CN106366323A - Easily water dispersible polyester resin - Google Patents
Easily water dispersible polyester resin Download PDFInfo
- Publication number
- CN106366323A CN106366323A CN201610850162.3A CN201610850162A CN106366323A CN 106366323 A CN106366323 A CN 106366323A CN 201610850162 A CN201610850162 A CN 201610850162A CN 106366323 A CN106366323 A CN 106366323A
- Authority
- CN
- China
- Prior art keywords
- polyester resin
- acid
- polyester
- polyhydric alcohol
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- 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
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
-
- 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
- C09D175/06—Polyurethanes from polyesters
-
- 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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides easily water dispersible polyester resin, composed of polyester chain segments and polyether chain segments having a ratio of 1:(0.5-3); a preparation method of the easily water dispersible polyester resin comprises the steps of subjecting two monomers, polyols and polyacids to esterification reaction until acid value is 10-18 mg KOH/g; adding polyether polyol in the reacted system of step 1) for chemical modification and grafting until the acid value is 3-9 mg KOH/g; adding trimellitic anhydride to the reacted system of step 2) until the acid value is 20-45 mg KOH/g and hydroxyl value is 60-100 mg KOH/g. The easily water dispersible polyester resin has good storage stability, takes little influence from ambient temperature, may be stored for 6 months and longer while standing at normal temperature, and is free of turbidity, gelling and whitening.
Description
Technical field
The invention belongs to paint spraying field is and in particular to one kind is easy to the scattered polyester resin of water, include this poly-
The preparation method of ester resin and purposes.
Background technology
Traditional solvent-borne coating (voc) containing volatile organic matter, can volatilize in film forming procedure and cause pollution, the having of volatilization
Machine thing also can cause secondary pollution to atmospheric environment.Therefore, traditional coating industry needs upgrading and transformation badly, and the low voc of water paint
Even zero voc discharge, also reduces the expense of solvent while lifting production environment, reduce production cost so that aqueouss apply
Material has more competitive advantage.Therefore with water paint progressively until replacing solvent based coating completely become inexorable trend.There is representative
Property waterborne polyester coating developed based on water dispersible polyester resin, have that gloss is high, adhesive force is strong, richness is high, resistance to punching
The features such as hitting property is excellent, both can be configured to water-based stoving paint with water soluble amino resin it is also possible to and hydrophilic polyisocyanate
It is configured to the water-borne wood coating of normal temperature cure, thus waterborne polyester coating is in all trades and professions such as automobile, canned food, building materials, household electrical appliances
In be all widely used, especially obtain the rapidest in coil coating and tin printing ink industry development.
At present, both at home and abroad to the research of water dispersible polyester resin a lot, the patent of such as recent report
cn200710028091.x、cn200710045920.5、cn201210466302.9、cn201310508754.3、
Cn201410397816.2, cn201510589134.6 etc., the polyester resin of preparation has certain water dispersible, but all cannot
The hydrolysis in aqueous of effectively solving polyester, stability cannot be ensured well.
With the development of water paint, the demand of water dispersible polyester resin will get more and more, the water of waterborne polyester
Numerical solution can limit the popularization of its application and development it is therefore necessary to the exploitation excellent water dispersible polyester of hydrolytic stability
Resin.
Content of the invention
Present invention seek to address that existing water dispersible polyester resin manufacture use during less stable defect, carry
It is easy to scattered polyester resin of water and preparation method thereof for one kind.
The strand being easy to the scattered polyester resin of water that the present invention provides is made up of polyester segment and polyether segment, two kinds
Than for 1:0.5-3, polyether segment is scattered in middle part or the end of polyester segment to the quantity of segment.Polyester segment is by with second two
Alcohol, 2- methyl-1,3-propanediol, 1,6-HD, neopentyl glycol, 1,4 cyclohexanedimethanols, 2- ethyl -2- butyl -1,3- third
Glycol, trimethylolpropane, 1,6- adipic acid, p-phthalic acid, M-phthalic acid, 1,4 cyclohexanedicarboxylic acid, trimellitic acid
Acid anhydride, 2,2- dihydromethyl propionic acid, 2,2- dimethylolpropionic acid are obtained by condensation polymerization under catalyst action for raw material.Polyethers
Segment is grafted in polyester segment through chemical modification by polyether polyol, and carries out chemistry and change by adding trimellitic anhydride
Property, obtains acid number and the higher polyester resin of hydroxyl value.
