CN115477718A - High-wear-resistance acrylic resin and preparation method thereof - Google Patents
High-wear-resistance acrylic resin and preparation method thereof Download PDFInfo
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- CN115477718A CN115477718A CN202211124079.XA CN202211124079A CN115477718A CN 115477718 A CN115477718 A CN 115477718A CN 202211124079 A CN202211124079 A CN 202211124079A CN 115477718 A CN115477718 A CN 115477718A
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- acrylic resin
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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
- 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
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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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
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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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
Abstract
The invention discloses a high wear-resistant acrylic resin and a preparation method thereof, wherein the high wear-resistant acrylic resin is prepared from 30-40% of styrene, 8-15% of hydroxypropyl ester, 8-15% of propyl butyl ester, 1-5% of 3-isocyanate propyl trimethoxy silane, 0.3-1.5% of methacrylic acid, 0.5-2% of initiator and 30-40% of dimethylbenzene by mass percentage. The experiment obtains the optimal raw material composition and proportion through a large amount of experiment screening, the optimal synthesis process is preferably obtained through a large amount of experiments, and the conversion rate of the invention is as high as 98.8%. The acrylic resin provided by the invention has excellent wear resistance, and the coating film has the advantages of good weather resistance, high adhesion, high hardness, good three-proofing performance and the like, and has good technical effects on comprehensive performance.
Description
Technical Field
The invention relates to a high-wear-resistance acrylic resin, in particular to a high-wear-resistance acrylic resin which has strong wear resistance, good thermal stability, excellent physical properties and easy popularization and application and a preparation method thereof, belonging to the technical field of high polymer resins.
Background
The acrylic resin has the characteristics of good transparency, bright color, good adhesive force, good toughness and the like, and is used in coating materials. However, in a specific environment, the use of common acrylic resin has certain performance defects, which mainly do not perform well in the aspects of wear resistance, weather resistance, water resistance, stain resistance and the like, and the development and application of the acrylic resin are influenced.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the prior art, the invention preferably adjusts the optimal composition of an acrylic resin monomer and an initiator, and simultaneously adds 3-isocyanate propyl trimethoxy silane, so as to preferably prepare the acrylic resin with strong wear resistance, good thermal stability, high adhesive force, strong weather resistance, large hardness and other excellent comprehensive properties.
Technical solution to achieve the above object, the present invention adopts the following technical solutions:
the high-wear-resistance acrylic resin is prepared from the following raw materials: styrene, hydroxypropyl ester, propyl butyl ester, 3-isocyanate propyl trimethoxy silane, methacrylic acid, an initiator and xylene;
preferably, the acrylic resin with high wear resistance is prepared from the following raw materials in percentage by mass:
30-40% of styrene, 8-15% of hydroxypropyl ester, 8-15% of propyl butyl ester, 1-5% of 3-isocyanate propyl trimethoxy silane, 0.3-1.5% of methacrylic acid, 0.5-2% of initiator and 30-40% of xylene.
Preferably, the acrylic resin with high wear resistance is prepared from the following raw materials in percentage by mass: 36.6% styrene, 11.4% hydroxypropyl, 11.4% propylbutyl, 3.2% 3-isocyanatopropyltrimethoxysilane, 0.6% methacrylic acid, 1.9% initiator, 34.9% xylene.
Preferably, the high abrasion resistant acrylic resin is obtained by using dicumyl peroxide as the initiator.
Preferably, in the preparation method of the high-wear-resistance acrylic resin, the 3-isocyanatopropyl trimethoxy silane has good wear resistance and impact resistance.
The preparation method of the high-wear-resistance acrylic resin comprises the following steps:
(1) Adding a xylene solvent into a reaction device, and heating to reflux;
(2) Uniformly mixing styrene, hydroxypropyl ester, propyl butyl ester, methacrylic acid and an initiator, and adding the mixture into a dropping funnel;
(3) And (2) when the temperature of the reaction device in the step (1) reaches 137-140 ℃ and reflows, beginning to dropwise add the mixture in the step (2), finishing dropping within 3.5-4 hours, preserving heat after finishing dropping, then supplementing an initiator, preserving heat, and finally adding 3-isocyanatopropyl trimethoxy silane and stirring for 1 hour to obtain the catalyst.
