CN115637098A - Preparation method of epoxy modified saturated polyester for coil back paint - Google Patents
Preparation method of epoxy modified saturated polyester for coil back paint Download PDFInfo
- Publication number
- CN115637098A CN115637098A CN202211346319.0A CN202211346319A CN115637098A CN 115637098 A CN115637098 A CN 115637098A CN 202211346319 A CN202211346319 A CN 202211346319A CN 115637098 A CN115637098 A CN 115637098A
- Authority
- CN
- China
- Prior art keywords
- parts
- epoxy
- resin
- saturated polyester
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 60
- 229920000728 polyester Polymers 0.000 title claims abstract description 60
- 239000003973 paint Substances 0.000 title claims abstract description 40
- 229920006395 saturated elastomer Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000010992 reflux Methods 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 239000003822 epoxy resin Substances 0.000 claims abstract description 36
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 36
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 27
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 23
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000008096 xylene Substances 0.000 claims abstract description 16
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 14
- 239000001361 adipic acid Substances 0.000 claims abstract description 14
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 11
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 14
- 239000000498 cooling water Substances 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000005070 sampling Methods 0.000 claims description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 abstract description 14
- 150000003839 salts Chemical class 0.000 abstract description 11
- 239000007921 spray Substances 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 238000012216 screening Methods 0.000 abstract description 3
- 239000003849 aromatic solvent Substances 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 2
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses epoxy modified saturated polyester for coil back paint, which is prepared from 75-85 parts of rigid dihydric alcohol, 30-36 parts of trihydric alcohol with a side chain, 125-145 parts of neopentyl glycol, 35-45 parts of adipic acid, 350-370 parts of phthalic anhydride, 6048-12 parts of epoxy resin, 8283-4 parts of epoxy resin, 25-35 parts of reflux xylene, 1-1.5 parts of color reducing agent, 180-200 parts of high-boiling-point aromatic solvent, 90-110 parts of propylene glycol monomethyl ether acetate, 40-60 parts of DBE solvent and 20-25 parts of ethylene glycol butyl ether. According to the invention, through the specific steps of screening various raw material compositions and reacting, the prepared epoxy modified saturated polyester improves the hardness and scratch resistance of the resin on the premise of ensuring the salt spray resistance, flexibility, adhesive force and other performances. Meanwhile, the consumption of epoxy is reduced, and the cost is greatly reduced by replacing isophthalic acid with low-cost phthalic anhydride.
Description
Technical Field
The invention relates to a preparation method of epoxy modified saturated polyester for coil back paint.
Background
The precoated coiled material back paint mainly plays a role in protecting the back of a coiled material, generally adopts a single layer, has a thin paint film, and requires that the paint film has good salt spray resistance, processability, hardness, MEK wiping resistance and scratch resistance.
The back paint in the prior art mainly comprises three types, one type is epoxy resin, the epoxy back paint is good in Methyl Ethyl Ketone (MEK) wiping resistance, good in adhesive force, high in hardness, good in salt spray resistance and poor in flexibility; the polyester back paint has good flexibility, but has slightly poor butanone (MEK) wiping resistance and relatively poor adhesive force and scratch resistance; the other type is epoxy modified polyester, the back paint performance of the epoxy modified polyester is between the two types, which already accounts for the mainstream of the market, but the existing epoxy modified polyester has the following disadvantages:
1, the resin has better performance, the epoxy resin accounts for 10 to 25 percent of the solid content of the modified resin, and the price of the epoxy resin is always high in the years, so that the cost is high, and the use is limited.
2, after the plates are coated, the plates are rolled and stacked together, the roll weight is at least 2 tons, the plates are mutually extruded and displaced in the transportation process, and the risk of indentation and scratching is caused, the hardness of the resin is always up to 3H, and the hardness and the scratch resistance are also improved.
In conclusion, the existing epoxy modified saturated polyester needs to reduce the cost, can expand the use range, and improves the hardness and scratch resistance of the resin on the premise of ensuring salt mist resistance, flexibility, adhesive force and the like.
