CN110527073A - A kind of high temperature resistant and extra-weather-proof powdery paints Silicon-containing Polyester resin - Google Patents
A kind of high temperature resistant and extra-weather-proof powdery paints Silicon-containing Polyester resin Download PDFInfo
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- CN110527073A CN110527073A CN201910838016.2A CN201910838016A CN110527073A CN 110527073 A CN110527073 A CN 110527073A CN 201910838016 A CN201910838016 A CN 201910838016A CN 110527073 A CN110527073 A CN 110527073A
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
- C08G63/6956—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/78—Preparation processes
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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
- C08G63/78—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
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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
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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
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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
- C09D5/18—Fireproof paints including high temperature resistant paints
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Abstract
The object of the present invention is to provide a kind of high temperature resistants and extra-weather-proof powdery paints Silicon-containing Polyester resin, mainly by polyalcohol: 30-46%wt, aromatic polycarboxylic acid 43-58%wt, branching agent: 0.0-2%wt, containing silicon material: 3-12%, acidolysis agent: 0-5%wt, esterification catalyst 0.03-0.15%wt, alcoholysis agent 0-3%, antioxidant 0-0.5%wt, curing accelerator 0-1%wt composition, it is two substitution silicone oil containing silicon material, dichlorosilane, one of disubstituted alkyl silane and disubstituted fragrant base silane, it can be with curing agent TGIC, hydroxyalkyl amide or blocked isocyanate, curing accelerator, pigment, filler, levelling agent and degasser etc. can be prepared into suitable for powdery paints resistant to high temperature, it is prepared into Powdery paints have gloss height in coating after solidification, mechanical performance is excellent, excellent flow leveling and weatherability and heat resistance.
Description
Technical field
The present invention relates to the polyester resin field of powdery paints more particularly to a kind of high temperature resistant and extra-weather-proof powdery paints
With Silicon-containing Polyester resin.
Background technique
Powdery paints obtains in coating metal surfaces widely answer at present as a kind of environmental type powdery paints
With.For powdery paints mainly with epoxy resin, polyester resin, polyurethane and acrylic acid etc. for matrix, main chain is generally carbon-at present
Carbon or carbon-oxide structure, are limited to its molecular structure, and heat resistance is very poor such as 280 DEG C of baking 1h dusting.Outdoor type powder applies
Material will receive natural cause such as solarization in use, drench with rain, aoxidizes, cold and hot variation and the effects of microorganism, causing property
The phenomenon that capable of gradually decreasing, i.e. aging.The ability that powdery paints restrains or delays natural aging is known as resistance to natural aging, referred to as
Weatherability.In powder coating formulation composition, polyester resin is main film forming substance, is to determine weather-proof main of powdery paints
Ingredient.The main chain of conventional polyester resin is carbon-carbon bond at present, is limited to the factor of itself, and weather resistance is relatively low.
Compared with common organic resin, due to the presence of silicon-oxygen key in organic siliconresin, so that its heat resistance is very
The outstanding 3 hours light-protection rates that can such as be on active service at 400 DEG C are greater than 50%.Therefore powdery paints industry is passed through frequently with polyester tree at present
The mode that rouge and organic siliconresin are total to agent realizes the promotion of heat resistance.The advantage of the high bond energy of silicon oxygen bond is again such that its weather resistance
It is obviously improved.However since the compatibility of organic siliconresin and polyester resin is poor, under conditions of direct co-extrusion there is
Be unevenly distributed, all have a significant impact to the adhesive force of the hardness on surface, gloss, mechanical performance, eventually lead to the property of film
It can not be readily accepted by customers.
An object of the present invention is to provide a kind of heat-resisting and weather resistance excellent powdery paints Silicon-containing Polyester resin use
Silicon-containing Polyester resin.
The second object of the present invention is to provide above-mentioned heat-resisting and weather resistance excellent powdery paints Silicon-containing Polyester resin to use
The preparation method of Silicon-containing Polyester resin.
