CN115637098B - 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
- CN115637098B CN115637098B CN202211346319.0A CN202211346319A CN115637098B CN 115637098 B CN115637098 B CN 115637098B CN 202211346319 A CN202211346319 A CN 202211346319A CN 115637098 B CN115637098 B CN 115637098B
- Authority
- CN
- China
- Prior art keywords
- parts
- resin
- epoxy
- saturated polyester
- epoxy modified
- 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.)
- Active
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 54
- 229920000728 polyester Polymers 0.000 title claims abstract description 39
- 239000003973 paint Substances 0.000 title claims abstract description 33
- 229920006395 saturated elastomer Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000010992 reflux Methods 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 22
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 20
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000008096 xylene Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000001361 adipic acid Substances 0.000 claims abstract description 11
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 11
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims abstract description 7
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000498 cooling water Substances 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 abstract description 14
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 11
- 239000007921 spray Substances 0.000 abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 229920000180 alkyd Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229940035429 isobutyl alcohol Drugs 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical class C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 150000002009 diols Chemical class 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
- 229940100573 methylpropanediol Drugs 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- Epoxy Resins (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses epoxy modified saturated polyester for coiled material back paint, which is prepared from 75-85 parts of rigid dihydric alcohol, 30-36 parts of triol with side chains, 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 refluxing xylene, 1-1.5 parts of color reducer, 180-200 parts of high-boiling aromatic hydrocarbon solvent, 90-110 parts of propylene glycol methyl ether acetate, 40-60 parts of DBE solvent and 20-25 parts of ethylene glycol butyl ether. The invention screens out various raw material compositions and specific reaction steps through experiments, and the prepared epoxy modified saturated polyester improves the hardness and scratch resistance of the resin on the premise of ensuring the performances of salt spray resistance, flexibility, adhesive force and the like. Meanwhile, the consumption of epoxy is reduced, phthalic anhydride with low cost is used for replacing isophthalic acid, and the cost is greatly reduced.
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 the coiled material, generally adopts a single layer, has thinner paint film, and requires the paint film to have better salt spray resistance, processability, hardness, MEK wiping resistance and scratch resistance.
The prior art back paint is mainly divided into three types, namely epoxy resin, and the epoxy back paint has good butanone (MEK) wiping resistance, good adhesive force, high hardness, good salt spray resistance and poor flexibility; the polyester type back paint has good flexibility, but has poor butanone (MEK) wiping resistance, and relatively poor adhesive force and scratch resistance; the other type is epoxy modified polyester, the performance of the epoxy modified polyester back paint is between the two types, and the epoxy modified polyester has been the main stream of the market, but the existing epoxy modified polyester has the following disadvantages:
1, the epoxy resin has good performance, the epoxy resin accounts for 10-25% of the modified resin, the price of the epoxy resin is always high in several years, the cost is high, and the use is limited.
2, because the plates are rolled and piled together after being coated, the rolling weight is at least 2 tons, the plates are mutually extruded and displaced in the transportation process, the risks of generating indentation and scratch are generated, and the hardness of the resin is always 3H at the highest, so that the hardness and scratch resistance are also improved.
In summary, the cost of the existing epoxy modified saturated polyester is reduced, the application surface can be enlarged, and the hardness and scratch resistance of the resin are improved on the premise of ensuring salt spray resistance, flexibility, adhesive force and the like.
Disclosure of Invention
The invention aims to: the epoxy modified saturated polyester for the back paint has the advantages of improving the hardness and scratch resistance of the resin 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 process for its preparation.
The technical scheme is as follows: in order to achieve the above purpose, the invention adopts the following technical scheme:
the epoxy modified saturated polyester for the 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 triol with side chains, 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 refluxing xylene, 1-1.5 parts of a color reducer, 180-200 parts of a high-boiling aromatic hydrocarbon solvent, 90-110 parts of propylene glycol methyl ether acetate (PMA), 40-60 parts of a DBE solvent and 20-25 parts of ethylene glycol butyl ether.
Preferably, the epoxy modified saturated polyester for the coil back paint is characterized in that the rigid dihydric alcohol is at least one or a mixture of ethylene glycol and 1, 2-propylene glycol.