Disclosure of Invention
The purpose of the invention is as follows: the epoxy modified saturated polyester for the back paint has the advantages of improving the hardness and scratch resistance of resin and being low in cost on the premise of ensuring salt spray resistance, flexibility, adhesive force and the like. It is another object of the present invention to provide a method for preparing the same.
The technical scheme is as follows: in order to achieve the above purpose, the invention adopts the technical scheme that:
an epoxy modified saturated polyester for coil back paint is prepared from the following raw materials in parts by weight:
75-85 parts of rigid dihydric alcohol, 30-36 parts of trihydric alcohol with a side chain, 125-145 parts of neopentyl glycol, 35-45 parts of adipic acid, 350-370 parts of phthalic anhydride, 604-12 parts of epoxy resin, 8283-4 parts of epoxy resin, 25-35 parts of reflux xylene, 1-1.5 parts of a color reducing agent, 180-200 parts of a high-boiling-point aromatic hydrocarbon solvent, 90-110 parts of propylene glycol monomethyl ether acetate (PMA), 40-60 parts of a DBE solvent and 20-25 parts of ethylene glycol monobutyl ether.
Preferably, the epoxy modified saturated polyester for coil back paint is characterized in that the rigid diol is at least one of ethylene glycol and 1,2-propylene glycol or a mixture thereof.
Preferably, the epoxy modified saturated polyester for coil back paint is one or a mixture of at least one of trimethylolpropane and trimethylolethane as the trihydric alcohol with side chains
Preferably, the epoxy resin 604 is bisphenol a epoxy resin produced by Jiangsu Sandeli chemical engineering Co., ltd, and the epoxy equivalent of the epoxy resin is 800-900.
Preferably, the epoxy resin 828 is bisphenol a epoxy resin produced by Jiangsu Sandeli chemical engineering Co., ltd, and the epoxy equivalent of the epoxy resin is 184-194.
Preferably, the epoxy modified saturated polyester for coil back paint is prepared from at least one of 100# solvent (with distillation range of 160-175 ℃ and density of 0.862-0.875) and 150# solvent (with distillation range of 180-210 ℃ and density of 0.800-0.900) or a mixture thereof as the high-boiling-point aromatic hydrocarbon solvent.
Preferably, the coil back paint epoxy modified saturated polyester is prepared by using at least one of hypophosphorous acid and triphenyl phosphite or a mixture of hypophosphorous acid and triphenyl phosphite.
Preferably, the DBE is an electronic grade mixed dibasic acid ester manufactured by Jiangsu Sanmu group Co.
Preferably, the epoxy modified saturated polyester for coil back paint is PMA which is high-grade propylene glycol monomethyl ether acetate self-produced by Jiangsu Sanmu group Co.
The invention relates to a preparation method of epoxy modified saturated polyester for coil back paint, which comprises the following steps:
1) Putting rigid dihydric alcohol, trihydric alcohol with a side chain, neopentyl glycol, adipic acid, phthalic anhydride and a color reducing agent into a reaction kettle according to the parts by weight, heating, stirring, putting epoxy resin 604, and opening a column to cool water; closing a reflux valve of the reflux tank, slowly heating under the condition of strictly controlling the temperature of a distillation head to be not more than 100-105 ℃, measuring the acid value, and taking the resin to measure the viscosity;
the mass ratio of the resin to the mixed solvent is 12:8, mixing the solvent in a mass ratio of 7:1:0.5 xylene: isobutanol: PMA;
viscosity: 8-10 second Grignard;
2) Opening a reflux valve after the acid value viscosity is qualified, cooling water Guan Lizhu, slowly adding epoxy resin 828 and refluxing dimethylbenzene, heating, refluxing, carrying out esterification reaction, sampling, and carrying out central control:
the mass ratio of the resin to the mixed solvent is 12:8, mixing the solvent in a mass ratio of 7:1:0.5 xylene: isobutanol: PMA;
the acid value is less than or equal to 7mgKOH/g; viscosity: 30-35 second Grignard;
3) And immediately cooling after the polyester is qualified, adding a high-boiling-point aromatic hydrocarbon solvent, DBE, ethylene glycol monobutyl ether and PMA in sequence, and cooling to obtain the epoxy modified saturated polyester.
