阅读说明：本技术 阳离子电沉积涂料色浆用研磨树脂及其制备方法 (Cation electrodeposition coating mill base grind resin and preparation method thereof ) 是由 郭辉 陈海波 赵颖 朱婷婷 陈豪杰 方林 尤钊 于 2019-09-17 设计创作，主要内容包括：本发明涉及阳离子电沉积涂料色浆用研磨树脂及其制备方法,引入C9氢化石油树脂衍生结构从而使得产品对无机颜填料具有优良的润湿性和包覆性,所制备的色浆具有良好的分散研磨效果和高温储存能力,可制备高固含、高颜基比的色浆,同时提供产品优异的耐腐蚀性、基材附着力,并显著提高产品的耐紫外线和耐候性能。(The present invention relates to cation electrodeposition coating mill base grind resins and preparation method thereof, C9 hydrogenated petroleum resin derivative structure is introduced so that product has excellent wetability and covering property to inorganic color stuffing, prepared mill base has good dispersion grinding effect and high-temperature storage ability, the mill base of large arch dam, high pigment can be prepared, the excellent corrosion resistance of product, substrate adhesive force are provided simultaneously, and significantly improves the UV resistant and weather resistance of product.)

1. a kind of preparation method of cation electrodeposition coating mill base grind resin, it is characterised in that successively include following step It is rapid:

120-200 parts by weight of bisphenol A and 70-120 parts by weight methyl-isobutyl are added into 558 parts by weight of base epoxy resin 1 part of catalyst is added in ketone, and -190 DEG C of progress open loop chain extending reaction 30-50 minutes of 130 DEG C of temperature, preparing epoxide equivalent is 300- 500 linear epoxy resin,

Linear epoxy resin made from 500 parts by weight is taken, 250 parts by weight C9 hydrogenated petroleum resin derivatives are added, 1 weight is added Part catalyst, 150 DEG C of -200 DEG C of progress open loop chain extending reactions of temperature, preparing epoxide equivalent is 700-900 with pectinate texture Epoxy resin,

The epoxy resin of pectinate texture made from 500 parts by weight is taken, 100-200 parts by weight cosolvent is added, after being warming up to 80 DEG C, 40-70 parts by weight organic amine compound is slowly added dropwise into resin, time for adding is maintained at 20-40 minutes, rises after being added dropwise to complete Temperature to 100 DEG C insulation reaction 1 hour, reaction terminates to be cooled to 60 DEG C of dischargings and obtain intermediate resin,

Intermediate resin made from 500 parts by weight is warming up to 70 DEG C, 30-60 parts by weight organic monoacid is added and neutralizes, in 60-70 DEG C After heat preservation 1 hour, 60 DEG C of additions, 500 parts of deionized waters are cooled to, are dispersed 1 hour.

2. the preparation method of cation electrodeposition coating mill base grind resin as described in claim 1, it is characterised in that institute The catalyst stated includes triphenyl phosphorus, tri-phenyl-phosphorus bromide, dimethyl benzylamine, imidazoles, methylimidazole or 2- ethyl 4- methyl Imidazoles.

3. the preparation method of cation electrodeposition coating mill base grind resin as described in claim 1, it is characterised in that institute The C9 hydrogenated petroleum resin derivative stated is obtained by C9 Petropols hydrogenation modification, has C9 Petropols main structure simultaneously Hydroxyl group containing 1%-10%.

4. the preparation method of cation electrodeposition coating mill base grind resin as described in claim 1, feature is described C9 hydrogenated petroleum resin derivative use Johanna Lüttge RUTGERS LA100, PLA300, LA700 or LA1200.

5. the preparation method of cation electrodeposition coating mill base grind resin as described in claim 1, it is characterised in that have It includes diethylamine, methyl butyl amine, monoethanolamine, diethanol amine, N- methylethanolamine, 1,3- dimethyl that machine amine compounds, which use, One of propylamine is a variety of, or uses kitimine organic amine.