As a preferable scheme, the preparation method of the high-wear-resistance acrylic resin is characterized in that in the step (3), when the temperature of a reaction device in the step (1) reaches 137-140 ℃, reflux is started, the mixture in the step (2) is dripped, the dripping is finished within 3.5-4 hours, the temperature is kept for 1 hour after the dripping is finished, then an initiator is supplemented, the temperature is kept for 1-1.5 hours, and finally 3-isocyanate propyl trimethoxy silane is added and stirred for 1 hour, so that the high-wear-resistance acrylic resin is obtained.
Has the beneficial effects that: compared with the prior art, the invention has the following advantages:
the invention selects 3-isocyanate propyl trimethoxy silane and dicumyl peroxide, and ensures that the resin has high conversion rate which reaches 98.8 percent by longer dropping time and a method of preserving heat again after replenishing the initiator at higher reaction temperature of more than 137 ℃ by adopting a large amount of experimental screening and adopting a conventional process and preferably adjusting the optimal composition of an acrylic resin monomer, the 3-isocyanate propyl trimethoxy silane and an initiator system. The acrylic resin prepared by the invention has proper viscosity, and simultaneously, the coating film has excellent comprehensive properties such as wear resistance, high adhesion, high hardness, good flexibility and the like.
Detailed Description
Example 1
1. The high-wear-resistance acrylic resin is prepared from the following raw materials in percentage by mass: 36.6% styrene, 11.4% hydroxypropyl, 11.4% propylbutyl, 3.2% 3-isocyanatopropyltrimethoxysilane, 0.6% methacrylic acid, 1.9% initiator (dicumyl peroxide), 34.9% xylene.
2. The preparation method of the high-wear-resistance acrylic resin comprises the following steps:
(1) 625.6 g of xylene are added to the reaction apparatus, stirred and heated to reflux (137-140 ℃);
(2) Uniformly mixing 11.4 g of quantitative methacrylic acid, 205.2 g of hydroxypropyl ester, 205.2 g of butyl acrylate, 661.2 g of styrene and 34.2 g of initiator dicumyl peroxide (DCP), and adding the mixture into a dropping funnel;
(3) And (2) after the temperature of the reaction device in the step (1) reaches 137-140 ℃ and reflux, dropwise adding the mixed monomer and the initiator in the step (2), completing dripping for 3.5-4h, preserving heat for 1h after finishing dripping, supplementing 0.6 g of dicumyl peroxide (DCP), preserving heat for 1-1.5h, finally adding 57 g of 3-isocyanatopropyl trimethoxy silane, and stirring for 1h to obtain the catalyst, wherein the conversion rate of the final reaction can reach 98.8%, and the solid content of the resin is 64.2%.
3. The prepared acrylic resin and various ingredients shown in the following table 1 are mixed uniformly according to a certain proportion, and stirred for 30 minutes by a high-speed dispersion machine to prepare the acrylic resin industrial varnish, wherein the coating thickness is about 50 micrometers. The detection performance is shown in table 2.
TABLE 1 formulation composition of acrylic Industrial varnishes
| Name of raw materials | Weight (g) |
| Example 1 acrylic resin | 69 |
| N3390 curing agent | 2 |
| Toluene | 10 |
| Acetic acid ethyl ester | 19 |
| Defoaming agent AX3301 | 0.1 |
| Levelling agent FM5410 | 0.1 |
TABLE 2 film property test results
| Appearance of the product | Smooth without particles |
| Hardness (Pencil scratch) | 3H |
| Impact (recoil) (kg. Cm) | 50 |
| Adhesion (circle drawing method) | Level 1 |
| Gloss (E) | 95 |
| Abrasion index | 52 |
Wherein, the hardness (pencil scratch) is measured according to GB/T6739-1996 film coating pencil hardness measurement method; impact (recoil) was measured according to GBT1732-93 determination of impact resistance of paint films; the adhesion (the drawing method) is determined according to GB/T1720-79 (89) paint film adhesion determination method; gloss was measured according to GB/T9754-2007 determination of 20, 60 and 85 specular gloss of paint films of paints and varnishes containing no metallic pigment (60 ℃ is the standard); the abrasion index is measured in accordance with GB/T1768-79 (89) method for measuring the abrasion resistance of paint films.
Comparative example 1
1. A preparation method of acrylic resin comprises the following steps:
(1) 625.6 g of xylene are added to the reaction apparatus, stirred and heated to reflux (137-140 ℃);
(2) Uniformly mixing 11.4 g of quantitative methacrylic acid, 205.2 g of hydroxypropyl ester, 262.2 g of butyl acrylate, 661.2 g of styrene and 34.2 g of initiator dicumyl peroxide (DCP), and adding the mixture into a dropping funnel;
(3) And (2) when the temperature of the reaction device in the step (1) reaches 137-140 ℃ and refluxing is carried out, dropwise adding the mixed monomer and the initiator in the step (2), completing dropwise adding for 3.5-4h, preserving heat for 1h after dropwise adding, supplementing 0.6 g of dicumyl peroxide (DCP), and preserving heat for 1-1.5h to obtain the catalyst, wherein the conversion rate of the final reaction is 95.4% and the solid content of the resin is 62%.
2. The acrylic resin obtained was mixed with the ingredients shown in Table 3 below in a ratio and stirred for 30 minutes by a high-speed disperser to obtain an industrial varnish of acrylic resin having a film thickness of about 50 μm. The detection performance is shown in table 4.
TABLE 3 composition of acrylic Industrial varnish formulations
TABLE 4 test results
| Appearance of the product | Smooth without particles |
| Hardness (Pencil scratch) | H |
| Impact (recoil) (kg. Cm) | 30 |
| Adhesion force | Stage 2 |
| Gloss of | 87 |
| Abrasion index | 102 |
Wherein, the hardness (pencil scratch) is measured according to GB/T6739-1996 film coating pencil hardness measurement method; impact (recoil) was measured according to GBT1732-93 determination of impact resistance of paint films; the adhesion (ring drawing method) is tested according to GB/T1720-79 (89) paint film adhesion determination method; the gloss is determined in accordance with GB/T9754-2007 determination of the 20, 60 and 85 specular gloss of paint films of paints and varnishes which are metal pigment-free (60 ℃ C.) and the abrasion index is determined in accordance with GB/T1768-79 (89) determination of the abrasion resistance of the paint films.
The results of the property tests in tables 2 and 4 show that the conversion rate of the synthesis and the solid content of the resin are reduced when the 3-isocyanatopropyltrimethoxysilane component is deleted. And the abrasion resistance, the hardness, the adhesive force, the impact resistance and the like are obviously reduced, which shows that the composition of the acrylic resin monomer, the 3-isocyanate propyl trimethoxy silane and the initiator system has important influence on the comprehensive performance of the paint film.
Comparative example 2
A preparation method of acrylic resin for industrial baking varnish comprises the following steps:
(1) 625.6 g of xylene are added to the reaction apparatus, stirred and heated to reflux (137-140 ℃);
(2) Uniformly mixing 11.4 g of methacrylic acid, 205.2 g of hydroxypropyl ester, 232.2 g of butyl propionate, 661.2 g of styrene and 34.2 g of dicumyl peroxide (DCP) serving as an initiator, and adding the mixture into a dropping funnel;
(3) And (2) when the temperature of the reaction device in the step (1) reaches 137-140 ℃ and reflows, dropwise adding the mixed monomer and the initiator in the step (2), finishing dropping for 3.5-4h, keeping the temperature for 1h after finishing dropping, supplementing 0.6 g of dicumyl peroxide (DCP), keeping the temperature for 1-1.5h, finally adding 30 g of 3-isocyanatopropyl trimethoxy silane, and stirring for 1h to obtain the epoxy resin, wherein the conversion rate of the final reaction is 96.9%, and the solid content of the resin is 63%.
The acrylic resin obtained in comparative example 2 and the ingredients shown in Table 5 below were mixed in a ratio and stirred for 30 minutes by a high-speed disperser to prepare industrial varnishes of acrylic resin having a film thickness of about 50 μm. The detection properties are shown in Table 6.
TABLE 5 formulation composition of acrylic Industrial varnishes
TABLE 6 film property test results
| Appearance of the product | Smooth without particles |
| Hardness (Pencil scratch) | H-2H |
| Impact (recoil) (kg. Cm) | 40 |
| Adhesion (circle drawing method) | 1-2 stages |
| Gloss (E) | 89 |
| Abrasion index | 84 |
Wherein, the hardness (pencil scratch) is measured according to GB/T6739-1996 film coating pencil hardness measuring method; impact (recoil) was measured according to GBT1732-93 determination of impact resistance of paint films; the adhesion (ring drawing method) is determined according to GB/T1720-79 (89) paint film adhesion determination method; the gloss is determined in accordance with the determination of 20, 60 and 85 specular gloss of paint films of GB/T9754-2007 paints and varnishes containing no metallic pigment (based on 60), and the abrasion index is determined in accordance with GB/T1768-79 (89) determination of the abrasion resistance of the paint film.
The performance test results in tables 2 and 6 show that when the amount of 3-isocyanatopropyltrimethoxysilane is reduced and the amount of butyl propionate is increased, the conversion rate of the synthesis and the solid content of the resin are reduced. And the hardness, the adhesive force, the impact resistance and the like are weakened, which shows that the dosage of the acrylic resin monomer and the 3-isocyanate propyl trimethoxy silane has certain influence on the comprehensive performance of the paint film.
Example 2
1. The high-wear-resistance acrylic resin is prepared from the following raw materials in percentage by mass: 40% styrene, 15% hydroxypropyl, 15% propylbutyl, 5% 3-isocyanatopropyltrimethoxysilane, 1% methacrylic acid, 2% initiator (dicumyl peroxide), 32% xylene.
2. The preparation method is the same as example 1.
Example 3
1. The high-wear-resistance acrylic resin is prepared from the following raw materials in percentage by mass: 35% of styrene, 10% of hydroxypropyl, 10% of butyl propyl, 2.5% of 3-isocyanatopropyltrimethoxysilane, 0.5% of methacrylic acid, 2% of an initiator (dicumyl peroxide), 40% of xylene.
The preparation method is the same as example 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (7)
1. The high-wear-resistance acrylic resin is characterized by being prepared from the following raw materials: styrene, hydroxypropyl ester, propyl butyl ester, 3-isocyanate propyl trimethoxy silane, methacrylic acid, an initiator and xylene.
2. The acrylic resin with high wear resistance as claimed in claim 1, which is prepared from the following raw materials in percentage by mass: 30-40% of styrene, 8-15% of hydroxypropyl ester, 8-15% of propyl butyl ester, 1-5% of 3-isocyanate propyl trimethoxy silane, 0.3-1.5% of methacrylic acid, 0.5-2% of initiator and 30-40% of xylene.
3. The acrylic resin with high wear resistance as claimed in claim 1, which is prepared from the following raw materials in percentage by mass: 36.6% styrene, 11.4% hydroxypropyl, 11.4% propylbutyl, 3.2% 3-isocyanatopropyltrimethoxysilane, 0.6% methacrylic acid, 1.9% initiator, 34.9% xylene.
4. The acrylic resin with high abrasion resistance according to claim 1, wherein said initiator is dicumyl peroxide.
5. The method for preparing the acrylic resin with high abrasion resistance as claimed in any one of claims 1 to 4, comprising the steps of:
(1) Adding a xylene solvent into a reaction device, and heating to reflux;
(2) Uniformly mixing styrene, hydroxypropyl ester, propyl butyl ester, methacrylic acid and an initiator, and adding the mixture into a dropping funnel;
(3) And (2) after the temperature of the reaction device in the step (1) reaches 137-140 ℃ and reflux, beginning to dropwise add the mixture in the step (2), finishing dropping within 3.5-4 hours, preserving heat after finishing dropping, then supplementing an initiator, preserving heat, finally adding 3-isocyanate propyl trimethoxy silane, and stirring for 1 hour to obtain the catalyst.
6. The preparation method of the acrylic resin with high wear resistance as claimed in claim 5, wherein in the step (3), when the temperature of the reaction device in the step (1) reaches 137-140 ℃, reflux is started, the mixture in the step (2) is dripped, dripping is completed within 3.5-4 hours, heat preservation is performed for 1 hour after dripping is completed, then the initiator is supplemented, and heat preservation is performed for 1-1.5 hours, so as to obtain the acrylic resin with high wear resistance.
7. Use of a high abrasion resistance acrylic resin as claimed in any one of claims 1 to 4 in the preparation of a high abrasion resistance coating.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211124079.XA CN115477718A (en) | 2022-09-15 | 2022-09-15 | High-wear-resistance acrylic resin and preparation method thereof |
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| CN202211124079.XA CN115477718A (en) | 2022-09-15 | 2022-09-15 | High-wear-resistance acrylic resin and preparation method thereof |
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| CN115477718A true CN115477718A (en) | 2022-12-16 |
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| CN202211124079.XA Pending CN115477718A (en) | 2022-09-15 | 2022-09-15 | High-wear-resistance acrylic resin and preparation method thereof |
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