As a preferable scheme, the preparation method of the epoxy modified saturated polyester for the coil back paint comprises the following steps:
1) Putting 75-85 parts by mass of rigid dihydric alcohol, 30-36 parts by mass of trihydric alcohol with a side chain, 125-145 parts by mass of neopentyl glycol, 35-45 parts by mass of adipic acid, 350-370 parts by mass of phthalic anhydride and 1-1.5 parts by mass of a color reducing agent into a reaction kettle, heating to 155 ℃, trial stirring, stirring for 10 minutes, then putting 8-12 parts by mass of epoxy 604, and opening column cooling water. Closing a reflux valve of the reflux tank, slowly heating under the premise of strictly controlling the temperature of a distillation head not to exceed 102 ℃, continuously heating to 225-235 ℃, preserving heat, and measuring the acid value (less than 25). Taking the resin as viscosity.
Resin: mixed solvent =12:8, mixed solvent = xylene: isobutanol: PMA =7:1:0.5
Viscosity: 8-10 second grid tube
2) Opening a reflux valve after the acid value viscosity is qualified, cooling water Guan Lizhu, slowly adding 3-4 epoxy 828 and 25-35 refluxing dimethylbenzene, refluxing and esterifying at 220-230 ℃, and sampling and controlling after 2-3 hours: resin: mixed solvent =12:8, mixed solvent = xylene: isobutanol: PMA =7:1:0.5;
the acid value is less than or equal to 7mgKOH/g; viscosity: 30-35 second Grignard;
3) Cooling down the polyester immediately after the polyester is qualified, adding 180-200 parts of high boiling point aromatic hydrocarbon solvent, 40-60 parts of DBE, 20-25 parts of butyl cellosolve and 90-110 parts of PMA in sequence when the polyester is cooled down to 180 ℃, and cooling down the polyester to below 100 ℃ to obtain the epoxy modified saturated polyester with the solid content of 59-61%.
The invention mainly aims to overcome the defects of the epoxy modified saturated polyester for the back paint by the following schemes.
1. The invention discovers that when raw materials are screened, if isophthalic acid and terephthalic acid are used as polybasic acid according to the traditional thought, satisfactory performance is required to be obtained when epoxy modified saturated polyester is synthesized, and the amount of epoxy resin is not reduced at all. Traditionally, it is believed that the ortho structure of phthalic anhydride tends to form lactones, which tend to reduce molecular weight, which is detrimental to flexibility and salt spray resistance. The invention discovers, through screening, that polyatomic acid is directly matched with phthalic anhydride and adipic acid, the phthalic anhydride accounts for about 90%, and the adipic acid accounts for about 10%, so that the epoxy resin accounts for about 2% of the solid of the modified resin, and the performance of the existing epoxy modified polyester can be achieved. The phthalic anhydride, the epoxy resin and the dihydric alcohol can form a trimolecular complex for reaction to form a body structure, so that the molecular weight of the resin is improved, the flexibility and the salt spray resistance of the resin are improved, and the unexpected technical effect of achieving twice the half the effort is achieved. The common use of the epoxy resin and the dihydric alcohol is difficult to form a trimolecular complex for reaction with the isophthalic acid and the terephthalic acid to form a body-shaped structure.
2. In the raw materials of the invention, rigid dihydric alcohol and phthalic anhydride are creatively matched to improve the hardness of the resin, the rigid dihydric alcohol and phthalic anhydride together account for about 70 percent of the solid content of the modified resin, and the flexibility is adjusted by 5 percent of adipic acid (accounting for the solid content of the modified resin); two steps of chain extension with low molecular weight epoxy 828 to further increase molecular weight increase flexibility.
