CN112759720A - Boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin and preparation method and application thereof - Google Patents

Boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin and preparation method and application thereof Download PDF

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CN112759720A
CN112759720A CN202110033516.6A CN202110033516A CN112759720A CN 112759720 A CN112759720 A CN 112759720A CN 202110033516 A CN202110033516 A CN 202110033516A CN 112759720 A CN112759720 A CN 112759720A
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CN112759720B (en
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杨胜廷
范晓东
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Guangdong Ritop Fine Chemical Co ltd
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    • 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
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    • 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

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Abstract

The invention discloses a boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin which comprises the following components in parts by weight: 25-45 parts of A part polyester monomer, 1-5 parts of B part acrylic resin monomer, 5-15 parts of C part acrylic resin monomer, 3-7 parts of cosolvent, 0.2-1 part of initiator, 1-4 parts of neutralizer and 38-48 parts of deionized water; the A part polyester monomer comprises polyalcohol and polybasic acid, the B part acrylic resin monomer comprises methacrylic acid phosphate or acrylic acid epoxy phosphate, and the C part acrylic resin monomer comprises acrylic acid. The phosphorus-containing waterborne acrylic modified polyester dispersoid resin prepared by the invention has better water dispersibility, can be used in amino baking varnish coating, can obviously improve the boiling resistance and mechanical property of coating film of the coating and the adhesive force of the coating film to metal materials, and has high glossiness.

Description

Boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin and preparation method and application thereof
Technical Field
The invention belongs to the technical field of boiling-resistant paint materials, and particularly relates to a boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin, and a preparation method and application thereof.
Background
The water-based paint is one of the development directions of environment-friendly paints, takes water as a dispersion medium, and has the advantages of no toxicity, environmental protection, low VOC content and the like. The water-based paint mainly comprises water-based acrylic acid, water-based polyurethane, water-based polyester, water-based epoxy oxygen and the like, wherein the water-based polyester paint is a representative water-based paint and is widely used for protecting and decorating metal surfaces.
The ester bond of the water-based polyester is easy to hydrolyze, so that the water boiling resistant performance of a paint film is poor, and the application of the water-based polyester in the water boiling resistant paint is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin as well as a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin comprises the following components in parts by weight: 25-45 parts of A-part polyester monomer, 1-5 parts of B-part acrylic resin monomer, 5-15 parts of C-part acrylic resin monomer, 3-7 parts of cosolvent, 0.2-1 part of initiator, 1-4 parts of neutralizer and 38-48 parts of deionized water.
Further, the part a polyester monomer includes a polyol and a polyacid. Preferably, the polyol comprises at least one of 1,6 hexanediol, polycarbonate diol, methyl propylene glycol, neopentyl glycol, 1,4 butanediol, glycidyl versatate, trimethylolpropane. Preferably, the polybasic acid comprises at least one of phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, maleic anhydride, fumaric acid. Preferably, the ratio of polyhydric alcohol to polybasic acid is (1.05 to 1.15): 1. the hydrolysis resistance of the polyester is better under the condition of the proportion.
It will be understood by those skilled in the art that the polyol refers to a monomer capable of introducing hydroxyl groups to the resin and the polyacid refers to a monomer capable of introducing carboxyl groups to the resin.
Further, the B part acrylic resin monomer comprises at least one of methacrylic acid phosphate and acrylic acid epoxy phosphate.
Further, the C-part acrylic resin monomer includes at least one of acrylic acid, glycidyl versatate, methacrylic acid, isobornyl methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, styrene, butyl acrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, cyclohexyl methacrylate.
