CN107266666A - A kind of also to bloom low temperature hydroxyalkyl amide cured powder paint polyester resin and preparation method thereof - Google Patents
A kind of also to bloom low temperature hydroxyalkyl amide cured powder paint polyester resin and preparation method thereof Download PDFInfo
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- CN107266666A CN107266666A CN201710261701.4A CN201710261701A CN107266666A CN 107266666 A CN107266666 A CN 107266666A CN 201710261701 A CN201710261701 A CN 201710261701A CN 107266666 A CN107266666 A CN 107266666A
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- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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- 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
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
Abstract
The present invention relates to a kind of polyester resin for powder coating and preparation method thereof, there is provided a kind of also to bloom low temperature hydroxyalkyl amide cured powder paint saturation terminal carboxyl polyester resin and preparation method thereof, above-mentioned polyester resin is formed by the main component of following mass percent through melt polymerization：Polyol component A, polyacid component B, hydrogenated dimer acids component C, esterification catalyst component D, alcoholysis agent component E and antioxidant component F；Follow the steps below：Plus component A, then component B, component C and component D are put into, gradually heat up while stirring；Fusion esterification condensation reaction；Component E is added, acidolysis reaction is carried out；Depressor response；Add component F, stirring reaction；Cooling discharge, cooling crush.Low temperature hydroxyalkyl amide cured powder paint film provided by the present invention has good low-temperature resistance solidification frosting, good pliability and excellent levelability, and paint film has excellent decoration performance and barrier propterty.
Description
Technical field
The present invention relates to a kind of polyester resin for powder coating and preparation method thereof, and in particular to a kind of also to bloom low temperature hydroxyl
Alkylamide solidification powder coating polyester resin and preparation method thereof.
Background technology
The natural calamity triggered with global warming increasingly takes place frequently, and the environmental consciousness of people and requirement more increase
By force.Powdery paints " four E " popular in the world due to complying fully with (economic, environmental protection, efficient, performance are remarkable) principle, and it is public
It is green environmental friendly coatingses to recognize, and is one of four general orientation of coatings industry development and research.However, the levelling of powdery paints and solidification temperature
Degree is higher, and the film forming solidification temperature of ordinary powder coating is between 180~220 DEG C, and baking time is about 10~30min.Such as
This high temperature, it is prolonged in the case of, only metal material can just be born, and this aspect limits the application field of powdery paints,
The development of powdery paints is limited, on the other hand, high temperature and the condition of cure of long period are necessarily required to the substantial amounts of energy and disappeared
Consumption, this makes powdery paints not save.
Energy-conserving and environment-protective are the themes of world today's development, and because the performances such as environmental protection are protruded, powdery paints will gradually replace molten
Agent coating, main development direction and development trend as coatings industry reduce the solidification temperature of powdery paints, make powdery paints
It is achieving environmental protection and energy saving, it is the inexorable trend of powdery paints future development, is also the object of current scientific research emphasis tackling key problem.
Compared with conventional high-temperature cured powder paint, low temperature cured powder coating at least has two big advantages.First, due to
The film-forming temperature of low temperature cured powder coating is lower, can save the substantial amounts of energy.Show according to the study, the film-forming of coating
Temperature often declines 10 DEG C, can about save 10% energy.Second, because the solidification temperature of low temperature cured powder coating is low,
Its application field is just greatly expanded, it can be widely used in medium density fibre board (MDF) (MDF), timber, paper, plastics, electronics member
On the heatsensitive substrates such as part (resistance, electric capacity, magnet coil etc.).
To make low temperature cured powder coating film that there is good levelling and crosslinking curing performance, it is desirable to main body tree used
Fat has higher glass transition temperature (Tg), relatively low melt viscosity and higher solidification crosslinking active.At present on low
Warm cured powder paint largely reports that research and application of the industry to low temperature cured powder coating are main in pure epoxy resin
Curing system and polyester-epoxy hybrid architecture, at home foreign countries have some applications, also have many reports, such as Chinese patent Shen
Please CN101735432A report it is a kind of 160 DEG C/15min solidify acid number be 67~74mgKOH/g, viscosity be 1200~
2500mPas (200 DEG C) mixed powder coating low-temperature setting carboxyl saturated polyester resin and preparation method thereof.The U.S.
