CN109517151A - A kind of polyester resin and preparation method thereof of high-leveling energy - Google Patents
A kind of polyester resin and preparation method thereof of high-leveling energy Download PDFInfo
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- CN109517151A CN109517151A CN201811385802.3A CN201811385802A CN109517151A CN 109517151 A CN109517151 A CN 109517151A CN 201811385802 A CN201811385802 A CN 201811385802A CN 109517151 A CN109517151 A CN 109517151A
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- polyester resin
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- leveling energy
- leveling
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 42
- 239000004645 polyester resin Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 229920000728 polyester Polymers 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 114
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 25
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000005259 measurement Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- -1 hexadecyldimethyl benzyl ammonium tertiary amine Chemical class 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 6
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 235000013847 iso-butane Nutrition 0.000 claims 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 description 11
- 230000002776 aggregation Effects 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 235000015511 Liquidambar orientalis Nutrition 0.000 description 2
- 239000004870 Styrax Substances 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 241000736148 Styrax Species 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- PRZSXZWFJHEZBJ-UHFFFAOYSA-N thymol blue Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C PRZSXZWFJHEZBJ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A kind of polyester resin and preparation method thereof of high-leveling energy of the present invention.The specific scheme is that a kind of polyester resin of high-leveling energy, according to parts by weight, including following raw material: 32.4~34.9 parts of dihydric alcohol, 70.8~72.2 parts of polyacid, 0.5~0.8 part of trimethylolpropane, 1.6~1.8 parts of antiplastering aid, 0.001~0.01 part of polyester slice, 0.07~0.15 part of antioxidant, 0.3~0.6 part of curing accelerator and 0.3~0.7 part of surfactant.The present invention solves the problems, such as polyester resin feed stock unsuitable large-scale production at high cost in the prior art, and polyester resin prepared by the present invention not only reduces cost, and the polyester resin of preparation has excellent levelability, and various aspects of performance is all up to standard.
Description
Technical field
The present invention relates to a kind of polyester resin and preparation method thereof of high-leveling energy.
Background technique
Polyester resin is the maximum resin raw material of China's powdery paints industry dosage, polyester resin for powder coating be with
The high molecular polymer that polyacid is reacted with polyhydric alcohol, and polyester resin for powder coating is wanted in component design
The features such as considering comminuted, film the weatherability of powdery paints storage stability and levelability, polyester resin, and influence these
The principal element of performance characteristics is the selection of polyacid or polyalcohol, reasonable alkyd equivalent proportion and the control extent of reaction and technique
Condition is to prepare the key technology of high molecular weight polyester resins.However, guaranteeing that each performance is all up to standard in existing technology
In the case of, the higher cost expended is not appropriate for being mass produced.So the present invention provides a kind of in save the cost
In the case of, the proportion and preparation method thereof of various aspects of performance high-leveling polyester resin all up to standard.
Summary of the invention
The object of the present invention is to provide a kind of polyester resin and preparation method thereof of high-leveling energy.
For achieving the above object, the technical scheme adopted by the invention is that:
The present invention provides a kind of proportions of the polyester resin of high-leveling energy, according to parts by weight, including following raw material:
32.4~34.9 parts of dihydric alcohol, 70.8~72.2 parts of polyacid, 0.5~0.8 part of trimethylolpropane, antiplastering aid 1.6~1.8
Part, 0.001~0.01 part of polyester slice, 0.07~0.15 part of antioxidant, 0.3~0.6 part of curing accelerator and surfactant
0.3~0.7 part.
Preferably, according to parts by weight, the dihydric alcohol includes 2.0~2.5 parts of neopentyl glycol, diethylene glycol (DEG) 7.9~8.3
Part, 7.5~8.1 parts of ethylene glycol and 15.0~16.0 parts of propylene glycol；The polyacid includes 64.5~65.5 parts of terephthalic acid (TPA)
With 6.3~6.7 parts of trimellitic anhydride.
Preferably, antiplastering aid is mica, kaolin or silica, and the antioxidant is triphenyl phosphite, the solidification
Promotor is hexadecyldimethyl benzyl ammonium tertiary amine or octadecyldimethyl tertiary amine, and the surfactant is stearic acid.