On one hand, the invention optimizes the types of synthetic monomers of the polyester, selects the polybasic acid and the polyhydric alcohol with better hydrolysis resistance for polymerization, and optimizes the mixture ratio of the polybasic acid and the polyhydric alcohol. On the other hand, the invention adopts the phosphorus-containing acrylic resin monomer of the B part to carry out graft modification on the polyester, and the graft modification of the monomer can effectively improve the adhesive force of the polyester to a metal substrate and can also improve the water dispersibility of the polyester; in addition, the invention also adopts the acrylic resin monomer at the C part to graft and modify the polyester, and the monomer can effectively improve the boiling resistance of the polyester. Surprisingly, the inventor finds in the research process that the effect of simultaneously using the acrylic resin monomer B and the acrylic resin monomer C to graft and modify the polyester is more remarkable than that of singly grafting the acrylic resin monomer C to improve the boiling resistance.
Preferably, the cosolvent comprises at least one of methyl 3-methoxypropionate and butyl propylene glycol ether. The cosolvent is an environment-friendly solvent, has good dissolving capacity and is compatible with water.
Preferably, the cosolvent consists of methyl 3-methoxypropionate and propylene glycol butyl ether, and the mass ratio of methyl 3-methoxypropionate: and (3) 1 is propylene glycol butyl ether (1-2). The inventor finds that the water dispersibility of the prepared dispersion resin is better when the methyl 3-methoxypropionate and the propylene glycol butyl ether are compounded and used according to the proportion.
Preferably, the cosolvent consists of methyl 3-methoxypropionate and propylene glycol butyl ether, and the mass ratio of methyl 3-methoxypropionate: propylene glycol butyl ether is 1.5: 1. The inventors have found through experiments that when methyl 3-methoxypropionate and propylene glycol butyl ether are compounded in the above ratio, the dispersion resin obtained has the best water dispersibility.
Preferably, the initiator comprises at least one of benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate and dicumyl peroxide.
Preferably, the neutralizing agent comprises at least one of triethylamine, dimethylethanolamine, and ammonia.
In another aspect, the invention further provides a preparation method of the boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin, which comprises the following steps:
(1) synthesizing a polyester: putting the A part of polyester monomer into a reaction kettle, introducing nitrogen, heating to raise the temperature, starting stirring when the temperature is raised to 120-130 ℃, continuing to raise the temperature at the speed of 8-12 ℃/h after the temperature is raised to 160 ℃, keeping the temperature until the acid value is 4-8 mg/g (calculated by KOH) when the temperature is raised to 230 ℃, and then cooling to 160 ℃ and keeping the temperature;
(2) adding a cosolvent into the system in the step (1), adding a mixture consisting of the acrylic resin monomers of the B part and the acrylic resin monomers of the C part and an initiator with the dosage of 20-50% for 120-200 min, carrying out heat preservation reaction for 1-2 h, adding the rest of initiator, and carrying out heat preservation reaction for 2-2.5 h;
(3) and (3) cooling the reaction system obtained in the step (2) to 90 +/-2 ℃, adding a neutralizing agent, cooling to 80 +/-2 ℃ after the neutralization reaction is finished, then adding deionized water, and uniformly dispersing to obtain the boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersoid resin.
In another aspect, the invention also provides the application of the boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin in a waterborne coating.
Preferably, the water-based paint is a water-based amino baking paint.
Preferably, the content of the boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin in the waterborne acrylic amino baking paint is 70-75 parts.
On the other hand, the invention also provides a water-based polyester amino baking paint which comprises the following components in parts by weight: 70-75 parts of boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin, 15-20 parts of waterborne amino resin, 3-5 parts of an auxiliary agent and 4-10 parts of deionized water.
Preferably, the auxiliary agent comprises at least one of a ByK-190 wetting dispersant, a ByK-022 defoaming agent, a Digao Tego-410 flatting agent, propylene glycol methyl ether and a neutralizing agent.
Preferably, the neutralizing agent comprises at least one of triethylamine, dimethylethanolamine, and ammonia.
