CN102060979B - Novel epoxy modified resin for anti-corrosion primer and one-step preparation method thereof - Google Patents
Novel epoxy modified resin for anti-corrosion primer and one-step preparation method thereof Download PDFInfo
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- CN102060979B CN102060979B CN 201010567194 CN201010567194A CN102060979B CN 102060979 B CN102060979 B CN 102060979B CN 201010567194 CN201010567194 CN 201010567194 CN 201010567194 A CN201010567194 A CN 201010567194A CN 102060979 B CN102060979 B CN 102060979B
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Abstract
The invention relates to a novel epoxy modified resin for a anti-corrosion primer, comprising the following components in percentage by weight: 20-35% of polyalcohol mixture, 15-20% of polyprotic acid mixture, 15-20% of epoxy resin mixture, 0.2-0.3% of organic matter catalyst and 44.7-54.8% of solvent. The invention also provides a preparation method for the novel epoxy modified resin for the anti-corrosion primer. The novel epoxy modified resin for the anti-corrosion primer has the advantages of excellent adhesive force with a metal base material, good dryness, high crosslinking density, and excellent flexibility, hardness and anticorrosion capability.
Description
[technical field]
The present invention relates to a kind of epoxy modified resin, specifically, is that a kind of novel anticorrosion erosion priming paint is with epoxy modified resin and one-step preppn process thereof.
[background technology]
The resin that the protection against corrosion priming paint of existing market supply is used is to be formed by polyvalent alcohol and polyprotonic acid esterification.Molecular weight is in the 10000-15000 scope, and hydroxyl value has good snappiness and pencil hardness in 60-110mg KOH/g scope.But because hydroxyl value is on the low side, molecule crosslinked insufficient, cause hardness of film, dryness and the preservative property of protection against corrosion priming paint poor, occur bad phenomenon such as rust class after the application in short-term.
Chinese patent document CN:101372600A discloses a kind of double-component epoxide resin type anti-rust lacquer and preparation method, and this invention provides a kind of double-component epoxide resin type anti-rust lacquer and preparation method, and the weight percent component of first component comprises: epoxy resin 15-25%; Modified petroleum resin 10-20%, pigment 30-40%, filler 2-5%; Auxiliary agent 5-6%, solvent 10-20%, the weight percent component of second component comprises: polyamide curing agent 50-60%; Modification cashew nut oil solidifying agent 10-20%; Solvent 30-40%, first component viscosity is 3.0-8.0Pas, the weight proportion of first component and second component is 2-6: 1.But also do not appear in the newspapers at present with epoxy modified resin and one-step preppn process thereof about novel anticorrosion erosion priming paint.
[summary of the invention]
The objective of the invention is to deficiency of the prior art, provide a kind of novel anticorrosion erosion priming paint to use epoxy modified resin.
One purpose more of the present invention is that the preparation method of a kind of novel anticorrosion erosion priming paint with epoxy modified resin is provided.
For realizing above-mentioned purpose; The technical scheme that the present invention takes is: a kind of novel anticorrosion erosion priming paint is used epoxy modified resin; Described epoxy modified resin adopts single stage method to be polymerized under the effect of catalyzer by polyvalent alcohol, polyprotonic acid, epoxy resin; Then with solvent to rare, process by following component by weight percentage:
Polyol blends 20-35%
Polyprotonic acid mixture 15-20%
Epoxy resin composition 15-20%
Catalytic organism agent 0.2-0.3%
Solvent 44.7-54.8%.
The component of described epoxy resin and weight percent content are:
E-03 epoxy resin 15-50%
E-12 epoxy resin 15-80%
E-44 epoxy resin 15-50%.
The component of described polyol blends and weight percent content are:
Tetramethylolmethane 50-75%
TriMethylolPropane(TMP) 5-25%
Glycerine 7-25%.
The component of described polyprotonic acid mixture and weight percent content are:
Hexanodioic acid 2-10%
Unsaturated fatty acids 40-60%
M-phthalic acid 3-10%
Terephthalic acid 0-15%
Phthalic anhydride 10-15%.
Described solvent component and weight percent content are:
YLENE 10-25%
The heavy aromatic solvent 50-70% that contains C9-C10
Butyl glycol ether 5-10%.
Described organotin catalysts is selected from dibutyl tin laurate, a kind of in dimethyl-oxalic acid tin or the dibutyl tin acetate.
For realizing above-mentioned second purpose, the technical scheme that the present invention takes is: a kind of novel anticorrosion erosion priming paint adopts one-step synthesis process with the preparation method of epoxy modified resin; With the polyprotonic acid mixture, polyol blends, epoxy resin composition are heated to 150-200 ℃; Add organotin catalysts again; Continue to be heated to 210-230 ℃, reaction times 5-10 hour, then with solvent to rare to solids content 45-55%.