3. The invention creatively adopts the matching of high molecular weight epoxy resin 604 and low molecular weight epoxy resin 828, wherein the epoxy resin 604: epoxy 828=3:1, directly putting the epoxy resin 604 and the polyol polybasic acid into a reaction kettle in the first step, wherein the epoxy resin 604 has a large molecular weight, the reaction activity is lower than that of epoxy 828, the reaction is stable, and the first purpose is achieved. If epoxy 828 is used in the first step, epoxy 828 reacts vigorously with phthalic anhydride to form a gum. After the first step of reaction is finished, polyester prepolymer is formed, the prepolymer has large molecular weight and low acidity, and then chain extension is carried out by two steps of epoxy 828 to form the polymer resin which is required by the invention. The epoxy resin 604 and 828 of the invention not only has the function of chain extension, but also has the function of epoxy which can provide resin adhesive force and salt mist resistance, and obtains good technical effect.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the invention screens out various reaction raw material compositions and reaction concrete steps through a large number of experiments to prepare the epoxy modified saturated polyester for the coil back paint. On the premise of ensuring the salt spray resistance, the flexibility, the adhesive force and other properties, the hardness and the scratch resistance of the resin are improved. Meanwhile, the consumption of epoxy resin is reduced, phthalic anhydride with low cost is adopted to replace isophthalic acid, the cost is greatly reduced, and the cost performance of the resin is improved.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Embodiments of the present invention will be described in detail with reference to examples, in which specific conditions are not specified, according to conventional conditions or conditions recommended by manufacturers. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The following examples have the following raw material compositions as shown in table 1:
table 1 composition of raw materials for each example
The preparation method of the quick-drying high-performance alkyd resin comprises the following steps:
1) Rigid dihydric alcohol, trihydric alcohol with side chain, neopentyl glycol, adipic acid, phthalic anhydride and color reducing agent are put into a reaction kettle according to the raw materials of the above examples 1 to 5, the temperature is raised to 155 ℃, the mixture is tried to be stirred, epoxy 604 is put into the mixture after the mixture is stirred for 10 minutes, and column cooling water is opened. Closing a reflux valve of the reflux tank, slowly heating under the premise of strictly controlling the temperature of a distillation head not to exceed 102 ℃, continuously heating to 225-235 ℃, preserving heat, and measuring the acid value (less than 25). The viscosity of the resin was measured to the following value.
Resin: the mass ratio of the mixed solvent is 12:8, wherein the mixed solvent is prepared from the following components in a mass ratio of 7:1:0.5 xylene, isobutanol and PMA. Viscosity: 8-10 second format tube.
2) Opening a reflux valve after the acid value viscosity is qualified, cooling water Guan Lizhu, slowly adding epoxy 828 and refluxing dimethylbenzene, refluxing and esterifying at 220-230 ℃, and sampling after 2-3 hours until the sampling central control reaches the following value:
resin: the mass ratio of the mixed solvent is 12:8, wherein the mixed solvent is prepared from the following components in a mass ratio of 7:1:0.5 xylene, isobutanol and PMA. The acid value is less than or equal to 7mgKOH/g. Viscosity: 30-35 second format tube.
3) Cooling down the polyester immediately after the polyester is qualified, adding a high boiling point aromatic hydrocarbon solvent, DBE, ethylene glycol monobutyl ether and PMA in sequence when the polyester is cooled down to 180 ℃, and cooling down the polyester to below 100 ℃ to obtain the epoxy modified saturated polyester with the solid content of 59-61%. Comparative example 1 (market mainstream epoxy modified polyester)
1) 50 parts of neopentyl glycol, 172 parts of methyl propylene glycol, 14 parts of trimethylolpropane, 50 parts of adipic acid, 80 parts of phthalic anhydride, 128 parts of isophthalic acid, 90 parts of terephthalic acid and 0.3 part of monobutyl tin oxide are put into a reaction kettle in parts by mass, heated to 155 ℃, stirred for trial, and after stirring for 10 minutes, 85 parts of epoxy 604 is put into the reaction kettle, and column cooling water is opened. Closing a reflux valve of a reflux tank, slowly heating under the premise of strictly controlling the temperature of a distillation head not to exceed 102 ℃, continuously heating to 240-250 ℃, keeping the temperature until the resin is clear and transparent, cooling water Guan Lizhu, opening the reflux valve of the reflux tank, adding 30 parts of reflux dimethylbenzene, refluxing and esterifying at 220-230 ℃, and after 2-3 hours, sampling and controlling the temperature to reach the following values:
the mass ratio of resin to xylene is 11:9; the acid value is less than or equal to 8mgKOH/g; viscosity: 8-12 second format tube.