As a preferred embodiment, the epoxy modified saturated polyester for coil back coating is one in which the triol with side chain is at least one or a mixture of trimethylol propane and trimethylol ethane
As a preferable scheme, the epoxy modified saturated polyester for the coil back paint is prepared from bisphenol A type epoxy resin with the epoxy equivalent of 800-900 and manufactured by Jiangsu Sanmu chemical industry Co., ltd.
As a preferable scheme, the epoxy modified saturated polyester for the coil back paint is characterized in that the epoxy resin 828 is bisphenol A type epoxy resin produced by Jiangsu Sanmu chemical Co., ltd, and the epoxy equivalent is 184-194.
As a preferable scheme, the epoxy modified saturated polyester for the coil back paint is at least one or a mixture of 100# solvent (the distillation range is 160-175 ℃ and the density is 0.862-0.875) and 150# solvent (the distillation range is 180-210 ℃ and the density is 0.800-0.900).
As a preferable scheme, the epoxy modified saturated polyester for the coil back paint is characterized in that the color reducing agent is at least one or a mixture of hypophosphorous acid and triphenyl phosphite.
As a preferable scheme, the epoxy modified saturated polyester for the coil back paint is prepared from DBE which is electronic-grade mixed dibasic acid ester self-produced by Jiangsu Sanmu group Co.
As a preferable scheme, the epoxy modified saturated polyester for the coil back paint is prepared from PMA, which is high-grade propylene glycol methyl 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) Adding rigid dihydric alcohol, triol 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, adding epoxy resin 604 and cooling water of a vertical column; closing a reflux valve of a reflux tank, slowly heating up under the premise of strictly controlling the temperature of a distillation head to be not more than 100-105 ℃, measuring an acid value, and taking resin to measure viscosity;
the mass ratio of the resin to the mixed solvent is 12:8, the mass ratio of the mixed solvent is 7:1:0.5 xylene: isobutanol: PMA;
viscosity: 8-10 seconds format tube;
2) After the acid value and viscosity are qualified, a reflux valve is opened, guan Lizhu cooling water is added slowly, epoxy resin 828 and refluxing xylene are added slowly, and after heating reflux esterification reaction, sampling is carried out for central control:
the mass ratio of the resin to the mixed solvent is 12:8, the mass ratio of the mixed solvent is 7:1:0.5 xylene: isobutanol: PMA;
the acid value is less than or equal to 7mgKOH/g; viscosity: a 30-35 second format tube;
3) And cooling immediately after the epoxy modified saturated polyester is qualified, and sequentially adding high-boiling aromatic hydrocarbon solvent, DBE, ethylene glycol butyl ether and PMA, 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 of:
1) Adding 75-85 parts by weight of rigid dihydric alcohol, 30-36 parts by weight of triol with side chains, 125-145 parts by weight of neopentyl glycol, 35-45 parts by weight of adipic acid, 350-370 parts by weight of phthalic anhydride and 1-1.5 parts by weight of color reducer into a reaction kettle, heating to 155 ℃, stirring in a test mode, adding 8-12 parts by weight of epoxy 604 after stirring for 10 minutes, and opening a column to cool water. And (3) closing a reflux valve of a reflux tank, slowly heating up under the premise of strictly controlling the temperature of the distillation head to be not more than 102 ℃, continuously heating up to 225-235 ℃, preserving heat, and measuring an acid value (less than 25). Taking resin as viscosity.
Resin: mixed solvent = 12: mixed solvent = xylene: isobutanol: pma=7: 1:0.5
Viscosity: 8-10 second format tube
2) After the acid value and viscosity are qualified, a reflux valve is opened, guan Lizhu cooling water is added, 3-4 of epoxy 828 and 25-35 of reflux xylene are slowly added, reflux esterification is carried out at 220-230 ℃, sampling and central control are carried out after 2-3 hours: resin: mixed solvent = 12: mixed solvent = xylene: isobutanol: pma=7: 1:0.5;
the acid value is less than or equal to 7mgKOH/g; viscosity: a 30-35 second format tube;
3) Immediately cooling to 180 ℃ after being qualified, and adding 180-200 high boiling aromatic hydrocarbon solvent, 40-60 DBE, 20-25 ethylene glycol butyl ether and 90-110 PMA in sequence, and cooling to below 100 ℃ to obtain the epoxy modified saturated polyester with 59-61% of solid content.
The invention mainly improves the defects of the epoxy modified saturated polyester for the prior back paint through the following schemes.
1. The invention discovers that when synthesizing the epoxy modified saturated polyester through screening raw materials, if isophthalic acid and terephthalic acid are used for polybasic acid according to the traditional thought, the satisfactory performance is required to be obtained, and the amount of epoxy resin is not reduced at all. Traditionally, phthalic anhydride is considered to have an ortho-structure, which is prone to lactone formation, and tends to lower molecular weight, which is detrimental to flexibility and salt spray resistance. The invention is found through screening that the polybasic acid directly adopts phthalic anhydride and adipic acid to match, the phthalic anhydride accounts for about 90 percent, the adipic acid accounts for about 10 percent, and thus the epoxy resin accounts for about 2 percent of the solid content 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 three-molecule complex to react to form a three-dimensional structure, so that the molecular weight of the resin is increased, the flexibility and salt spray resistance of the resin are improved, and unexpected technical effects of twice as much effort are achieved. And the common use of isophthalic acid and terephthalic acid is difficult to react with epoxy resin and dihydric alcohol to form a three-molecule complex body, so that a three-dimensional structure is formed.
2. In the raw materials, rigid dihydric alcohol and phthalic anhydride are creatively adopted to match to improve the hardness of the resin, the sum of the rigid dihydric alcohol and the phthalic anhydride accounts for about 70 percent of the solid amount of the modified resin, and adipic acid accounting for 5 percent of the solid amount of the modified resin is used for adjusting the flexibility; the two step further chain extension with low molecular weight epoxy 828 increases molecular weight to increase flexibility.
3. The invention creatively adopts the matching of high molecular weight epoxy resin 604 and low molecular weight epoxy resin 828, and epoxy 604: epoxy 828 = 3:1, in the first step, the epoxy resin 604 and the polyhydric alcohol polybasic acid are directly put into a reaction kettle, the molecular weight of the epoxy resin 604 is large, the reaction activity is lower than that of the epoxy 828, and the reaction is stable and the purpose of the first item is achieved. If epoxy 828 is used in the first step, epoxy 828 will react vigorously with phthalic anhydride to form a gum. And after the first step of reaction is finished, forming a polyester prepolymer which has high molecular weight and low acidity, and then performing two-step chain extension by using epoxy 828 to react to form the polymer resin intended by the invention. The epoxy resin 604 and 828 of the invention not only plays a role in chain extension, but also plays a role in providing resin adhesion and salt spray resistance to epoxy, and achieves good technical effects.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
the epoxy modified saturated polyester for coil back paint is prepared by screening various reaction raw material compositions and specific reaction steps through a large number of experiments. On the premise of ensuring the performances of salt spray resistance, flexibility, adhesive force and the like, the hardness and 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, which are not to be construed as specific conditions, either as normal conditions or as recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The compositions of the raw materials in the following examples are shown in Table 1:
table 1 raw material composition of each example
The preparation method of the quick-drying high-performance alkyd resin comprises the following steps:
1) According to the above examples 1 to 5, a rigid diol, a triol having a side chain, neopentyl glycol, adipic acid, phthalic anhydride and a color reducing agent were put into a reaction vessel, and the mixture was stirred while being stirred at 155℃for 10 minutes, and then epoxy 604 was put into the reaction vessel, followed by cooling with a column. And (3) closing a reflux valve of a reflux tank, slowly heating up under the premise of strictly controlling the temperature of the distillation head to be not more than 102 ℃, continuously heating up to 225-235 ℃, preserving heat, and measuring an acid value (less than 25). The viscosity of the resin was taken to reach the following value.
Resin: mixed solvent mass ratio 12:8, wherein the mixed solvent is prepared from the following components in mass ratio 7:1:0.5 xylene, isobutyl alcohol and PMA. Viscosity: 8-10 second format tube.
2) After the acid value and viscosity are qualified, a reflux valve is opened, guan Lizhu cooling water is slowly added with epoxy 828 and refluxing xylene, reflux esterification is carried out at 220-230 ℃, and after 2-3 hours, sampling and central control are carried out to achieve the following values:
resin: mixed solvent mass ratio 12:8, wherein the mixed solvent is prepared from the following components in mass ratio 7:1:0.5 xylene, isobutyl alcohol and PMA. The acid value is less than or equal to 7mgKOH/g. Viscosity: 30-35 seconds format tube.