On the other hand, the invention also provides a preparation method of the water-based polyester amino baking paint, which comprises the following steps: and mixing and uniformly dispersing the boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin, the waterborne amino resin and the auxiliary agent, then adding deionized water, filtering and discharging to obtain the waterborne polyester amino baking paint.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, through optimization of a formula and a process, firstly, polybasic acid with better hydrolysis resistance and polyhydric alcohol are polymerized to prepare polyester, and then, the polyester is further subjected to graft modification by adopting a B part phosphorus-containing acrylic resin monomer and a C part acrylic resin monomer, so that the boiling resistance, the metal adhesion and the water dispersibility of the polyester are further enhanced. The phosphorus-containing waterborne acrylic modified polyester dispersion resin prepared by the formula and the method has good water dispersibility, can be used in amino baking paint, can obviously improve the boiling resistance and the mechanical property of a paint film and the adhesive force of the paint film to a metal material, and has high glossiness.
Detailed Description
The technical solutions will be described clearly and completely in the following with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Sources of raw materials in examples and comparative examples:
component name Trade name or model number
Acrylic resin monomer B (monomer B) Methacrylic acid phosphoric ester
Acrylic resin monomer C (monomer C for short) Methacrylic acid methyl ester
Initiator Benzoyl peroxide
Neutralizing agent Triethylamine
Aqueous amino resin CYMEL303
The component composition of the A part polyester monomer 1 (A monomer 1 for short) is as follows: polycarbonate diol and fumaric acid, wherein the mass ratio of the polycarbonate diol to the fumaric acid is 1: 1.
The component composition of the A part polyester monomer 2 (A monomer 2 for short) is as follows: polycarbonate diol and fumaric acid, wherein the mass ratio of the polycarbonate diol to the fumaric acid is 1.05: 1.
The component composition of the A part polyester monomer 3 (A monomer 3 for short) is as follows: polycarbonate diol and fumaric acid, wherein the mass ratio of the polycarbonate diol to the fumaric acid is 1.1: 1.
The component composition of the A part polyester monomer 4 (A monomer 4 for short) is as follows: polycarbonate diol and fumaric acid, wherein the mass ratio of the polycarbonate diol to the fumaric acid is 1.15: 1.
The component composition of the A-part polyester monomer 5 (A monomer 5 for short) is as follows: polycarbonate diol and fumaric acid, wherein the mass ratio of the polycarbonate diol to the fumaric acid is 1.2: 1.
The cosolvent 1 comprises the following components: methyl 3-methoxypropionate and propylene glycol butyl ether, wherein the mass ratio of the methyl 3-methoxypropionate to the propylene glycol butyl ether is 1: 1.
The cosolvent 2 comprises the following components: methyl 3-methoxypropionate and propylene glycol butyl ether, wherein the mass ratio of the methyl 3-methoxypropionate to the propylene glycol butyl ether is 1.5: 1.
The cosolvent 3 comprises the following components: methyl 3-methoxypropionate and propylene glycol butyl ether, wherein the mass ratio of the methyl 3-methoxypropionate to the propylene glycol butyl ether is 2: 1.
The cosolvent 4 is 3-methoxypropionic acid methyl ester.
Cosolvent 5 is propylene glycol butyl ether.
Performance test standard:
the gloss was tested in accordance with GB/T9754-2007;
the hardness of the paint film is tested according to GB/T6739-2006;
impact resistance was tested according to GB/T1732-1993;
water resistance was tested according to GB/T1733-1993;
the adhesion was tested according to GB/T1720-;
boiling resistance: after boiling water test for 2h, the coating should not fall off, blister or other defects after boiling water test, allowing slight color change.