CN101307220A discloses a kind of organosilicon modified polyester electronic packaging material, mainly passes through organosilicon tree
Rouge and alcohol realize that there is silicon oxygen bonds in resin backbone by way of alcoholysis, at present commercialized organic siliconresin in industry
There is a large amount of three to replace with quaternary silicon atom, autohemagglutination is equally easy after alcoholysis, therefore production is caused to be not easy
Control.CN102167807A and CN102167807B discloses a kind of heat-resisting hydroxy resin, and composition principle is equally to use
Organic siliconresin and polyalcohol are realized in resin backbone by way of alcoholysis.CN102838740A,CN103073711A,
CN104987501A、CN104987501B、CN103131142A、CN102757727B、CN103980474A、CN105733417A
The preparation method of polyester resin containing organosilicon is disclosed, is equally the side that alcoholysis is passed through using silicone intermediate and polyalcohol
Formula realizes the synthesis of containing silicone resin to realize the high temperature resistance of matrix.What therefore it equally existed autohemagglutination in synthesis process can
It can and cause production difficult.CN105418905A and CN104829819A discloses the production technology of Silicon-containing Polyester resin, leads to
It crosses and the mode of polyalcohol, polyacid and silicone intermediate whole investment reaction kettle is synthesized into siliceous mechanism resin, equally exist
It is uncontrollable in synthesis process.CN106220838A and CN106883399A also discloses the system of silicone modified polyester resin
Preparation Method is mainly to carry out in liquid or solvent, therefore tempera painting phenomenon will not occur, and is not suitable for powdery paints polyester
Resin art.CN108165169AE and CN108165144A discloses a kind of synthesis of organic siliconresin, mainly by using
Phenyl trichlorosilane is equal to hydrolysis in the mixed solution of water and toluene and prepares intermediate, and the presence that there is water and solvent causes
Production technology, which needs to remove solvent, leads to complex process, and the monomer easily formed after the hydrolysis of the monomers such as trichlorosilane has 3 officials
Energy degree is easy autohemagglutination, and it is more difficult to control in this way.CN109280468A discloses a kind of extra-weather-proof powdery paints with organic-silicon-modified
The preparation method of polyester resin, largely using dimethyl silicone polymer, phenyl silicone etc. in raw material, wherein polyphenylene silicon
There may be monosubstituted, three substitutions and four to replace in oxygen alkane, causes the uncontrollable of reaction.CN109988491A discloses a kind of resistance to
High temperature powder coating Silicon-containing Polyester resin, but it is not related to super-weathering resistance energy.Therefore market in urgent need one kind is in process of production
Autohemagglutination, heat-resisting and excellent weather resistance powdery paints Silicon-containing Polyester resin will not occur, and simple production process is easy to control.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of high temperature resistant and extra-weather-proof powdery paints with Silicon-containing Polyester tree
Rouge, mainly by polyalcohol: 30-46%wt, aromatic polycarboxylic acid 43-58%wt, branching agent: 0.0-2%wt contains silicon material: 3-12%,
Acidolysis agent: 0-5%wt, esterification catalyst 0.03-0.15%wt, alcoholysis agent 0-3%, antioxidant 0-0.5%wt, curing accelerator 0-1%
Wt composition is in two substitution silicone oil, dichlorosilane, disubstituted alkyl silane and disubstituted fragrant base silane containing silicon material
One kind；Its number average molecular weight is in 2500-5000 g/mol, glass transition temperature (Tg) >=56 DEG C, can and curing agent
TGIC, hydroxyalkyl amide or blocked isocyanate, curing accelerator, pigment, filler, levelling agent and degasser etc. can be made
For at powdery paints resistant to high temperature is suitable for, the powdery paints being prepared into has gloss height in coating after solidification, mechanical
Performance is excellent, excellent flow leveling and weatherability and heat resistance.
The object of the present invention is to provide a kind of high temperature resistants and extra-weather-proof powdery paints Silicon-containing Polyester resin, by following heavy
The Material synthesis of amount percentage forms: polyalcohol: 30-46%wt；Aromatic polycarboxylic acid 43-58%wt；Branching agent: 0.0-2%wt；Contain
Silicon material: 3-12%；Acidolysis agent: 0-5%wt；Esterification catalyst 0.03-0.15%wt；Alcoholysis agent 0-3%；Antioxidant 0-0.5%
wt；Curing accelerator 0-1%wt；It is two substitution silicone oil, dichlorosilane, disubstituted alkyl silane and two substitutions containing silicon material
One of fragrant base silane.
Further improvement lies in that: the polyalcohol uses neopentyl glycol (NPG), ethylene glycol (EG), cyclohexanedimethanol
(CHDM) and one of 3-hydroxypivalic acid neopentyl glycol ester (HPHP) or a variety of person's compositions, preferably at least containing NPG and its use
Amount >=70%wt.
Further improvement lies in that: the branching agent is using in trimethylolpropane (TMP) and trimethylolethane (TME)
One or two kinds of mixing.
Further improvement lies in that: the aromatic polycarboxylic acid is using one in phthalic acid (PTA) and M-phthalic acid (IPA)
The mixture of kind or both, preferably at least contains IPA and its dosage is not less than 70%.
Further improvement lies in that: using phosphite ester, (three [2.4- di-tert-butyl-phenyl] phosphite esters resist the antioxidant
Oxygen agent 626) and Hinered phenols antioxidant (four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, antioxidant
1010) mode compounded, the gross mass based on resin, usage amount is 0-0.5%wt.
Further improvement lies in that: the alcoholysis agent uses one of neopentyl glycol or trimethylolpropane or two kinds
Composition preferably includes neopentyl glycol and trimethylolpropane.
Further improvement lies in that: the curing accelerator agent uses tetraethylammonium bromide, 4 bromide, three second of benzyl
Ammonium chloride, in triphenyl ethyl phosphonium bromide phosphine, the one or several kinds of dibutyl tin dilaurate, the gross mass based on resin,
Its usage amount is 0.01-1%wt.
Further improvement lies in that: the catalyst is tin catalyst, preferred Dibutyltin oxide, tributyltin oxide,
Dihydroxy dibutyl tin oxide, stannous oxalate, one of Mono-n-butyltin or several, the gross mass based on resin make
Dosage is 0.03-0.15%wt.
Further improvement lies in that: the acidolysis agent uses M-phthalic acid (IPA), adipic acid (ADA), Isosorbide-5-Nitrae hexamethylene two
The mixing of one or more of formic acid (CHDA) and fumaric acid (FCC), preferably at least containing IPA and its dosage is not less than 50%.
Further improvement lies in that: it is two substitution silicone oil, preferably dimethicone or diethyl containing silicon material
Silicone oil or diphenyl silicone oil.
Further improvement lies in that: it is dichlorosilane, preferably dimethyldichlorosilane or diethyl containing silicon material
Dichlorosilane or diphenyl silane.
Further improvement lies in that: it is disubstituted alkyl silane containing silicon material, preferably dimethylformamide dimethyl oxygroup
Silane, dimethyl diethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyl dimethoxy
One of silane and diphenyl diethoxy silane.
Further improvement lies in that: it is disubstituted fragrant base silane, preferably diphenyl dimethoxy containing silicon material
Base silane or diphenyl diethoxy silane.
Further improvement lies in that: it can be terminal carboxyl polyester resin, hydroxyl telechelic polyester resin and difunctional polyester tree
Rouge.
Further improvement lies in that: when it is terminal carboxyl polyester resin, acid value 25-55 (unit mgKOH/g tree
Rouge)；When it is hydroxyl telechelic polyester resin, hydroxyl value range 25-120 (unit mgKOH/g resin)；When it reunites for difunctionality
When ester resin, acid value 15-55, hydroxyl value range is 15-55 (unit mgKOH/g resin).
Further improvement lies in that: when its be terminal carboxyl polyester resin when, synthetic method are as follows: by the polyalcohol of formula ratio,
Branching agent and containing silicon material investment reaction kettle in heating and melting, 195 DEG C are then being to slowly warm up in nitrogen atmosphere to aneroid
Body production, is then cooled to 140-185 degrees Celsius and by aromatic acid and suitable catalyst while putting into reaction kettle, in nitrogen
It is to slowly warm up to 235-255 DEG C in atmosphere and maintains, sample detection acid value (AV) reaches 5-20 (unit after system clarification
MgKOH/g resin) when secondary acidolysis agent IPA, ADA, CHDA and FCC etc. is added and maintains to carry out acidolysis at 235-250 DEG C of temperature
Sealing end.230-240 DEG C and vacuum (- 0.1MPA) polycondensation are cooled to when the acid value 35-70 of polyester for a period of time, so that polyester
Acid value reaches 25-55.With being cooled to 180-230 DEG C of throwing antioxidant and curing accelerator later and maintain blowing after 5-30min.
Further improvement lies in that: when its be hydroxyl telechelic polyester resin when, synthetic method are as follows: by the polyalcohol of formula ratio,
Branching agent and containing silicon material investment reaction kettle in heating and melting, 195 DEG C are then being to slowly warm up in nitrogen atmosphere to aneroid
Body production, is then cooled to 140-185 degrees Celsius and by aromatic acid and suitable catalyst while putting into reaction kettle, in nitrogen
It is to slowly warm up to 235-255 DEG C in atmosphere and maintains, sample detection acid value (AV) reaches 5-20 (unit after system clarification
MgKOH/g resin) when be cooled to 230-240 DEG C and vacuum (- 0.1MPA) polycondensation for a period of time so that the acid value < 2 of polyester.With
It is cooled to 180-230 DEG C of throwing antioxidant and curing accelerator later and maintains blowing after 5-30min.
Further improvement lies in that: when it is difunctional polyester resin, synthetic method are as follows: by the polynary of formula ratio
Alcohol, branching agent and containing silicon material investment reaction kettle in heating and melting, 195 DEG C are then being to slowly warm up in nitrogen atmosphere to nothing
Liquid production is then cooled to 140-185 DEG C and by aromatic acid and suitable catalyst while putting into reaction kettle, in nitrogen atmosphere
In be to slowly warm up to 235-255 DEG C and maintain, sample detection acid value (AV) reaches 5-20 (unit mgKOH/g after system clarification
Resin) when secondary acidolysis agent IPA, ADA, CHDA and FCC etc. is added and maintain at 235-250 DEG C of temperature carry out acidolysis sealing end.To
230-240 DEG C and vacuum (- 0.1MPA) polycondensation are cooled to when the acid value 30-70 of polyester for a period of time, so that the acid value of polyester reaches
To 25-55.It is then cooled at 210-230 DEG C and throws alcoholysis agent and maintain to be cooled to -0.07MPa at 180-225 DEG C after 20min
It maintains 5min to throw antioxidant and curing accelerator later and maintains blowing after 5-30min.
Further improvement lies in that: its number average molecular weight is in 2500-5000 g/mol, glass transition temperature (Tg) >=56
DEG C, 60 DEG C of more preferred Tg >.
Further improvement lies in that: itself and curing agent: isocyanuric acid three-glycidyl ester (TGIC), hydroxyalkyl amide (HAA)
It is prepared into blocked isocyanate, curing accelerator, pigment, filler, levelling agent and degasser suitable for high temperature resistant and super resistance to
The powdery paints of time.
Beneficial effects of the present invention: the present invention is mainly by polyalcohol: 30-46%wt, aromatic polycarboxylic acid 43-58%wt, branching
Agent: 0.0-2%wt contains silicon material: 3-12%, acidolysis agent: 0-5%wt, esterification catalyst 0.03-0.15%wt, alcoholysis agent 0-3%,
Antioxidant 0-0.5%wt, curing accelerator 0-1%wt composition are two to replace silicone oil, dichlorosilane, disubstituted containing silicon material
One of alkyl silane and disubstituted fragrant base silane；Its number average molecular weight is in 2500-5000 g/mol, glass transition
Temperature (Tg) >=56 DEG C, can with curing agent TGIC, hydroxyalkyl amide or blocked isocyanate, curing accelerator, pigment,
Filler, levelling agent and degasser etc. can be prepared into the powdery paints that is prepared into suitable for powdery paints resistant to high temperature
Coating has gloss height after solidification, and mechanical performance is excellent, excellent flow leveling and weatherability and heat resistance.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention will be described in further detail with reference to the examples below, the embodiment
For explaining only the invention, it is not intended to limit the scope of the present invention..
Preparation method: in 5 liters of glass reaction kettles, the polyalcohol of formula ratio, branching agent and the investment containing silicon material is anti-
Heating and melting in kettle is answered, then 195 DEG C is being to slowly warm up in nitrogen atmosphere to no liquid production, is then being cooled to 140-185
Degree Celsius and aromatic acid and suitable catalyst are put into reaction kettle simultaneously, 235-255 DEG C is to slowly warm up in nitrogen atmosphere
And maintain, it is added when sample detection acid value (AV) reaches 5-15 (unit mgKOH/g resin, similarly hereinafter) after system clarification secondary
Acidolysis agent IPA, ADA, CHDA and FCC etc. simultaneously maintain to carry out acidolysis sealing end at 235-250 DEG C of temperature.Acid value to polyester, which reaches, to be set
230-240 DEG C and vacuum polycondensation are cooled to after definite value for a period of time, so that the acid value of polyester and hydroxyl value reach setting range.With
After be cooled to throw at 210-230 DEG C and alcoholysis agent and maintain 20min；It is finally cooled to -0.07MPa at 180-230 DEG C and maintains 5min
Antioxidant and curing accelerator are thrown later and maintain blowing after 5-30min.Wherein the acid value Con trolling index of different phase is same
It marks in table 1.
1. saturated polyester resin formula of table, control acid value and performance in production process.
The performance of the saturated polyester resin synthesized with the present invention can be embodied the performance of manufactured powdery paints.This is sent out
Saturated polyester resin A ~ F of bright embodiment synthesis and respectively at curing agent (three-glycidyl chlorinated isocyanurates (TGIC)), levelling
Agent, titanium dioxide, barium sulfate, styrax and 701B etc. are mixed after weighing up according to the ratio in table 2, are melted and are distinguished with screw extruder
Powdery paints is made after extrusion, tabletting, broken and sieving.Then by powder paint in the iron after surface granosealing
On plate, after solidifying under suitable condition of cure as a result the various performances of test system are shown in then by the various performances of testing coating
Table 3.
The secondary performance of 2. powdery paints of table summarizes.
| A | A | A | A | A | A | |
| Resin/g | 558 | 558 | 480 | 552 | 540 | 558 |
| TGIC/g | 42 | 42 | 0 | 48 | 60 | 42 |
| T105/g | 0 | 0 | 120 | 0 | 0 | 60 |
| Levelling agent/g | 10 | 10 | 10 | 10 | 10 | 10 |
| Styrax/g | 3 | 3 | 3 | 3 | 3 | 3 |
| 701b/g | 3 | 3 | 3 | 3 | 3 | 3 |
| Barium sulfate/g | 250 | 250 | 250 | 250 | 250 | 250 |
| Titanium dioxide/g | 150 | 150 | 150 | 150 | 150 | 150 |
| Condition of cure | 200/10min | 200/10min | 200/10min | 200/10min | 200/10min | 200/10min |
The performance for the powdery paints that 3. different resins of table are prepared into
Remarks 1: data test standard are as follows: UVB-313nm；Condensation: 40+-3 DEG C, 4h；50+-3 DEG C of illumination, 0.75W/
(m2.nm), 4h；
It can be seen that comparison is not added with the polyester resin of organosilicon from table 3, of the present invention heat-resisting and weather resistance is excellent
Coating of the powdery paints Silicon-containing Polyester resin after being prepared into powder coating solidification has that gloss is high, heat resistance is excellent, machine
The feature that tool performance is excellent, water boiling resistance performance is excellent and weather resistance is excellent.
The present invention can be described with others without prejudice to the concrete form of spirit or essential characteristics of the invention.The present invention
The embodiment above can only all be considered the description to invention rather than limit, it is full to be such as not limited to carboxyl end group of the present invention
With the one-step method preparation method of polyester resin.Using one-step method preparation method, i.e., by polyalcohol, aromatic polycarboxylic acid, aliphatic polyol
The mode that acid, branching agent, acidolysis agent and esterification catalyst carry out esterification condensation reaction after mixing is prepared into saturated resin,
It is available polyester resin of the present invention.Therefore all substantial technologicals according to the present invention are made to the above embodiment
Any trickle amendment, equivalent variations modification, belong in the range of technical solution of the present invention.
Claims (20)
1. a kind of high temperature resistant and extra-weather-proof powdery paints Silicon-containing Polyester resin, it is characterised in that: by following weight percent
Material synthesis form: polyalcohol: 30-46%wt；Aromatic polycarboxylic acid 43-58%wt；Branching agent: 0.0-2%wt；Containing silicon material:
3-12%；Acidolysis agent: 0-5%wt；Esterification catalyst 0.03-0.15%wt；Alcoholysis agent 0-3%；Antioxidant 0-0.5%wt；Solidification promotes
Agent 0-1%wt；It is two substitution silicone oil, dichlorosilane, disubstituted alkyl silane and disubstituted fragrant base silane containing silicon material
One of.
2. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, it is characterised in that:
The polyalcohol uses neopentyl glycol (NPG), ethylene glycol (EG), cyclohexanedimethanol (CHDM) and 3-hydroxypivalic acid neopentyl glycol
One of ester (HPHP) or a variety of person's compositions preferably at least contain NPG and its dosage >=70%wt.
3. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, it is characterised in that:
The branching agent is using one of trimethylolpropane (TMP) and trimethylolethane (TME) or two kinds of mixing.
4. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, it is characterised in that:
The aromatic polycarboxylic acid uses the mixture of one of phthalic acid (PTA) and M-phthalic acid (IPA) or both, preferably
At least contain IPA and its dosage is not less than 70%.
5. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, it is characterised in that:
The antioxidant uses phosphite ester (three [2.4- di-tert-butyl-phenyl] phosphite esters, antioxidant 626) and Hinered phenols antioxygen
The mode of agent (four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, antioxidant 1010) compounding, based on tree
The gross mass of rouge, usage amount are 0-0.5%wt.
6. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, it is characterised in that:
The alcoholysis agent uses one of neopentyl glycol or trimethylolpropane or two kinds of compositions, preferably includes new penta
Two pure and mild trimethylolpropanes.
7. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, it is characterised in that:
The curing accelerator agent uses tetraethylammonium bromide, 4 bromide, benzyltriethylammoinium chloride, triphenyl ethyl phosphonium bromide
In phosphine, the one or several kinds of dibutyl tin dilaurate, the gross mass based on resin, usage amount is 0.01-1%wt.
8. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, it is characterised in that:
The catalyst is tin catalyst, preferably Dibutyltin oxide, tributyltin oxide, dihydroxy dibutyl tin oxide, oxalic acid Asia
Tin, one of Mono-n-butyltin or several, the gross mass based on resin, usage amount are 0.03-0.15%wt.
9. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, it is characterised in that:
The acidolysis agent is using M-phthalic acid (IPA), adipic acid (ADA), Isosorbide-5-Nitrae cyclohexane cyclohexanedimethanodibasic (CHDA) and fumaric acid (FCC)
One or more of mixing, preferably at least containing IPA and its dosage is not less than 50%.
10. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, feature exist
In: it is two substitution silicone oil, preferably dimethicone or diethyl silicone oil or diphenyl silicone oil containing silicon material.
11. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, feature exist
In: it is dichlorosilane, preferably dimethyldichlorosilane or diethyl dichlorosilane or diphenyl silicon containing silicon material
Alkane.
12. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, feature exist
In: it is disubstituted alkyl silane containing silicon material, preferably dimethyldimethoxysil,ne, dimethyl diethoxy silicon
Alkane, diethyldimethoxysilane, diethyldiethoxysilane, dimethoxydiphenylsilane and diphenyl diethoxy silicon
One of alkane.
13. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, feature exist
In: it is disubstituted fragrant base silane, preferably dimethoxydiphenylsilane or diphenyl diethoxy containing silicon material
Base silane.
14. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, feature exist
In: it can be terminal carboxyl polyester resin, hydroxyl telechelic polyester resin and difunctional polyester resin.
15. a kind of high temperature resistant as claimed in claim 14 and extra-weather-proof powdery paints Silicon-containing Polyester resin, feature exist
In: when it is terminal carboxyl polyester resin, acid value 25-55 (unit mgKOH/g resin)；When it is hydroxyl telechelic polyester
When resin, hydroxyl value range 25-120 (unit mgKOH/g resin)；When it is difunctional polyester resin, acid value
For 15-55, hydroxyl value range is 15-55 (unit mgKOH/g resin).
16. a kind of high temperature resistant as claimed in claim 15 and extra-weather-proof powdery paints Silicon-containing Polyester resin, feature exist
In: when it is terminal carboxyl polyester resin, synthetic method are as follows: thrown by the polyalcohol of formula ratio, branching agent and containing silicon material
Enter heating and melting in reaction kettle, is then being to slowly warm up to 195 DEG C in nitrogen atmosphere to no liquid production, is then being cooled to 140-
185 degrees Celsius and aromatic acid and suitable catalyst are put into reaction kettle simultaneously, 235-255 is to slowly warm up in nitrogen atmosphere
DEG C and maintain, after system clarification after sample detection acid value (AV) reach 5-20 (unit mgKOH/g resin) when secondary acidolysis is added
Agent IPA, ADA, CHDA and FCC etc. simultaneously maintain to carry out acidolysis sealing end at 235-250 DEG C of temperature.It is dropped when the acid value 35-70 of polyester
Temperature to 230-240 DEG C and vacuum (- 0.1MPA) polycondensation for a period of time so that the acid value of polyester reaches 25-55.With being cooled to later
180-230 DEG C of throwing antioxidant and curing accelerator simultaneously maintain blowing after 5-30min.
17. a kind of high temperature resistant as claimed in claim 15 and extra-weather-proof powdery paints Silicon-containing Polyester resin, feature exist
In: when it is hydroxyl telechelic polyester resin, synthetic method are as follows: thrown by the polyalcohol of formula ratio, branching agent and containing silicon material
Enter heating and melting in reaction kettle, is then being to slowly warm up to 195 DEG C in nitrogen atmosphere to no liquid production, is then being cooled to 140-
185 degrees Celsius and aromatic acid and suitable catalyst are put into reaction kettle simultaneously, 235-255 is to slowly warm up in nitrogen atmosphere
DEG C and maintain, after system clarification after sample detection acid value (AV) reach 5-20 (unit mgKOH/g resin) when be cooled to 230-
240 DEG C and vacuum (- 0.1MPA) polycondensation for a period of time so that the acid value < 2 of polyester.Resist with being cooled to 180-230 DEG C later and throwing
Oxygen agent and curing accelerator simultaneously maintain blowing after 5-30min.
18. a kind of high temperature resistant as claimed in claim 15 and extra-weather-proof powdery paints Silicon-containing Polyester resin, feature exist
In: when it is difunctional polyester resin, synthetic method are as follows: by the polyalcohol of formula ratio, branching agent and contain silicon material
Heating and melting in reaction kettle is put into, then 195 DEG C is being to slowly warm up in nitrogen atmosphere to no liquid production, is then being cooled to
140-185 DEG C and aromatic acid and suitable catalyst are put into reaction kettle simultaneously, 235-255 is to slowly warm up in nitrogen atmosphere
DEG C and maintain, after system clarification after sample detection acid value (AV) reach 5-20 (unit mgKOH/g resin) when secondary acidolysis is added
Agent IPA, ADA, CHDA and FCC etc. simultaneously maintain to carry out acidolysis sealing end at 235-250 DEG C of temperature.It is dropped when the acid value 30-70 of polyester
Temperature to 230-240 DEG C and vacuum (- 0.1MPA) polycondensation for a period of time so that the acid value of polyester reaches 25-55.Then it is cooled to
Alcoholysis agent is thrown at 210-230 DEG C and 20min is maintained to be cooled to -0.07MPa at 180-225 DEG C later maintains to throw antioxygen after 5min
Agent and curing accelerator simultaneously maintain blowing after 5-30min.
19. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, feature exist
In: its number average molecular weight is in 2500-5000 g/mol, glass transition temperature (Tg) >=56 DEG C, 60 DEG C of more preferred Tg >.
20. a kind of high temperature resistant as described in claim 1 and extra-weather-proof powdery paints Silicon-containing Polyester resin, feature exist
In: itself and curing agent: isocyanuric acid three-glycidyl ester (TGIC), hydroxyalkyl amide (HAA) and blocked isocyanate, solidification
Promotor, pigment, filler, levelling agent and degasser are prepared into suitable for high temperature resistant and extra-weather-proof powdery paints.
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| CN110903471A (en) * | 2019-12-04 | 2020-03-24 | 浙江光华科技股份有限公司 | Organosilicon modified polyester copolymer for powder coating and preparation method thereof |
| CN111234192A (en) * | 2020-03-26 | 2020-06-05 | 山东福司特新材料科技有限公司 | Preparation method of organic silicon modified saturated polyester resin with high weather resistance |
| CN112142965A (en) * | 2020-10-22 | 2020-12-29 | 安徽神剑新材料股份有限公司 | Silicon-containing polyester resin, preparation method thereof and low-surface-tension powder coating |
| CN112625229A (en) * | 2020-12-22 | 2021-04-09 | 黄山市强力化工有限公司 | High-temperature-oxidation-resistant low-viscosity synthetic ester and preparation method and application thereof |
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