Patent US5262510, which is reported a kind of, to be 52mgKOH/g in the acid number of 160 DEG C of solidifications, and viscosity is 1500~2000mPas
The low-temperature cured terminal carboxyl polyester resin of (200 DEG C), mainly using neopentyl glycol, diethylene glycol (DEG), BDO, terephthaldehyde
Acid, Isosorbide-5-Nitrae-cyclohexane dimethyl carbinol, pyromellitic dianhydride etc. are synthesized.United States Patent (USP) US5637654 reports one kind can be solid at 140 DEG C
The low temperature curing polyester resin of change, mainly using neopentyl glycol, Isosorbide-5-Nitrae-cyclohexane dimethyl carbinol, terephthalic acid (TPA), M-phthalic acid,
Fumaric acid, maleic anhydride etc. are synthesized.Current low temperature cured powder coating and resin are primarily present following several respects problem：1st, matrix
The glass transition temperature of resin is too low, causes resin and the bin stability that coating is made poor, easily caking.2nd, matrix resin
Melt viscosity it is big, cause film melt viscosity big, film levelability is poor, and apparent dicoration is not good.3rd, between matrix and curing agent
Solidify crosslinking active too high or too low, during solidification crosslinking, reactivity is too high, and film levelling is poor；Reactivity is too low, during solidification
Between it is long, solidification crosslinking degree is low, influence coating machinery performance.4th, the easy frosting in surface, shadow when low temperature cured powder coating solidifies
Loud film coated surface performance and performance, are that this some use introduces unsaturated carboxylic acid or acid anhydrides, such as maleic anhydride and richness
Horse acid, but thus can cause the unstable of resin property and property.
Low-temperature setting energy-conservation powdery paints refers to powdery paints of the solidification temperature in 150~160 DEG C of solidifications, relative to common
Type powder coating (solidification temperature is at 180~220 DEG C) more energy efficient environmental protection with relatively low solidification temperature.
The content of the invention
The present invention first purpose be for existing low temperature cured powder coating exist drawbacks described above there is provided one kind
Also to bloom low temperature cured powder coating polyester resin, makes its obtained polyester resin be applied to polyester-HAA (hydroxyalkyl amide)
Cured powder paint, obtained powdery paints solidifies obtained film under the conditions of 150-160 DEG C/12-20min to be had well
Flow leveling and good chalking resistance energy, while can effectively improve cured paint film shock resistance and bending etc. mechanicalness
Can, the paint solidification paint film has excellent decoration performance and barrier propterty.The powdery paints can be applied to various weather-proof dresses
Decorations property field.
Second object of the present invention is to provide the preparation method of above-mentioned polyester resin.
First purpose of the present invention is achieved through the following technical solutions：
A kind of also to bloom low temperature hydroxyalkyl amide cured powder paint saturation terminal carboxyl polyester resin, acid number 34.0~
40.0mgKOH/g, hydroxyl value is less than 5.0mgKOH/g, melts 2000~4000mPas/200 DEG C of rotary viscosity, glass transition
Temperature Tg is 55.0~65.0 DEG C, and number-average molecular weight is 2000~5000, and weight average molecular weight is 5000~10000, and it is by following
The main component of mass percent is formed through melt polymerization：
Further, the hydrogenated dimer acids component C be hydrogenation dimerization soy(a)-bean oil fatty acid, hydrogenation dimerization ready denier oil acid,
Hydrogenate the mixture of one or both of dimerization rapeseed oil fatty acid, hydrogenation dimerization cotton oil aliphatic acid any of the above mass ratio.
Further, the polyol component A be neopentyl glycol, 2- methyl isophthalic acids, ammediol, 2- butyl -2- ethyl -1,
The mixture of one or both of ammediol and 1,4-CHDM, trimethylolpropane any of the above mass ratio.
Further, the polyacid component B is adipic acid, succinic acid, terephthalic acid (TPA), M-phthalic acid, Isosorbide-5-Nitrae-hexamethylene
The mixture of one or both of alkane dioctyl phthalate and trimellitic anhydride any of the above mass ratio.
Further, the esterification catalyst component D is Mono-n-butyltin, Dibutyltin oxide, dihydroxy butyl chlorination
One or both of tin, stannous oxalate any of the above than mixture.
Further, the acidolysis agent component E is that one or both of adipic acid, M-phthalic acid, trimellitic anhydride are appointed
The mixture of meaning part by weight.
Further, the antioxidant component F be AT-215, AT-215 be by antioxidant 1010 (four (3,5- di-t-butyls-
4- hydroxyls) benzenpropanoic acid pentaerythritol ester) and irgasfos 168 (three (2,4- tert-butyl-phenyl) phosphite esters) with quality 1：2 ratio
Example is mixed.
Second object of the present invention is realized by following technical scheme：
A kind of also to bloom low temperature hydroxyalkyl amide cured powder paint saturation terminal carboxyl polyester resin preparation method, by with
Lower step is carried out：
(1) in the reactor 3000ml of heater, agitator and distillation column is had, the polyalcohol group of formula ratio is added
Divide A, normal pressure is warming up to 110-130 DEG C；The polyacid component B, hydrogenated dimer acids component C and esterification catalyst of formula ratio are put into again
Component D, gradually heats up while stirring；
(2) temperature of charge rises to 165-175 DEG C, and esterification starts, and esterification water starts to generate and steam by distillation column,
Control distillation top end vapor (steam) temperature is at 99 DEG C ± 2 DEG C；Gradually heat up, esterification water is distillated in esterification, treat that material temperature rises to
At 248 DEG C ± 2 DEG C, insulation reaction is carried out；When distillation column top gas temperature is decreased to less than 70 DEG C, while esterification water water yield reaches reason
By water yield 95% and more than, insulation terminates；
(3) acidolysis agent component E, the insulation reaction 100-120min under the conditions of 244 DEG C -246 DEG C are added；
(4) after insulation reaction terminates ,-0.097-- 0.098MPa is progressively evacuated to, in 240 DEG C-242 DEG C of vacuum bar
Continue to react 90-120min under part；
(5) after Depressor response terminates, 200 DEG C are gradually cooled to, antioxidant component F, stirring reaction 15-30min is added,
Discharging；After cooling crush, a kind of colourless or light yellow clear granular substance is obtained.
Further, above synthesis process is carried out all in nitrogen protective atmosphere encloses.
The saturated carboxyl polyester resin synthesized by preparation method provided by the present invention, with hydroxyalkanamide (curing agent
T105, Ningbo South Sea chemical company product, hydroxyl equivalent：80-84g/eq, melting range：120-130 DEG C), pigment, filler and each
Auxiliary addition agent mixing is planted, is extruded through melting mixing, low-temperature setting polyester-hydroxyl alkane is made in cooling tabletting, broken, grind into powder
Base acid amides powdery paints.
Hydrogenated dimer acids, refer to that the unrighted acid using the aliphatic acid in natural oil as the straight chain of key component is being urged
Under agent effect, by the dimer of itself polycondensation such as Diel-Alder addition reactions, then hydrogenated reaction, make in dimer not
Saturated bond be hydrogenated with saturation and be made, hydrogenated dimer acids are the dimer (fatty acid) yls of saturation, with lighter color and it is thermally-stabilised good the features such as.
Hydrogenated dimer acids are the mixtures of a variety of isomers, chain isomer, the monocyclic isomery of monocyclic long side chain for having acyclic long side chain
Bicyclic isomers of body and bicyclic long side chain etc. is constituted.Using different aliphatic acid (soy(a)-bean oil fatty acid, cotton oil aliphatic acid, tall oil
Aliphatic acid, rapeseed oil fatty acid etc.) hydrogenated dimer acids obtained by polymerization hydrogenation (hydrogenation dimerization soy(a)-bean oil fatty acid, hydrogenation dimerization cotton
Fatty acid oil, hydrogenation dimerization ready denier oil acid, hydrogenation dimerization rapeseed oil fatty acid etc.) contain acyclic, monocyclic, bicyclic isomers
Proportion have certain difference.
The beneficial effects of the invention are as follows：(1) polyester resin prepared by this method is due to introducing with long-chain side base
Hydrogenated dimer acids and change polyester resin molecule segment structure, upset the regularity of polyester resin molecule segment, reduced
The crystallinity of polyester resin molecule, so as to improve the low-temperature resistance solidification frosting of polyester-hydroxyalkylamides powdery paints.(2)
Because the chain that the hydrogenated dimer acids of long-chain side base introduce the acyclic long side chain contained in polyester resin main chain, hydrogenated dimer acids is different
It is flexible that the bicyclic isomer structure of structure body, the monocyclic isomers of monocyclic long side chain and bicyclic long side chain can significantly increase strand
Property, make film that there is higher pliability.(3) introducing of hydrogenated dimer acids can significantly reduce the melt viscosity of polyester resin, make
Polyester resin has good moisture dispersibility to color stuffing, so that film has excellent levelability.Therefore it is made from it
Polyester-hydroxyalkylamides powdery paints film there is excellent low-temperature resistance solidification frosting, good pliability and excellent
Levelability, paint film has excellent decoration performance and barrier propterty.The powdery paints can be applied to various weather-proof ornamental necks
Domain.
Brief description of the drawings
Fig. 1 is the chain hydrogenated dimer acids isomer structure formula of the acyclic long side chain of the present invention；
Fig. 2 is the monocyclic hydrogenated dimer acids isomer structure formula of the monocyclic long side chain of the present invention；
Fig. 3 is the bicyclic hydrogenated dimer acids isomer structure formula of the bicyclic long side chain of the present invention.
Embodiment
The invention will be further described with reference to embodiments, but following embodiments are only intended to in the present invention
Appearance is illustrated, rather than limitation, therefore any change within the meaning and scope equivalent to the claims of the present invention,
All it is considered as being included within the scope of the claims.
The invention will be further described with reference to embodiments, and table 1 is also to bloom low temperature cured powder coating polyester
The embodiment of resin, wherein example A refer to comparative formula substantially for polyester resin, as the comparative example of the present invention, implement
Example B~E is embodiments of the invention.
Embodiment A
Building-up process, which is embodied, is：(1) in the reactor 3000ml of heater, agitator and distillation column is had,
The mass fraction for adding formula ratio is 750 parts of polyol component A (wherein 675 parts neopentyl glycols, 75 parts of 2- methyl isophthalic acids, 3- third
Glycol), normal pressure is warming up to 110-130 DEG C；The mass fraction for putting into formula ratio again is 1155 parts of polyacid component B (wherein 990
Part terephthalic acid (TPA), 90 parts of M-phthalic acids, 75 parts of adipic acids) and mass fraction for 2.5 parts of esterification catalyst component D (wherein
2.5 parts are Mono-n-butyltin), gradually heat up while stirring.(2) temperature of charge rises to 165-175 DEG C, and esterification starts,
Esterification water starts to generate and steam by distillation column, and control distillation top end vapor (steam) temperature is at 99 DEG C ± 2 DEG C；Gradually heat up, side
Esterification side esterification water is distillated, when material temperature rises to 248 DEG C ± 2 DEG C, carries out insulation reaction；When distillation column top gas temperature drop is to small
When 70 DEG C, at the same esterification water water yield reach theoretical water yield 95% and more than, insulation terminates.(3) mass fraction is added
For 120 parts of acidolysis agent component E (wherein 95 parts are M-phthalic acid, and 25 parts are trimellitic anhydride), in 244 DEG C of -246 DEG C of conditions
Lower insulation reaction 100-120min.(4) after insulation reaction terminates, be progressively evacuated to-0.097-- 0.098MPa, 240 DEG C-
Continue to react 90-120min under 242 DEG C of vacuum condition.(5) after Depressor response terminates, 200 DEG C are gradually cooled to, quality is added
Number is 7.5 parts of antioxidant component F (wherein 7.5 parts AT-215), stirring reaction 15-30min, discharging；After cooling crush, obtain
To a kind of colourless or light yellow clear granular substance.(6) above synthesis process should all be carried out in nitrogen protective atmosphere encloses.System
The physical and chemical index of the polyester resin obtained is shown in Table the embodiment A shown in 1.
Embodiment B
Building-up process, which is embodied, is：(1) in the reactor 3000ml of heater, agitator and distillation column is had,
The mass fraction for adding formula ratio is 725 parts of polyol component A (wherein 590 parts neopentyl glycols, 60 parts of 2- methyl isophthalic acids, 3- third
Glycol, 75 parts of 1,4-CHDMs), normal pressure is warming up to 110-130 DEG C；The mass fraction for putting into formula ratio again is 1080
Part polyacid component B (wherein 990 parts are terephthalic acid (TPA), 90 parts of M-phthalic acids), the hydrogenation dimerization that mass fraction is 60 parts
Acid constituents C (wherein 60 parts hydrogenation dimerization soy(a)-bean oil fatty acid) and mass fraction are 2.5 parts of esterification catalyst component D (wherein 2.5
Part is Mono-n-butyltin), gradually heat up while stirring.(2) temperature of charge rises to 165-175 DEG C, and esterification starts, esterification
Water starts to generate and steam by distillation column, and control distillation top end vapor (steam) temperature is at 99 DEG C ± 2 DEG C；Gradually heat up, side esterification
Border ring esterification water is distillated, when material temperature rises to 248 DEG C ± 2 DEG C, carries out insulation reaction；When distillation column top gas temperature is decreased to less than 70
DEG C when, while esterification water water yield reach theoretical water yield 95% and more than, insulation terminates.(3) it is 120 to add mass fraction
Part acidolysis agent component E (wherein 95 parts are M-phthalic acid, and 25 parts are trimellitic anhydride), is incubated under the conditions of 244 DEG C -246 DEG C
React 100-120min.(4) after insulation reaction terminates ,-0.097-- 0.098MPa is progressively evacuated to, at 240 DEG C-242 DEG C
Vacuum condition under continue react 90-120min.(5) after Depressor response terminates, 200 DEG C are gradually cooled to, mass fraction is added
For 7.5 parts of antioxidant component F (wherein 7.5 parts are AT-215), stirring reaction 15-30min, discharging；After cooling crush, obtain
A kind of colourless or light yellow clear granular substance.(6) above synthesis process should all be carried out in nitrogen protective atmosphere encloses.It is made
The physical and chemical index of polyester resin be shown in Table embodiment B shown in 1.
Embodiment C
Building-up process, which is embodied, is：(1) in the reactor 3000ml of heater, agitator and distillation column is had,
Add the mass fraction of formula ratio for 746 parts polyol component A (wherein 656 parts neopentyl glycols, 15 parts of 2- butyl -2- ethyls -
1,3-PD, 75 parts of 1,4-CHDMs), normal pressure is warming up to 110-130 DEG C；The mass fraction for putting into formula ratio again is
1080 parts of polyacid component B (wherein 960 parts are terephthalic acid (TPA), 120 parts of M-phthalic acids), hydrogen that mass fraction is 30 parts
It is 3 parts of esterification catalyst component D (its to change dimerization acid constituents C (the wherein 30 parts appropriate youngster's fatty acid oils of hydrogenation dimerization) and mass fraction
In 3 parts be stannous oxalate), gradually heat up while stirring.(2) temperature of charge rises to 165-175 DEG C, and esterification starts, esterification
Water starts to generate and steam by distillation column, and control distillation top end vapor (steam) temperature is at 99 DEG C ± 2 DEG C；Gradually heat up, side esterification
Border ring esterification water is distillated, when material temperature rises to 248 DEG C ± 2 DEG C, carries out insulation reaction；When distillation column top gas temperature is decreased to less than 70
DEG C when, while esterification water water yield reach theoretical water yield 95% and more than, insulation terminates.(3) adding mass fraction is
107.5 parts of acidolysis agent component E (wherein 82.5 parts are adipic acid, and 25 parts are trimellitic anhydride), protect under the conditions of 244 DEG C -246 DEG C
Temperature reaction 100-120min.(4) after insulation reaction terminates ,-0.097-- 0.098 MPa is progressively evacuated to, at 240 DEG C-242
DEG C vacuum condition under continue react 90-120min.(5) after Depressor response terminates, 200 DEG C are gradually cooled to, mass parts are added
Number is 7.5 parts of antioxidant component F (wherein 7.5 parts are AT-215), stirring reaction 15-30min, discharging；After cooling crush,
Obtain a kind of colourless or light yellow clear granular substance.(6) above synthesis process should all be carried out in nitrogen protective atmosphere encloses.
The physical and chemical index of obtained polyester resin is shown in Table the embodiment C shown in 1.
Embodiment D
Building-up process, which is embodied, is：(1) in the reactor 3000ml of heater, agitator and distillation column is had,
The mass fraction for adding formula ratio is 719 parts of polyol component A (wherein 614 parts neopentyl glycols, 75 parts of 2- methyl isophthalic acids, 3- third
Glycol, 30 parts of 2- butyl -2- ethyls -1,3-PDs), normal pressure is warming up to 110-130 DEG C；The mass fraction of formula ratio is put into again
It it is 60 parts for 1080 parts of polyacid component B (wherein 930 parts are terephthalic acid (TPA), 150 parts of M-phthalic acids), mass fraction
Hydrogenated dimer acids component C (wherein 60 parts hydrogenation dimerization rapeseed oil fatty acid) and mass fraction are 3 parts of esterification catalyst component D
(wherein 3 parts are stannous oxalate), gradually heats up while stirring.(2) temperature of charge rises to 165-175 DEG C, and esterification starts, ester
Change water to start to generate and steam by distillation column, control distillation top end vapor (steam) temperature is at 99 DEG C ± 2 DEG C；Gradually heat up, side ester
Change border ring esterification water to distillate, when material temperature rises to 248 DEG C ± 2 DEG C, carry out insulation reaction；When distillation column top gas temperature is decreased to less than
At 70 DEG C, at the same esterification water water yield reach theoretical water yield 95% and more than, insulation terminates.(3) adding mass fraction is
120 parts of acidolysis agent component E (wherein 95 parts are M-phthalic acid, and 25 parts are trimellitic anhydride), protect under the conditions of 244 DEG C -246 DEG C
Temperature reaction 100-120min.(4) after insulation reaction terminates ,-0.097-- 0.098 MPa is progressively evacuated to, at 240 DEG C-242
DEG C vacuum condition under continue react 90-120min.(5) after Depressor response terminates, 200 DEG C are gradually cooled to, mass parts are added
Number is 7.5 parts of antioxidant component F (wherein 7.5 parts are AT-215), stirring reaction 15-30min, discharging；After cooling crush,
Obtain a kind of colourless or light yellow clear granular substance.(6) above synthesis process should all be carried out in nitrogen protective atmosphere encloses.
The physical and chemical index of obtained polyester resin is shown in Table the embodiment D shown in 1.
Embodiment E
Building-up process, which is embodied, is：(1) in the reactor 3000ml of heater, agitator and distillation column is had,
Add the mass fraction of formula ratio for 759 parts polyol component A (wherein 654 parts neopentyl glycols, 45 parts of 2- butyl -2- ethyls -
1,3-PD, 60 parts of 1,4-CHDMs), normal pressure is warming up to 110-130 DEG C；The mass fraction for putting into formula ratio again is
1080 parts of polyacid component B (wherein 990 parts terephthalic acid (TPA)s, 90 parts of M-phthalic acids), hydrogenations two that mass fraction is 75 parts
Polyacids component C (wherein 45 parts hydrogenation dimerization soy(a)-bean oil fatty acids, 30 parts of hydrogenation dimerization appropriate youngster's fatty acid oils) and mass fraction are 3
The esterification catalyst component D (wherein 1.5 parts Mono-n-butyltins, 1.5 parts of stannous oxalates) of part, gradually heats up while stirring.(2)
Temperature of charge rises to 165-175 DEG C, and esterification starts, and esterification water starts to generate and steam by distillation column, controls distillation column
Top vapor (steam) temperature is at 99 DEG C ± 2 DEG C；Gradually heat up, esterification water is distillated in esterification, treat that material temperature rises to 248 DEG C ± 2 DEG C
When, carry out insulation reaction；When distillation column top gas temperature is decreased to less than 70 DEG C, while esterification water water yield reaches theoretical water yield
95% and more than, insulation terminates.(3) it is that (wherein 95 parts are M-phthalic acid, 25 to 120 parts of acidolysis agent component E to add mass fraction
Part is trimellitic anhydride), the insulation reaction 100-120min under the conditions of 244 DEG C -246 DEG C.(4) after insulation reaction terminates, progressively
- 0.097-- 0.098MPa is evacuated to, continues to react 90-120min under 240 DEG C-242 DEG C of vacuum condition.(5) depressurize
After reaction terminates, 200 DEG C are gradually cooled to, adding the antioxidant component F that mass fraction is 7.5 parts, (wherein 7.5 parts are AT-
215), stirring reaction 15-30min, discharging；After cooling crush, a kind of colourless or light yellow clear granular substance is obtained.(6) with
Upper synthesis process should all be carried out in nitrogen protective atmosphere encloses.The physical and chemical index of obtained polyester resin is shown in Table shown in 1
Embodiment E.
The raw material proportioning and physical and chemical index of the polyester resin of table 1
Note：The acid number of resin tests the standard detection according to GB/T 6743-2008
The melting rotary viscosity of resin tests the standard detection according to GB/T 9751.1-2008
The glass transition temperature of resin determines the standard detection according to GB/T 19466.2-2004
The softening point measurement of resin according to GB/T27808-2011 standard detection
The performance of polyester resin synthesized by the present invention needs to apply by the way that low-temperature setting polyester-hydroxyalkylamides powder is made
The performance of material embodies, the saturation terminal carboxyl polyester resin that will be synthesized by preparation method provided by the present invention, with hydroxyl alkane acid amides
(curing agent T105, Ningbo South Sea chemical company product, hydroxyl equivalent：80-84g/eq, melting range：120-130 DEG C), pigment, fill out
Material and the mixing of various auxiliary addition agents, are extruded through melting mixing, and low-temperature setting is made in cooling tabletting, broken, grind into powder
Polyester-hydroxyalkylamides powdery paints.
The low-temperature setting polyester-hydroxyalkylamides powder coating formulation of table 2 and film performance
Note：
1. curing agent T105：Hydroxyalkyl amide (Ningbo South Sea chemical company), equivalent：82g/mol
2.GLP588：The special levelling agent of powdery paints (the polyacrylate stream of Ningbo South-sea Chemical Co., Ltd.'s production
Flat agent)
3.BLC701701：Powdery paints with optical brightener (ripple South Sea Chemical Co., Ltd. produce acrylate copolymer be
The powdery paints additive of main body)
4th, titanium dioxide r902：Powdery paints is with pigment (du pont company)
5th, blanc fixe W5HB：Powdery paints is with filler (Shaanxi enrichment company)
6th, styrax：Powdery paints degasser
7. Resin A, resin B ... resin E in table, are embodiment A, embodiment B ... the embodiments E in table 1 successively
Obtained resin.Example is to add transparent powder paint made from auxiliary material using above-mentioned resin.
8. chalking resistance method of testing：
1. heat up method of testing：The model sprayed is put into room temperature baking box, by baking box heating by 10 DEG C/min heatings
Speed keeps 15min to baking temperature in baking temperature, takes out model, and gloss is tested after maintenance and is wiped with red cloth, is surveyed
60 ° of gloss of examination and observation film frosting situation
2. constant temperature method of testing：The good model of baking-curing is placed in 150 DEG C of baking boxes, constant temperature keeps 24h, taken out
Model, is wiped after maintenance with red cloth, observes film frosting situation
9. powdery paints film performance testing standard
The thickness of film tests the standard detection according to GB/T 13452.2-2008
The measurement of luster of film according to GB/T1743-1979 standard detection
The solvent resistant rubbing test of film according to GB 23989-2009 standard detection
The adhesive force of film tests the standard detection according to GB/T 9286-1998
The impact property of film tests the standard detection according to GB-T1732-1993
It can illustrate that low-temperature setting polyester-hydroxyalkyl is made in the polyester resin synthesized by the present invention by above-described embodiment
There is acid amides powdery paints, the powdery paints that its coating relative contrast example A normal polyester resin is made excellent low-temperature resistance to consolidate
Change frosting, good pliability and excellent levelability, paint film has excellent decoration performance and barrier propterty.The powder is applied
Material can be applied to various weather-proof ornamental fields.
Claims (9)
1. a kind of also to bloom low temperature hydroxyalkyl amide cured powder paint saturation terminal carboxyl polyester resin, it is characterised in that：Acid
34.0~40.0mgKOH/g of value, hydroxyl value is less than 5.0mgKOH/g, melts 2000~4000mPas/200 DEG C of rotary viscosity, glass
Glass transition temperature Tg is 55.0~65.0 DEG C, and number-average molecular weight is 2000~5000, and weight average molecular weight is 5000~10000,
It is formed by the main component of following mass percent through melt polymerization：
2. also to bloom low temperature hydroxyalkyl amide cured powder paint according to claim 1 is with saturation terminal carboxyl polyester tree
Fat, it is characterised in that：The hydrogenated dimer acids component C is hydrogenation dimerization soy(a)-bean oil fatty acid, hydrogenation dimerization ready denier oil acid, hydrogen
Change the mixture of one or both of dimerization rapeseed oil fatty acid, hydrogenation dimerization cotton oil aliphatic acid any of the above mass ratio.