6. the preparation method of cation electrodeposition coating mill base grind resin as described in claim 1, it is characterised in that help Solvent is used including any in butyl glycol ether, glycol hexyl ether, butyl, propylene glycol monomethyl ether, propandiol butyl ether It is one or more of.

7. the preparation method of cation electrodeposition coating mill base grind resin as described in claim 1, it is characterised in that have It includes one of formic acid, acetic acid, lactic acid or a variety of that machine weak acid, which uses,.

8. a kind of cation electrodeposition coating mill base using any preparation method preparation of claim 1 ~ 7 uses grinding tree Rouge.

Technical field

The present invention relates to cation electrodeposition coating mill base grind resins and preparation method thereof.

Background technique

Cation electrodeposition coating, can each portion of metal works to shape, structure complexity since its painting operation is excellent Position carry out uniform coating the characteristics of, and formed film have good physical and chemical properties, so automobile, tricycle, It is widely used in the industries such as machinery, hardware.Cation electrodeposition coating is mainly by the two group groupings of mill base and lotion at present At, in practical application, have efficient stable in electrocoating paint application process recycles characteristic, so that electrocoating paint Mill base of the mill base relative to other types coating has higher requirement to mill base dispersibility and stability.Especially in summer height Warm weather, the storage stability of mill base are even more that will be greatly reduced.And as mill base is constantly to large arch dam, the hair in high pigment direction Exhibition, existing grind resin are even more to be difficult to meet needs.

Patent CN107216705A discloses a kind of cathode electrodip painting mill base grind resin, and preparation method is to pass through amine Change and castor oil is introduced into the main chain of grind resin by acidification, the main performance of castor oil is introduced into electrophoretic paint, is increased to charcoal Black covering property improves grinding efficiency during the grinding process, and wherein castor oil and the molar ratio of epoxy resin epoxide epoxy group group are 1:1-1:1.5 preferably 1:1-1:1.2.But the high-temperature stability that the grind resin prepares mill base is still bad, and is not suitable for preparation The mill base of large arch dam, high pigment, while the introducing of castor oil reduces the corrosion resistance of product.

Summary of the invention

The purpose of the present invention is to provide a kind of large arch dams with high-temperature stability, the cationic electrodeposition of high pigment Pigment printing paste grind resin with and preparation method thereof.

The preparation method of the grind resin the following steps are included:

120-200 parts by weight of bisphenol A and 70-120 parts by weight methyl tert-butyl are added into 558 parts by weight of base epoxy resin 1 part of catalyst is added in base ketone, and -190 DEG C of progress open loop chain extending reaction 30-50 minutes of 130 DEG C of temperature, preparing epoxide equivalent is The linear epoxy resin of 300-500,

Linear epoxy resin made from 500 parts by weight is taken, 250 parts by weight C9 hydrogenated petroleum resin derivatives are added, is added 1 Part by weight of catalyst, 150 DEG C of -200 DEG C of progress open loop chain extending reactions of temperature, preparing epoxide equivalent is 700-900 with pectination The epoxy resin of structure,

The epoxy resin of pectinate texture made from 500 parts by weight is taken, 100-200 parts by weight cosolvent is added, is warming up to 80 After DEG C, 40-70 parts by weight organic amine compound is slowly added dropwise into resin, time for adding is maintained at 20-40 minutes, is added dropwise to complete After be warming up to 100 DEG C of insulation reactions 1 hour, reaction terminates to be cooled to 60 DEG C of dischargings and obtain intermediate resin,

Intermediate resin made from 500 parts by weight is warming up to 70 DEG C, 30-60 parts by weight organic monoacid is added and neutralizes, in 60- After 70 DEG C keep the temperature 1 hour, 60 DEG C of additions, 500 parts of deionized waters are cooled to, are dispersed 1 hour.

Above-mentioned preparation method further has following optimization processing step:

The catalyst includes triphenyl phosphorus, tri-phenyl-phosphorus bromide, dimethyl benzylamine, imidazoles, methylimidazole or 2- Ethyl 4-methylimidazole.