3) Immediately cooling after being qualified, and when the temperature is reduced to 180 ℃, adding high boiling aromatic hydrocarbon solvent, DBE, ethylene glycol butyl ether and PMA in sequence, and cooling 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) The reaction kettle is filled with 50 parts by mass of neopentyl glycol, 172 parts by mass of methyl propylene glycol, 14 parts by mass of trimethylolpropane, 50 parts by mass of adipic acid, 80 parts by mass of phthalic anhydride, 128 parts by mass of isophthalic acid, 90 parts by mass of terephthalic acid and 0.3 part by mass of monobutyl tin oxide, the temperature is raised to 155 ℃, stirring is started, after stirring for 10 minutes, 85 parts by mass of epoxy 604 is added, and cooling water is filled into an open column. Closing a reflux valve of a reflux tank, slowly heating up under the premise of strictly controlling the temperature of a distillation head not to exceed 102 ℃, continuously heating up to 240-250 ℃ for heat preservation until resin is clear and transparent, opening Guan Lizhu cooling water, opening the reflux valve of the reflux tank, adding 30 parts of reflux xylene, carrying out reflux esterification at 220-230 ℃, and sampling and central control after 2-3 hours until the temperature reaches the following values:
the mass ratio of the resin to the dimethylbenzene is 11:9, a step of performing the process; the acid value is less than or equal to 8mgKOH/g; viscosity: 8-12 second format tube.
2) Immediately cooling to 180 ℃ after being qualified, adding 260 parts of 150# solvent, 70 parts of DBE, 40 parts of ethylene glycol butyl ether and cooling to below 100 ℃ in sequence to obtain the epoxy modified saturated polyester with the solid content of 59-61%.
Comparative example 2 (pure polyester)
1) 153 parts by mass of neopentyl glycol, 95 parts by mass of methylpropanediol, 30 parts by mass of trimethylolpropane, 105 parts by mass of adipic acid, 120 parts by mass of phthalic anhydride, 50 parts by mass of isophthalic acid, 126 parts by mass of terephthalic acid and 0.3 part by mass of monobutyl tin oxide are put into a reaction kettle, and the temperature is raised to 155 ℃ to test stirring and open column cooling water. Closing a reflux valve of a reflux tank, slowly heating up under the premise of strictly controlling the temperature of a distillation head not to exceed 102 ℃, continuously heating up to 240-250 ℃ for heat preservation until resin is clear and transparent, opening Guan Lizhu cooling water, opening the reflux valve of the reflux tank, adding 30 parts of reflux xylene, carrying out reflux esterification at 220-230 ℃, and sampling and central control after 2-3 hours until the following qualified values are reached:
the mass ratio of the resin to the dimethylbenzene is 12:8, acid value less than or equal to 8mgKOH/g, viscosity: 8-12 seconds format tube;
2) And immediately cooling to 180 ℃ after the product is qualified, and adding 250 parts of 150# solvent, 80 parts of 100# solvent, 20 parts of DBE and 20 parts of ethylene glycol butyl ether into the mixture in sequence to obtain the epoxy modified saturated polyester with the solid content of 59-61%.
Application example 1
1. Alkyd resins obtained in examples 1-5 and comparative examples 1 and 2 were prepared according to the following color paint formulation in Table 2, and the alkyd resins were ground and dispersed to prepare color paints.
TABLE 2 color paint formulation
2. Color paint detection
Curing plate temperature: 240 ℃ for 50 seconds;
the following tests were carried out on the paints prepared in examples 1 to 5 and comparative examples 1 and 2, and the specific paint test results are shown in table 3:
TABLE 3 color paint test results
The experimental results show that the epoxy modified saturated polyester for the coiled material back paint is prepared by screening various reaction raw material compositions through a large number of experiments, particularly through compatibility of epoxy resin 604, epoxy resin 828 and phthalic anhydride and compatibility of rigid dihydric alcohol and phthalic anhydride. On the premise of ensuring the performances of salt spray resistance, flexibility, adhesive force and the like, the hardness and scratch resistance of the resin can be greatly improved. And simultaneously, the consumption of epoxy 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. In particular, the resin of example 5 of the present invention has the best salt spray resistance, solvent resistance and other properties, and achieves good technical effects.
Claims (1)
1. The preparation method of the epoxy modified saturated polyester for the coil back paint is characterized by comprising the following steps of:
1) 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 and 1.2 parts of triphenyl phosphite are put into a reaction kettle according to parts by weight, stirring is started when the temperature is raised to 155 ℃, 604 12 parts of epoxy resin is put into the reaction kettle after stirring is performed for 10 minutes, and cooling water is started; closing a reflux valve of a reflux tank, slowly heating up to 225-235 ℃ continuously under the premise of strictly controlling the temperature of the distillation head to be not more than 102 ℃, and keeping the temperature, wherein the measured acid value is less than 25; taking resin to test viscosity;
the mass ratio of the resin to the mixed solvent is 12:8, the mass ratio of the mixed solvent is 7:1:0.5 xylene: isobutanol: PMA;
viscosity: 8-10 seconds format tube;
2) After the acid value and viscosity are qualified, a reflux valve is opened, guan Lizhu cooling water is slowly added with 828 parts by weight of epoxy resin and 32 parts by weight of reflux xylene, the mixture is heated to 220-230 ℃ for reflux esterification reaction for 2-3 hours, and then sampling and central control are carried out:
the mass ratio of the resin to the mixed solvent is 12:8, the mass ratio of the mixed solvent is 7:1:0.5 xylene: isobutanol: PMA;
the acid value is less than or equal to 7mgKOH/g; viscosity: a 30-35 second format tube;
3) And immediately cooling to 180 ℃ after the mixture is qualified, and adding 40 parts of high-boiling aromatic hydrocarbon 100# solvent, 150# 160 parts of high-boiling aromatic hydrocarbon, 50 parts of DBE, 23 parts of ethylene glycol butyl ether and 95 parts of PMA in sequence according to parts by weight, and cooling to below 100 ℃ to obtain the epoxy modified saturated polyester with the solid content of 59-61%.
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 CN115637098A (en) | 2023-01-24 |
| CN115637098B true 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 |
|---|---|
| CN115637098A (en) | 2023-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1754737B1 (en) | Polyester resin and thermosetting aqueous coating composition | |
| EP3835379A1 (en) | Polyester resin composition, powder coating and workpiece | |
| WO2021031377A1 (en) | Polyester resin used for graphene-containing powder coating | |
| CN112646156A (en) | Polyphenylene sulfide ether ketone modified waterborne alkyd resin and preparation method thereof | |
| CN113861398A (en) | Polyester resin containing diphenyl ether structure, powder coating and preparation method thereof | |
| CN113604137B (en) | Scratch-resistant epoxy modified polyester back paint for coiled material with high coating rate and preparation method thereof | |
| TW313581B (en) | ||
| CN115637098B (en) | Preparation method of epoxy modified saturated polyester for coil back paint | |
| CN111944137B (en) | Epoxidized polyester resin for weather-resistant high-impact-resistance powder coating and preparation method thereof | |
| US4829132A (en) | Resinous composition containing polyester resin, for coating use | |
| KR20110002457A (en) | Printing ink composition for seamless can | |
| CN113150257B (en) | Polyester resin, preparation method thereof and application thereof in wet-on-wet process | |
| CN112521838B (en) | Extinction transparent polyester resin composition and preparation method and application thereof | |
| CN114656861A (en) | Water-based silicon-modified polyester coil steel coating and preparation method thereof | |
| CN111234192B (en) | Preparation method of organic silicon modified saturated polyester resin with high weather resistance | |
| CN115612078B (en) | Diethylenetriamine modified saturated polyester resin and preparation method thereof | |
| CN111944132A (en) | Primer alkyd resin and preparation method and application thereof | |
| CN110615889A (en) | Polyester resin for crystallography powder coating and preparation method and application thereof | |
| CN113461922B (en) | Low-acid-value polyester resin for ultralow-temperature curing powder coating and preparation method thereof | |
| CN114196000B (en) | High-coating Tg scratch-resistant TMA-free polyester resin, preparation method thereof and powder coating | |
| CN106957414A (en) | High solid is from dry alkyd resin and preparation method thereof | |
| CN109749067B (en) | Polyester resin with excellent flexibility for powder coating and preparation method thereof | |
| CN109824879B (en) | Epoxy cured 70:30 polyester resin with excellent leveling property and solvent resistance and preparation method thereof | |
| CN104788653A (en) | Stable-storage saturated polyester resin with high acid value and preparation method thereof | |
| CN112457750A (en) | Indoor AB dry-mixed extinction powder coating and preparation method thereof |
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 |