Adopt one-step synthesis process, with polyprotonic acid mixture, polyol blends; Epoxy resin composition is heated to 160-190 ℃, adds organotin catalysts again, continues to be heated to 210-230 ℃; Reaction times 7-9 hour, then with solvent to rare to solids content 45-55%.
Adopt one-step synthesis process, with the polyprotonic acid mixture, polyol blends, epoxy resin composition are heated to 180 ℃, add organotin catalysts again, continue to be heated to 210-230 ℃, 8 hours reaction times, then with solvent to rare to solids content 45-55%.
The invention has the advantages that:
1, epoxy modified resin of the present invention to metal base have excellent adhesive attraction, dryness is good, the paint film that crosslinked back generates is tough and tensile;
2, because hydroxyl value reaches 120-160mgKOH/g; Cross-linking density is higher, has excellent flexibility, hardness and chemical-resistant, and it is supporting to be easy to topcoat of all kinds; Effectively improve lasting antirust corrosion resistance, overcome the defective of hardness of film in the background technology, dryness and preservative property difference.
[embodiment]
Below in conjunction with form embodiment provided by the invention is elaborated.
Embodiment 1
2.80 kilograms glycerine (100%), 2.11 kilograms TriMethylolPropane(TMP), 5.25 kilograms tetramethylolmethane, 4.21 kilograms E-44 epoxy resin, 6.94 kilograms E-12 epoxy resin, 2.86 kilograms adipic acid, 7.26 kilograms Tetra hydro Phthalic anhydride, 1.98 kilograms m-phthalic acid, 18.23 kilograms unsaturated fatty acids, 6.8 kilograms YLENE are added reaction kettle; Slowly be heated to 180 ℃, treat to add 1.6 kilograms of dimethyl-oxalic acid tin catalysts after the fusion, continue progressively to be heated to 210-230 ℃; Reaction times was controlled at 8 hours; Final reaction reaches acid number 10.0mgKOH/g, viscosity 15 seconds, 3.02 kilograms of aquifer yields; Use 26.8 kilopond aromatic solvents (C9-C10) then; 6 kg ethylene glycol butyl ether, filter to solids content 55% rare, packing.
Performance test such as following table 1:
Table 1
| Project | Test result |
| Quality solids content (%) | 55 |
| Viscosity (second) | 15.5 |
| Acid number (mg KOH/g) | 9.8 |
| Molecular weight | 61000 |
| Hydroxyl value (mg KOH/g) | 150 |
Embodiment 2
1.81 kilograms glycerine (100%), 1.63 kilograms TriMethylolPropane(TMP), 4.98 kilograms tetramethylolmethane, 4.21 kilograms E-44 epoxy resin, 5.21 kilograms E-03 epoxy resin, 8.98 kilograms Tetra hydro Phthalic anhydride, 19.32 kilograms unsaturated fatty acids, 6.8 kilograms YLENE are added reaction kettle; Slowly be heated to 180 ℃, treat to add 1.0 kilograms of dibutyl tin acetate catalyzer after the fusion, continue progressively to be heated to 220 ℃; Reaction times was controlled at 7 hours; Final reaction reaches acid number 11mgKOH/g, viscosity 21 seconds, 2.2 kilograms of aquifer yields; Use 28 kilopond aromatic solvents (C9-C10) then; 8 kg ethylene glycol butyl ether, filter to solids content 50% rare, packing.
Performance test such as following table 2:
Table 2
| Project | Test result |
| Quality solids content (%) | 50 |
| Viscosity (second) | 21.5 |
| Acid number (mg KOH/g) | 10.8 |
| Molecular weight | 70000 |
| Hydroxyl value (mg KOH/g) | 130 |
Embodiment 3
2.35 kilograms glycerine (100%), 1.63 kilograms TriMethylolPropane(TMP), 6.57 kilograms tetramethylolmethane, 6.54 kilograms E-12 epoxy resin, 3.21 kilograms E-03 epoxy resin, 8.21 kilograms Tetra hydro Phthalic anhydride, 3.21 kilograms m-phthalic acid, 20.62 kilograms unsaturated fatty acids, 6.8 kilograms YLENE are added reaction kettle; Slowly be heated to 170 ℃, treat to add 1.1 kilograms of dibutyltin dilaurate catalysts after the fusion, continue to be heated to 210 ℃; Reaction times was controlled at 8 hours; Final reaction reaches acid number 11mgKOH/g, viscosity 25 seconds, 2.89 kilograms of aquifer yields; Use 41.4 kilopond aromatic solvents (C9-C10) then; 12.2 the kg ethylene glycol butyl ether, filters to solids content 45% rare, packing.