The C9 hydrogenated petroleum resin derivative is obtained by C9 Petropols hydrogenation modification, has C9 Petropols Main structure and hydroxyl group containing 1%-10%.

The C9 hydrogenated petroleum resin derivative using Johanna Lüttge RUTGERS LA100, PLA300, LA700 or LA1200。

Organic amine compound use including diethylamine, methyl butyl amine, monoethanolamine, diethanol amine, N- methylethanolamine, One of 1,3- dimethyl propylamine is a variety of, or uses kitimine organic amine.

Using in cosolvent includes butyl glycol ether, glycol hexyl ether, butyl, propylene glycol monomethyl ether, propylene glycol Any one or a few in butyl ether.

It includes one of formic acid, acetic acid, lactic acid or a variety of that organic monoacid, which uses,.

Mill base prepared by the present invention have good dispersion grinding effect and high-temperature storage ability, can prepare large arch dam, The mill base of high pigment, while the excellent corrosion resistance of product, substrate adhesive force are provided, and significantly improve the UV resistant of product And weather resistance.

Specific embodiment

Hereinafter, be described further for the present invention in conjunction with the embodiments, embodiment is only used for illustrating rather than limit Determine protection scope of the present invention.

A. linear epoxy resin is prepared

120-200 parts of bisphenol-As and 70-120 parts of methyl iso-butyl ketone (MIBK)s are added into 558 parts of base epoxy resins, are added 1 part Catalyst, -190 DEG C of progress open loop chain extending reaction 30-50 minutes of 130 DEG C of temperature prepare the linear loop that epoxide equivalent is 300-500 Oxygen resin.

B. C9 hydrogenated petroleum resin derivative structure is introduced

250 parts of C9 hydrogenated petroleum resin derivatives are added in the linear epoxy resin for taking 500 parts of step a to obtain, and are added 1 part Catalyst, 150 DEG C of -200 DEG C of progress open loop chain extending reactions of temperature, preparing epoxide equivalent is 700-900 with pectinate texture Epoxy resin.

C. aminated compounds is introduced

The epoxy resin for the pectinate texture for taking 500 parts of step b to obtain is added 100-200 parts of cosolvents, is warming up to 80 DEG C Afterwards, 40-70 parts of organic amine compounds are slowly added dropwise into resin, time for adding is maintained at 20-40 minutes, heats up after being added dropwise to complete To 100 DEG C insulation reaction 1 hour, reaction terminate be cooled to 60 DEG C of dischargings, it is spare.

D. weak acid neutralizes

500 parts of step c resin obtained is warming up to 70 DEG C, 30-60 parts of organic monoacids are added, 60-70 DEG C keeps the temperature 1 hour The tertiary amine salt for obtaining the derivative structure of hydrogenated petroleum resin containing C9 afterwards is cooled to 60 DEG C of additions, 500 parts of deionized waters, dispersion 1 It discharges after hour, that is, is formed and contain C9 hydrogenated petroleum resin derivative structure grind resin.

In above-mentioned reaction, as catalysts, including but not limited to triphenyl phosphorus, tri-phenyl-phosphorus bromide, dimethylbenzyl Amine, imidazoles, methylimidazole, any one in 2- ethyl 4-methylimidazole.

C9 hydrogenated petroleum resin derivative is from C9 Petropols (structure is shown in formula I) hydrogenation modification, not only With C9 Petropols main structure, simultaneously containing the hydroxyl group of 1%-10%.Like derivatives have Johanna Lüttge RUTGERS: LA100, PLA300, LA700, LA1200 etc..

Organic amine compound: including diethylamine, methyl butyl amine, monoethanolamine, diethanol amine, N- methylethanolamine, 1, 3- dimethyl propylamine etc.；Additionally include kitimine organic amine.

Cosolvent: including butyl glycol ether, glycol hexyl ether, butyl, propylene glycol monomethyl ether, propandiol butyl ether etc. In any one or a few.

Organic monoacid: including formic acid, acetic acid, lactic acid etc..