The present invention also provides a kind of preparation methods of the polyester resin of high-leveling energy, comprising the following steps:
(1) precise above-mentioned raw materials, sequentially add in a kettle neopentyl glycol, diethylene glycol (DEG), ethylene glycol, propylene glycol and
Trimethylolpropane is heated；
(2) after the completion of heating, continue to sequentially add into reaction kettle terephthalic acid (TPA), antiplastering aid, Mono-n-butyltin and
Polyester slice is heated up and continues to stir；
(3) after observing reaction water outlet, heating rate is reduced, and continue to heat up, is warming up to 165~220 DEG C；
(4) after step (3) reaches assigned temperature, heating rate is improved, reaction is warming up to and is no longer discharged, is then added anti-
Oxygen agent, and keep temperature-resistant, until being no longer discharged；
(5) reaction kettle top temperature drop stops heating and stirring to after 70~80 DEG C, then starts to vacuumize for the first time, sample,
Reactant acid value and viscosity are measured, until the acid value of reactant and viscosity reach provincial standard, then stops vacuumizing；
(6) when the temperature in reaction kettle is down to 200~220 DEG C, trimellitic anhydride is added in a kettle, stirs evenly
Afterwards, start to vacuumize for the second time；
(7) after the completion of vacuumizing for the second time, curing accelerator and surfactant is added into reaction kettle, stirs evenly
Afterwards, that is, polyester resin is prepared.
Preferably, in step (1), the temperature after heating is 55~65 DEG C.
Preferably, in step (2), heating rate is 9~12 DEG C/min, and mixing speed is 60~150r/min.
Preferably, in step (3), heating rate is 4~6 DEG C/min.
Preferably, in step (4), heating rate is 9~12 DEG C/min, and raised temperature is 220~250 DEG C.
Preferably, in step (5), the reading of the first vacuum meter vacuumized is 0.08~0.10MPa, and the duration is
0.8~1.5h；In step (6), the reading of the vacuum meter vacuumized for the second time is 0.07~0.09MPa, the duration is 1~
2h。
Preferably, in step (6), stirring hastens as 60~150r/min, and mixing time is 30~50min；Step (7)
In, stirring hastens as 60~150r/min, and mixing time is 10~20min.
Key reaction principle of the polyester resin disclosed in this invention in preparation process are as follows:
(1)
(2)
(3)
The invention has the following advantages:
1, in polyester resin proportion disclosed in this invention, the molar ratio of alkyd is 6:4, is guaranteeing that the molar ratio is constant
In the case of, it by adjusting formula, reduces the dosage of propylene glycol to the greatest extent, while cost is reduced, guarantees the polyester resin of preparation
Acid value, viscosity, softening point and agglomeration temperature touch the mark requirement, be suitble to large-scale production.
2, in the method disclosed by the invention for preparing polyester resin, by the control extent of reaction and process conditions, to make
Standby polyester resin satisfactory out, and have both high-leveling.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention describe clear, perfectly, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, originally
Field those of ordinary skill other embodiments obtained without making creative work, belong to guarantor of the present invention
The range of shield.
The preparation of 1 polyester resin of embodiment
The present embodiment is arranged 5 repetitions and tests, and raw material dosage see the table below 1, is all made of following steps and carries out polyester resin
Preparation.
1 raw material dosage of table
| Raw material | Repeat 1 | Repeat 2 | Repeat 3 | Repeat 4 | Repeat 5 |
| Neopentyl glycol/g | 200 | 210 | 225 | 226 | 227 |
| Diethylene glycol (DEG)/g | 830 | 820 | 810 | 800 | 790 |
| Ethylene glycol/g | 810 | 800 | 791 | 770 | 750 |
| Propylene glycol/g | 1500 | 1540 | 1566 | 1580 | 1600 |
| Terephthalic acid (TPA)/g | 6450 | 6480 | 6504 | 6530 | 6550 |
| Trimellitic anhydride/g | 630 | 640 | 650 | 660 | 670 |
| Trimethylolpropane/g | 80 | 80 | 69 | 60 | 50 |
| Silica/g | 160 | 165 | 175 | 178 | 180 |
| Polyester slice/g | 0.1 | 0.4 | 0.6 | 0.8 | 1 |
| Triphenyl phosphite/g | 9 | 10 | 12 | 13 | 14 |
| Hexadecyldimethyl benzyl ammonium tertiary amine/g | 30 | 35 | 46 | 52 | 60 |
| Stearic acid/g | 30 | 40 | 50 | 60 | 70 |
Note: in above-mentioned raw materials, polyester slice is that high molecular weight polyesters are sliced K2100.
Preparation step are as follows:
(1) raw material in precise table 1 sequentially adds neopentyl glycol, diethylene glycol (DEG), ethylene glycol, the third two in a kettle
Pure and mild trimethylolpropane, is heated, and the temperature being heated to is 60 DEG C；The volume of reaction kettle is selected according to the dosage of raw material
It selects；
(2) after the completion of heating, continue to sequentially add into reaction kettle terephthalic acid (TPA), silica, Mono-n-butyltin and
Polyester slice is heated up and continues to stir, and is continued stirring until step (4) and is stopped after the reaction was completed, heating rate be 10 DEG C/
Min, mixing speed 100r/min；
(3) after observing reaction water outlet, reduction heating rate to 5 DEG C/min, and it is continuously heating to 220 DEG C；
(4) after step (3) reaches assigned temperature, raising heating rate to 10 DEG C/min, and 235 DEG C are warming up to, if 1
It is no longer discharged in~2min, illustrates that esterification is completed；If being still discharged, continue to heat up, up to 240 DEG C, then plus
Enter triphenyl phosphite, at this moment no longer heat up, and keep temperature-resistant, until being no longer discharged；
(5) reaction kettle top temperature drop is waited to measure the acid of reactant for the first time to heating and stirring, sampling after 75 DEG C, is stopped
Value and viscosity；It is then turned on vacuum pump, starts to vacuumize for the first time, the reading of vacuum meter is 0.09MPa, duration 1h；
Sub-sampling again carries out second of the acid value and viscosity for measuring reactant, if acid value and viscosity reach standard, stopping is vacuumized,
If it does not meet the standards, then continue to vacuumize, this standard for being refers to standard shown in the following table 2, is also possible to other standards；
(6) when the temperature in reaction kettle is down to 220 DEG C, trimellitic anhydride is added in a kettle, stirring hasten for
Under 100r/min, 40min is stirred, after mixing, sampling, third time measures acid value and viscosity；Then it is true to start second of pumping
Sky, the reading of vacuum meter are 0.08MPa, duration 1.5h, are sampled, the 4th measurement acid value and viscosity；
(7) after the completion of vacuumizing for the second time, hexadecyldimethyl benzyl ammonium tertiary amine and stearic acid is added into reaction kettle, is stirring
It hastens to stir evenly under conditions of mixing time is 15min for 100r/min, that is, polyester resin is prepared, sample, the 5th
Secondary measurement acid value and viscosity, and measure softening point.
2 technical performance index of table
| Project | Technical indicator |
| Acid value/mgKOHg-1 | 50~52 |
| Viscosity/Pas | 28~32 |
| Softening point/DEG C | 102~104 |
| Agglomeration temperature/DEG C | ≥52 |
| Plate face glossiness/Gu | > 90 |
| Positive intensity of counter assault/kgcm | ≥50 |
(1) measurement of acid value
The measurement of acid value uses titration in the present embodiment, the specific steps are as follows: firstly, weighing 0.5~2g sample, sets
In conical flask, sample size depends on the size of expected acid value.Then the N of 25mL is added, N- dimethylformamide is placed in
Heating (220 DEG C) to sample is fully dissolved in solution above electrothermal furnace.Flask is put into cooling in cold water basin again, is rocked, is prevented
Only flask is burst；It is cooled to room temperature, 1~2 drop thymol blue indicator solution is added dropwise, is titrated with potassium hydroxide-ethanol solution, to molten
Stopping when liquid has just become indigo plant writes down the amount of the potassium hydroxide-ethanol solution of consumption if colour-fast in 30s is titration end-point, calculates
As a result it see the table below shown in 3.Acid value X is calculated as follows:
The volume of ethanolic potassium hydroxide standard solution, mL before V- is titrated in formula；
V0The volume of ethanolic potassium hydroxide standard solution, mL after titration；
The molar concentration of c- ethanolic potassium hydroxide standard solution, mol/L；
M- sample mass, g.
3 acid value measuring value of table
Unit: mgKOH/g
As the result is shown: with the increase of propylene glycol, the amount of ethylene glycol and diethylene glycol (DEG) is reduced, and is measured for the first time and for the second time
Acid value reduces, this be it is lower than propylene glycol because of the boiling point of diethylene glycol (DEG) and ethylene glycol, activity is higher, and reaction is fast, be easy esterification water outlet, and
Vapor is easy to take away unreacted alcohol, so at this moment acid value can be higher, and when the amount of diethylene glycol (DEG) and ethylene glycol is when reducing, band
The alcohol walked will be reduced, and acid value will reduce.
(2) measurement of viscosity
Viscosity in the present embodiment is measured using D3MS3LT type cone and plate viscometer, and each style measurement is three times, comprehensive
Average value three times is the viscosity of style, and measurement result see the table below shown in 4.
4 viscosity measurement of table
| Repeat 1 | Repeat 2 | Repeat 3 | Repeat 4 | Repeat 5 | |
| It measures for the first time | 12.0 | 15.0 | 14.5 | 13.5 | 12.0 |
| Second of measurement | 10.6 | 13.5 | 13.0 | 12.5 | 11.5 |
| Third time measures | 18.0 | 20.0 | 19.0 | 16.5 | 13.0 |
| 4th measurement | 30.0 | 36.0 | 34.0 | 31.0 | 30.0 |
| 5th measurement | 28.0 | 32.0 | 30.0 | 29.5 | 28.0 |
Unit: Pas
As the result is shown: with the increase of Propanediol, measuring viscosity and be stepped up, this is because neopentyl glycol and the third two
Alcohol has methyl, there is branch, so viscosity is big.2 are repeated from formula, 3 is repeated, repeat 4 and repeats 5 as can be seen that reducing three
The amount of hydroxymethyl-propane, measurement viscosity reduce, this is because there are three hydroxy functional groups for trimethylolpropane, there is branch.
(3) measurement of softening point
Softening point is seen below using the full-automatic bituminous softening-point test device measurement of SYD-2806F, measurement result in the present embodiment
Shown in table 5.
5 softening point measurement value of table
| Repeat 1 | Repeat 2 | Repeat 3 | Repeat 4 | Repeat 5 | |
| Softening point/DEG C | 102 | 104 | 103 | 102 | 102 |
As the result is shown: softening point is influenced by viscosity to a certain degree, so can be seen that softening from the measurement of 4 viscosity of table
Point increases with the increase of viscosity.
(4) measurement of agglomeration temperature
The measurement that obtained polyester resin carries out agglomeration temperature is tested to 5 repetitions in the present embodiment, is surveyed using baking oven
Determine the method for agglomeration temperature, weigh 5 polyester resin sample 5g respectively and be placed in conical flask, be numbered, opens baking oven heating
To 50 DEG C, 5 conical flasks are put into baking oven, taking-up sees whether agglomerate after heating 30min, and the conical flask of agglomeration is taken out；It will
The conical flask not agglomerated continues to be put into baking oven, and baking oven is warming up to 51 DEG C, continues to heat 30min, repeat the above steps, until
All samples agglomeration.The agglomeration temperature of measurement see the table below shown in 6.
6 agglomeration temperature measured value of table
| Repeat 1 | Repeat 2 | Repeat 3 | Repeat 4 | Repeat 5 | |
| Agglomeration temperature/DEG C | 51 | 52 | 54 | 55 | 57 |
As the result is shown: the agglomeration temperature of the sample of above-mentioned 5 formulas preparation is higher than 50 DEG C.
The preparation of 2 powdery paints of embodiment
The polyester resin of 5 formula preparations in embodiment 1 is used to prepare powdery paints by the present embodiment, and raw material dosage is shown in
Shown in the following table 7.