2) And immediately cooling after the polyester is qualified, and when the temperature is reduced to 180 ℃, adding 260 parts of 150# solvent, 70 parts of DBE and 40 parts of butyl cellosolve in sequence, and cooling to below 100 ℃ to obtain the epoxy modified saturated polyester with the solid content of 59-61%.
COMPARATIVE EXAMPLE 2 (pure polyester)
1) 153 parts of neopentyl glycol, 95 parts of methyl propylene glycol, 30 parts of trimethylolpropane, 105 parts of adipic acid, 120 parts of phthalic anhydride, 50 parts of isophthalic acid, 126 parts of terephthalic acid and 0.3 part of monobutyl tin oxide are put into a reaction kettle, heated to 155 ℃, stirred for trial, and cooled by opening a column. Closing a reflux valve of a reflux tank, slowly heating under the premise of strictly controlling the temperature of a distillation head not to exceed 102 ℃, continuously heating to 240-250 ℃, keeping the temperature until the resin is clear and transparent, cooling water Guan Lizhu, opening the reflux valve of the reflux tank, adding 30 parts of reflux dimethylbenzene, refluxing and esterifying at 220-230 ℃, and controlling the conditions in sampling after 2-3 hours to reach the following qualified values:
the mass ratio of resin to xylene is 12:8, acid value of less than or equal to 8mgKOH/g, viscosity: 8-12 second Grignard tubes;
2) And immediately cooling after the polyester is qualified, and when the temperature is reduced to 180 ℃, adding 250 parts of 150# solvent, 80 parts of 100# solvent, 20 parts of DBE and 20 parts of butyl cellosolve in sequence, and cooling to below 100 ℃ to obtain the epoxy modified saturated polyester with the solid content of 59-61%.
Application example 1
1. The alkyd resins obtained in examples 1 to 5 and comparative examples 1 and 2 were blended according to the paint formulation shown in Table 2 below, and ground and dispersed to prepare paints.
TABLE 2 colored paint formulations
2. Colored paint detection
Curing the plate temperature: 240 ℃ for 50 seconds;
the colored paints prepared in the above examples 1 to 5 and comparative examples 1 and 2 were tested as follows, and the specific test results of the colored paints are shown in table 3:
TABLE 3 colored paint test results
The experimental results show that the epoxy modified saturated polyester for the coil back paint is prepared by screening various reaction raw materials through a large number of experiments, particularly by the compatibility of the epoxy resin 604, the epoxy resin 828 and the phthalic anhydride and the compatibility of the rigid dihydric alcohol and the phthalic anhydride. On the premise of ensuring the salt spray resistance, the flexibility, the adhesive force and other properties, the hardness and the scratch resistance of the resin can be greatly improved. And meanwhile, the consumption of epoxy is reduced, the phthalic anhydride with low cost is adopted to replace the isophthalic acid, the cost is greatly reduced, and the cost performance of the resin is improved. Particularly, by comparison, the resin of example 5 of the present invention has the best salt spray resistance, solvent resistance, etc., and achieves good technical effects.