Examples 1 to 5
Examples 1 to 5 provide a phosphorus-containing aqueous acrylic modified polyester dispersion resin, the formulation of which is shown in table 1, and the preparation method thereof is as follows:
(1) synthesizing a polyester: putting the A part of polyester monomer into a reaction kettle, introducing nitrogen, heating to raise the temperature, starting stirring when the temperature is raised to 120-130 ℃, continuing to raise the temperature at the speed of 8-12 ℃/h after the temperature is raised to 160 ℃, keeping the temperature until the acid value is 4-8 mg/g (calculated by KOH) when the temperature is raised to 230 ℃, and then cooling to 160 ℃ and keeping the temperature;
(2) adding a cosolvent into the system in the step (1), adding a mixture consisting of the acrylic resin monomers of the B part and the acrylic resin monomers of the C part and an initiator with the dosage of 20-50% for 120-200 min, carrying out heat preservation reaction for 1-2 h, adding the rest of initiator, and carrying out heat preservation reaction for 2-2.5 h;
(3) and (3) cooling the reaction system obtained in the step (2) to 90 +/-2 ℃, adding a neutralizing agent, cooling to 80 +/-2 ℃ after the neutralization reaction is finished, then adding deionized water, and uniformly dispersing to obtain the phosphorus-containing waterborne acrylic modified polyester dispersion resin.
Comparative examples 1 to 6: comparative examples 1 to 6 provide aqueous polyester dispersion resins having the formulations shown in Table 1, and the preparation methods thereof were according to the preparation methods of examples 1 to 5.
TABLE 1
Figure BDA0002892546620000061
Figure BDA0002892546620000071
Note: in the table, "-" indicates that the component was not added.
And (3) performance testing:
firstly, the type of the cosolvent is effective for abnormal viscosity thickening in the dilution process, and in order to investigate the influence of the cosolvents 1-5 on the water dispersion performance of the resin, the following item test of table 2 is carried out. Wherein the viscosity was measured at 25 ℃ by using an NDJ-1 type rotational viscometer.
TABLE 2
Sample (I) Mass fraction of solids% Viscosity, mPas Water-dispersible
Example 2 45.5 2000 Good effect
Example 4 45.6 1950 Is excellent in
Example 5 44.3 2250 Good effect
Comparative example 1 44.1 2600 In general
Comparative example 2 44.2 2450 In general
From the test results in table 2, it can be seen that under the same conditions of monomers, initiators and the like, the mass fractions of the solid contents of the resins of examples 2, 4 to 5 and comparative examples 1 to 2 are not obviously different, but the dissolving capacities of the resins of examples 2 and 4 to 5 are obviously superior to those of the resins of comparative examples 1 to 2, which shows that when methyl 3-methoxypropionate and propylene glycol butyl ether are compounded for use, the dissolving capacity of the resin can be obviously improved, so that the resin has good water dispersibility.
Secondly, the acrylic acid modified polyester dispersion resins prepared in examples 1 to 3 and comparative examples 3 to 6 are respectively used as resin dispersions, then polyester amino baking varnish is prepared according to the following formula, the performances of paint films obtained by the polyester amino baking varnish are tested, and the test results are shown in table 3.
The polyester amino baking varnish consists of the following components in parts by weight: 72 parts of resin dispersoid, 18 parts of CYMEL303 aqueous amino resin, 0.5 part of BYK-190 wetting dispersant, 0.2 part of BYK-022 defoaming agent, 0.2 part of Tego-410 flatting agent, 3 parts of propylene glycol methyl ether, 0.2 part of dimethylethanolamine and 5.9 parts of deionized water.
TABLE 3
Figure BDA0002892546620000081
As can be seen from the test results of table 3: in the paint films of the examples 1-3 and the comparative examples 3-4, the water resistance of the examples 1-3 is obviously better than that of the comparative examples 3-4, which shows that the ratio of the polyalcohol to the polyacid in the A-part polyester monomer influences the water resistance of the polyester, and the ratio of the polyalcohol to the polyacid is (1.05-1.15): the polyester synthesized by the proportion of 1 has better hydrolysis resistance. In the paint films of the embodiment 2 and the comparative examples 5 to 6, the comprehensive performance of the embodiment 2 is obviously superior to that of the comparative examples 5 to 6, and particularly the boiling resistance, which shows that the effect of simultaneously using the phosphorus-containing acrylic resin monomer B and the acrylic resin monomer C to graft and modify the polyester is better.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin is characterized by comprising the following components in parts by weight: 25-45 parts of A part polyester monomer, 1-5 parts of B part acrylic resin monomer, 5-15 parts of C part acrylic resin monomer, 3-7 parts of cosolvent, 0.2-1 part of initiator, 1-4 parts of neutralizer and 38-48 parts of deionized water; the A part polyester monomer comprises polyalcohol and polybasic acid; the B part acrylic resin monomer comprises at least one of methacrylic acid phosphate and acrylic acid epoxy phosphate; the C part acrylic resin monomer comprises at least one of acrylic acid, glycidyl versatate, methacrylic acid, isobornyl methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, styrene, butyl acrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and cyclohexyl methacrylate.