7 raw material dosage of table
| Polyester resin | Titanium dioxide | Precipitating reagent | Levelling agent | Brightener | Styrax | Wax | |
| Dosage/g | 220 | 200 | 222 | 10 | 8 | 5 | 5 |
The step of preparation are as follows:
(1) raw material in precise table 7 stirs the addition of titanium dioxide, precipitating reagent, levelling agent, brightener, styrax and wax
It mixes in bucket, is uniformly mixed；
(2) material after mixing is poured into double screw extruder, the melting extrusion at 200 DEG C；
(3) material of extrusion is cooled to room temperature, removes the material most started when squeezing out, avoiding can in double screw extruder
It can there are last remaining solids；
(4) material after cooling is put into pulverizer and is crushed 3~4 times, and smashed material is crossed into 500 meshes；
(5) fine powder after taking a part to sieve is fitted into spray gun, then one piece of clean metal plate is taken to be hung on the room that re-packs
Interior hanging, spray gun sprays 3~4 times up and down at 20~30cm of metal plate；
(6) metal plate is removed, the dust on surface is blown away, metal plate is placed in 200 DEG C of baking oven and heats 15min, is solidified
After take out, be cooled to room temperature, with calibrator and photometric determination coating thickness and glossiness.
Calibrator selects AR930 coating thickness detector in the present embodiment, and photometer selects WGG60-E Grossmeters, test knot
Fruit see the table below shown in 8.
8 plate face effect of table
| Coating thickness/μm | Glossiness/Gu | Positive intensity of counter assault/kgcm | |
| Repeat 1 | 70~90 | 90 | 50 |
| Repeat 2 | 70~90 | 93 | 51 |
| Repeat 3 | 70~90 | 96 | 52 |
| Repeat 4 | 70~90 | 95 | 50 |
| Repeat 5 | 70~90 | 96 | 50 |
As the result is shown: it is smooth to go out the higher metal sheet surface of levelability by visual observations, the lower plate face of levelability compared with
To be coarse, and glossiness can also reflect that the height of levelability, formula repetition 3 and the levelability for repeating 5 are preferable from side, and
Glossiness is high.In conjunction with the technical indicator of table 2, finally show that formula repeats the polyester resin that 3 prepare and both reached corresponding technology
Index is optimum proportioning for having very high levelability again after powdery paints.
Embodiment described above is only that preferred embodiment of the invention is described, and is not carried out to the scope of the present invention
It limits, without departing from the spirit of the design of the present invention, those of ordinary skill in the art make technical solution of the present invention
Various changes and improvements, should all fall into claims of the present invention determine protection scope in.
Claims (10)
1. a kind of polyester resin of high-leveling energy, which is characterized in that according to parts by weight, including following raw material: dihydric alcohol
32.4~34.9 parts, 70.8~72.2 parts of polyacid, 0.5~0.8 part of trimethylolpropane, 1.6~1.8 parts of antiplastering aid, polyester
0.001~0.01 part of slice, 0.07~0.15 part of antioxidant, 0.3~0.6 part of curing accelerator and surfactant 0.3~0.7
Part.
2. a kind of polyester resin of high-leveling energy according to claim 1, it is characterised in that: according to parts by weight, institute
Stating dihydric alcohol includes 2.0~2.5 parts of neopentyl glycol, 7.9~8.3 parts of diethylene glycol (DEG), 7.5~8.1 parts of ethylene glycol and propylene glycol 15.0
~16.0 parts；The polyacid includes 64.5~65.5 parts and 6.3~6.7 parts of trimellitic anhydride of terephthalic acid (TPA).
3. a kind of polyester resin of high-leveling energy according to claim 1, it is characterised in that: antiplastering aid is mica, height
Ridge soil or silica, the antioxidant are triphenyl phosphite, and the curing accelerator is hexadecyldimethyl benzyl ammonium tertiary amine or ten
Eight alkyl dimethyl tertiary amides, the surfactant are stearic acid.