Claims (10)
1. The epoxy modified saturated polyester for the coil back paint is characterized by comprising the following components in parts by weight: the feed is prepared from the following raw materials in parts by weight:
75-85 parts of rigid dihydric alcohol, 30-36 parts of trihydric alcohol with a side chain, 125-145 parts of neopentyl glycol, 35-45 parts of adipic acid, 350-370 parts of phthalic anhydride, 8-12 parts of epoxy resin, 828-4 parts of epoxy resin, 25-35 parts of reflux xylene, 1-1.5 parts of a color reducing agent, 180-200 parts of a high-boiling-point aromatic hydrocarbon solvent, 90-110 parts of propylene glycol monomethyl ether acetate, 40-60 parts of a DBE solvent and 20-25 parts of ethylene glycol butyl ether.
2. The epoxy modified saturated polyester for coil back paint as claimed in claim 1, wherein the rigid diol is at least one of ethylene glycol and 1,2-propylene glycol or a mixture thereof.
3. The epoxy modified saturated polyester for coil back paint according to claim 1, wherein the side chain-containing triol is at least one or a mixture of trimethylolpropane and trimethylolethane.
4. The epoxy modified saturated polyester for coil back paint as claimed in claim 1, wherein the epoxy resin 604 is bisphenol a epoxy resin produced by Jiangsu Sandelian chemical industries, ltd, having an epoxy equivalent of 800-900.
5. The epoxy modified saturated polyester for coil back paint as claimed in claim 1, wherein the epoxy resin 828 is bisphenol a epoxy resin produced by Jiangsu Sandelian chemical industries, ltd, having an epoxy equivalent of 184-194.
6. The epoxy modified saturated polyester for coil back paint as claimed in claim 1, wherein the high boiling point aromatic hydrocarbon solvent is at least one or a mixture of 100# solvent with distillation range of 160-175 ℃ and density of 0.862-0.875 and 150# solvent with distillation range of 180-210 ℃ and density of 0.800-0.900.
7. The epoxy modified saturated polyester for coil back paint as claimed in claim 1, wherein the color reducing agent is at least one of hypophosphorous acid and triphenyl phosphite or a mixture thereof.
8. The preparation method of the epoxy modified saturated polyester for coil back paint as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
1) Putting rigid dihydric alcohol, trihydric alcohol with side chains, neopentyl glycol, adipic acid, phthalic anhydride and a color reducing agent into a reaction kettle according to parts by weight, heating, stirring, putting epoxy resin 604, and opening a column to obtain cooling water; closing a reflux valve of the reflux tank, slowly heating under the condition of strictly controlling the temperature of a distillation head to be not more than 100-105 ℃, measuring the acid value, and taking the resin to measure the viscosity;
the mass ratio of the resin to the mixed solvent is 12:8, mixing the solvent in a mass ratio of 7:1:0.5 xylene: isobutanol: PMA;
viscosity: 8-10 second Grignard;
2) Opening a reflux valve after the acid value viscosity is qualified, cooling water Guan Lizhu, slowly adding epoxy resin 828 and refluxing dimethylbenzene, heating, refluxing, carrying out esterification reaction, sampling, and carrying out central control:
the mass ratio of the resin to the mixed solvent is 12:8, mixing the solvent in a mass ratio of 7:1:0.5 xylene: isobutanol: PMA;
the acid value is less than or equal to 7mgKOH/g; viscosity: 30-35 second Grignard;
3) And immediately cooling after the polyester is qualified, adding a high-boiling-point aromatic hydrocarbon solvent, DBE, ethylene glycol monobutyl ether and PMA in sequence, and cooling to obtain the epoxy modified saturated polyester.
9. The preparation method of the epoxy modified saturated polyester for coil back paint according to claim 8, characterized by comprising the following steps:
1) Putting rigid dihydric alcohol, trihydric alcohol with a side chain, neopentyl glycol, adipic acid, phthalic anhydride and a color reducing agent into a reaction kettle according to the parts by weight, heating to 155 ℃, starting stirring for 10 minutes, then putting epoxy resin 604, and starting column cooling water. Closing a reflux valve of the reflux tank, slowly heating under the premise of strictly controlling the temperature of a distillation head not to exceed 102 ℃, continuously heating to 225-235 ℃, keeping the temperature, measuring the acid value to be less than 25, and taking the resin as the viscosity.
