CN106565965A - Hyperbranched hydroxyl polyester resin, and preparation method and application of hyperbranched hydroxyl polyester resin - Google Patents
Hyperbranched hydroxyl polyester resin, and preparation method and application of hyperbranched hydroxyl polyester resin Download PDFInfo
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- CN106565965A CN106565965A CN201610975961.3A CN201610975961A CN106565965A CN 106565965 A CN106565965 A CN 106565965A CN 201610975961 A CN201610975961 A CN 201610975961A CN 106565965 A CN106565965 A CN 106565965A
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive 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
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Abstract
The invention discloses hyperbranched hydroxyl polyester resin, and a preparation method and an application of the hyperbranched hydroxyl polyester resin.The preparation method of the hyperbranched hydroxyl polyester resin comprises the following steps: 1) according to molar fraction, 1 part of dicarboxylic anhydride and 2-4 parts of polyhydric alcohol are mixed in a reaction kettle, paratoluenesulfonic acid and an organic solvent are added for reaction at 105-125 degrees under nitrogen protection, then 4-10 parts of phthalic anhydride are added, and reaction for 2-3h is carried out; and 2) according to molar fraction, 6-10 parts of epoxy compounds are added to a matrix prepared in the step 1), a catalyst and an organic solvent are added for reaction for 4-6h at 105-1130 degrees under the nitrogen protection till an acid value is less than 10mgKOH/g, and cooling and discharging are carried out. The solid content of the hyperbranched hydroxyl polyester resin reaches above 70%, and the viscosity is 3000-12000mPa.s. High solid-content bi-component polyurethane dope prepared with the adoption of the hyperbranched hydroxyl polyester resin has high construction solid content, low VOC content, high film hardness, good heat resistance and outstanding anti-corrosion property.
Description
Technical field
The present invention relates to a kind of polyester resin, more particularly to a kind of hyperbranched hydroxy polyester resin and preparation method thereof with should
With, belong to fine chemistry industry synthesis field.
Background technology
The development trend of coating is that development environment friendly coating includes high solid coating, water paint, powdery paints
It is coating material solidified with UV.Hyper-branched polyester has the three-dimensional spherical of highly branched, compact conformation, and molecule inter-chain entanglement is few, in solution
Or molten condition, viscosity is low compared with the linear polymer of same molecular amount.Hyper-branched polyester can be reduced into dope viscosity for coating,
Increase coating application solids content, reduce VOC (VOC) content in coating.In addition, hyperbranched hydroxyl is poly-
Ester resin contains multiple hydroxyls, can prepare high-performance double-component polyurethane coating.The preparation of hyperbranched hydroxyl polyester is frequently with AB2
Type monomer such as dihydromethyl propionic acid is progressively polymerized with polyhydric alcohol and is obtained, and is to reduce viscosity frequently with fatty acid such as Oleic acid, lauric acid
Deng or caprolactone blocking modification is carried out to which, there is high cost, course of reaction is complicated, the high viscosity for hyper-branched polyester still
Greatly, what is had is solid at normal temperatures.Another preparation method is that (B3 is mono- for the alcohol of acid (A2 monomers) and the three-functionality-degree of two degrees of functionality
Body) prepared by polycondensation reaction, such as Chinese invention patent application CN 101583650A is disclosed using polybasic carboxylic acid and its is derived
Thing and polyol reaction synthesis of super branched polyester, are that height glues even solid, Zhi Nengjia under the hyper-branched polyester room temperature of its synthesis
Enter substantial amounts of solvent to use.Additionally, hyper-branched polyester acid number prepared by the method is higher, the difficult control of reaction end, easily
Form gelling product；The preparation method for seeking the hyper-branched polyester of high-solid lower-viscosity remains the study hotspot and difficulty in the field
Point.
The content of the invention
An object of the present invention is to provide a kind of hyperbranched hydroxy polyester resin and preparation method thereof, its synthesis technique letter
Single, raw material is cheap and easy to get, reaction temperature is less than 120 DEG C, no coupling product water generating, flows back without the need for benzene kind solvent, with safe, green
Colour circle protects the advantage with energy-conservation；The reaction end of the technique is easy to control, process is simple, will not form gelling product；It is obtained
Hyperbranched hydroxy polyester resin, solid low containing high, viscosity, the glossy good, mechanical hardness of film prepared using which is high, anticorrosion
Performance is strong, adhesiveness is good and the characteristics of excellent medium-resistance.
The second object of the present invention is to provide application of the highly filled hydroxy polyester resin in coating, the coating
It is the double-component polyurethane coating containing hyperbranched hydroxy polyester resin.
To reach above-mentioned purpose, the technical solution used in the present invention is：
A kind of preparation method of hyperbranched hydroxy polyester resin, comprises the steps：
1) by molar fraction, the polyhydric alcohol of 1 part of dibasic acid anhydride and 2-4 parts is mixed in reactor, and adds binary
The 0.1%-0.5% p-methyl benzenesulfonic acid and organic solvent of anhydride quality reacts 2-3h under 105-125 DEG C of nitrogen protection to system
It is transparent；4-10 part phthalic anhydrides are continuously added, 2-3h is reacted；
2) by molar fraction, in step 1) 6-10 part epoxides are added in the substrate for preparing, and add catalyst
Under 105-130 DEG C of nitrogen protection, reaction 4-6h is less than 10mgKOH/g to acid number with organic solvent, and cooling discharge is overspend
Change hydroxy polyester resin；
Described catalyst is tetraethylammonium bromide, tetrabutyl ammonium bromide, cetyl ammonium bromide and ammonium bromide and tetraoctyl ammonium bromide
In one or more mixture.
Further to realize the object of the invention, it is preferable that the polyhydric alcohol is glycerol, trimethylolpropane, three hydroxyl first
One or more mixture in base ethane, 1,2,4- butantriols, tetramethylolmethane, double trimethylolpropane and Bis(pentaerythritol).
Preferably, described dibasic acid anhydride be pyromellitic acid anhydride, 3,3', 4,4'- diphenyl ether tetraformic dianhydrides, 3,
3', 4,4'- benzophenone tetracarboxylic dianhydride, 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,
One or more mixture in 6- tetracarboxylic dianhydrides, cyclobutanetetracarboxylic dianhydride and 3,3', 4,4'- biphenyl tetracarboxylic dianhydride.
Preferably, step 1) and step 2) described in organic solvent be all ethyl acetate, butyl acetate, propylene glycol monomethyl ether vinegar
One or more mixture in acid esters, isopropyl acetate and butanone；Step 1) organic solvent consumption be dibasic acid anhydride
2-4 times of quality；Step 2) organic solvent consumption for epoxide mass fraction 80-150%.
Preferably, described epoxide is epoxychloropropane, butyl glycidyl ether, benzyl glycidyl ether, pungent
One or more in base glycidyl ether, C12-C14 glycidyl ethers and tertiary carbonic acid glycidyl ester (Cardura E10P)
Mixture.
Preferably, 0.5%-1.5% of the addition of the catalyst for epoxide mass fraction.
Preferably, by percentage to the quality, the raw material of the hyperbranched hydroxy polyester resin is consisted of：Polyhydric alcohol 7.6-
18.5%, dibasic acid anhydride 4.4-15.9%, phthalic anhydride 20.2-33.5%, epoxide 17.1-47.2%, p-methyl benzenesulfonic acid
0.1-0.5%, catalyst 0.1-0.5%, organic solvent 10-20%.
A kind of hyperbranched hydroxy polyester resin, is obtained by above-mentioned preparation method, the hydroxy polyester resin hydroxyl percentage composition
3-9%, solids content 70-85%, at 25 DEG C, viscosity is 3000-12000mPas.
Application of the highly filled hydroxy polyester resin in coating.
The coating contains highly filled hydroxy polyester resin and polyurethane curing agent；Described polyurethane curing agent and height
Solids content hydroxy polyester resin mol ratio NCO：OH=1-1.5:1；Described polyurethane curing agent is toluene di-isocyanate(TDI)
Trimer (Bayer Desmodur IL1451), toluene di-isocyanate(TDI)/trimethylolpropane addition product (Bayer
Desmodur L75) and hexamethylene diisocyanate trimer (Bayer Desmodur N3390) and biuret (Bayer
Desmodur N75) in one or more mixture.
The know-why of the present invention is as follows：
(1) first reacted with dianhydride with polyhydric alcohol, by dianhydride open loop, the dianhydride of per molecule and 2 molecules or more as far as possible
Polyol reaction is generated and carries terminal hydroxy group and end carboxyl super branched oligomer, and then its hydroxyl is reacted with phthalic anhydride again, is generated
The only petchem of end carboxyl；
(2) the relatively low degree of functionality of viscosity is obtained with epoxide closing c-terminuses again on the basis of step (1) higher
Hydroxyl telechelic polyester resin.By the species for changing epoxide, you can obtain the hydroxyl polyester of different molecular structures and performance
Resin.
(3) hydroxy polyester resin can continue to generate carboxyl with anhydride alternation response, change anhydride with epoxide
Ratio, can make reaction alternately go down, obtain the hydroxyl polyester of different molecular weight, realize the adjustability of molecular structure.
Relative to prior art, the present invention has advantages below：
(1) high solid low viscosity：Resin solids of the present invention reach more than 70%, and viscosity is between 3000-12000mPas；
(2) this synthesis technique is simple, raw material is cheap and easy to get, reaction temperature is less than 120 DEG C, no coupling product water generating, need not
Benzene kind solvent flows back, and has the advantages that safety, environmental protection and energy-conservation；The reaction end of the technique is easy to control, process is simple, no
Gelling product can be formed；
(3) resin-made of the present invention is standby adopts dianhydride for raw material, can give film high rigidity and excellent heat resistance, in addition
The characteristics of its film also has high gloss, Strong corrosion resistant and excellent medium-resistance.
(4) raw material of the present invention is cheap and easy to get, environmentally safe, environmental protection, and this reaction does not produce water byproduct, reaction
Temperature is low, and less than 120 DEG C can react, and operation is simple；
(5) low VOC content：Resin of the present invention is because of its special spherical dissaving structure, linear compared to equimolecular quantity
Its dissolubility in a solvent of compound is larger, therefore dissolving solvent for use is less or even can effectively can drop without solvent
Low construction VOC emission, can be with effective protection environment；
Description of the drawings
Fig. 1 is the hyperbranched hydroxy polyester resin HBP-1 structural representations of product in embodiment 1；
Fig. 2 is the hyperbranched hydroxy polyester resin HBP-2 structural representations of product in embodiment 2.
Specific embodiment
To be best understood from the present invention, the present invention will be further described with reference to the accompanying drawings and examples, needs explanation
, changed based on the non-creativeness that the embodiment of the present invention is made, belong to the scope of protection of the invention.
The Desmophen 670BA contrasted in embodiment are that the hydroxyl of the slight collateralization of Bayer Cohan wound company production gathers
Ester resin, is mainly used in dual-component polyurethane system, and film has excellent weathering stability and outstanding low temperature flexibility, is
Existing market occupation rate is than larger a polyester resin.
In example below, the performance of hydroxy polyester resin and bicomponent polyurethane coating is detected using following methods：Root
NDJ-1 type rotary viscosity design determining resin viscosities are used according to GB/T21059-2007；Resin is determined according to GB/T 6743-2008
Acid number；The dried coating film time is determined according to GB/T 1728-1989；Hardness of film is determined according to GB/T 6739-2006；According to
GB/T9286-1998 determines film adhesive；Film impact resistance is determined according to GB/T 1732-1993；According to GB/T 9754-
2007 determine coating film gloss using 60 ° of angle WGG60-E4 types Grossmeters；Soaking at room temperature method is adopted according to GB/T 5209-1985
Determine water-resistance property of coating；According to other performances of the measure coating such as GB/T 23985-2009.
Embodiment 1
A kind of hyperbranched hydroxy polyester resin (HBP-1), composition of raw materials mass percent composition is if table 1 is not (including catalysis
Agent)：
Table 1
(2) preparation technology of the hyperbranched hydroxy polyester resin (HBP-1), comprises the following steps：
Pyromellitic acid dianhydride, tetramethylolmethane, ethyl acetate are pressed into given mass mixing uniformly in reactor, and addition is urged
Agent p-methyl benzenesulfonic acid (the 0.5% of anhydride quality) reaction 2h under 120 DEG C of nitrogen protections；Continuously add the benzene of given quality
Acid anhydride, reacts 3h；Epoxychloropropane is added, and adds catalyst tetraethylammonium bromide (the 1.0% of epoxide mass fraction)
Under 110 DEG C of nitrogen protections, reaction 4h is less than 10mgKOH/g to acid number with butanone, and cooling discharge obtains hyperbranched hydroxyl polyester
Resin (HBP-1).Accompanying drawing 1 illustrates that the HBP-1 is the tetramethylolmethane (tetra functional) with pyromellitic acid dianhydride (two degrees of functionality) as core
For the ideal structure of the hyperbranched hydroxyl polyester of the first generation of polyhydric alcohol, 2*4=8 hydroxyl is contained in its branched structure end, and second
In generation, is to continue with reacting the hyper-branched polyester to form that 2*8=16 hydroxyl is contained in branched structure end with pyromellitic acid dianhydride, then
React successively, embodiment 1 is control viscosity, simply prepare the hyperbranched hydroxyl polyester of the first generation, subsequent embodiment is similar to.
(3) performance of hyperbranched hydroxy polyester resin (HBP-1)：Outward appearance：Pale yellow transparent；Admittedly contain：82%；Viscosity (25
℃)：3140mPa·s；Acid number：8.1mgKOH/g；OH%=4.5%；
(4) in terms of mass parts, the preparation composition situation such as table 2 below of double-component polyurethane coating：
Table 2
Above-mentioned formula material is added in container, under the rotating speed of 600r/min, low speed is uniformly dispersed, with the filter cloth of 400 mesh
Double-component polyurethane coating is obtained after filtration.The coating is carried out on plank and tinplate sheet film respectively, it is solid under room temperature
Change and be dried 7 days.
(5) film performance is determined, is compared with Cohan wound Desmophen 670BA performances, it is as shown in table 3 below：
Table 3
Upper table 3 illustrates that hyperbranched hydroxy polyester resin (HBP-1) film of the present invention has the machines such as high glaze and high rigidity
Tool performance, resistance to water are also outstanding than rival.HBP-1 resins are first reacted with dianhydride with tetramethylolmethane, are generated with end
Hydroxyl and end carboxyl super branched oligomer, then blocked with phthalic anhydride, then carboxyl is transformed into into hydroxyl, reaction end with epoxide
It is easily controllable, gelling product will not be formed；But also can further reduce viscosity.The reaction does not need high temperature, no by-product
Thing water generating, makees solvent without the need for benzene class and its homologue.And can pass through to change the species of small molecule polyol and dianhydride can be with
Different types of petchem is generated, so as to obtain the polyester resin of different performance.Above-mentioned polyester molecule has 8 hydroxyl officials
Energy degree, it is bigger with firming agent crosslink density, the chemical resistance of film can be effectively improved, and by changing the kind of epoxide
Class, you can obtain the polyester resin of different molecular structures and different chemical property.On the other hand, the polyester of present invention synthesis has
Dissaving structure, is blocked with epoxide, and product viscosity is little, and dilution property more preferably, under Construction State contains higher admittedly, if used
Epoxide containing the larger alkyl structure of molecular weight can further reduce viscosity.Upper table explanation is manufactured in the present embodiment
Hyperbranched hydroxy polyester resin performance when for double-component polyurethane coating is almost completely superior to what Cohan creation was produced
Desmophen 670BA, construct VOC as little as 350g/L, fully meets the tax-free requirement of country, while completely no benzene series solvent,
Safety and environmental protection.
Embodiment 2
(1) a kind of hyperbranched hydroxy polyester resin (HBP-2), composition of raw materials mass percent composition such as table 4 is not (including urging
Agent)：
Table 4
(2) preparation technology of the hyperbranched hydroxy polyester resin (HBP-2), comprises the following steps：
Pyromellitic dianhydride, trimethylolpropane, ethyl acetate are pressed into given mass mixing uniformly in reactor, and is added
Catalyst p-methyl benzenesulfonic acid (the 0.4% of anhydride quality) reaction 3h under 115 DEG C of nitrogen protections；Continuously add the benzene of given quality
Acid anhydride, reacts 2h；Add epoxychloropropane, and add catalyst cetyl ammonium bromide (epoxide mass fraction
0.5%) 5h being reacted under 130 DEG C of nitrogen protections and being less than 10mgKOH/g to acid number with ethyl acetate, cooling discharge is overspend
Change hydroxy polyester resin (HBP-2).Accompanying drawing 2 illustrates that the HBP-2 is with pyromellitic acid dianhydride (two degrees of functionality) as core trihydroxy methyl
Ideal structure of the propane (three-functionality-degree) for the hyperbranched hydroxyl polyester of the first generation of polyhydric alcohol, 2*3 is contained in its branched structure end
=6 hydroxyls, the second filial generation are the hyper-branched polyesters containing 12 hydroxyls, and this provides the hyperbranched ideal structure of the first generation.
(3) performance of hyperbranched hydroxy polyester resin (HBP-2)：Outward appearance：Pale yellow transparent；Admittedly contain：80.2%；Viscosity (25
℃)：3200mPa·s；Acid number：8.8mgKOH/g；OH%=5.2%；
(4) in terms of mass parts, the preparation composition situation such as table 5 below of double-component polyurethane coating：
Table 5
Above-mentioned formula material is added in container, under the rotating speed of 600r/min, low speed is uniformly dispersed, with the filter cloth of 400 mesh
Double-component polyurethane coating is obtained after filtration.The coating is carried out on plank and tinplate sheet film respectively, it is solid under room temperature
Change and be dried 7 days.
(5) film performance is determined, is compared with Cohan wound Desmophen 670BA performances, it is as shown in table 6 below：
Table 6
Embodiment 3
(1) a kind of hyperbranched hydroxy polyester resin (HBP-3), composition of raw materials mass percent composition such as table 7 is not (including urging
Agent)：
Table 7
(2) preparation technology of the hyperbranched hydroxy polyester resin (HBP-3), comprises the following steps：
By 3,3', 4,4'- diphenyl ether tetraformic dianhydrides, double trimethylolpropane, propylene glycol methyl ether acetate are by given matter
Amount mix homogeneously is in reactor, and adds catalyst p-methyl benzenesulfonic acid (the 0.1% of anhydride quality) under the protection of 105 DEG C of nitrogen
Reaction 3h；The phthalic anhydride of given quality is continuously added, 2h is reacted；E10P is added, and adds catalyst tetraethylammonium bromide (epoxidation
1.2%) protecting in 120 DEG C of nitrogen with propylene glycol methyl ether acetate for compound mass fraction react down 5h to be less than to acid number
10mgKOH/g, cooling discharge obtain hyperbranched hydroxy polyester resin (HBP-3).
(3) performance of hyperbranched hydroxy polyester resin (HBP-3)：Outward appearance：Pale yellow transparent；Admittedly contain：70%；Viscosity (25
℃)：5770mPa·s；Acid number：9.6mgKOH/g；OH%=4.3%；
(4) in terms of mass parts, the preparation composition situation such as table 8 below of double-component polyurethane coating：
Table 8
Above-mentioned formula material is added in container, under the rotating speed of 600r/min, low speed is uniformly dispersed, with the filter cloth of 400 mesh
Double-component polyurethane coating is obtained after filtration.The coating is carried out on plank and tinplate sheet film respectively, it is solid under room temperature
Change and be dried 7 days.
(5) film performance is determined, is compared with Cohan wound Desmophen 670BA performances, it is as shown in table 9 below：
Table 9
Embodiment 4
(1) a kind of hyperbranched hydroxy polyester resin (HBP-4), composition of raw materials mass percent composition such as table 10 (do not include
Catalyst)：
Table 10
(2) preparation technology of the hyperbranched hydroxy polyester resin (HBP-4), comprises the following steps：
By 3,3', 4,4'- benzophenone tetracarboxylic dianhydrides, triethylol propane, butyl acetate are uniform by given mass mixing
In reactor, and add catalyst p-methyl benzenesulfonic acid (the 0.2% of anhydride quality) reaction 2.5h under 125 DEG C of nitrogen protections；
The phthalic anhydride of given quality is continuously added, 3h is reacted；Butyl glycidyl ether is added, and adds catalyst tetrabutyl ammonium bromide (ring
Oxygen compound mass fraction 1.5%) and butyl acetate is less than 10mgKOH/g to acid number in the lower reaction 6h of 105 DEG C of nitrogen protection,
Cooling discharge, obtains hyperbranched hydroxy polyester resin (HBP-4).
(3) performance of hyperbranched hydroxy polyester resin (HBP-4)：Outward appearance：Pale yellow transparent；Admittedly contain：80%；Viscosity (25
℃)：6880mPa·s；Acid number：7.8mgKOH/g；OH%=4.2%；
(4) in terms of mass parts, the preparation composition situation such as table 11 below of double-component polyurethane coating：
Table 11
Above-mentioned formula material is added in container, under the rotating speed of 600r/min, low speed is uniformly dispersed, with the filter cloth of 400 mesh
Double-component polyurethane coating is obtained after filtration.The coating is carried out on plank and tinplate sheet film respectively, it is solid under room temperature
Change and be dried 7 days.
(5) film performance is determined, is compared with Cohan wound Desmophen 670BA performances, it is as shown in table 12 below：
Table 12
Embodiment 5
(1) a kind of hyperbranched hydroxy polyester resin (HBP-5), composition of raw materials mass percent composition such as table 13 (do not include
Catalyst)：
Table 13
(2) preparation technology of the hyperbranched hydroxy polyester resin (HBP-5), comprises the following steps：
By 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids, 1,2,4- butantriols, butanone by given mass mixing uniformly in reaction
In kettle, and add catalyst p-methyl benzenesulfonic acid (the 0.5% of anhydride quality) reaction 2h under 110 DEG C of nitrogen protections；Continuously add
The phthalic anhydride of given quality, reacts 2.5h；By given quality, benzyl glycidyl ether is added in substrate prepared by step (1),
And add catalyst tetrabutyl ammonium bromide (the 0.8% of epoxide mass fraction) and butanone lower anti-in 130 DEG C of nitrogen protections
Answer 4h to acid number less than 10mgKOH/g, cooling discharge obtains hyperbranched hydroxy polyester resin (HBP-5).
(3) performance of hyperbranched hydroxy polyester resin (HBP-5)：Outward appearance：Pale yellow transparent；Admittedly contain：85%；Viscosity (25
℃)：3790mPa·s；Acid number：6.6mgKOH/g；OH%=3.6%；
(4) in terms of mass parts, the preparation composition situation such as table 14 below of double-component polyurethane coating：
Table 14
Above-mentioned formula material is added in container, under the rotating speed of 600r/min, low speed is uniformly dispersed, with the filter cloth of 400 mesh
Double-component polyurethane coating is obtained after filtration.The coating is carried out on plank and tinplate sheet film respectively, it is solid under room temperature
Change and be dried 7 days.
(5) film performance is determined, is compared with Cohan wound Desmophen 670BA performances, it is as shown in table 15 below：
Table 15
Embodiment 6
(1) a kind of hyperbranched hydroxy polyester resin (HBP-6), composition of raw materials mass percent composition such as table 16 (do not include
Catalyst)：
Table 16
(2) preparation technology of the hyperbranched hydroxy polyester resin (HBP-6), comprises the following steps：
By bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydrides, Bis(pentaerythritol), isopropyl acetate by given matter
Amount mix homogeneously is in reactor, and adds catalyst p-methyl benzenesulfonic acid (the 0.2% of anhydride quality) under the protection of 125 DEG C of nitrogen
Reaction 2h；The phthalic anhydride of given quality is continuously added, 3h is reacted；By given quality, add in substrate prepared by step (1) pungent
Base glycidyl ether, and add catalyst tetrabutyl ammonium bromide (the 0.8% of epoxide mass fraction) and isopropyl acetate
Under 110 DEG C of nitrogen protections, reaction 4h is less than 10mgKOH/g to acid number, and cooling discharge obtains hyperbranched hydroxy polyester resin
(HBP‐6)。
(3) performance of hyperbranched hydroxy polyester resin (HBP-6)：Outward appearance：Pale yellow transparent；Admittedly contain：74.9%；Viscosity (25
℃)：11760mPa·s；Acid number：8.9mgKOH/g；OH%=3.6%；
(4) in terms of mass parts, the preparation composition situation such as table 17 below of double-component polyurethane coating：
Table 17
Above-mentioned formula material is added in container, under the rotating speed of 600r/min, low speed is uniformly dispersed, with the filter cloth of 400 mesh
Double-component polyurethane coating is obtained after filtration.The coating is carried out on plank and tinplate sheet film respectively, it is solid under room temperature
Change and be dried 7 days.
(5) film performance is determined, is compared with Cohan wound Desmophen 670BA performances, as shown in the table 18：
Table 18
Embodiment 7
(1) a kind of hyperbranched hydroxy polyester resin (HBP-7), composition of raw materials mass percent composition such as table 19 (do not include
Catalyst)：
Table 19
(2) preparation technology of the hyperbranched hydroxy polyester resin (HBP-7), comprises the following steps：
By cyclobutanetetracarboxylic dianhydride, trimethylolpropane, butyl acetate by given mass mixing uniformly in reactor,
And add catalyst p-methyl benzenesulfonic acid (the 0.9% of anhydride quality) reaction 2.5h under 125 DEG C of nitrogen protections；Continuously add given
The phthalic anhydride of quality, reacts 3h；By given quality, C is added in substrate prepared by step (1)12‐C14Glycidyl ether, and plus
Enter catalyst ammonium bromide and tetraoctyl ammonium bromide (the 0.5% of epoxide mass fraction) and butyl acetate lower anti-in 130 DEG C of nitrogen protections
Answer 5h to acid number less than 10mgKOH/g, cooling discharge obtains hyperbranched hydroxy polyester resin.
(3) performance of hyperbranched hydroxy polyester resin (HBP-7)：Outward appearance：Pale yellow transparent；Admittedly contain：75.0%；Viscosity (25
℃)：9780mPa·s；Acid number：7.9mgKOH/g；OH%=3.5%；
(4) in terms of mass parts, the preparation composition situation such as table 20 below of double-component polyurethane coating：
Table 20
Above-mentioned formula material is added in container, under the rotating speed of 600r/min, low speed is uniformly dispersed, with the filter cloth of 400 mesh
Double-component polyurethane coating is obtained after filtration.The coating is carried out on plank and tinplate sheet film respectively, it is solid under room temperature
Change and be dried 7 days.
(5) film performance is determined, is compared with Cohan wound Desmophen 670BA performances, it is as shown in table 21 below：
Table 21
Embodiment 8
(1) a kind of hyperbranched hydroxy polyester resin (HBP-8), composition of raw materials mass percent composition such as table 22 (do not include
Catalyst)：
Table 22
(2) preparation technology of the hyperbranched hydroxy polyester resin (HBP-8), comprises the following steps：
By 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides, tetramethylolmethane, isopropyl acetate are by given mass mixing uniformly in anti-
In answering kettle, and add catalyst p-methyl benzenesulfonic acid (the 0.4% of anhydride quality) reaction 2.5h under 115 DEG C of nitrogen protections；Continue
The phthalic anhydride of given quality is added, 3h is reacted；By given quality, epoxychloropropane is added in substrate prepared by step (1), and
Catalyst tetrabutyl ammonium bromide (the 1.0% of epoxide mass fraction) and isopropyl acetate is added to protect in 130 DEG C of nitrogen
Lower reaction 5h is less than 10mgKOH/g to acid number, and cooling discharge obtains hyperbranched hydroxy polyester resin.
(3) hyperbranched hydroxy polyester resin (HBP-8)：Outward appearance：Pale yellow transparent；Admittedly contain：83.2%；Viscosity (25 DEG C)：
6120mPa·s；Acid number：7.7mgKOH/g；OH%=3.9%；
(4) in terms of mass parts, the preparation composition situation such as table 23 below of double-component polyurethane coating：
Table 23
Above-mentioned formula material is added in container, under the rotating speed of 600r/min, low speed is uniformly dispersed, with the filter cloth of 400 mesh
Double-component polyurethane coating is obtained after filtration.The coating is carried out on plank and tinplate sheet film respectively, it is solid under room temperature
Change and be dried 7 days.
(5) film performance is determined, is compared with Cohan wound Desmophen 670BA performances, it is as shown in table 24 below：
Table 24
Embodiment 9
(1) a kind of hyperbranched hydroxy polyester resin (HBP-9), composition of raw materials mass percent composition such as table 25 (do not include
Catalyst)：
Table 25
(2) preparation technology of the hyperbranched hydroxy polyester resin (HBP-9), comprises the following steps：
Pyromellitic dianhydride, glycerol, ethyl acetate are pressed into given mass mixing uniformly in reactor, and adds catalysis
Agent p-methyl benzenesulfonic acid (the 0.5% of anhydride quality) reaction 2.5h under 105 DEG C of nitrogen protections；Continuously add the benzene of given quality
Acid anhydride, reacts 2.5h；By given quality, epoxychloropropane is added in substrate prepared by step (1), and adds catalyst four pungent
The reaction 6h under 130 DEG C of nitrogen protections is little to acid number for base ammonium bromide (the 0.5% of epoxide mass fraction) and ethyl acetate
In 10mgKOH/g, cooling discharge, hyperbranched hydroxy polyester resin (HBP-9) is obtained.
(3) hyperbranched hydroxy polyester resin (HBP-9)：Outward appearance：Pale yellow transparent；Admittedly contain：76.2%；Viscosity (25 DEG C)：
4120mPa·s；Acid number：8.7mgKOH/g；OH%=3.9%；
(4) in terms of mass parts, the preparation composition situation such as table 26 below of double-component polyurethane coating：
Table 26
Above-mentioned formula material is added in container, under the rotating speed of 600r/min, low speed is uniformly dispersed, with the filter cloth of 400 mesh
Double-component polyurethane coating is obtained after filtration.The coating is carried out on plank and tinplate sheet film respectively, it is solid under room temperature
Change and be dried 7 days.
(5) film performance is determined, is compared with Cohan wound Desmophen 670BA performances, it is as shown in table 27 below：
Table 27
Embodiment 2-9 is all many of three, tetrahydroxylic alcohol and two anhydride reactants, generating portion end carboxyl and terminal hydroxy group with embodiment 1
Arm dendrimer, then the compound for generating end group whole carboxyl is reacted with phthalic anhydride, finally there is open loop with epoxide
Reaction sealed carboxyl, prepares hyperbranched hydroxy polyester resin, and water is not produced in course of reaction, and reaction temperature is relatively low, in technique more
Plus it is easy.Embodiment 2-9 gives the hydroxyl of the different high-solid lower-viscosity of different polyhydric alcohol, epoxy compound species processability and gathers
Ester.Comparing traditional polyprotic acid and the reaction of polyester being generated with polyhydric alcohol, the present invention does not use benezene material to do water entrainer and solvent, work
Easier in skill, energy-saving and safety and environmental protection；Film prepared by the present invention has excellent ornamental and yellowing resistance.This
Invention can substantially reduce coating application VOC content, environmental protection.
Claims (10)
1. a kind of preparation method of hyperbranched hydroxy polyester resin, it is characterised in that comprise the steps：
1) by molar fraction, the polyhydric alcohol of 1 part of dibasic acid anhydride and 2-4 parts is mixed in reactor, and adds dibasic acid anhydride
The reaction 2-3h under 105-125 DEG C of nitrogen protection is transparent to system for the 0.1%-0.5% p-methyl benzenesulfonic acid and organic solvent of quality；
4-10 part phthalic anhydrides are continuously added, 2-3h is reacted；
2) by molar fraction, in step 1) 6-10 part epoxides are added in the substrate for preparing, and add catalyst and have
Machine solvent reaction 4-6h under 105-130 DEG C of nitrogen protection is less than 10mgKOH/g to acid number, and cooling discharge obtains hyperbranched hydroxyl
Base polyester resin；
During described catalyst is tetraethylammonium bromide, tetrabutyl ammonium bromide, cetyl ammonium bromide and ammonium bromide and tetraoctyl ammonium bromide
One or more mixture.
2. the preparation method of hyperbranched hydroxy polyester resin according to claim 1, it is characterised in that the polyhydric alcohol is
Glycerol, trimethylolpropane, trimethylolethane, 1,2,4- butantriols, tetramethylolmethane, double trimethylolpropane and double seasons penta
One or more mixture in tetrol.
3. the preparation method of hyperbranched hydroxy polyester resin according to claim 1, it is characterised in that described binary acid
Acid anhydride is pyromellitic acid anhydride, 3,3', 4,4'- diphenyl ether tetraformic dianhydrides, 3,3', 4,4'- benzophenone tetracarboxylic dianhydrides, 4,
4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydrides, cyclobutanetetracarboxylic two
One or more mixture in acid anhydride and 3,3', 4,4'- biphenyl tetracarboxylic dianhydride.
4. the preparation method of hyperbranched hydroxy polyester resin according to claim 1, it is characterised in that step 1) and step
2) organic solvent described in is all in ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, isopropyl acetate and butanone
Plant or various mixture；Step 1) consumption of the organic solvent is 2-4 times of dibasic acid anhydride quality；Step 2) it is described organic molten
80-150% of the consumption of agent for epoxide mass fraction.
5. the preparation method of hyperbranched hydroxy polyester resin according to claim 1, it is characterised in that described epoxidation
Compound is epoxychloropropane, butyl glycidyl ether, benzyl glycidyl ether, octyl glycidyl ether, C12-C14 (+)-2,3-Epoxy-1-propanols
One or more mixture in ether and tertiary carbonic acid glycidyl ester.
6. the preparation method of hyperbranched hydroxy polyester resin according to claim 1, it is characterised in that the catalyst
0.5%-1.5% of the addition for epoxide mass fraction.
7. the preparation method of hyperbranched hydroxy polyester resin according to claim 1, it is characterised in that with mass percent
Meter, the raw material of the hyperbranched hydroxy polyester resin are consisted of：Polyhydric alcohol 7.6-18.5%, dibasic acid anhydride 4.4-15.9%, benzene
Acid anhydride 20.2-33.5%, epoxide 17.1-47.2%, p-methyl benzenesulfonic acid 0.1-0.5%, catalyst 0.1-0.5% are organic
Solvent 10-20%.
8. a kind of hyperbranched hydroxy polyester resin, it is characterised in that：Its preparation method system by described in any one of claim 1-7
, hydroxy polyester resin hydroxyl percentage composition 3-9%, solids content 70-85%, at 25 DEG C, viscosity is 3000-
12000mPa·s。
9. application of the highly filled hydroxy polyester resin in coating described in claim 8.
10. application of the highly filled hydroxy polyester resin in coating according to claim 9, it is characterised in that：It is described
Coating contains highly filled hydroxy polyester resin and polyurethane curing agent；Described polyurethane curing agent and highly filled hydroxyl
Polyester resin mol ratio NCO：OH=1-1.5:1；Described polyurethane curing agent is toluene diisocyanate trimer, toluene two
One or more in isocyanates/trimethylolpropane addition product and hexamethylene diisocyanate trimer and biuret is mixed
Compound.
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