3. also to bloom low temperature hydroxyalkyl amide cured powder paint according to claim 1 is with saturation terminal carboxyl polyester tree
Fat, it is characterised in that：The polyol component A is neopentyl glycol, 2- methyl isophthalic acids, ammediol, 2- butyl -2- ethyls -1,3-
The mixture of one or both of propane diols and 1,4-CHDM, trimethylolpropane any of the above mass ratio.
4. also to bloom low temperature hydroxyalkyl amide cured powder paint according to claim 1 is with saturation terminal carboxyl polyester tree
Fat, it is characterised in that：The polyacid component B is adipic acid, succinic acid, terephthalic acid (TPA), M-phthalic acid, Isosorbide-5-Nitrae-hexamethylene
The mixture of one or both of dioctyl phthalate and trimellitic anhydride any of the above mass ratio.
5. also to bloom low temperature hydroxyalkyl amide cured powder paint according to claim 1 is with saturation terminal carboxyl polyester tree
Fat, it is characterised in that：The esterification catalyst component D is Mono-n-butyltin, Dibutyltin oxide, dihydroxy butyl chlorination
One or both of tin, stannous oxalate any of the above than mixture.
6. also to bloom low temperature hydroxyalkyl amide cured powder paint according to claim 1 is with saturation terminal carboxyl polyester tree
Fat, it is characterised in that：The acidolysis agent component E is that one or both of adipic acid, M-phthalic acid, trimellitic anhydride are any
The mixture of part by weight.
7. also to bloom low temperature hydroxyalkyl amide cured powder paint according to claim 1 is with saturation terminal carboxyl polyester tree
Fat, it is characterised in that：The antioxidant component F is AT-215, and AT-215 is by antioxidant 1010 (four (3,5- di-t-butyl -4-
Hydroxyl) benzenpropanoic acid pentaerythritol ester) and irgasfos 168 (three (2,4- tert-butyl-phenyl) phosphite esters) with quality 1：2 ratio
Mix.
8. a kind of also to bloom low temperature hydroxyalkyl amide cured powder paint as described in any one of claim 1~7 uses saturation end
The preparation method of carboxyl polyester resin, is carried out according to the following steps：
(1) in the reactor 3000ml of heater, agitator and distillation column is had, the polyol component A of formula ratio is added,
Normal pressure is warming up to 110-130 DEG C；The polyacid component B, hydrogenated dimer acids component C and esterification catalyst component of formula ratio are put into again
D, gradually heats up while stirring；
(2) temperature of charge rises to 165-175 DEG C, and esterification starts, and esterification water starts to generate and steam by distillation column, controls
Top end vapor (steam) temperature is distilled at 99 DEG C ± 2 DEG C；Gradually heat up, esterification water is distillated in esterification, treat that material temperature rises to 248 DEG C
At ± 2 DEG C, insulation reaction is carried out；When distillation column top gas temperature is decreased to less than 70 DEG C, while esterification water water yield reaches that theory goes out
Water 95% and more than, insulation terminates；
(3) acidolysis agent component E, the insulation reaction 100-120min under the conditions of 244 DEG C -246 DEG C are added；
(4) after insulation reaction terminates ,-0.097-- 0.098MPa is progressively evacuated to, under 240 DEG C-242 DEG C of vacuum condition
Continue to react 90-120min；
(5) after Depressor response terminates, 200 DEG C are gradually cooled to, antioxidant component F, stirring reaction 15-30min, discharging is added；
After cooling crush, a kind of colourless or light yellow clear granular substance is obtained.
9. also to bloom low temperature hydroxyalkyl amide cured powder paint saturation terminal carboxyl polyester resin according to claim 8
Preparation method, it is characterised in that：Above synthesis process is carried out all in nitrogen protective atmosphere encloses.
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Application publication date: 20171020 |