The mass ratio of the resin to the mixed solvent is 12:8, mixing the solvent in a mass ratio of 7:1:0.5 xylene: isobutanol: PMA;
viscosity: 8-10 second Grignard;
2) Opening a reflux valve after the acid value viscosity is qualified, cooling water Guan Lizhu, slowly adding epoxy resin 828 and refluxing dimethylbenzene, heating to 220-230 ℃ for refluxing esterification reaction for 2-3 hours, sampling, and controlling:
the mass ratio of the resin to the mixed solvent is 12:8, mixing the solvent in a mass ratio of 7:1:0.5 xylene: isobutanol: PMA;
the acid value is less than or equal to 7mgKOH/g; viscosity: 30-35 second Grignard;
3) Cooling down the polyester immediately after the polyester is qualified, adding a high boiling point aromatic hydrocarbon solvent, DBE, ethylene glycol monobutyl ether and PMA in sequence when the polyester is cooled down to 180 ℃, and cooling down the polyester to below 100 ℃ to obtain the epoxy modified saturated polyester with the solid content of 59-61%.
10. The epoxy modified saturated polyester for the coil back paint is characterized by being prepared from the following raw materials in parts by weight:
85 parts of ethylene glycol, 20 parts of trimethylolpropane, 13 parts of trimethylolethane, 125 parts of neopentyl glycol, 35 parts of adipic acid, 370 parts of phthalic anhydride, 0.3 part of hypophosphorous acid, 1.2 parts of triphenyl phosphite, 604 parts of epoxy resin, 828 4 parts of epoxy resin, 32 parts of xylene, 40 parts of high-boiling-point aromatic hydrocarbon 100# solvent, 150#160 parts of high-boiling-point aromatic hydrocarbon, 50 parts of DBE, 23 parts of ethylene glycol butyl ether and 95 parts of PMA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211346319.0A CN115637098B (en) | 2022-10-31 | 2022-10-31 | Preparation method of epoxy modified saturated polyester for coil back paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211346319.0A CN115637098B (en) | 2022-10-31 | 2022-10-31 | Preparation method of epoxy modified saturated polyester for coil back paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115637098A true CN115637098A (en) | 2023-01-24 |
| CN115637098B CN115637098B (en) | 2023-11-03 |
Family
ID=84947559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211346319.0A Active CN115637098B (en) | 2022-10-31 | 2022-10-31 | Preparation method of epoxy modified saturated polyester for coil back paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115637098B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827717A (en) * | 2005-03-02 | 2006-09-06 | 上海电气集团上海电机厂有限公司 | Process for preparing impregnating resin for electrical purposes |
| 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 |
| CN102060979A (en) * | 2010-11-29 | 2011-05-18 | 上海涂料有限公司振华造漆厂 | Novel epoxy modified resin for anti-corrosion primer and one-step preparation method thereof |
| CN103044667A (en) * | 2012-12-21 | 2013-04-17 | 江苏三木化工股份有限公司 | Alkyd resin for amino baking paint and preparation method thereof |
| CN103193986A (en) * | 2013-01-31 | 2013-07-10 | 华南理工大学 | Epoxy-terminated silicone oil-modified hydroxyl-terminated hyperbranched polyester, and preparation method and application thereof |
| CN103450721A (en) * | 2012-06-01 | 2013-12-18 | 天津中油渤星工程科技有限公司 | Epoxy deck paint and manufacture method thereof |
| CN110894392A (en) * | 2019-11-29 | 2020-03-20 | 安徽壹信通讯科技有限公司 | High-performance two-component epoxy primer for rail transit and preparation process thereof |
| RU2741878C1 (en) * | 2019-12-25 | 2021-01-29 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Polyester paint composition for application onto sheet and coil substrate |
-
2022
- 2022-10-31 CN CN202211346319.0A patent/CN115637098B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827717A (en) * | 2005-03-02 | 2006-09-06 | 上海电气集团上海电机厂有限公司 | Process for preparing impregnating resin for electrical purposes |
| 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 |