Performance test such as following table 3:
Table 3
| Project | Test result |
| Quality solids content (%) | 45 |
| Viscosity (second) | 27 |
| Acid number (mg KOH/g) | 10.9 |
| Molecular weight | 98000 |
| Hydroxyl value (mg KOH/g) | 144 |
Embodiment 4
2.50 kilograms glycerine (100%), 1.63 kilograms TriMethylolPropane(TMP), 6.51 kilograms tetramethylolmethane, 4.21 kilograms E-03 epoxy resin, 6.54 kilograms E-12 epoxy resin, 7.26 kilograms Tetra hydro Phthalic anhydride, 1.98 kilograms m-phthalic acid, 19.32 kilograms unsaturated fatty acids, 6.8 kilograms YLENE are added reaction kettle; Slowly be heated to 190 ℃, treat to add 1.6 kilograms of dimethyl-oxalic acid tin catalysts after the fusion, continue progressively to be heated to 230 ℃; Reaction times was controlled at 5 hours; Final reaction reaches acid number 10.0mgKOH/g, viscosity 25 seconds, 3.02 kilograms of aquifer yields; Use 26.8 kilopond aromatic solvents (C9-C10) then; 6 kg ethylene glycol butyl ether, filter to solids content 55% rare, packing.
Performance test such as following table 4:
Table 4
| Project | Test result |
| Quality solids content (%) | 55 |
| Viscosity (second) | 25 |
| Acid number (mg KOH/g) | 10.6 |
| Molecular weight | 65000 |
| Hydroxyl value (mg KOH/g) | 140 |
Embodiment 5
2.35 kilograms glycerine (100%), 1.63 kilograms TriMethylolPropane(TMP), 6.57 kilograms tetramethylolmethane, 6.54 kilograms E-12 epoxy resin, 3.21 kilograms E-03 epoxy resin, 8.21 kilograms Tetra hydro Phthalic anhydride, 3.21 kilograms m-phthalic acid, 20.62 kilograms unsaturated fatty acids, 6.8 kilograms YLENE are added reaction kettle; Slowly be heated to 150 ℃, treat to add 1.1 kilograms of dibutyltin dilaurate catalysts after the fusion, continue to be heated to 210 ℃; Reaction times was controlled at 9 hours; Final reaction reaches acid number 11mgKOH/g, viscosity 25 seconds, 2.89 kilograms of aquifer yields; Use 40.4 kilopond aromatic solvents (C9-C10) then; 12.2 the kg ethylene glycol butyl ether, filters to solids content 50% rare, packing.
Performance test such as following table 5:
Table 5
| Project | Test result |
| Quality solids content (%) | 50 |
| Viscosity (second) | 24 |
| Acid number (mg KOH/g) | 10.7 |
| Molecular weight | 80000 |
| Hydroxyl value (mg KOH/g) | 135 |
Embodiment 6
2.20 kilograms glycerine (100%), 1.59 kilograms TriMethylolPropane(TMP), 6.60 kilograms tetramethylolmethane, 6.54 kilograms E-12 epoxy resin, 3.21 kilograms E-03 epoxy resin, 8.21 kilograms Tetra hydro Phthalic anhydride, 3.21 kilograms m-phthalic acid, 20.62 kilograms unsaturated fatty acids, 6.8 kilograms YLENE are added reaction kettle; Slowly be heated to 200 ℃, treat to add 1.2 kilograms of dibutyltin dilaurate catalysts after the fusion, continue to be heated to 230 ℃; Reaction times was controlled at 10 hours; Final reaction reaches acid number 10mg KOH/g, viscosity 25 seconds, 2.89 kilograms of aquifer yields; Use 41.4 kilopond aromatic solvents (C9-C10) then; 12.2 the kg ethylene glycol butyl ether, filters to solids content 55% rare, packing.
Performance test such as following table 6:
Table 6
| Project | Test result |
| Quality solids content (%) | 55 |
| Viscosity (second) | 27 |
| Acid number (mg KOH/g) | 10.9 |
| Molecular weight | 96000 |
| Hydroxyl value (mg KOH/g) | 150 |
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the inventive method; Can also make some improvement and replenish, these improvement and replenish and also should be regarded as protection scope of the present invention.
Claims (9)
1. a protection against corrosion priming paint is used epoxy modified resin; Described epoxy modified resin adopts single stage method to be polymerized under the effect of catalyzer by polyvalent alcohol, polyprotonic acid, epoxy resin; Use the solvent latting drown then, it is characterized in that, process by following component by weight percentage:
The weight percent sum of each component is 100%.
