CN111995715A - Preparation method of step-by-step modified waterborne alkyd resin and waterborne alkyd resin - Google Patents
Preparation method of step-by-step modified waterborne alkyd resin and waterborne alkyd resin Download PDFInfo
- Publication number
- CN111995715A CN111995715A CN202010653041.6A CN202010653041A CN111995715A CN 111995715 A CN111995715 A CN 111995715A CN 202010653041 A CN202010653041 A CN 202010653041A CN 111995715 A CN111995715 A CN 111995715A
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- alkyd resin
- waterborne alkyd
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The disclosure relates to a preparation method of step-by-step modified waterborne alkyd resin and the waterborne alkyd resin prepared by the method. The preparation method comprises the following steps: a. preparing an acrylic prepolymer; b. preparing acrylic acid modified water-based alkyd resin; and c, preparing the styrene modified waterborne alkyd resin. The stepwise modification process disclosed by the invention can reduce the loss of double bonds in molecules, and the prepared waterborne alkyd resin has the advantages of both acrylic acid and styrene on the basis of the traditional alkyd resin, has the characteristics of environmental protection, good water solubility, high hardness, high drying speed and the like, and meets the current environmental protection requirements and trends.
Description
Technical Field
The disclosure belongs to the field of coatings, and particularly relates to a preparation method of an acrylic acid and styrene step-by-step modified waterborne alkyd resin, and a waterborne alkyd resin prepared from the same.
Background
The alkyd resin has the advantages of easily available raw materials, low cost, high coating film drying speed, excellent glossiness, hardness and durability and good construction performance, so that the alkyd resin is widely applied to the fields of bridges, machinery, vehicles, ships, airplanes, instruments and the like, and plays a very important role in the paint industry. The traditional solvent-based alkyd resin contains a large amount of organic solvent, which causes air pollution and a large amount of waste of resources and energy. Therefore, the alkyd resin is in the development direction of the alkyd resin, and simultaneously meets the environmental protection requirement. However, compared with the traditional solvent type, the water-based alkyd resin has many defects, such as slow drying speed, low hardness, and incapability of meeting construction requirements on water resistance and solvent resistance, so that the modification of the water-based alkyd resin is beneficial to further development of the water-based alkyd resin and practically meets the social development requirements.
CN109575194A discloses a waterborne alkyd resin modified by epoxy resin, rosin, styrene and acrylate and a preparation method thereof, in the patent application, the epoxy resin, the rosin and other raw materials are firstly used for preparing an alkyd resin prepolymer, and then the styrene and the acrylate are uniformly mixed and then are dripped for polymerization reaction. The polymerization method has the advantages that the addition amount of acrylic acid and styrene monomers must be strictly controlled, the homopolymerization reaction of the monomers is easy to occur, the system compatibility is poor, and the storage stability is influenced. Meanwhile, acrylic acid and styrene monomers consume too much double bonds in the alkyd resin chain, affecting the air-drying rate.
Disclosure of Invention
In order to solve the above problems, repeated experiments by the inventors of the present disclosure have found that the above problems can be solved by a stepwise modification process, the properties of the modified waterborne alkyd resin, such as water solubility, hardness, drying speed, etc., are improved comprehensively, double bonds in the alkyd resin chain are not lost, and the drying property of a paint film is not affected, and the present disclosure is completed on the basis.
An object of the present disclosure is to provide a method for preparing a stepwise modified water-based alkyd resin with good water solubility, high hardness and fast drying speed.
It is another object of the present disclosure to provide waterborne alkyds prepared therefrom.
According to one aspect of the present disclosure, there is provided a method for preparing a step-modified waterborne alkyd resin, comprising the steps of:
a. preparation of acrylic prepolymer: adding 21-26 parts by weight of methyl methacrylate, 50-65 parts by weight of xylene, 3-7 parts by weight of butyl acrylate and 1-3 parts by weight of molecular weight regulator into a three-neck flask, heating to 100 ℃ and 130 ℃ under stirring, mixing and dropwise adding 4-6 parts by weight of acrylic monomer and 0.5-1 part by weight of initiator, supplementing 0.5-1 part by weight of initiator after dropwise adding is finished, and carrying out heat preservation reaction for 1-2h to obtain an acrylic prepolymer after dropwise adding is finished;
b. preparation of acrylic acid modified waterborne alkyd resin: adding 25-35 parts by weight of vegetable oleic acid, 18-30 parts by weight of polyhydric alcohol, 22-30 parts by weight of phthalic anhydride, 10-20 parts by weight of the acrylic prepolymer prepared in the step a and 1-2 parts by weight of a water-carrying agent into a three-neck flask according to the weight percentage, heating to 180 ℃ under the protection of nitrogen, preserving the heat for 1h, continuously heating to 240 ℃ of 200-;
c. preparing styrene modified waterborne alkyd resin: and (b) adding 87-94 parts by weight of the acrylic acid modified waterborne alkyd resin prepared in the step (b) into a three-necked bottle, heating to 100-130 ℃, stirring, slowly dropping a mixture of 5-10 parts by weight of styrene and 0.5-1 part by weight of an initiator, preserving heat for 1-1.5h, additionally dropping 0.5-1 part by weight of the initiator twice, preserving heat for 1-1.5h respectively, reducing the pressure, extracting a water carrying agent, cooling to 80 ℃, adding a neutralizing agent to control the pH of the solution to be 7-8, adding 20-25 parts by weight of a cosolvent, uniformly stirring, and adding water for dilution to obtain the stepwise modified waterborne alkyd resin.
According to one aspect of the present disclosure, there is provided a waterborne alkyd prepared by the above-described method.
Advantageous effects
The preparation method of the stepwise modified waterborne alkyd resin disclosed by the invention has the following beneficial effects:
(1) the alkyd resin is compositely modified by styrene and acrylic acid step by step, so that the performances of water solubility, hardness, drying speed and the like of the alkyd resin are comprehensively improved.
(2) Firstly, an acrylic acid prepolymer is synthesized, acrylic acid and acrylic ester are grafted on a molecular chain of alkyd resin through esterification reaction, double bonds cannot be lost, and the drying performance of a paint film is not influenced.
Detailed Description
To make the features and effects of the present invention comprehensible to those having ordinary knowledge in the art, general description and definitions are made with respect to terms and phrases mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In this document, the terms "comprising," "including," "having," "containing," or any other similar term, are intended to be open-ended franslational phrase (open-ended franslational phrase) and are intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements is not limited to only those elements recited herein, but may include other elements not expressly listed but generally inherent to such composition or article. In addition, unless expressly stated to the contrary, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". For example, the condition "a or B" is satisfied in any of the following cases: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), both a and B are true (or present). Furthermore, in this document, the terms "comprising," including, "" having, "" containing, "and" containing "are to be construed as specifically disclosed and to cover both closed and semi-closed conjunctions, such as" consisting of … "and" consisting essentially of ….
All features or conditions defined herein as numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have covered and specifically disclosed all possible subranges and individual numerical values within the ranges, particularly integer numerical values. For example, a description of a range of "1 to 8" should be considered to have specifically disclosed all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, and so on, particularly subranges bounded by all integer values, and should be considered to have specifically disclosed individual values such as 1, 2, 3, 4, 5, 6, 7, 8, and so on, within the range. Unless otherwise indicated, the foregoing explanatory methods apply to all matters contained in the entire disclosure, whether broad or not.
If an amount or other value or parameter is expressed as a range, preferred range, or a list of upper and lower limits, it is to be understood that all ranges subsumed therein for any pair of that range's upper or preferred value and that range's lower or preferred value, whether or not such ranges are separately disclosed, are specifically disclosed herein. Further, when a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
In this context, numerical values should be understood to have the precision of the number of significant digits of the value, provided that the object of the invention is achieved. For example, the number 40.0 should be understood to cover a range from 39.50 to 40.49.
In this document, where Markush group (Markush group) or Option language is used to describe features or examples of the invention, those skilled in the art will recognize that a sub-group of all elements or any individual element within a Markush group or list of options may also be used to describe the invention. For example, if X is described as "selected from the group consisting of1、X2And X3The group "also indicates that X has been fully described as X1Is claimed with X1And/or X2Claim (5). Furthermore, where Markush group or option terms are used to describe features or examples of the invention, those skilled in the art will recognize that any combination of sub-groups of all elements or individual elements within the Markush group or option list can also be used to describe the invention. Accordingly, for example, if X is described as "selected from the group consisting of1、X2And X3Group consisting of "and Y is described as" selected from Y1、Y2And Y3The group "formed indicates that X has been fully described as X1Or X2Or X3And Y is Y1Or Y2Or Y3Claim (5).
The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary of the invention or the following detailed description or examples.
According to one embodiment of the present disclosure, there is provided a method for preparing a step-modified waterborne alkyd resin, the method comprising the steps of:
a. preparation of acrylic prepolymer: adding 21-26 parts by weight of methyl methacrylate, 50-65 parts by weight of xylene, 3-7 parts by weight of butyl acrylate and 1-3 parts by weight of molecular weight regulator into a three-neck flask, heating to 100 ℃ and 130 ℃ under stirring, mixing and dropwise adding 4-6 parts by weight of acrylic monomer and 0.5-1 part by weight of initiator, supplementing 0.5-1 part by weight of initiator after dropwise adding is finished, and carrying out heat preservation reaction for 1-2h to obtain an acrylic prepolymer after dropwise adding is finished;
b. preparation of acrylic acid modified waterborne alkyd resin: adding 25-35 parts by weight of vegetable oleic acid, 18-30 parts by weight of polyhydric alcohol, 22-30 parts by weight of phthalic anhydride, 10-20 parts by weight of the acrylic prepolymer prepared in the step a and 1-2 parts by weight of a water-carrying agent into a three-neck flask according to the weight percentage, heating to 180 ℃ under the protection of nitrogen, preserving the heat for 1h, continuously heating to 240 ℃ of 200-;
c. preparing styrene modified waterborne alkyd resin: and (b) adding 87-94 parts by weight of the acrylic acid modified waterborne alkyd resin prepared in the step (b) into a three-necked bottle, heating to 100-130 ℃, stirring, slowly dropping a mixture of 5-10 parts by weight of styrene and 0.5-1 part by weight of an initiator, preserving heat for 1-1.5h, additionally dropping 0.5-1 part by weight of the initiator twice, preserving heat for 1-1.5h respectively, reducing the pressure, extracting a water carrying agent, cooling to 80 ℃, adding a neutralizing agent to control the pH of the solution to be 7-8, adding 20-25 parts by weight of a cosolvent, uniformly stirring, and adding water for dilution to obtain the stepwise modified waterborne alkyd resin.
In an embodiment of the present disclosure, the molecular weight regulator in step a comprises one or a combination of several selected from n-dodecyl mercaptan, t-dodecyl mercaptan, thioethyl alcohol and linear methyl styrene dimer.
By using the molecular weight regulator, the molecular weight of the acrylic prepolymer can be effectively regulated, and the excessive viscosity of the system can be prevented.
In an embodiment of the present disclosure, the initiators in steps a and c each independently comprise one selected from benzoyl peroxide, benzoyl tert-butyl peroxide and methyl ethyl ketone peroxide, or a combination of several thereof.
By using the above-mentioned initiator, the polymerization can be initiated at a relatively mild temperature, and the polymerization rate can be easily controlled.
In an embodiment of the present disclosure, the vegetable oil acid in step b includes one selected from the group consisting of linoleic acid, ricinoleic acid, lauric acid, cottonseed oil acid, corn oil acid, soybean oil fatty acid, and coconut oil acid, or a combination of several thereof.
By using the vegetable oil acid, oxygen in air can be absorbed in the film forming process, a free radical synthesis film is generated at normal temperature, and then the film is stacked to form a film, so that the dryness of the resin is endowed.
In an embodiment of the present disclosure, the polyol in step b includes one selected from trimethylolpropane, glycerol, pentaerythritol, neopentyl glycol, propylene glycol and diethylene glycol, or a combination of several.
By using the polyhydric alcohol, the esterification can be carried out with the vegetable oleic acid, the esterification rate can be improved, and the process cost can be reduced.
In an embodiment of the present disclosure, the polybasic acid in step b comprises one or a combination of several selected from isophthalic acid, terephthalic acid, phthalic anhydride, trimellitic anhydride, adipic acid, 2, 6-naphthalene dicarboxylic acid and maleic anhydride.
By esterifying hydroxyl groups with the above-mentioned polybasic acids, chemical resistance and weather resistance can be imparted to the alkyd resin.
In an embodiment of the present disclosure, the water-carrying agent in steps b and c comprises one or a combination of several selected from petroleum ether, benzene, toluene, xylene, cyclohexane, chloroform and carbon tetrachloride.
By using the water-carrying agent, water can be effectively removed in the subsequent process, and the reaction conversion rate is improved.
In an embodiment of the present disclosure, the neutralizing agent in step c comprises one selected from n.n-dimethylethanolamine, triethylamine and ammonia water, or a combination of several thereof.
By using the above neutralizing agent, the resin is provided with good water dispersibility and good storage stability.
In an embodiment of the present disclosure, the cosolvent in step c comprises one selected from the group consisting of ethylene glycol butyl ether, propylene glycol methyl ether and glycerol dimethyl ether, or a combination of several thereof.
By using the cosolvent, the viscosity of the resin paint can be reduced, and the film forming is assisted.
According to another embodiment of the present disclosure, there is provided a waterborne alkyd prepared by the above method.
The following will further illustrate a waterborne alkyd resin and a preparation method thereof according to the present invention with reference to specific examples, so as to more fully and clearly illustrate the technical solution of the present invention.
Example 1:
a. preparation of acrylic prepolymer: adding 21 parts by weight of methyl methacrylate, 50 parts by weight of dimethylbenzene, 3 parts by weight of butyl acrylate and 1 part by weight of molecular weight regulator into a three-neck flask, stirring, heating to 100 ℃, mixing and dropwise adding 4 parts by weight of acrylic monomer and 0.5 part by weight of initiator, supplementing 1 part by weight of initiator after dropwise adding is finished, and carrying out heat preservation reaction for 2 hours after dropwise adding is finished. Cooling and discharging for later use;
b. preparation of acrylic acid modified waterborne alkyd resin: adding 25 parts by weight of soybean oil and oleic acid, 18 parts by weight of pentaerythritol, 22 parts by weight of phthalic anhydride, 10 parts by weight of acrylic prepolymer and 1 part by weight of xylene into a three-neck flask, heating to 180 ℃ under the protection of nitrogen, preserving heat for 1h, continuously heating to 230 ℃, carrying out esterification reaction for 6h, and reacting until the acid value is reduced to 15 mgKOH/g. Adding 5 parts by weight of trimellitic anhydride, continuously reacting at 180 ℃ until the acid value is less than 35mgKOH/g, cooling, and discharging for later use;
c. preparing styrene modified waterborne alkyd resin: adding 89 parts by weight of acrylic acid modified waterborne alkyd resin into a three-neck flask, heating to 100 ℃, stirring, slowly dropping a mixture of 5 parts by weight of styrene and 0.5 part by weight of an initiator, preserving heat for 1h, adding 0.5 part by weight of the initiator in two additional drops, preserving heat for 1h respectively, reducing pressure, extracting a water-carrying agent, cooling to 80 ℃, adding a neutralizing agent, controlling the pH of a solution to be 7, adding 20 parts by weight of a cosolvent, stirring uniformly, adding a proper amount of water for dilution, dispersing uniformly at a high speed by using a dispersion machine, and discharging to obtain the acrylic acid and styrene stepwise modified waterborne alkyd resin.
Example 2:
a. preparation of acrylic prepolymer: adding 25 parts by weight of methyl methacrylate, 60 parts by weight of dimethylbenzene, 6 parts by weight of butyl acrylate and 2 parts by weight of molecular weight regulator into a three-neck flask, stirring, heating to 100 ℃, mixing and dropwise adding 5 parts by weight of acrylic monomer and 1 part by weight of initiator, supplementing 1 part by weight of initiator after dropwise adding is finished, and after dropwise adding is finished, carrying out heat preservation reaction for 2 hours. Cooling and discharging for later use;
b. preparation of acrylic acid modified waterborne alkyd resin: 30 parts by weight of soybean oil oleic acid, 25 parts by weight of pentaerythritol, 25 parts by weight of phthalic anhydride, 15 parts by weight of acrylic prepolymer and 1.5 parts by weight of xylene are added into a three-neck flask, and the mixture is heated to 180 ℃ under the protection of nitrogen, kept warm for 1h, continuously heated to 230 ℃ for esterification reaction for 6h, and reacted until the acid value is reduced to 15 mgKOH/g. Adding 8 parts by weight of trimellitic anhydride, continuously reacting at 180 ℃ until the acid value is less than 35mgKOH/g, cooling, and discharging for later use;
c. preparing styrene modified waterborne alkyd resin: adding 89 parts by weight of acrylic acid modified waterborne alkyd resin into a three-neck flask, heating to 100 ℃, stirring, slowly dropping a mixture of 8 parts by weight of styrene and 0.8 part by weight of an initiator, preserving heat for 1h, adding 0.8 part by weight of the initiator in a supplementing manner twice, preserving heat for 1h respectively, reducing pressure, extracting a water-carrying agent, cooling to 80 ℃, adding a neutralizing agent, controlling the pH of the solution to be 7-8, adding 25 parts by weight of cosolvent, stirring uniformly, adding a proper amount of water for dilution, dispersing uniformly at high speed by using a dispersing machine, and discharging to obtain the acrylic acid and styrene stepwise modified waterborne alkyd resin.
Example 3:
a. preparation of acrylic prepolymer: adding 25 parts by weight of methyl methacrylate, 65 parts by weight of dimethylbenzene, 7 parts by weight of butyl acrylate and 3 parts by weight of molecular weight regulator into a three-neck flask, stirring, heating to 100 ℃, mixing and dropwise adding 6 parts by weight of acrylic monomer and 1 part by weight of initiator, supplementing 1 part by weight of initiator after dropwise adding is finished, and after dropwise adding is finished, carrying out heat preservation reaction for 2 hours. Cooling and discharging for later use;
b. preparation of acrylic acid modified waterborne alkyd resin: adding 35 parts by weight of soybean oil oleic acid, 30 parts by weight of pentaerythritol, 30 parts by weight of phthalic anhydride, 20 parts by weight of acrylic prepolymer and 2 parts by weight of xylene into a three-neck flask, heating to 180 ℃ under the protection of nitrogen, preserving heat for 1h, continuously heating to 230 ℃, carrying out esterification reaction for 6h, and reacting until the acid value is reduced to 15 mgKOH/g. Adding 10 parts by weight of trimellitic anhydride, continuously reacting at 180 ℃ until the acid value is less than 35mgKOH/g, cooling, and discharging for later use;
c. preparing styrene modified waterborne alkyd resin: adding 89 parts by weight of acrylic acid modified waterborne alkyd resin into a three-neck flask, heating to 100 ℃, stirring, slowly dropping a mixture of 10 parts by weight of styrene and 1 part by weight of an initiator, preserving heat for 1h, adding 1 part by weight of the initiator in a supplementing manner twice, preserving heat for 1h respectively, reducing pressure, extracting a water-carrying agent, cooling to 80 ℃, adding a neutralizing agent, controlling the pH of the solution to be 7-8, adding 25 parts by weight of a cosolvent, stirring uniformly, adding a proper amount of water for dilution, dispersing uniformly at a high speed by using a dispersion machine, and discharging to obtain the acrylic acid and styrene stepwise modified waterborne alkyd resin.
Comparative example 1
a. Adding 35 parts by weight of soybean oil oleic acid, 30 parts by weight of pentaerythritol, 30 parts by weight of phthalic anhydride and 2 parts by weight of xylene into a three-neck flask, heating to 180 ℃ under the protection of nitrogen, keeping the temperature for 1h, continuously heating to 230 ℃, carrying out esterification reaction for 6h, and reacting until the acid value is reduced to 15 mgKOH/g. Cooling to 100 ℃;
b. uniformly mixing 8 parts by weight of styrene, 11 parts by weight of methyl methacrylate, 7 parts by weight of butyl methacrylate, 5 parts by weight of methacrylic acid and 1 part by weight of benzoyl peroxide, dropwise adding the mixture into the prepared resin at a constant speed for 3 hours, and simultaneously supplementing 0.2 part by weight of benzoyl peroxide every hour. After the dropwise addition is finished, the temperature is kept for 2h at 120 ℃, and the temperature is reduced to 80 ℃;
c. adding a neutralizing agent, controlling the pH value of the solution to be 7, adding 25 parts by weight of cosolvent, uniformly stirring, adding a proper amount of water for dilution, uniformly dispersing at a high speed by using a dispersion machine, and discharging to obtain the waterborne alkyd resin.
As described above, in comparative example 1, the acrylic and styrene modifications were simultaneously performed in step b, rather than stepwise as described in the examples.
In order to illustrate the performances of the modified waterborne alkyd resins prepared in the examples of the invention and the comparative examples in a comparative way by comparison, a varnish prepared by adding a proper amount of waterborne drier into the modified waterborne alkyd resin is coated on the surface of standard tinplate, and the modified waterborne alkyd resin is subjected to performance detection after being placed at room temperature for 7 days. The test results are shown in Table 1.
Test methods and basis:
the surface dry time and the actual dry time test method refer to GB/T1728-1989;
reference is made to GB/T1733-1993 for water resistance testing;
the adhesion force grade test method refers to GB/T9286-1998;
the impact resistance test method is described in GB/T1732-1993.
TABLE 1 Performance test results for different alkyd resins
From the results of table 1 above, it can be seen that the alkyd resins obtained by stepwise modification of examples 1 to 3 of the present disclosure have significantly reduced open and close times and significantly improved water resistance, adhesion and impact resistance, as compared to the alkyd resin of comparative example 1, which is simultaneously modified with acrylic acid and styrene. Thus, the step-modified waterborne alkyd of the present disclosure may be more effectively used in advanced coatings.
The above embodiments are merely exemplary in nature and are not intended to limit the claimed embodiments or the application or uses of such embodiments. In this document, the term "exemplary" represents "as an example, instance, or illustration. Any exemplary embodiment herein is not necessarily to be construed as preferred or advantageous over other embodiments.
In addition, while at least one exemplary embodiment or comparative example has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations are possible. It should also be appreciated that the embodiments described herein are not intended to limit the scope, applicability, or configuration of the claimed subject matter in any way. Rather, the foregoing implementations will provide those of ordinary skill in the art with a convenient road map for implementing the described embodiment or embodiments. Further, various changes may be made in the function and arrangement of elements without departing from the scope defined in the claims, which includes known equivalents and all foreseeable equivalents at the time of filing this patent application.
Claims (10)
1. A preparation method of step-by-step modified water-based alkyd resin comprises the following steps:
a. preparation of acrylic prepolymer: adding 21-26 parts by weight of methyl methacrylate, 50-65 parts by weight of xylene, 3-7 parts by weight of butyl acrylate and 1-3 parts by weight of molecular weight regulator into a three-neck flask, heating to 100 ℃ and 130 ℃ under stirring, mixing and dropwise adding 4-6 parts by weight of acrylic monomer and 0.5-1 part by weight of initiator, supplementing 0.5-1 part by weight of initiator after dropwise adding is finished, and carrying out heat preservation reaction for 1-2h to obtain an acrylic prepolymer after dropwise adding is finished;
b. preparation of acrylic acid modified waterborne alkyd resin: adding 25-35 parts by weight of vegetable oleic acid, 18-30 parts by weight of polyhydric alcohol, 22-30 parts by weight of phthalic anhydride, 10-20 parts by weight of the acrylic prepolymer prepared in the step a and 1-2 parts by weight of a water-carrying agent into a three-neck flask according to the weight percentage, heating to 180 ℃ under the protection of nitrogen, preserving the heat for 1h, continuously heating to 240 ℃ of 200-;
c. preparing styrene modified waterborne alkyd resin: and (b) adding 87-94 parts by weight of the acrylic acid modified waterborne alkyd resin prepared in the step (b) into a three-necked bottle, heating to 100-130 ℃, stirring, slowly dropping a mixture of 5-10 parts by weight of styrene and 0.5-1 part by weight of an initiator, preserving heat for 1-1.5h, additionally dropping 0.5-1 part by weight of the initiator twice, preserving heat for 1-1.5h respectively, reducing the pressure, extracting a water carrying agent, cooling to 80 ℃, adding a neutralizing agent to control the pH of the solution to be 7-8, adding 20-25 parts by weight of a cosolvent, uniformly stirring, and adding water for dilution to obtain the stepwise modified waterborne alkyd resin.
2. The method of preparing a step-modified waterborne alkyd according to claim 1, wherein,
the molecular weight regulator in step a comprises one or more of n-dodecyl mercaptan, tert-dodecyl mercaptan, thioethyl alcohol and linear methyl styrene dimer.
3. The method of preparing a step-modified waterborne alkyd according to claim 1, wherein,
the initiators in steps a and c each independently comprise one or a combination of several selected from benzoyl peroxide, benzoyl tert-butyl peroxide and methyl ethyl ketone peroxide.
4. The method of preparing a step-modified waterborne alkyd according to claim 1, wherein,
the vegetable oil acid in step b comprises one or more selected from linoleic acid, ricinoleic acid, lauric acid, cottonseed oil acid, corn oil acid, soybean oil fatty acid and coconut oil acid.
5. The method of preparing a step-modified waterborne alkyd according to claim 1, wherein,
the polyol in step b comprises one or more selected from trimethylolpropane, glycerol, pentaerythritol, neopentyl glycol, propylene glycol and diethylene glycol.
6. The method of preparing a step-modified waterborne alkyd according to claim 1, wherein,
the polybasic acid in step b comprises one or a combination of several selected from isophthalic acid, terephthalic acid, phthalic anhydride, trimellitic anhydride, adipic acid, 2, 6-naphthalene dicarboxylic acid and maleic anhydride.
7. The method of preparing a step-modified waterborne alkyd according to claim 1, wherein,
the water-carrying agent in steps b and c comprises one or more of petroleum ether, benzene, toluene, xylene, cyclohexane, chloroform and carbon tetrachloride.
8. The method of preparing a step-modified waterborne alkyd according to claim 1, wherein,
the neutralizing agent in step c comprises one or a combination of several selected from the group consisting of n.n-dimethylethanolamine, triethylamine and ammonia.
9. The method of preparing a step-modified waterborne alkyd according to claim 1, wherein,
the cosolvent in the step c comprises one or a combination of ethylene glycol butyl ether, propylene glycol methyl ether and glycerol dimethyl ether.
10. A modified waterborne alkyd resin prepared using the method of any of claims 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010653041.6A CN111995715B (en) | 2020-07-08 | 2020-07-08 | Preparation method of step-by-step modified waterborne alkyd resin and waterborne alkyd resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010653041.6A CN111995715B (en) | 2020-07-08 | 2020-07-08 | Preparation method of step-by-step modified waterborne alkyd resin and waterborne alkyd resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111995715A true CN111995715A (en) | 2020-11-27 |
| CN111995715B CN111995715B (en) | 2023-03-31 |
Family
ID=73466739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010653041.6A Active CN111995715B (en) | 2020-07-08 | 2020-07-08 | Preparation method of step-by-step modified waterborne alkyd resin and waterborne alkyd resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111995715B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB735764A (en) * | 1952-10-15 | 1955-08-31 | Ici Ltd | Improvements in or relating to the manufacture of alkyd resins |
| US4273690A (en) * | 1979-10-09 | 1981-06-16 | E. I. Du Pont De Nemours And Company | Coating compositions of an alkyd-acrylic graft copolymer |
| CN102643392A (en) * | 2012-05-21 | 2012-08-22 | 中国科学院新疆理化技术研究所 | Synthesis method of styrene/acrylate-modified quick-drying water-based alkyd resin |
-
2020
- 2020-07-08 CN CN202010653041.6A patent/CN111995715B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB735764A (en) * | 1952-10-15 | 1955-08-31 | Ici Ltd | Improvements in or relating to the manufacture of alkyd resins |
| US4273690A (en) * | 1979-10-09 | 1981-06-16 | E. I. Du Pont De Nemours And Company | Coating compositions of an alkyd-acrylic graft copolymer |
| CN102643392A (en) * | 2012-05-21 | 2012-08-22 | 中国科学院新疆理化技术研究所 | Synthesis method of styrene/acrylate-modified quick-drying water-based alkyd resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111995715B (en) | 2023-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102993424B (en) | Novel acrylic acid modified alkyd resin and method for preparing same | |
| CN102675653B (en) | Method for preparing waterborne acrylic modified alkyd emulsion | |
| CN109734884B (en) | Deep drawing resistant waterborne acrylic modified polyester resin and preparation method thereof | |
| CN108129667B (en) | Phosphate/polyurethane modified waterborne alkyd resin and preparation method thereof | |
| CN112250850B (en) | Environment-friendly alkyd resin and preparation method and application thereof | |
| CN111848883B (en) | Preparation method of waterborne acrylic modified epoxy resin and coating thereof | |
| CN110527413B (en) | Acrylic acid modified waterborne alkyd dispersion and preparation method and application thereof | |
| CN103951818A (en) | Sulphonic acid type water-based unsaturated polyester and application of sulphonic acid type water-based unsaturated polyester in coating | |
| CN110156933A (en) | A kind of high weather resistant water-thinned alkyd paint lotion of quick-drying bloom and preparation method | |
| CN109593335B (en) | Carboxyl-containing polystyrene microsphere modified waterborne alkyd resin and preparation method thereof | |
| CN107141400A (en) | The preparation method of super siccative varnish Hydroxylated acrylic resin | |
| CN112029070A (en) | Water-based epoxy resin, preparation method thereof and water-based epoxy insulating impregnating varnish | |
| CN111848878A (en) | Aqueous acrylic acid dispersion and preparation method and application thereof | |
| CN109517512B (en) | High-solid-content two-component coating and application thereof | |
| CN102633915A (en) | Method for preparing photocurable resin from animal and vegetable triglyceride and photocurable resin prepared by method | |
| CN111995715B (en) | Preparation method of step-by-step modified waterborne alkyd resin and waterborne alkyd resin | |
| CN108546485B (en) | High-solid-content organic-inorganic hybrid resin and preparation method thereof | |
| EP1853642A1 (en) | Self-crosslinking alkyd dispersion | |
| CN110790870A (en) | Modified hydroxyl acrylic resin, preparation method and modified hydroxyl acrylic ester coating | |
| US4124551A (en) | Aliphatic hydrocarbon solvent reducible acrylic enamel of improved quality | |
| CN111995738B (en) | Water-based alkyd resin and preparation method thereof | |
| CN114507324B (en) | Water-based acrylic acid modified alkyd hybrid resin, preparation method, coating and application thereof | |
| JPS6152185B2 (en) | ||
| CN111196873A (en) | Alkyd resin, double-crosslinked alkyd acrylate dispersion comprising alkyd resin, preparation method and application | |
| CN112759720B (en) | Boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |