component 2 is added drop-wise to component 1
In, 1~2 is added dropwise when small, and it is 93~105oC then to maintain temperature, when reaction 6 is small, obtains Hydroxylated acrylic resin；
(3) Hydroxylated acrylic resin is pressed：Curing agent hexamethylene diisocyanate trimer：Catalyst dibutyltin dilaurylate
Mass ratio be 1：0.04：0.001, room temperature is uniformly mixed, and obtains Hydroxylated acrylic resin coating.
2. a kind of Hydroxylated acrylic resin coating as claimed in claim 1, it is characterised in that described（1）The original of 10wt%
Material and auxiliary material are added in the reactor with agitating device, are warming up to 93oC, and rotating speed is stirred for 300r/min, reaction
Time 2 h, obtains component 1；Mixed solvent is that mass ratio is 8：The mixing of 1 sec-butyl acetate and propylene glycol methyl ether acetate
Solvent;
Described（2）Component 2 is added dropwise in component 1 using dropwise addition mode, 1 is added dropwise when small, maintains always anti-under 97oC
Answer 6 it is small when, obtain Hydroxylated acrylic resin.
3. a kind of Hydroxylated acrylic resin coating as claimed in claim 2, it is characterised in that described（1）The original of 10wt%
Material and auxiliary material are added in the reactor with agitating device, are warming up to 100oC, rotating speed is stirred for 300r/min, instead
Between seasonable 1.5 it is small when, obtain component 1；The mixed solvent is that mass ratio is 4：1 sec-butyl acetate 3 and propylene glycol monomethyl ether
The mixed solvent of acetate;
Described（2）Surplus stock and auxiliary material are mixed and made into mixed solution again, will using the mode of dropwise addition as component 2
Component 2 is added drop-wise in component 1, and 2 are added dropwise when small, is maintained 100oC always, when reaction 6 is small, is obtained hydroxy acrylic acid tree
Fat.
4. a kind of Hydroxylated acrylic resin coating as claimed in claim 2, it is characterised in that described（1）The original of 10wt%
Material and auxiliary material are added in the reactor with agitating device, are warming up to 105oC, rotating speed is stirred for 300r/min, instead
Between seasonable 1 it is small when, obtain component 1；Mixed solvent is that mass ratio is 0.6：1 sec-butyl acetate and propylene glycol methyl ether acetate
Mixed solvent;
Described（2）Component 2 is added drop-wise in component 1 using dropwise addition mode, 1 is added dropwise when small, maintains 105oC always,
React 6 it is small when, obtain Hydroxylated acrylic resin.
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| CN201711331648.7A CN107936812A (en) | 2017-12-13 | 2017-12-13 | A kind of preparation method of Hydroxylated acrylic resin coating |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109913057A (en) * | 2019-04-11 | 2019-06-21 | 益帆涂料(无锡)有限公司 | A kind of cash dispenser shell large arch dam Lacquer finish coating |
| CN110003381A (en) * | 2019-03-07 | 2019-07-12 | 何嘉妍 | A kind of resist sagging resin and preparation method thereof |
| CN110079205A (en) * | 2019-05-23 | 2019-08-02 | 西华大学 | A kind of no-solvent type Hydroxylated acrylic resin coating and its preparation method and application |
| CN112920308A (en) * | 2021-03-31 | 2021-06-08 | 重庆三峡油漆股份有限公司 | AOE intermediate, hydroxy acrylic resin containing AOE intermediate and preparation method thereof |
| CN112961557A (en) * | 2021-03-02 | 2021-06-15 | 中山市海兰德化工有限公司 | Low-VOC solvent type coating and preparation method thereof |
-
2017
- 2017-12-13 CN CN201711331648.7A patent/CN107936812A/en active Pending
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| 胡鑫鑫: "双组份丙烯酸酯类涂料树脂的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003381A (en) * | 2019-03-07 | 2019-07-12 | 何嘉妍 | A kind of resist sagging resin and preparation method thereof |
| CN110003381B (en) * | 2019-03-07 | 2021-03-26 | 何嘉妍 | Anti-sagging resin and preparation method thereof |
| CN109913057A (en) * | 2019-04-11 | 2019-06-21 | 益帆涂料(无锡)有限公司 | A kind of cash dispenser shell large arch dam Lacquer finish coating |
| CN110079205A (en) * | 2019-05-23 | 2019-08-02 | 西华大学 | A kind of no-solvent type Hydroxylated acrylic resin coating and its preparation method and application |
| CN110079205B (en) * | 2019-05-23 | 2021-04-27 | 西华大学 | Solvent-free hydroxyl acrylic resin coating and preparation method and application thereof |
| CN112961557A (en) * | 2021-03-02 | 2021-06-15 | 中山市海兰德化工有限公司 | Low-VOC solvent type coating and preparation method thereof |
| CN112920308A (en) * | 2021-03-31 | 2021-06-08 | 重庆三峡油漆股份有限公司 | AOE intermediate, hydroxy acrylic resin containing AOE intermediate and preparation method thereof |
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Application publication date: 20180420 |