2. epoxy modified resin according to claim 1 is characterized in that, the component of described epoxy resin and weight percent content are:
E-03 epoxy resin 15-50%
E-12 epoxy resin 15-80%
E-44 epoxy resin 15-50%
The weight percent sum of each component is 100%.
3. epoxy modified resin according to claim 2 is characterized in that, the component of described polyol blends and weight percent content are:
Tetramethylolmethane 50-75%
TriMethylolPropane(TMP) 5-25%
Glycerine 7-25%.
4. epoxy modified resin according to claim 3 is characterized in that, the component of described polyprotonic acid mixture and weight percent content are:
The weight percent sum of each component is 100%.
5. epoxy modified resin according to claim 4 is characterized in that, described solvent component and weight percent content are:
YLENE 10-25%
The heavy aromatic solvent 50-70% that contains C9-C10
Butyl glycol ether 5-10%
The weight percent sum of each component is 100%.
6. epoxy modified resin according to claim 5 is characterized in that, described catalytic organism agent is selected from dibutyl tin laurate, a kind of in dimethyl-oxalic acid tin or the dibutyl tin acetate.
7. the preparation method of epoxy modified resin according to claim 1 is characterized in that, adopts one-step synthesis process; With the polyprotonic acid mixture, polyol blends, epoxy resin composition are heated to 150-200 ℃; Add organotin catalysts again; Continue to be heated to 210-230 ℃, reaction times 5-10 hour, use the solvent latting drown then to solids content 45-55%.
8. the preparation method of epoxy modified resin according to claim 7 is characterized in that, adopts one-step synthesis process; With the polyprotonic acid mixture, polyol blends, epoxy resin composition are heated to 160-190 ℃; Add organotin catalysts again; Continue to be heated to 210-230 ℃, reaction times 7-9 hour, use the solvent latting drown then to solids content 45-55%.
9. the preparation method of epoxy modified resin according to claim 8 is characterized in that, adopts one-step synthesis process; With the polyprotonic acid mixture, polyol blends, epoxy resin composition are heated to 180 ℃; Add organotin catalysts again; Continue to be heated to 210-230 ℃, in 8 hours reaction times, use the solvent latting drown then to solids content 45-55%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010567194 CN102060979B (en) | 2010-11-29 | 2010-11-29 | Novel epoxy modified resin for anti-corrosion primer and one-step preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010567194 CN102060979B (en) | 2010-11-29 | 2010-11-29 | Novel epoxy modified resin for anti-corrosion primer and one-step preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102060979A CN102060979A (en) | 2011-05-18 |
| CN102060979B true CN102060979B (en) | 2012-12-12 |
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| CN 201010567194 Expired - Fee Related CN102060979B (en) | 2010-11-29 | 2010-11-29 | Novel epoxy modified resin for anti-corrosion primer and one-step preparation method thereof |
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| CN104119777B (en) * | 2014-06-27 | 2016-05-18 | 深圳市赛亚气雾剂有限公司 | A kind of waterborne metallic anticorrosion paint for packing machine and preparation method thereof |
| CN113980256A (en) * | 2021-11-30 | 2022-01-28 | 珠海展辰新材料股份有限公司 | Water-based alkyd resin and preparation method thereof |
| CN115637098B (en) * | 2022-10-31 | 2023-11-03 | 江苏三木化工股份有限公司 | Preparation method of epoxy modified saturated polyester for coil back paint |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1970601A (en) * | 2006-12-06 | 2007-05-30 | 上海振华造漆厂 | Epoxy modified polyester resin for paint of coil back surface and its preparation method |
| CN101148496A (en) * | 2007-10-26 | 2008-03-26 | 上海振华造漆厂 | Polyester resin for coiled material finishing paint and its preparing process |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1970601A (en) * | 2006-12-06 | 2007-05-30 | 上海振华造漆厂 | Epoxy modified polyester resin for paint of coil back surface and its preparation method |
| CN101148496A (en) * | 2007-10-26 | 2008-03-26 | 上海振华造漆厂 | Polyester resin for coiled material finishing paint and its preparing process |
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| CN102060979A (en) | 2011-05-18 |
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Owner name: SHANGHAI HUAYI FINE CHEMICAL INDUSTRY CO., LTD. Free format text: FORMER OWNER: ZHENHUA COATING MANUFACTURING FACTORY OF SHANGHAI COATINGS CO., LTD. Effective date: 20150504 |
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Effective date of registration: 20150504 Address after: Minhang District town of Shanghai city in 201108 Patentee after: SHANGHAI HUAYI FINE CHEMICAL CO., LTD. Address before: 200331 No. 1167, Gulang Road, Shanghai, Putuo District Patentee before: Zhenhua Coating Manufacturing Factory of Shanghai Coatings Co., Ltd. |
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