4. a kind of preparation method of the polyester resin of described in any item high-levelings energy, feature exist according to claim 1~3
In: the following steps are included:
(1) precise above-mentioned raw materials sequentially add neopentyl glycol, diethylene glycol (DEG), ethylene glycol, propylene glycol and three hydroxyls in a kettle
Methylpropane is heated；
(2) after the completion of heating, continue to sequentially add terephthalic acid (TPA), antiplastering aid, Mono-n-butyltin and polyester into reaction kettle
Slice, is heated up and continues to stir；
(3) after observing reaction water outlet, heating rate is reduced, and continue to heat up, is warming up to 165~220 DEG C；
(4) after step (3) reaches assigned temperature, heating rate is improved, reaction is warming up to and is no longer discharged, antioxygen is then added
Agent, and keep temperature-resistant, until being no longer discharged；
(5) reaction kettle top temperature drop stops heating and stirring to after 70~80 DEG C, then starts to vacuumize for the first time, sample, measurement
Reactant acid value and viscosity then stop vacuumizing until the acid value of reactant and viscosity reach provincial standard；
(6) when the temperature in reaction kettle is down to 200~220 DEG C, trimellitic anhydride is added in a kettle, after mixing evenly, opens
Beginning vacuumizes for the second time；
(7) after the completion of vacuumizing for the second time, curing accelerator and surfactant are added into reaction kettle, after mixing evenly, i.e.,
Polyester resin is prepared.
5. a kind of preparation method of the polyester resin of high-leveling energy according to claim 4, it is characterised in that: step
(1) in, the temperature after heating is 55~65 DEG C.
6. a kind of preparation method of the polyester resin of high-leveling energy according to claim 4, it is characterised in that: step
(2) in, heating rate is 9~12 DEG C/min, and mixing speed is 60~150r/min.
7. a kind of preparation method of the polyester resin of high-leveling energy according to claim 4, it is characterised in that: step
(3) in, heating rate is 4~6 DEG C/min.
8. a kind of preparation method of the polyester resin of high-leveling energy according to claim 4, it is characterised in that: step
(4) in, heating rate is 9~12 DEG C/min, and raised temperature is 220~250 DEG C.
9. a kind of preparation method of the polyester resin of high-leveling energy according to claim 4, it is characterised in that: step
(5) in, the reading of the first vacuum meter vacuumized is 0.08~0.10MPa, and the duration is 0.8~1.5h；In step (6),
The reading of the vacuum meter vacuumized for the second time is 0.07~0.09MPa, and the duration is 1~2h.
10. a kind of preparation method of the polyester resin of high-leveling energy according to claim 4, it is characterised in that: step
(6) in, stirring hastens as 60~150r/min, and mixing time is 30~50min；In step (7), stirring hastens as 60~
150r/min, mixing time are 10~20min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655644A (en) * | 2019-10-12 | 2020-01-07 | 黄山市向荣新材料有限公司 | 60/40 polyester resin for low-gloss powder coating and three-kettle combined preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417589A (en) * | 2011-11-23 | 2012-04-18 | 安徽神剑新材料股份有限公司 | Preparation method for low temperature curing polyester resin with high leveling performance |
| CN104231241A (en) * | 2013-06-23 | 2014-12-24 | 扬州市欣宝树脂有限公司 | Preparation method of indoor economic universal polyester resin |
| CN105254863A (en) * | 2015-10-31 | 2016-01-20 | 安徽神剑新材料股份有限公司 | Mixed polyester resin and preparation method and powder coating thereof |
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2018
- 2018-11-20 CN CN201811385802.3A patent/CN109517151A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417589A (en) * | 2011-11-23 | 2012-04-18 | 安徽神剑新材料股份有限公司 | Preparation method for low temperature curing polyester resin with high leveling performance |
| CN104231241A (en) * | 2013-06-23 | 2014-12-24 | 扬州市欣宝树脂有限公司 | Preparation method of indoor economic universal polyester resin |
| CN105254863A (en) * | 2015-10-31 | 2016-01-20 | 安徽神剑新材料股份有限公司 | Mixed polyester resin and preparation method and powder coating thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655644A (en) * | 2019-10-12 | 2020-01-07 | 黄山市向荣新材料有限公司 | 60/40 polyester resin for low-gloss powder coating and three-kettle combined preparation method thereof |
| CN110655644B (en) * | 2019-10-12 | 2021-09-07 | 黄山市向荣新材料有限公司 | 60/40 polyester resin for low-gloss powder coating and three-kettle combined preparation method thereof |
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