2. The boiling resistant phosphorus containing waterborne acrylic modified polyester dispersion resin of claim 1, wherein the polyol comprises at least one of 1,6 hexanediol, polycarbonate diol, methyl propylene glycol, neopentyl glycol, 1,4 butanediol, glycidyl versatate, trimethylolpropane.
3. The boiling resistant phosphorus containing waterborne acrylic modified polyester dispersion resin of claim 1, wherein the polyacid comprises at least one of phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, maleic anhydride, fumaric acid.
4. The boiling-resistant phosphorus-containing aqueous acrylic modified polyester dispersion resin according to claim 1, wherein the mass ratio of the polyhydric alcohol to the polybasic acid is (1.05-1.15): 1.
5. the boiling-resistant phosphorus-containing aqueous acrylic modified polyester dispersion resin of claim 1, wherein the cosolvent comprises methyl 3-methoxypropionate and butyl propylene glycol ether, and the mass ratio of methyl 3-methoxypropionate: and (3) 1 is propylene glycol butyl ether (1-2).
6. The boiling-resistant phosphorus-containing aqueous acrylic modified polyester dispersion resin of claim 1, wherein the cosolvent comprises methyl 3-methoxypropionate and butyl propylene glycol ether, and the mass ratio of methyl 3-methoxypropionate: propylene glycol butyl ether is 1.5: 1.
7. The boiling resistant phosphorus containing waterborne acrylic modified polyester dispersion resin of claim 1, wherein the initiator comprises at least one of benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, dicumyl peroxide.
8. The boiling resistant phosphorus containing waterborne acrylic modified polyester dispersion resin of claim 1, wherein the neutralizing agent comprises at least one of triethylamine, dimethylethanolamine, ammonia.
9. The preparation method of the boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin according to any one of claims 1 to 8, comprising the following steps:
(1) synthesizing a polyester: putting the A part of polyester monomer into a reaction kettle, introducing nitrogen, heating to raise the temperature, starting stirring when the temperature is raised to 120-130 ℃, continuing to raise the temperature at the speed of 8-12 ℃/h after the temperature is raised to 160 ℃, keeping the temperature until the acid value is 4-8 mg/g (calculated by KOH) when the temperature is raised to 230 ℃, and then cooling to 160 ℃ and keeping the temperature;
(2) adding a cosolvent into the system in the step (1), adding a mixture consisting of the acrylic resin monomers of the B part and the acrylic resin monomers of the C part and an initiator with the dosage of 20-50% for 120-200 min, carrying out heat preservation reaction for 1-2 h, adding the rest of initiator, and carrying out heat preservation reaction for 2-2.5 h;
(3) and (3) cooling the reaction system obtained in the step (2) to 90 +/-2 ℃, adding a neutralizing agent, cooling to 80 +/-2 ℃ after the neutralization reaction is finished, then adding deionized water, and uniformly dispersing to obtain the boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersoid resin.
10. The use of the boiling-resistant phosphorus-containing aqueous acrylic modified polyester dispersion resin according to any one of claims 1 to 8 in an aqueous coating; preferably, the water-based paint is a water-based amino baking paint.
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Denomination of invention: A water resistant and phosphorus containing waterborne acrylic modified polyester dispersion resin and its preparation method and application

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