| CN102060979A (en) * | 2010-11-29 | 2011-05-18 | 上海涂料有限公司振华造漆厂 | Novel epoxy modified resin for anti-corrosion primer and one-step preparation method thereof |
| CN103450721A (en) * | 2012-06-01 | 2013-12-18 | 天津中油渤星工程科技有限公司 | Epoxy deck paint and manufacture method thereof |
| CN103044667A (en) * | 2012-12-21 | 2013-04-17 | 江苏三木化工股份有限公司 | Alkyd resin for amino baking paint and preparation method thereof |
| CN103193986A (en) * | 2013-01-31 | 2013-07-10 | 华南理工大学 | Epoxy-terminated silicone oil-modified hydroxyl-terminated hyperbranched polyester, and preparation method and application thereof |
| CN110894392A (en) * | 2019-11-29 | 2020-03-20 | 安徽壹信通讯科技有限公司 | High-performance two-component epoxy primer for rail transit and preparation process thereof |
| RU2741878C1 (en) * | 2019-12-25 | 2021-01-29 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Polyester paint composition for application onto sheet and coil substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115637098B (en) | 2023-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3835379A1 (en) | Polyester resin composition, powder coating and workpiece | |
| WO2021031377A1 (en) | Polyester resin used for graphene-containing powder coating | |
| CN102391439B (en) | Epoxy ester modified aqueous alkyd resin and preparation method thereof | |
| CN110511365A (en) | A kind of engineering machinery polyester resin | |
| CA2109329A1 (en) | Polyester-based coating compositions having high pigment-to-binder ratios | |
| CN112646156A (en) | Polyphenylene sulfide ether ketone modified waterborne alkyd resin and preparation method thereof | |
| CN111533892A (en) | Polyester resin for high-weather-resistance low-temperature TGIC (triglycidyl isocyanurate) curing powder coating and preparation method thereof | |
| CN112062941A (en) | 6040 type polyester resin and preparation method thereof | |
| CN112063276A (en) | Polyester resin for indoor TMA-free matt powder coatings | |
| CN111944137B (en) | Epoxidized polyester resin for weather-resistant high-impact-resistance powder coating and preparation method thereof | |
| CN113604137A (en) | Scratch-resistant epoxy modified polyester back paint for coiled material with high coating rate and preparation method thereof | |
| CN115637098A (en) | Preparation method of epoxy modified saturated polyester for coil back paint | |
| US20230174710A1 (en) | Hydroxyl-terminated polyester resin, preparation method therefor and use thereof | |
| CN1635039A (en) | Method for preparing novel B level high speed polyurethane enamelled wire paint | |
| CN113150257B (en) | Polyester resin, preparation method thereof and application thereof in wet-on-wet process | |
| CN114656861A (en) | Water-based silicon-modified polyester coil steel coating and preparation method thereof | |
| CN112521838B (en) | Extinction transparent polyester resin composition and preparation method and application thereof | |
| CN113999376A (en) | high-Tg high-impact-resistance polyester resin for dual-curable powder coating and preparation method and application thereof | |
| CN115612078B (en) | Diethylenetriamine modified saturated polyester resin and preparation method thereof | |
| CN111944132A (en) | Primer alkyd resin and preparation method and application thereof | |
| WO2014171402A1 (en) | Polyester resin, and aqueous dispersion prepared using same | |
| CN111234192A (en) | Preparation method of organic silicon modified saturated polyester resin with high weather resistance | |
| CN110903471A (en) | Organosilicon modified polyester copolymer for powder coating and preparation method thereof | |
| CN110467874A (en) | A kind of preparation process of thermosetting powder coating modified polyester resin | |
| CN114196000B (en) | High-coating Tg scratch-resistant TMA-free polyester resin, preparation method thereof and powder coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |