CN111978473A - Synthetic method of modified hydroxyl acrylic resin - Google Patents
Synthetic method of modified hydroxyl acrylic resin Download PDFInfo
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- CN111978473A CN111978473A CN202010899645.9A CN202010899645A CN111978473A CN 111978473 A CN111978473 A CN 111978473A CN 202010899645 A CN202010899645 A CN 202010899645A CN 111978473 A CN111978473 A CN 111978473A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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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
- 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
- C09D151/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Abstract
The invention discloses a synthetic method of modified hydroxyl acrylic resin, which comprises the following steps: mixing polyurethane modified chlorinated polypropylene and mesitylene, pressurizing and heating the mixture to dissolve the mixture in a nitrogen atmosphere, then slowly adding an initiator di-tert-butyl peroxide, methyl methacrylate, styrene, butyl methacrylate, deuterated glycidyl oleate, acrylic acid and mesitylene under the conditions of pressurizing and heating, and after the addition, carrying out heat preservation reaction to obtain a modified hydroxyl acrylic resin mixed solution. According to the method, the modified chlorinated polypropylene and the hydroxy acrylic resin are adopted, and various groups are introduced into a molecular chain to improve the cohesive force, the bonding strength and the polarity of the modified chlorinated polypropylene and the hydroxy acrylic resin, so that the obtained resin has high adhesive force to a base material, particularly a PP base material, is excellent in water resistance, and can be used for preparing a PP coating which is directly coated.
Description
Technical Field
The invention belongs to the field of acrylic polymers, and particularly relates to a synthetic method of modified hydroxyl acrylic resin.
Background
Chlorinated polypropylene (CPP) is an important chemical modified Product of Polypropylene (PP), and is a white or yellowish solid, tasteless and nontoxic, the chlorine content can be up to 67%, the melting point can be different according to the chlorine content, and the decomposition temperature is 180-190 ℃ between 100-120 ℃. Can be dissolved in other solvents except fatty acid and alcohol, and has better compatibility with most resins.
As the application of polypropylene gradually develops toward specialization and diversification, higher requirements are put forward on the performance of CPP. Because CPP has less molecular polarity and low solubility in polar solvent, the CPP has weak adhesion to polar materials and poor compatibility with coating resin, has low adhesion with finish paint when used as primer, has insufficient gasoline resistance and water resistance, and is difficult to compound.
An initiator is needed in the synthesis process of the acrylic resin, and the dosage of the initiator is usually about 1.5-4 percent at present. The initiator not only affects the molecular weight and molecular weight distribution of the polymer, but also affects the properties of the acrylic resin. For example, unreacted initiator can oxidize the resin at high temperature to darken the color and affect the quality of the resin. The more initiator not only increases the cost, but also causes the reaction to be too fast, the reaction is not easy to control, unsafe factors on the production are increased, and the reaction time is prolonged. It also results in increased decomposition products, affects product durability and is prone to odor generation.
In order to improve the adhesive force of the CPP polymer and further develop the application range of the acrylic resin, the molecular chain structure and the preparation method of the CPP polymer need to be improved from the aspects of chemical structure modification, reaction conditions and the like, so that the polymer has wider application prospect.
Disclosure of Invention
The invention aims to provide a synthetic method of a modified hydroxy acrylic resin based on the prior art. The resin obtained by the method has high adhesion to base materials, particularly PP base materials, and has the advantages of good glossiness, excellent water resistance, good compatibility with other resins and the like.
A synthetic method of modified hydroxyl acrylic resin comprises the following steps: mixing polyurethane modified chlorinated polypropylene and mesitylene, pressurizing and heating the mixture to dissolve the mixture in a nitrogen atmosphere, then slowly adding an initiator di-tert-butyl peroxide, methyl methacrylate, styrene, butyl methacrylate, deuterated glycidyl oleate, acrylic acid and mesitylene under the conditions of pressurizing and heating, and after the addition, carrying out heat preservation reaction to obtain a modified hydroxyl acrylic resin mixed solution.
The reaction of the invention is carried out under pressurization, and the high-performance modified hydroxy acrylic resin is obtained under the condition of low initiator consumption by various control means such as pressurization, reaction temperature increase, raw material adjustment and the like.
In one embodiment, the nitrogen is introduced to an absolute pressure of 0.11 to 0.3MPa, more preferably, to an absolute pressure of 0.15 to 0.2 MPa.
In one technical scheme, the temperature of the heat preservation reaction is 160-165 ℃.
The method can improve the reaction speed, and the heat preservation reaction can be completed within 0.5h
In the resin and the synthesis method thereof, the mass part of the polyurethane modified chlorinated polypropylene is 12 to 18 parts, preferably 13 to 16 parts. The present invention can employ various commercially available polyurethane-modified chlorinated polypropylenes known in the art.
The amount of methyl methacrylate is 20 to 40 parts by mass, preferably 25 to 35 parts by mass.
The amount of styrene is 15 to 35 parts by mass, preferably 20 to 35 parts by mass.
The mass portion of the butyl methacrylate is 10 to 20 portions, preferably 10 to 15 portions.
The mass part of the deuterated glycidyl oleate is 2-5 parts, preferably 3-5 parts.
The amount of acrylic acid is 4 to 8 parts by mass, preferably 4 to 7 parts by mass.
The mass portion of the initiator di-tert-butyl peroxide is 0.5-1.0 portion, preferably 0.5-0.8 portion.
The amount of the solvent mesitylene can be adjusted as required, and in one scheme, the total amount of the mesitylene is 20-50 parts.
The invention also provides a modified hydroxyl acrylic resin which is prepared by reacting polyurethane modified chlorinated polypropylene, methyl methacrylate, styrene, butyl methacrylate, deuterated glycidyl oleate, acrylic acid, initiator di-tert-butyl peroxide and solvent mesitylene at the absolute pressure of 0.11-0.3MPa and the temperature of 160-165 ℃. Wherein the amounts of the respective raw materials and the specific reaction conditions are as described above.
The reaction of the invention is carried out under pressurization, and the high-performance modified hydroxy acrylic resin is obtained under the condition of low initiator consumption by various control means such as pressurization, reaction temperature increase, raw material adjustment and the like.
According to the method, the modified chlorinated polypropylene and the hydroxy acrylic resin are adopted, and various groups are introduced into a molecular chain to improve the cohesive force, the bonding strength and the polarity of the modified chlorinated polypropylene and the hydroxy acrylic resin, so that the obtained resin has high adhesive force to a base material, particularly a PP base material, is good in glossiness, excellent in water resistance and good in compatibility with other resins, and can be used for preparing a PP coating which is directly coated.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
A synthetic method of modified hydroxyl acrylic resin comprises the following steps: after 15kg of polyurethane modified chlorinated polypropylene and 20kg of mesitylene are mixed, the mixture is pressurized to the absolute pressure of 0.2MPa in the nitrogen atmosphere and heated and refluxed to be mixed and dissolved, then 0.6kg of initiator di-tert-butyl peroxide, 25kg of methyl methacrylate, 30kg of styrene, 14kg of butyl methacrylate, 3kg of deuterated glycidyl oleate, 5kg of acrylic acid and 25kg of mesitylene are slowly added under the conditions of pressurization and the temperature of 162-165 ℃, and after the addition is finished, the mixture is subjected to heat preservation reaction for 20min to obtain a modified hydroxyl acrylic resin mixed solution, wherein the number is 1.
Example 2
A synthetic method of modified hydroxyl acrylic resin comprises the following steps: 13kg of polyurethane modified chlorinated polypropylene and 20kg of mesitylene are mixed, pressurized to the absolute pressure of 0.2MPa in the nitrogen atmosphere, heated, refluxed, mixed and dissolved, then 0.6kg of initiator di-tert-butyl peroxide, 33kg of methyl methacrylate, 26kg of styrene, 12kg of butyl methacrylate, 4kg of deuterated glycidyl oleate, 5kg of acrylic acid and 25kg of mesitylene are slowly added under the pressurization and the temperature of 162-165 ℃, and after the addition is finished, the heat preservation reaction is carried out for 20min, so as to obtain a modified hydroxyl acrylic resin mixed solution, wherein the number is 2.
Example 3
A synthetic method of modified hydroxyl acrylic resin comprises the following steps: 16kg of polyurethane modified chlorinated polypropylene and 28kg of mesitylene are mixed, pressurized to the absolute pressure of 0.2MPa in the nitrogen atmosphere, heated, refluxed, mixed and dissolved, then 0.5kg of initiator di-tert-butyl peroxide, 31kg of methyl methacrylate, 30kg of styrene, 13kg of butyl methacrylate, 3kg of deuterated glycidyl oleate, 6kg of acrylic acid and 25kg of mesitylene are slowly added under the pressurization and the temperature of 162-165 ℃, and after the addition is finished, the heat preservation reaction is carried out for 20min, so as to obtain a modified hydroxyl acrylic resin mixed solution, wherein the number is 3.
Example 4
A synthetic method of modified hydroxyl acrylic resin comprises the following steps: 14kg of polyurethane modified chlorinated polypropylene and 20kg of mesitylene are mixed, pressurized to the absolute pressure of 0.2MPa in the nitrogen atmosphere, heated, refluxed, mixed and dissolved, then 0.5kg of initiator di-tert-butyl peroxide, 35kg of methyl methacrylate, 33kg of styrene, 15kg of butyl methacrylate, 4kg of deuterated glycidyl oleate, 4kg of acrylic acid and 25kg of mesitylene are slowly added under the pressurization and the temperature of 162-165 ℃, and after the addition is finished, the heat preservation reaction is carried out for 20min, so as to obtain a modified hydroxyl acrylic resin mixed solution, wherein the number is 4.
Comparative example 1
A synthetic method of modified hydroxyl acrylic resin comprises the following steps: after 15kg of chlorinated polypropylene and 20kg of mesitylene are mixed, the mixture is pressurized to the absolute pressure of 0.2MPa in the nitrogen atmosphere and heated and refluxed to be mixed and dissolved, then 0.6kg of initiator di-tert-butyl peroxide, 25kg of methyl methacrylate, 30kg of styrene, 14kg of butyl methacrylate, 3kg of deuterated glycidyl oleate, 5kg of acrylic acid and 25kg of mesitylene are slowly added under the pressurization and the temperature of 162-165 ℃, and after the addition is finished, the mixture is subjected to heat preservation reaction for 20min to obtain a modified hydroxyl acrylic resin mixed solution, wherein the number is 5.
Comparative example 2
A synthetic method of modified hydroxyl acrylic resin comprises the following steps: after 15kg of chlorinated polypropylene and 20kg of mesitylene are mixed, the mixture is heated and refluxed and dissolved under the nitrogen atmosphere, then 0.6kg of initiator di-tert-butyl peroxide, 25kg of methyl methacrylate, 30kg of styrene, 14kg of butyl methacrylate, 5kg of acrylic acid and 25kg of mesitylene are slowly added at the temperature of 162-165 ℃, and after the addition is finished, the mixture is subjected to heat preservation reaction for 120min to obtain a modified hydroxyl acrylic resin mixed solution, wherein the number is 6.
Example 5
And (3) directly coating the hydroxyl acrylic resin solution with each number on a PP plate, and testing the adhesive force and the coating film glossiness of the PP plate. As can be seen from the table below, the adhesion of the resin obtained by the process on PP sheets can reach 0 grade, while the gloss with force is inferior to that of the present application both in comparative example 1 using unmodified chlorinated polypropylene and in comparative example 2 without using pressurized and deuterated glycidyl oleate.
TABLE 1
| Numbering | 1 | 2 | 3 | 4 | 5 | 6 |
| Gloss/% | 93.1 | 93.6 | 91.5 | 92.8 | 88.7 | 85.1 |
| Adhesion/degree | 0 | 0 | 0 | 0 | 1 | 2 |
| Water resistance | 8 hours | 8 hours | 8 hours | 8 hours | 4 hours | 3 hours |
Note: and (3) testing the glossiness of the coating film: the solution is coated on a polypropylene plate to form a film, and the glossiness of the film is measured by a ZGM1022 glossiness instrument (reflection angle 60 degrees) after drying.
And (3) testing water resistance: and (3) soaking 10 batches of coated PP plates in boiling water, observing the time when the film is abnormally changed, and recording and counting the average time when the film is abnormally changed.
As can be seen from Table 1, the resins obtained using either unmodified chlorinated polypropylene or using the existing preparation methods of hydroxyacrylic resins are still not satisfactory in gloss, adhesion and water resistance. The resin solution obtained by the method has better effects in the three aspects.
Example 6
Mixing the hydroxyl acrylic resin solution with acrylic resin according to the proportion of 1: 2, mixing, observing whether the materials have a layering phenomenon or not after mixing, and testing the compatibility of the materials. Wherein the No. 7 directly adopts chlorinated polypropylene solution.
TABLE 2
| Numbering | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Compatibility | 0 | 0 | 0 | 0 | 1 | 1 | 1 |
Note: 0 means no delamination, and 1 means delamination.
As can be seen from Table 2, the chlorinated polypropylene-modified resin or the resin obtained by the conventional method for preparing a hydroxy acrylic resin still has poor compatibility with acrylic resin at a content of 33.3%. The resins of the present application overcome this deficiency.
Claims (9)
1. A synthetic method of modified hydroxyl acrylic resin is characterized by comprising the following steps: mixing polyurethane modified chlorinated polypropylene and mesitylene, pressurizing and heating the mixture to dissolve the mixture in a nitrogen atmosphere, then slowly adding an initiator di-tert-butyl peroxide, methyl methacrylate, styrene, butyl methacrylate, deuterated glycidyl oleate, acrylic acid and mesitylene under the conditions of pressurizing and heating, and after the addition, carrying out heat preservation reaction to obtain a modified hydroxyl acrylic resin mixed solution.
2. The method for synthesizing a modified hydroxyacrylic acid resin according to claim 1, wherein nitrogen gas is introduced to an absolute pressure of 0.11 to 0.3 MPa.
3. The method for synthesizing a modified hydroxyacrylic acid resin according to claim 1, wherein nitrogen gas is introduced to an absolute pressure of 0.15 to 0.2 MPa.
4. The method for synthesizing modified hydroxy acrylic resin as defined in claim 1, wherein the reaction temperature is 160-165 ℃.
5. The method for synthesizing modified hydroxy acrylic resin according to claim 1, wherein the amount of the polyurethane modified chlorinated polypropylene is 12-18 parts by mass, the amount of the methyl methacrylate is 20-40 parts by mass, the amount of the styrene is 15-35 parts by mass, and the amount of the butyl methacrylate is 10-20 parts by mass.
6. The method for synthesizing modified hydroxy acrylic resin as claimed in claim 1, wherein the amount of deuterated glycidyl oleate is 2-5 parts by mass and the amount of acrylic acid is 4-8 parts by mass.
7. The method for synthesizing modified hydroxy acrylic resin according to claim 1, wherein the amount of the initiator di-tert-butyl peroxide is 0.5 to 1.0 part by mass.
8. A modified hydroxyl acrylic resin is characterized in that the modified hydroxyl acrylic resin is prepared by reacting polyurethane modified chlorinated polypropylene, methyl methacrylate, styrene, butyl methacrylate, deuterated glycidyl oleate, acrylic acid, initiator di-tert-butyl peroxide and solvent mesitylene under the absolute pressure of 0.11-0.3MPa and the temperature of 160-165 ℃.
9. The modified hydroxy acrylic resin as claimed in claim 8, wherein the polyurethane modified chlorinated polypropylene is used in an amount of 12 to 18 parts by mass, the methyl methacrylate is used in an amount of 20 to 40 parts by mass, the styrene is used in an amount of 15 to 35 parts by mass, the butyl methacrylate is used in an amount of 10 to 20 parts by mass, the deuterated glycidyl oleate is used in an amount of 2 to 5 parts by mass, the acrylic acid is used in an amount of 4 to 8 parts by mass, and the initiator is di-tert-butyl peroxide is used in an amount of 0.5 to 1.0 part by mass.
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| CN202010899645.9A CN111978473A (en) | 2020-08-31 | 2020-08-31 | Synthetic method of modified hydroxyl acrylic resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114525073A (en) * | 2021-12-25 | 2022-05-24 | 山西中涂交通科技股份有限公司 | Two-component polyurethane marking paint and preparation method thereof |
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2020
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114525073A (en) * | 2021-12-25 | 2022-05-24 | 山西中涂交通科技股份有限公司 | Two-component polyurethane marking paint and preparation method thereof |
| CN114525073B (en) * | 2021-12-25 | 2022-08-23 | 山西中涂交通科技股份有限公司 | Two-component polyurethane marking paint and preparation method thereof |
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Application publication date: 20201124 |