Concrete technical scheme is as follows:
One kind is easy to the scattered polyester resin of water, and the described scattered polyester resin of water that is easy to is by polyester segment and polyether chain
Duan Zucheng, the quantity of described polyester segment and polyether segment is than for 1:0.5-3；
The described scattered preparation method of polyester resin of water that is easy to comprises the steps:
Step 1): be there is esterification in polyhydric alcohol and two kinds of monomers of polyprotic acid, until acid number is 10-18mgkoh/g；
Step 2): in step 1) reaction after the completion of system in add polyether polyol carry out chemical modification grafting, until
Acid number is 3-9mgkoh/g；
Step 3): in step 2) reaction after the completion of system in add trimellitic anhydride, until acid number be 20-45mgkoh/
G, hydroxyl value is 60-100mgkoh/g.
Preferably, the mass ratio of described polyhydric alcohol and two kinds of monomers of polyprotic acid is, polyhydric alcohol: polyprotic acid=(41-86):
(13-57)；
The quality of described polyether polyol accounts for polyhydric alcohol and the 5-20% of two kinds of monomer gross mass of polyprotic acid；
The quality of described trimellitic anhydride accounts for polyhydric alcohol and the 5-11% of two kinds of monomer gross mass of polyprotic acid.
Preferably, described polyhydric alcohol is ethylene glycol, 2- methyl isophthalic acid, ammediol, 1,6- hexanediol, neopentyl glycol, Isosorbide-5-Nitrae ring
One or more of hexane dimethanol, 2- ethyl -2- butyl -1,3- propylene glycol, trimethylolpropane.
Preferably, described polyprotic acid be 1,6- adipic acid, p-phthalic acid, M-phthalic acid, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic,
One or more of 2,2- dihydromethyl propionic acid, 2,2- dimethylolpropionic acid.
Preferably, number-average molecular weight m of described polyether polyoln0For 200-800g/mol, the knot of described polyether polyol
Structure is linear or branched structure.
Preferably, described step 1) in esterification in be also added into catalyst, described esterification be nitrogen protect
Under shield, mixing adds polyhydric alcohol and two kinds of raw material monomers of polyprotic acid and catalyst, is warmed up to 140 DEG C, opens blender, protects
Temperature, is warming up to 240 DEG C by 10 DEG C/min of heating rate, and being incubated to acid number is 10-18mgkoh/g；
Described step 3) be by step 2) reaction system be cooled to 180 DEG C, maintain the reflux for column temperature and be down to 75 DEG C, add
Trimellitic anhydride.
Preferably, described preparation method is further comprising the steps of:
Step 4): by step 3) reaction system be cooled to less than 100 DEG C, add cosolvent, be adjusted to mass fraction of solids
For 60-80%, stir, add nertralizer, ph value is adjusted to 7.0～9.0；
Step 5): by step 4) after the completion of reaction system in plus deionized water dilution, be 45- to mass fraction of solids
55%, finally obtain polyester resin.
Preferably, described catalyst is antimony oxide, stannous chloride, stannous octoate, Mono-n-butyltin, dibutyl oxygen
Change one or more of stannum, dibutyl tin laurate, monobutyl dihydroxy stannic chloride, butyl titanate；
It is 0.05-0.2% that the weight of described catalyst accounts for polyhydric alcohol and the percentage ratio of two kinds of total monomer weights of polyprotic acid.
Preferably, described cosolvent is n-butyl alcohol, ethylene glycol, butyl glycol ether, propylene-glycol ethyl ether, diethylene glycol fourth
One or more of ether；
Described nertralizer be one of ammonia, ethylenediamine, hexamethylene diamine, triethanolamine, triethylamine, dimethylethanolamine or
Multiple.
The present invention also provides a kind of preparation method being easy to the scattered polyester resin of water:
1), under nitrogen protection, mixing adds polyhydric alcohol and polyacid monomer raw material, including ethylene glycol 0-5 part, 2- methyl isophthalic acid,
Ammediol 0-5 part, 1,6-HD 0-5 part, neopentyl glycol 18-24 part, 1,4 cyclohexanedimethanol 12-20 parts, 2- ethyl-
2- butyl -1,3- propylene glycol 8-15 part, trimethylolpropane 3-12 part, 1,6- adipic acid 0-4 part, p-phthalic acid 0-8 part,
Phthalic acid 12-25 part, 1,4 cyclohexanedicarboxylic acid 1-10 part, 2,2- dihydromethyl propionic acid 0-5 part, 2,2- dimethylolpropionic acid
0-5 part and catalyst, are warmed up to 140 DEG C, open blender, insulation.It is warming up to 240 DEG C by 10 DEG C/min of heating rate, protect
Temperature to acid number is 10-18mgkoh/g.
2) add polyether polyol in reaction system, its quality accounts for the 5-20% of above-mentioned total monomer weight, continues insulation
To articulation point it is ensured that acid number is 3-9mgkoh/g.
3) it is cooled to 180 DEG C, maintains the reflux for column temperature and be down to 75 DEG C, add trimellitic anhydride, it is total that its quality accounts for above-mentioned monomer
The 5-11% of weight, insulation until resin transparent, obtain acid number be 20-45mgkoh/g, hydroxyl value be the tree of 60-100mgkoh/g
Fat.
4) it is cooled to less than 100 DEG C, adds cosolvent, being adjusted to mass fraction of solids is 70%, stirring adds neutralization
Agent, ph value is adjusted to 8.0～9.0.
5) amount of reordering deionized water dilution again, is (50 ± 2) % to mass fraction of solids, and last discharging obtains polyester tree
Fat.
The present invention also provides a kind of purposes according to above-mentioned polyester resin, and described purposes is to prepare waterborne polyester-amino tree
Fat paint or prepare waterborne polyester type polyurethane paint.
Beneficial effects of the present invention: the scattered polyester resin of water that is easy to of the present invention has good bin stability, is subject to
Ambient temperature effect is little, under room temperature resting state, can deposit more than 6 months, not muddy, not gel, non-whitening.Can be used for
Prepare waterborne polyester-amino resin coatings, can also be used for preparing waterborne polyester type polyurethane paint, be applied to multiple fields.
Specific embodiment
Below the specific embodiment of the present invention is described further:
In the embodiment of the present invention, polyester resin is made up of polyester segment and polyether segment, described polyester segment and polyether chain
The measuring method of the quantity ratio of section is as follows: 1) number-average molecular weight that gel chromatography tests first step product is mn1；2) coagulate
The number-average molecular weight that glue chromatography tests second step product is mn2；3) the quantity ratio of polyester segment and polyether segment can calculate
For 1:(mn2-mn1)/mn0.
Embodiment 1
1), under nitrogen protection, mixing adds polyhydric alcohol and polyacid monomer raw material, including 1,6- hexanediol 5kg, new penta 2
Alcohol 18kg, 1,4 cyclohexanedimethanol 10kg, 2- ethyl -2- butyl -1,3- propylene glycol 15kg, trimethylolpropane 3kg, to benzene
Dioctyl phthalate 18kg, M-phthalic acid 12kg, 1,4 cyclohexanedicarboxylic acid 10kg, 2,2- dihydromethyl propionic acid 5kg, 2,2- dihydroxy first
Base butanoic acid 4kg and antimony oxide 0.03kg, stannous chloride 0.02kg, are warmed up to 140 DEG C, open blender, insulation；By liter
Warm 10 DEG C/min of speed is warming up to 240 DEG C, and being incubated to acid number is 10-18mgkoh/g；2) add 5kg number equal in reaction system
Molecular weight is the polyether polyol of 400-600g/mol, continues insulation to articulation point it is ensured that acid number is 3-9mgkoh/g；3) lower the temperature
To 180 DEG C, maintain the reflux for column temperature and be down to 75 DEG C, add 11kg trimellitic anhydride, until resin transparent, obtaining acid number is for insulation
20-35mgkoh/g, hydroxyl value are the resin of 60-70mgkoh/g；4) it is cooled to less than 100 DEG C, for 1:1:1 just adding mass ratio
Butanol, ethylene glycol, butyl glycol ether, being adjusted to mass fraction of solids is 60%, and stirring adds dimethylethanolamine, ph
Value is adjusted to 8.0～9.0；5) amount of reordering deionized water dilution again, is 48% to mass fraction of solids, last discharging obtains polyester tree
Fat a, detection obtains the quantity of polyester segment and polyether segment in polyester resin a ratio for 1:0.59.
Embodiment 2
1), under nitrogen protection, mixing adds polyhydric alcohol and polyacid monomer raw material, including ethylene glycol 3kg, neopentyl glycol
14kg, 1,4 cyclohexanedimethanol 9kg, 2- ethyl -2- butyl -1,3- propylene glycol 6kg, trimethylolpropane 15kg, 1,6- oneself two
Sour 6kg, M-phthalic acid 18kg, 1,4 cyclohexanedicarboxylic acid 12kg, 2,2- dimethylolpropionic acid 7kg and stannous octoate
0.06kg, Mono-n-butyltin 0.06kg, are warmed up to 140 DEG C, open blender, insulation；Heat up by 10 DEG C/min of heating rate
To 240 DEG C, being incubated to acid number is 10-18mgkoh/g；2) 12kg number-average molecular weight is added to be 600-800g/ in reaction system
The polyether polyol of mol, continues insulation to articulation point it is ensured that acid number is 3-9mgkoh/g；3) it is cooled to 180 DEG C, maintain the reflux for
Column temperature is down to 75 DEG C, adds 6.6kg trimellitic anhydride, and until resin transparent, obtaining acid number is 20-35mgkoh/g, hydroxyl value for insulation
Resin for 60-70mgkoh/g；4) it is cooled to less than 100 DEG C, add mass ratio to be the butyl glycol ether of 1:1, propylene glycol second
Ether, being adjusted to mass fraction of solids is 75%, and stirring adds hexamethylene diamine, ph value is adjusted to 7.0～8.0；5) again the amount of reordering go from
Sub- water dilution, is 52% to mass fraction of solids, and last discharging obtains polyester resin b, and detection obtains polyester chain in polyester resin b
The quantity of section and polyether segment ratio is for 1:1.18.
Embodiment 3
1), under nitrogen protection, mixing adds polyhydric alcohol and polyacid monomer raw material, including ethylene glycol 1kg, 2- methyl isophthalic acid, 3-
Propylene glycol 5kg, neopentyl glycol 24kg, 1,4 cyclohexanedimethanol 20kg, 2- ethyl -2- butyl -1,3- propylene glycol 5kg, three hydroxyl first
Base propane 12kg, 1,6- adipic acid 14kg, M-phthalic acid 25kg, 1,4 cyclohexanedicarboxylic acid 10kg, 2,2- dihydroxymethyl third
Sour 5kg and monobutyl dihydroxy stannic chloride 0.1kg, butyl titanate 0.08kg, are warmed up to 140 DEG C, open blender, protect
Temperature；It is warming up to 240 DEG C by 10 DEG C/min of heating rate, being incubated to acid number is 10-18mgkoh/g；2) add in reaction system
24kg number-average molecular weight is the polyether polyol of 400-600g/mol, continues insulation to articulation point it is ensured that acid number is 3-9mgkoh/
g；3) it is cooled to 180 DEG C, maintains the reflux for column temperature and be down to 75 DEG C, add 13kg trimellitic anhydride, insulation, until resin transparent, obtains
Acid number is 20-35mgkoh/g, hydroxyl value is the resin of 60-70mgkoh/g；4) it is cooled to less than 100 DEG C, add n-butyl alcohol, be adjusted to
Mass fraction of solids is 70%, and stirring adds triethylamine, ph value is adjusted to 8.0～9.0；5) amount of reordering deionized water dilution again,
It is 50% to mass fraction of solids, last discharging obtains polyester resin c, detection obtains polyester segment and polyethers in polyester resin c
The quantity of segment is than for 1:2.78.
Comparative example 1
Comparative example 1 compared with Example 1, does not except for the difference that carry out step 3), by trimellitic anhydride in step 1) middle addition,
Polyprotic acid and polyhydric alcohol mixing add, and other conditions are same as Example 1, prepare polyester resin a1, and detection obtains polyester
In resin a1, the quantity of polyester segment and polyether segment is than for 1:0.6.
Comparative example 2
Comparative example 2 compared with Example 1, except for the difference that step 3) add the amount that is modified of trimellitic anhydride to subtract in reaction
It is 0.1kg less, other conditions are same as Example 1, prepare polyester resin a2, and detection obtains polyester chain in polyester resin a2
The quantity of section and polyether segment ratio is for 1:3.45.
Comparative example 3
Comparative example 3 compared with Example 1, except for the difference that step 2) add polyether polyol to carry out chemical graft and change in reaction
Property amount increase as 30kg, other conditions are same as Example 1, prepare polyester resin a3, and detection obtains polyester resin a3
The quantity of middle polyester segment and polyether segment is than for 1:0.05.
The polyester resin that above-described embodiment 1-2 and comparative example 1-3 are prepared places 6 respectively under room temperature illegal state
Individual month and 12 months, observe the stable case of polyester resin in 5, concrete effect such as table 1:
Table 1
From above-mentioned table 1 result can, either place 6 months or 12 months, the polyester that embodiment 1-2 mode obtains
Resin all occurs without muddiness or blushing, and the polyester resin a1 of comparative example 1 occurs muddy and turns white existing after placing 6 months
As the addition sequence of this explanation trimellitic anhydride is larger for the performance impact of product polyester resin, and trimellitic anhydride is in step
1) add in, a kind of multi-anhydride of offer is be provided and reacts with polyhydric alcohol participation fat polymerization, and by trimellitic anhydride in esterification
Add after polymerization and polyether polyol chemical modification, be modified again increasing the free carboxy in polymer, be to produce
Product hydrophilic is higher；Slight haze after placing 12 months or turn white in comparative example 2 and comparative example 3, and this explanation, in the present invention
In the proportion selecting, the stability of the polyester resin product obtaining is higher, stably holds time more long.
The polyester segment being detected from the polyester resin product that embodiment 1-3 and comparative example 1-3 obtain and polyether segment
Quantity ratio as can be seen that comparative example in quantity more low than substantially, its stabilizing effect is poor relative to embodiment 1-3.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is changed.Therefore, the invention is not limited in specific embodiment disclosed and described above, to invention
In the scope of the claims that a little modifications and changes should also be as fall into the present invention.Although additionally, employing in this specification
Some specific terms, but these terms are merely for convenience of description, do not constitute any restriction to the present invention.
Claims (10)
1. one kind is easy to the scattered polyester resin of water it is characterised in that the described scattered polyester resin of water that is easy to is by polyester chain
Section and polyether segment composition, the quantity of described polyester segment and polyether segment ratio is for 1:0.5-3；
The described scattered preparation method of polyester resin of water that is easy to comprises the steps:
Step 1): be there is esterification in polyhydric alcohol and two kinds of monomers of polyprotic acid, until acid number is 10-18mgkoh/g；
Step 2): in step 1) add polyether polyol to carry out chemical modification grafting, until acid number in system after the completion of reaction
For 3-9mgkoh/g；
Step 3): in step 2) reaction after the completion of system in add trimellitic anhydride, until acid number be 20-45mgkoh/g, hydroxyl
It is worth for 60-100mgkoh/g.
2. polyester resin according to claim 1 is it is characterised in that the quality of described polyhydric alcohol and two kinds of monomers of polyprotic acid
Than for polyhydric alcohol: polyprotic acid=(41-86): (13-57)；
The quality of described polyether polyol accounts for polyhydric alcohol and the 5-20% of two kinds of monomer gross mass of polyprotic acid；
The quality of described trimellitic anhydride accounts for polyhydric alcohol and the 5-11% of two kinds of monomer gross mass of polyprotic acid.
3. polyester resin according to claim 1 it is characterised in that described polyhydric alcohol be ethylene glycol, 2- methyl isophthalic acid, 3- third
Glycol, 1,6-HD, neopentyl glycol, 1,4 cyclohexanedimethanols, 2- ethyl -2- butyl -1,3- propylene glycol, trihydroxy methyl third
One or more of alkane.
4. polyester resin according to claim 1 is it is characterised in that described polyprotic acid is 1,6- adipic acid, terephthaldehyde
One of acid, M-phthalic acid, 1,4 cyclohexanedicarboxylic acid, 2,2- dihydromethyl propionic acid, 2,2- dimethylolpropionic acid or many
Kind.
5. polyester resin according to claim 1 is it is characterised in that number-average molecular weight m of described polyether polyoln0For
200-800g/mol, the structure of described polyether polyol is linear or branched structure.
6. polyester resin according to claim 1 is it is characterised in that described step 1) in esterification in be also added into
Catalyst, described esterification is under nitrogen protection, and mixing adds polyhydric alcohol and two kinds of raw material monomers of polyprotic acid and catalysis
Agent, is warmed up to 140 DEG C, opens blender, insulation, is warming up to 240 DEG C by 10 DEG C/min of heating rate, being incubated to acid number is 10-
18mgkoh/g；
Described step 3) be by step 2) reaction system be cooled to 180 DEG C, maintain the reflux for column temperature and be down to 75 DEG C, add inclined benzene
Three anhydride.
7. polyester resin according to claim 6 is it is characterised in that described preparation method is further comprising the steps of:
Step 4): by step 3) reaction system be cooled to less than 100 DEG C, add cosolvent, be adjusted to mass fraction of solids be 60-
80%, stirring, add nertralizer, ph value is adjusted to 7.0～9.0；
Step 5): by step 4) after the completion of reaction system in plus deionized water dilution, be 45-55% to mass fraction of solids,
Finally obtain polyester resin.
8. polyester resin according to claim 6 it is characterised in that described catalyst be antimony oxide, stannous chloride,
Stannous octoate, Mono-n-butyltin, Dibutyltin oxide, dibutyl tin laurate, monobutyl dihydroxy stannic chloride, metatitanic acid four fourth
One or more of ester；
It is 0.05-0.2% that the weight of described catalyst accounts for polyhydric alcohol and the percentage ratio of two kinds of total monomer weights of polyprotic acid.
9. polyester resin according to claim 7 is it is characterised in that described cosolvent is n-butyl alcohol, ethylene glycol, second
One or more of glycol butyl ether, propylene-glycol ethyl ether, butyl；
Described nertralizer is one of ammonia, ethylenediamine, hexamethylene diamine, triethanolamine, triethylamine, dimethylethanolamine or many
Kind.
10. a kind of purposes of polyester resin described in any one according to claim 1-9 is it is characterised in that described purposes is preparation
Waterborne polyester-amino resin coatings or prepare waterborne polyester type polyurethane paint.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610850162.3A CN106366323A (en) | 2016-09-26 | 2016-09-26 | Easily water dispersible polyester resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610850162.3A CN106366323A (en) | 2016-09-26 | 2016-09-26 | Easily water dispersible polyester resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106366323A true CN106366323A (en) | 2017-02-01 |
Family
ID=57897282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610850162.3A Pending CN106366323A (en) | 2016-09-26 | 2016-09-26 | Easily water dispersible polyester resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106366323A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905824A (en) * | 2017-04-20 | 2017-06-30 | 滁州市全丰物资有限公司 | A kind of aqueous polyester resin coating and preparation method thereof |
| CN107522821A (en) * | 2017-08-30 | 2017-12-29 | 佛山市高明同德化工有限公司 | A kind of coil coating acrylated polyester water-base resin and preparation method thereof |
| CN110713592A (en) * | 2018-07-11 | 2020-01-21 | 广东华润涂料有限公司 | High-solid low-viscosity resin composition containing polyether modified polyester |
| CN115322660A (en) * | 2022-09-13 | 2022-11-11 | 雅涂科技(张家港)有限公司 | Preparation method of solvent-free polyester resin coating |
| CN116178690A (en) * | 2023-01-09 | 2023-05-30 | 广东莱尔新材料科技股份有限公司 | Self-emulsifying water-based polyester resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212188A (en) * | 2011-04-22 | 2011-10-12 | 常州市科祥化工有限公司 | Polyester resin for aqueous coil coating and preparation method thereof |
| CN102887993A (en) * | 2011-07-19 | 2013-01-23 | 上海涂料有限公司技术中心 | Preparation method of waterborne polyester resin used in coil coatings and application thereof |
| CN104356370A (en) * | 2014-10-24 | 2015-02-18 | 广州擎天材料科技有限公司 | Terminal polyester resin for high filler filling quantity mixed type powder coating and preparation method of terminal polyester resin |
-
2016
- 2016-09-26 CN CN201610850162.3A patent/CN106366323A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212188A (en) * | 2011-04-22 | 2011-10-12 | 常州市科祥化工有限公司 | Polyester resin for aqueous coil coating and preparation method thereof |
| CN102887993A (en) * | 2011-07-19 | 2013-01-23 | 上海涂料有限公司技术中心 | Preparation method of waterborne polyester resin used in coil coatings and application thereof |
| CN104356370A (en) * | 2014-10-24 | 2015-02-18 | 广州擎天材料科技有限公司 | Terminal polyester resin for high filler filling quantity mixed type powder coating and preparation method of terminal polyester resin |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905824A (en) * | 2017-04-20 | 2017-06-30 | 滁州市全丰物资有限公司 | A kind of aqueous polyester resin coating and preparation method thereof |
| CN107522821A (en) * | 2017-08-30 | 2017-12-29 | 佛山市高明同德化工有限公司 | A kind of coil coating acrylated polyester water-base resin and preparation method thereof |
| CN107522821B (en) * | 2017-08-30 | 2020-05-19 | 佛山市高明同德化工有限公司 | Acrylic acid modified polyester water-based resin for coil coating and preparation method thereof |
| CN110713592A (en) * | 2018-07-11 | 2020-01-21 | 广东华润涂料有限公司 | High-solid low-viscosity resin composition containing polyether modified polyester |
| CN115322660A (en) * | 2022-09-13 | 2022-11-11 | 雅涂科技(张家港)有限公司 | Preparation method of solvent-free polyester resin coating |
| CN115322660B (en) * | 2022-09-13 | 2023-09-22 | 雅涂科技(张家港)有限公司 | Preparation method of solvent-free polyester resin coating |
| CN116178690A (en) * | 2023-01-09 | 2023-05-30 | 广东莱尔新材料科技股份有限公司 | Self-emulsifying water-based polyester resin and preparation method thereof |
| CN116178690B (en) * | 2023-01-09 | 2024-05-07 | 广东莱尔新材料科技股份有限公司 | Self-emulsifying water-based polyester resin and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106366323A (en) | Easily water dispersible polyester resin | |
| CN102712820B (en) | Radiation-curable water-based paint compositions | |
| CN102875945B (en) | The preparation method of polyester acrylate hybridization aqueous dispersion | |
| CN103555120B (en) | A kind of polyacrylate grafting modified poly ester water-borne coatings and its preparation method | |
| CN102432797B (en) | Hydroxyl-terminated alkyd resin-modified waterborne polyurethane and preparation method thereof | |
| CN103703038B (en) | Aqueous polyurethane resin dispersion and application thereof | |
| CN107522821A (en) | A kind of coil coating acrylated polyester water-base resin and preparation method thereof | |
| CN107868235A (en) | A kind of powdery paints difunctional polyester resin and preparation method thereof | |
| CN109880494B (en) | 50:50 polyester resin for indoor high-hardness and high-gloss powder and preparation method thereof | |
| CN104710598A (en) | Vegetable oleic acid modified epoxy resin and preparation method thereof, polymer containing vegetable oleic acid modified epoxy resin, and preparation method and application of polymer | |
| CN105907285B (en) | Super abrasive polyurethane floor coatings | |
| CN106700047A (en) | Modified high-solid low-viscous polyester resin, preparation method of modified high-solid low-viscous polyester resin, and application of modified high-solid low-viscous polyester resin in coating | |
| CN109486384A (en) | A kind of polyurea type Polyaspartic Ester-Based Coatings feedstock composition, from its coating and its preparation method and application | |
| CN104927036A (en) | Preparation methods for polyester polyol and alcohol-soluble plastic printing ink polyurethane bonding material | |
| CN106432703A (en) | Hydroxyl polyester resin with high solid content and preparation method and application thereof | |
| CN104292419B (en) | A kind of preparation method of High-performance green environmental protection coatings for furniture two component polyurethane modified unsaturated polyester | |
| US20080033138A1 (en) | Methods Of Producing Amine-Terminated Caprolactone Polymers And Uses Of The Produced Polymers | |
| CN111675793B (en) | Waterborne polyurethane modified acrylic resin and preparation method and application thereof | |
| CN104817682B (en) | A kind of hyperbranched hydroxy resin of graft modification and its preparation method and application | |
| CN105085890A (en) | Hydrophilic hyperbranched enclosed type isocyanate and preparation method thereof, and application of hydrophilic hyperbranched enclosed type isocyanate in coatings | |
| CN100549091C (en) | Composition epoxy resin and epoxy-polysiloxane coating composition | |
| CN109293874B (en) | Polyether-ether-ketone modified polyurethane aqueous resin and preparation method thereof | |
| CN113278139B (en) | Hydrolysis-resistant polyester resin for water-based coil primer coating and preparation method thereof | |
| CN102863879A (en) | Waterborne three-component polyester paint and preparation method thereof | |
| CN113388093B (en) | Hydrolysis-resistant polyester resin for water-based coil finish paint and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170201 |
|
| RJ01 | Rejection of invention patent application after publication |