CN107099024A - A kind of waterborne polyester of water boiling resistance excellent performance and preparation method thereof - Google Patents
A kind of waterborne polyester of water boiling resistance excellent performance and preparation method thereof Download PDFInfo
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- CN107099024A CN107099024A CN201710474842.4A CN201710474842A CN107099024A CN 107099024 A CN107099024 A CN 107099024A CN 201710474842 A CN201710474842 A CN 201710474842A CN 107099024 A CN107099024 A CN 107099024A
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
Abstract
The invention discloses a kind of waterborne polyester of water boiling resistance excellent performance, including the monomeric polyol at least containing two polyalcohols, at least polyacid monomer containing dimeric dibasic acid, branching agent, hydrophilic monomer, epoxy modifying agent and nertralizer, said components are respectively according to mass fraction：40 80 parts of monomeric polyol, 40 80 parts of polyacid monomer, 10 30 parts of branching agent, 10 50 parts of hydrophilic monomer, 10 30 parts of epoxy modifying agent, 10 20 parts of nertralizer.The waterborne polyester of the water boiling resistance excellent performance of the present invention had both had outstanding water boiling resistance performance, but also with good mechanical performance.
Description
Technical field
The present invention relates to a kind of waterborne polyester coating, specifically a kind of water boiling resistance, the waterborne polyester of resistant to hydrolysis and its system
Preparation Method.
Background technology
With continuing to develop for China's economy, the technology of factory coating is also increasingly perfect.Waterborne polyester coating is industry
One kind of water paint, it has the advantages that, glossiness good to the adhesive force of metal be good and solvent resistant, is provided simultaneously with excellent
Pliability and tensile property, so it is widely used in the external coating field of production equipment, metal material etc..However, poly-
Ester resin itself has ester bond structure, and shortcoming when it is used is also fairly obvious, is embodied in after storage process or film forming
It is the hydrolysis that can occur ester bond that film, which meets water, so as to cause significantly declining for film performance and influence the normal of polyester resin to make
With.Current solution is that polyester molecule chain is modified using acrylic resin or organic siliconresin, still, due to third
During the reaction of olefin(e) acid oligomer or silicone intermediate and polyester molecule chain, the mounting of its macro-radical can weaken strand
Flexibility, makes the pliability and impact property of reaction product be deteriorated.In addition, acrylic acid oligomer or silicone intermediate and polyester point
The problem of also occurring compatible poor between subchain, cause to produce lamination in film, significantly reduce the glossiness of film.
Chinese patent literature CN101654546A discloses a kind of hydrolysis resistant polyester resin composition, is blocked using terminal groups
Agent is blocked to polyester backbone.But the polyester resin is only to be blocked again after molecular backbone is formed, on the upside of its main chain
The ester group of group still have it is water-disintegrable, thus its improve hydrolysis property effect it is poor.And Chinese patent literature
CN101215730A then discloses a kind of polyester fiber being modified with hydrolysis-resisting agent, and it is using hydrolysis-resisting agent carbodiimides to poly-
Ester molecule main chain is blocked or reacts to improve the anti-hydrolytic resistance of polyester with hydroxyl.But carbodiimide is not suitable for
Dispersion system, one side carbodiimides meeting and hydroxyl reaction during storage, and destroy the steady of anionic dispersions
It is qualitative, cause polyester resin easily situation about being demulsified occur in emulsification system；Another aspect carbodiimides cost is higher, difficult
With industrially large-scale application.Therefore, a kind of excellent waterborne polyester of hydrolytic Resistance how is prepared, is current coated metal
One of significant technology issues of coating industry.
The content of the invention
Not only there is outstanding water boiling resistance performance it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of but also
Possesses good waterborne polyester of mechanical performance and preparation method thereof.
What the goal of the invention of the present invention was realized in：A kind of waterborne polyester of water boiling resistance excellent performance, it is characterised in that：
The waterborne polyester of the water boiling resistance excellent performance is including the monomeric polyol at least containing two polyalcohols, at least containing many of dimeric dibasic acid
First acid monomers, branching agent, hydrophilic monomer, epoxy modifying agent and nertralizer, said components are respectively according to mass fraction：It is polynary
40-80 parts of alcohol monomer, 40-80 parts of polyacid monomer, 10-30 parts of branching agent, 10-50 parts of hydrophilic monomer, epoxy modifying agent 10-30
Part, 10-20 parts of nertralizer.
Furtherly, monomeric polyol is the arbitrary proportion mixture of two polyalcohols and dihydric alcohol.
Furtherly, dihydric alcohol includes 1,3-PD, ethylene glycol, 1,4-CHDM, 3- methyl isophthalic acids, 5- penta
One kind in glycol is mixed with arbitrary proportion.
Furtherly, polyacid monomer is the arbitrary proportion mixture of dimeric dibasic acid and binary acid.
Furtherly, binary acid includes one in succinic acid, maleic acid, aromatic acid, terephthalic acid (TPA)
Plant or mixed with arbitrary proportion.
Furtherly, branching agent includes one kind or mixed with arbitrary proportion in pentaerythrite, trimethylolpropane, glycerine
Close.
Furtherly, hydrophilic monomer includes one kind or mixed with arbitrary proportion in dihydromethyl propionic acid, dimethylolpropionic acid
Close.
Furtherly, epoxy modifying agent is included in E44 epoxy resin, Glycidyl butyrate, tertiary carbonic acid glycidyl ester
One kind or mixed with arbitrary proportion.
Furtherly, nertralizer is organic amine, it include one kind in triethylamine, dimethylethanolamine, diethanol amine or
Mixed with arbitrary proportion.
Furtherly, the preparation method of the waterborne polyester of the water boiling resistance excellent performance comprises the following steps：
A) under normal temperature and pressure, monomeric polyol is separately added into the reactor provided with agitator, it is polyacid monomer, hydrophilic
Monomer, branching agent are simultaneously stirred until homogeneous, and then add esterification catalyst side below toward being passed through in reactor in lasting stirring
Nitrogen；
B) reactor is heated to 130-160 DEG C, heat time 0.5-2 hour, then insulation reaction 1-3 hours；
C) mixture obtained by b step is continued to be heated to 160-190 DEG C, heat time 0.5-2 hour, insulation reaction 2-4
Hour, then proceed to be heated to 190-230 DEG C, heat time 0.5-2 hour, insulation reaction 2-5 hours；
D) mixture obtained by step c is carried out slow cooling, epoxy modifying agent is added when temperature is down to 110-140 DEG C,
And insulation reaction 2-4 hours；
E) mixture obtained by Step d is carried out slow cooling, nertralizer is added when temperature is down to 50-90 DEG C, and be incubated
Reaction 0.5-1 hours；
F) 0.5-1 hours are persistently stirred toward deionized water is slowly added dropwise in mixture obtained by step e, while dropwise addition, so
Discharging can obtain the waterborne polyester of water boiling resistance excellent performance afterwards.
The present invention is improved to the waterborne polyester of prior art, and its advantage is as follows：
1st, in the waterborne polyester of water boiling resistance excellent performance of the invention, the binary polyester for employing two polyalcohols and dimeric dibasic acid is answered
Close reaction system.Except also containing highly resistant to hydrolysis long side chain radical simultaneously with terminal hydroxyl in the molecular chain structure of two polyalcohols
Except also there is highly resistant to hydrolysis long side-chain radical with terminal carboxylic acid group simultaneously in group, the molecular chain structure of dimeric dibasic acid, because
And the macromolecular chain structure containing oleophilic drainage base side chain can be formed in polyester melt polymerisation, play well shielding and
The hydrolysis of ester bond near protection, so that the water resistance of polyester is substantially improved.In addition, being respectively provided with flexibility in two polyalcohols and dimeric dibasic acid
Extremely strong side-chain structure, so polyester backbone possesses excellent Chain Flexibility, so that the mechanics for being effectively improved polyester film is strong
Degree and mechanical performance.
2nd, in the waterborne polyester of water boiling resistance excellent performance of the invention, employ two polyalcohols and dihydric alcohol and dimeric dibasic acid and
The compound system of binary acid.First, dihydric alcohol or binary acid can be to the rapid polymerization radical concentrations of the dimer in reaction system
Diluting effect to a certain extent is produced, and can effectively reduce polymerization speed of the dimer in chemical reaction, so as to avoid
Accessory substance and side reaction are produced in waterborne polyester system, the stability and reliability of waterborne polyester yield greatly improved, and make
Polymerisation is carried out at steady-state all the time.Secondly, the small molecule backbone of two polyalcohols and dimeric dibasic acid can be greatly improved
The macromolecular chain of waterborne polyester is flexible, so as to improve the mechanical performances such as the impact strength of waterborne polyester, tensile strength.
3rd, in the waterborne polyester of water boiling resistance excellent performance of the invention, the combinatorial chemistry of branching agent and hydrophilic monomer is employed
Structure.Produce intensive active branched groups in the long chain of two polyalcohols and dimeric dibasic acid using branching agent, and with hydrophilic list
The stronger network-like molecular chain structure of precursor reactant formation pliability, effectively increases the mechanical performance and mechanical property of polyester film
Energy.
4th, the waterborne polyester of water boiling resistance excellent performance of the invention employs heat stepwise and prepared by hypothermic response method, passes through
Heat stepwise and segmentation cool, and whole reaction is realized segmentation and carry out, the reaction for greatly improving two polyalcohols and dimeric dibasic acid is steady
It is qualitative, and the stable formation of branching type strand is ensure that, the generation of accessory substance is reduced, so as to improve what is entirely chemically reacted
Yield rate.
Embodiment
The waterborne polyester of the water boiling resistance excellent performance of the present invention includes monomeric polyol at least containing two polyalcohols, at least contained
There are polyacid monomer, branching agent, hydrophilic monomer, epoxy modifying agent and the nertralizer of dimeric dibasic acid, said components are according to mass fraction
It is respectively：40-80 parts of monomeric polyol, 40-80 parts of polyacid monomer, 10-30 parts of branching agent, 10-50 parts of hydrophilic monomer, ring
10-30 parts of oxygen modifying agent, 10-20 parts of nertralizer.Utilize the side chain terminal hydroxyl and the side chain terminal carboxylic acid of dimeric dibasic acid of two polyalcohols
Base is combined, and makes to form the macromolecular chain structure containing oleophilic drainage base side chain during polyester melt polymerisation, so as to lift polyester
Water resistance.Also, flexible extremely strong side-chain structure is respectively provided with two polyalcohols and dimeric dibasic acid, so polyester backbone possesses excellent
Chain Flexibility, so as to improve the mechanical strength and mechanical performance of polyester film.
The monomeric polyol of the present invention is using two polyalcohols and the arbitrary proportion mixture of dihydric alcohol, and dihydric alcohol includes 1,3-
One kind in propane diols, ethylene glycol, 1,4 cyclohexane dimethanol, 3- methyl isophthalic acids, 5- pentanediols is mixed with arbitrary proportion.It is first
First, two polyalcohols have the backbone with side chain terminal hydroxyl, and its strand possesses excellent side base and links ability and stronger
Strand activity, so that while polyester water-resistance property of coating is lifted, the mechanical performance and mechanical strength of film can be improved.And two
In addition to first alcohol terminal hydroxy group reactivity good except possessing, polymerization speed of two polyalcohols in chemical reaction can be also reduced, so that
Avoid and accessory substance and side reaction are produced in waterborne polyester system.
The polyacid monomer of the present invention is using dimeric dibasic acid and the arbitrary proportion mixture of binary acid, and binary acid includes fourth two
One kind in acid, maleic acid, aromatic acid, terephthalic acid (TPA) is mixed with arbitrary proportion.With monomeric polyol
System is similar, and dimeric dibasic acid has the backbone with side chain terminal carboxylic acid group, and its strand possesses excellent side base link ability
And stronger strand activity, so that while polyester water-resistance property of coating is lifted, the mechanical performance and mechanics of film can be improved
Intensity.And in addition to binary acid end carboxylic acid group's reactivity good except possessing, can also reduce dimeric dibasic acid poly- in chemical reaction
Sum velocity, accessory substance and side reaction are produced so as to avoid in waterborne polyester system.
When being chemically reacted, with dimeric dibasic acid, binary acid esterification occurs for two polyalcohols respectively, and dimeric dibasic acid is then distinguished
Occurs esterification with two polyalcohols, dihydric alcohol.In above-mentioned chemical reaction process, the side base of two polyalcohols and dimeric dibasic acid constantly occurs
Non- regularity is esterified Ligature, makes to mount different pendant groups in long chain structure, so as to reduce whole dimer
The alignment degree of molecular chain structure, improves the Chain Flexibility of waterborne polyester.
The branching agent of the present invention is included one kind in pentaerythrite, trimethylolpropane, glycerine or mixed with arbitrary proportion.
Pentaerythrite and glycerine are respectively provided with good molecular activity, and quickly its side base can be propped up on dimer strand interface
Change, so as to lift the side base link ability of dimer strand；Trimethylolpropane then possesses preferable molecular interface lubrication energy
Power and reactivity, can be sour small molecule in esterification reaction process and alcohol is rapidly introduced into polyester molecule chain, is formed hyper-branched
Molecular chain structure.
The hydrophilic monomer of the present invention includes one kind or mixed with arbitrary proportion in dihydromethyl propionic acid, dimethylolpropionic acid
Close.Dihydromethyl propionic acid and dimethylolpropionic acid are respectively provided with good chain extension ability, and make polyester formation self-emulsifying systems, can change
The mechanical property and mechanical strength of kind waterborne polyester.And dihydromethyl propionic acid and dimethylolpropionic acid carry primary hydroxyl and height
The hydroxy-acid group of steric hindrance is spent, wherein oh group can directly react with polyacid monomer and protect carboxylic group, so that
Stability and reliability that hydrophilic monomer is mounted on polyester molecule chain are ensured.
The epoxy modifying agent of the present invention is included in E44 epoxy resin, Glycidyl butyrate, tertiary carbonic acid glycidyl ester
One kind is mixed with arbitrary proportion.Said components have outstanding chemical stability in molecule Chain System, and its epoxy radicals exists
Good segment supporting role can be played in polyester long chain, so as to ensure the mechanical property of polyester molecule chain.
The nertralizer of the present invention is organic amine, it include one kind in triethylamine, dimethylethanolamine, diethanol amine or with
Arbitrary proportion is mixed.There is stronger particle affinity with highly polar amido in said components, and small point can be greatly decreased
The surface tension of minor structure, so as to improve the uniformity of polyester middle-molecular-weihydroxyethyl distribution.
According to coating water boiling resistance performance test (test environment：Aqueous polyester resin and special 303 amino resins of cyanogen according to one
Certainty ratio is deployed, is then equably sprayed on tinplate, by 180 degree baking-curing 30 minutes, base material after cooling
It is placed in 100 DEG C of boiling water continuous boiling to boil 4-8 hours, then base material is taken out natural air drying), water boiling resistance excellent performance of the invention
Waterborne polyester film bubbled without appearance within 3 hours, and changed colour and come off；Without two polyalcohols, dimeric dibasic acid, epoxy modifying agent
Modified fundamental type waterborne polyester film will bubble when water boils 0.5 hour, change colour.Surveyed according to GB/T 1732-93 standards
Calmly, the impact strength of the waterborne polyester film of water boiling resistance excellent performance of the invention is 3.5-5.5Mpa.
It is described in detail with reference to a pair of each embodiments of table, but does not therefore limit the invention to the implementation
In the range of example：
Embodiment 1
The present invention water boiling resistance excellent performance waterborne polyester include two polyalcohols, 1,3- propane diols, dimeric dibasic acid, succinic acid,
Pentaerythrite, dihydromethyl propionic acid, E44 epoxy resin, triethylamine, said components are respectively according to mass fraction：Two polyalcohols
20 parts, 20 parts of 1,3- propane diols, 20 parts of dimeric dibasic acid, 20 parts of succinic acid, 10 parts of pentaerythrite, 10 parts of dihydromethyl propionic acid, E44 rings
10 parts of oxygen tree fat, 10 parts of triethylamine.
The preparation method of the waterborne polyester of water boiling resistance excellent performance of the present invention comprises the following steps：
A) under normal temperature and pressure, monomeric polyol is separately added into the reactor provided with agitator, it is polyacid monomer, hydrophilic
Monomer, branching agent are simultaneously stirred until homogeneous, and then add esterification catalyst side below toward being passed through in reactor in lasting stirring
Nitrogen；
B) reactor is heated to 130 DEG C, 0.5 hour heat time, then insulation reaction 1 hour；
C) mixture obtained by b step is continued to be heated to 160 DEG C, 0.5 hour heat time, insulation reaction 2 hours, then
Continue to be heated to 190 DEG C, 0.5 hour heat time, insulation reaction 2 hours；
D) mixture obtained by step c is carried out slow cooling, epoxy modifying agent is added when temperature is down to 110 DEG C, and protect
Temperature reaction 2 hours；
E) mixture obtained by Step d is carried out slow cooling, nertralizer, and insulation reaction is added when temperature is down to 50 DEG C
0.5 hour；
F) toward deionized water is slowly added dropwise in mixture obtained by step e, 0.5 hour is persistently stirred while dropwise addition, then
Discharging can obtain the waterborne polyester of water boiling resistance excellent performance.
According to coating water boiling resistance performance test (test environment：Aqueous polyester resin and special 303 amino resins of cyanogen according to one
Certainty ratio is deployed, is then equably sprayed on tinplate, by 180 degree baking-curing 30 minutes, base material after cooling
It is placed in 100 DEG C of boiling water continuous boiling to boil 4 hours, then base material is taken out natural air drying), the water of water boiling resistance excellent performance of the invention
Property polyester film without there is foaming, change colour and come off.According to GB/T 1732-93 standard tests, water boiling resistance performance of the invention
The impact strength of excellent waterborne polyester film is 3.5Mpa.
Embodiment 2
The waterborne polyester of the water boiling resistance excellent performance of the present invention includes two polyalcohols, 1,3- propane diols, ethylene glycol, 1,4- hexamethylenes
Alkane dimethanol, 3- methyl isophthalic acids, 5- pentanediols, dimeric dibasic acid, succinic acid, maleic acid, aromatic acid, terephthalic acid (TPA),
Pentaerythrite, trimethylolpropane, glycerine, dihydromethyl propionic acid, dimethylolpropionic acid, E44 epoxy resin, butyric acid glycidol
Ester, tertiary carbonic acid glycidyl ester, triethylamine, dimethylethanolamine, diethanol amine, said components are other according to mass fraction point counting
For：Two 40 parts of polyalcohols, 10 parts of 1,3- propane diols, 10 parts of ethylene glycol, 10 parts of 1,4 cyclohexane dimethanol, 3- methyl isophthalic acids, 5- penta 2
10 parts of alcohol, 40 parts of dimeric dibasic acid, 10 parts of succinic acid, 10 parts of maleic acid, 10 parts of aromatic acid, 10 parts of terephthalic acid (TPA),
10 parts of pentaerythrite, 10 parts of trimethylolpropane, 10 parts of glycerine, 25 parts of dihydromethyl propionic acid, 25 parts of dimethylolpropionic acid, E44
10 parts of epoxy resin, 10 parts of Glycidyl butyrate, 10 parts of tertiary carbonic acid glycidyl ester, 5 parts of triethylamine, dimethylethanolamine 5
Part, 10 parts of diethanol amine.
The preparation method of the waterborne polyester of water boiling resistance excellent performance of the present invention comprises the following steps：
A) under normal temperature and pressure, monomeric polyol is separately added into the reactor provided with agitator, it is polyacid monomer, hydrophilic
Monomer, branching agent are simultaneously stirred until homogeneous, and then add esterification catalyst side below toward being passed through in reactor in lasting stirring
Nitrogen；
B) reactor is heated to 160 DEG C, 2 hours heat times, then insulation reaction 3 hours；
C) mixture obtained by b step is continued to be heated to 190 DEG C, 2 hours heat times, insulation reaction 4 hours, Ran Houji
It is continuous to be heated to 230 DEG C, 2 hours heat times, insulation reaction 5 hours；
D) mixture obtained by step c is carried out slow cooling, epoxy modifying agent is added when temperature is down to 140 DEG C, and protect
Temperature reaction 4 hours；
E) mixture obtained by Step d is carried out slow cooling, nertralizer, and insulation reaction is added when temperature is down to 90 DEG C
1 hour；
F) toward deionized water is slowly added dropwise in mixture obtained by step e, persistently stir 1 hour, then go out while dropwise addition
Material can obtain the waterborne polyester of water boiling resistance excellent performance.
According to coating water boiling resistance performance test (test environment：Aqueous polyester resin and special 303 amino resins of cyanogen according to one
Certainty ratio is deployed, is then equably sprayed on tinplate, by 180 degree baking-curing 30 minutes, base material after cooling
It is placed in 100 DEG C of boiling water continuous boiling to boil 8 hours, then base material is taken out natural air drying), the water of water boiling resistance excellent performance of the invention
Property polyester film without there is foaming, change colour and come off.According to GB/T 1732-93 standard tests, water boiling resistance performance of the invention
The impact strength of excellent waterborne polyester film is 5.5Mpa.
Embodiment 3
The waterborne polyester of the water boiling resistance excellent performance of the present invention includes two polyalcohols, ethylene glycol, 1,4 cyclohexane dimethanol, 3-
Methyl isophthalic acid, 5- pentanediols, dimeric dibasic acid, maleic acid, aromatic acid, terephthalic acid (TPA), trimethylolpropane, glycerine,
Dimethylolpropionic acid, Glycidyl butyrate, tertiary carbonic acid glycidyl ester, dimethylethanolamine, diethanol amine, said components are pressed
It is respectively according to mass fraction：Two 30 parts of polyalcohols, 10 parts of ethylene glycol, 5 parts of 1,4 cyclohexane dimethanol, 3- methyl isophthalic acids, 5- penta 2
5 parts of alcohol, 30 parts of dimeric dibasic acid, 10 parts of maleic acid, 5 parts of aromatic acid, 5 parts of terephthalic acid (TPA), trimethylolpropane 7
Part, 8 parts of glycerine, 20 parts of dimethylolpropionic acid, 10 parts of Glycidyl butyrate, 5 parts of tertiary carbonic acid glycidyl ester, dimethyl ethanol
6 parts of amine, 7 parts of diethanol amine.
The preparation method of the waterborne polyester of water boiling resistance excellent performance of the present invention comprises the following steps：
A) under normal temperature and pressure, monomeric polyol is separately added into the reactor provided with agitator, it is polyacid monomer, hydrophilic
Monomer, branching agent are simultaneously stirred until homogeneous, and then add esterification catalyst side below toward being passed through in reactor in lasting stirring
Nitrogen；
B) reactor is heated to 140 DEG C, 2 hours heat times, then insulation reaction 1.5 hours；
C) mixture obtained by b step is continued to be heated to 170 DEG C, 1 hour heat time, insulation reaction 2.5 hours, then
Continue to be heated to 200 DEG C, 1 hour heat time, insulation reaction 3 hours；
D) mixture obtained by step c is carried out slow cooling, epoxy modifying agent is added when temperature is down to 120 DEG C, and protect
Temperature reaction 2.5 hours；
E) mixture obtained by Step d is carried out slow cooling, nertralizer, and insulation reaction is added when temperature is down to 60 DEG C
0.5 hour；
F) toward deionized water is slowly added dropwise in mixture obtained by step e, 0.5 hour is persistently stirred while dropwise addition, then
Discharging can obtain the waterborne polyester of water boiling resistance excellent performance.
According to coating water boiling resistance performance test (test environment：Aqueous polyester resin and special 303 amino resins of cyanogen according to one
Certainty ratio is deployed, is then equably sprayed on tinplate, by 180 degree baking-curing 30 minutes, base material after cooling
It is placed in 100 DEG C of boiling water continuous boiling to boil 6 hours, then base material is taken out natural air drying), the water of water boiling resistance excellent performance of the invention
Property polyester film without there is foaming, change colour and come off.According to GB/T 1732-93 standard tests, water boiling resistance performance of the invention
The impact strength of excellent waterborne polyester film is 4Mpa.
Embodiment 4
The waterborne polyester of the water boiling resistance excellent performance of the present invention includes two polyalcohols, 1,3- propane diols, ethylene glycol, 1,4- hexamethylenes
Alkane dimethanol, dimeric dibasic acid, succinic acid, maleic acid, aromatic acid, pentaerythrite, glycerine, dihydromethyl propionic acid, two
Hydroxymethylbutyrate, E44 epoxy resin, tertiary carbonic acid glycidyl ester, triethylamine, diethanol amine, said components are according to mass fraction
It is respectively：Two 30 parts of polyalcohols, 10 parts of 1,3- propane diols, 10 parts of ethylene glycol, 10 parts of 1,4 cyclohexane dimethanol, dimeric dibasic acid 30
Part, 10 parts of succinic acid, 10 parts of maleic acid, 10 parts of aromatic acid, 10 parts of pentaerythrite, 10 parts of glycerine, dihydroxymethyl
15 parts of propionic acid, 15 parts of dimethylolpropionic acid, 10 parts of E44 epoxy resin, 10 parts of tertiary carbonic acid glycidyl ester, 8 parts of triethylamine, diethyl
8 parts of hydramine.
The preparation method of the waterborne polyester of water boiling resistance excellent performance of the present invention comprises the following steps：
A) under normal temperature and pressure, monomeric polyol is separately added into the reactor provided with agitator, it is polyacid monomer, hydrophilic
Monomer, branching agent are simultaneously stirred until homogeneous, and then add esterification catalyst side below toward being passed through in reactor in lasting stirring
Nitrogen；
B) reactor is heated to 150 DEG C, 1.5 hours heat times, then insulation reaction 2 hours；
C) mixture obtained by b step is continued to be heated to 180 DEG C, 1.5 hours heat times, insulation reaction 3 hours, then
Continue to be heated to 210 DEG C, 1.5 hours heat times, insulation reaction 4 hours；
D) mixture obtained by step c is carried out slow cooling, epoxy modifying agent is added when temperature is down to 130 DEG C, and protect
Temperature reaction 3 hours；
E) mixture obtained by Step d is carried out slow cooling, nertralizer, and insulation reaction is added when temperature is down to 70 DEG C
1 hour；
F) toward deionized water is slowly added dropwise in mixture obtained by step e, persistently stir 1 hour, then go out while dropwise addition
Material can obtain the waterborne polyester of water boiling resistance excellent performance.
According to coating water boiling resistance performance test (test environment：Aqueous polyester resin and special 303 amino resins of cyanogen according to one
Certainty ratio is deployed, is then equably sprayed on tinplate, by 180 degree baking-curing 30 minutes, base material after cooling
It is placed in 100 DEG C of boiling water continuous boiling to boil 7 hours, then base material is taken out natural air drying), the water of water boiling resistance excellent performance of the invention
Property polyester film without there is foaming, change colour and come off.According to GB/T 1732-93 standard tests, water boiling resistance performance of the invention
The impact strength of excellent waterborne polyester film is 4.5Mpa.
Embodiment 5
The waterborne polyester of the water boiling resistance excellent performance of the present invention includes two polyalcohols, 1,3- propane diols, ethylene glycol, 1,4- hexamethylenes
Alkane dimethanol, 3- methyl isophthalic acids, 5- pentanediols, dimeric dibasic acid, succinic acid, maleic acid, aromatic acid, terephthalic acid (TPA),
Pentaerythrite, trimethylolpropane, glycerine, dihydromethyl propionic acid, dimethylolpropionic acid, E44 epoxy resin, butyric acid glycidol
Ester, tertiary carbonic acid glycidyl ester, triethylamine, dimethylethanolamine, diethanol amine, said components are other according to mass fraction point counting
For：Two 40 parts of polyalcohols, 5 parts of 1,3- propane diols, 10 parts of ethylene glycol, 5 parts of 1,4 cyclohexane dimethanol, 3- methyl isophthalic acids, 5- pentanediols
10 parts, 40 parts of dimeric dibasic acid, 5 parts of succinic acid, 10 parts of maleic acid, 5 parts of aromatic acid, 10 parts of terephthalic acid (TPA), season penta
5 parts of tetrol, 10 parts of trimethylolpropane, 10 parts of glycerine, 20 parts of dihydromethyl propionic acid, 20 parts of dimethylolpropionic acid, E44 asphalt mixtures modified by epoxy resin
5 parts of fat, 10 parts of Glycidyl butyrate, 10 parts of tertiary carbonic acid glycidyl ester, 6 parts of triethylamine, 6 parts of dimethylethanolamine, diethyl
6 parts of hydramine.
The preparation method of the waterborne polyester of water boiling resistance excellent performance of the present invention comprises the following steps：
A) under normal temperature and pressure, monomeric polyol is separately added into the reactor provided with agitator, it is polyacid monomer, hydrophilic
Monomer, branching agent are simultaneously stirred until homogeneous, and then add esterification catalyst side below toward being passed through in reactor in lasting stirring
Nitrogen；
B) reactor is heated to 150 DEG C, 2 hours heat times, then insulation reaction 2.5 hours；
C) mixture obtained by b step is continued to be heated to 180 DEG C, 1.5 hours heat times, insulation reaction 3.5 hours, so
After continue to be heated to 220 DEG C, 2 hours heat times, insulation reaction 4.5 hours；
D) mixture obtained by step c is carried out slow cooling, epoxy modifying agent is added when temperature is down to 130 DEG C, and protect
Temperature reaction 3.5 hours；
E) mixture obtained by Step d is carried out slow cooling, nertralizer, and insulation reaction is added when temperature is down to 80 DEG C
1 hour；
F) toward deionized water is slowly added dropwise in mixture obtained by step e, persistently stir 1 hour, then go out while dropwise addition
Material can obtain the waterborne polyester of water boiling resistance excellent performance.
According to coating water boiling resistance performance test (test environment：Aqueous polyester resin and special 303 amino resins of cyanogen according to one
Certainty ratio is deployed, is then equably sprayed on tinplate, by 180 degree baking-curing 30 minutes, base material after cooling
It is placed in 100 DEG C of boiling water continuous boiling to boil 8 hours, then base material is taken out natural air drying), the water of water boiling resistance excellent performance of the invention
Property polyester film without there is foaming, change colour and come off.According to GB/T 1732-93 standard tests, water boiling resistance performance of the invention
The impact strength of excellent waterborne polyester film is 5Mpa.
Table one (ingredient units are mass fraction)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Two polyalcohols | 20 | 40 | 30 | 30 | 40 |
| 1,3- propane diols | 20 | 10 | 0 | 10 | 5 |
| Ethylene glycol | 0 | 10 | 10 | 10 | 10 |
| 1,4 cyclohexane dimethanol | 0 | 10 | 5 | 10 | 5 |
| 3- methyl isophthalic acids, 5- pentanediols | 0 | 10 | 5 | 0 | 10 |
| Dimeric dibasic acid | 20 | 40 | 30 | 30 | 40 |
| Succinic acid | 20 | 10 | 0 | 10 | 5 |
| Maleic acid | 0 | 10 | 10 | 10 | 10 |
| Aromatic acid | 0 | 10 | 5 | 10 | 5 |
| Terephthalic acid (TPA) | 0 | 10 | 5 | 0 | 10 |
| Pentaerythrite | 10 | 10 | 0 | 10 | 5 |
| Trimethylolpropane | 0 | 10 | 7 | 0 | 10 |
| Glycerine | 0 | 10 | 8 | 10 | 10 |
| Dihydromethyl propionic acid | 10 | 25 | 0 | 15 | 20 |
| Dimethylolpropionic acid | 0 | 25 | 20 | 15 | 20 |
| E44 epoxy resin | 10 | 10 | 0 | 10 | 5 |
| Glycidyl butyrate | 0 | 10 | 10 | 0 | 10 |
| Tertiary carbonic acid glycidyl ester | 0 | 10 | 5 | 10 | 10 |
| Triethylamine | 10 | 5 | 0 | 8 | 6 |
| Dimethylethanolamine | 0 | 5 | 6 | 0 | 6 |
| Diethanol amine | 0 | 10 | 7 | 8 | 6 |
Claims (10)
1. a kind of waterborne polyester of water boiling resistance excellent performance, it is characterised in that：The waterborne polyester bag of the water boiling resistance excellent performance
Include monomeric polyol at least containing two polyalcohols, at least polyacid monomer containing dimeric dibasic acid, branching agent, hydrophilic monomer, epoxy
Modifying agent and nertralizer, said components are respectively according to mass fraction：40-80 parts of monomeric polyol, polyacid monomer 40-80
Part, 10-30 parts of branching agent, 10-50 parts of hydrophilic monomer, 10-30 parts of epoxy modifying agent, 10-20 parts of nertralizer.
2. the waterborne polyester of water boiling resistance excellent performance according to claim 1, it is characterised in that：The monomeric polyol is two
The arbitrary proportion mixture of polyalcohols and dihydric alcohol.
3. the waterborne polyester of water boiling resistance excellent performance according to claim 2, it is characterised in that：The dihydric alcohol includes 1,3-
One kind in propane diols, ethylene glycol, 1,4 cyclohexane dimethanol, 3- methyl isophthalic acids, 5- pentanediols is mixed with arbitrary proportion.
4. the waterborne polyester of water boiling resistance excellent performance according to claim 1, it is characterised in that：The polyacid monomer is two
The arbitrary proportion mixture of polyacids and binary acid.
5. the waterborne polyester of water boiling resistance excellent performance according to claim 2, it is characterised in that：The binary acid includes fourth two
One kind in acid, maleic acid, aromatic acid, terephthalic acid (TPA) is mixed with arbitrary proportion.
6. the waterborne polyester of water boiling resistance excellent performance according to claim 1, it is characterised in that：The branching agent includes season penta
One kind in tetrol, trimethylolpropane, glycerine is mixed with arbitrary proportion.
7. the waterborne polyester of water boiling resistance excellent performance according to claim 1, it is characterised in that：The hydrophilic monomer includes two
One kind in hydroxymethyl propionic acid, dimethylolpropionic acid is mixed with arbitrary proportion.
8. the waterborne polyester of water boiling resistance excellent performance according to claim 1, it is characterised in that：The epoxy modifying agent includes
One kind in E44 epoxy resin, Glycidyl butyrate, tertiary carbonic acid glycidyl ester is mixed with arbitrary proportion.
9. the waterborne polyester of water boiling resistance excellent performance according to claim 1, it is characterised in that：The nertralizer is organic
Amine, it is included one kind in triethylamine, dimethylethanolamine, diethanol amine or mixed with arbitrary proportion.
10. a kind of preparation method of the waterborne polyester of the excellent performance of water boiling resistance according to claim 1, it is characterised in that：Institute
Preparation method is stated to comprise the following steps：
A) under normal temperature and pressure, monomeric polyol, polyacid monomer, hydrophilic list are separately added into the reactor provided with agitator
Body, branching agent are simultaneously stirred until homogeneous, and then add esterification catalyst side below toward being passed through nitrogen in reactor in lasting stirring
Gas；
B) reactor is heated to 130-160 DEG C, heat time 0.5-2 hour, then insulation reaction 1-3 hours；
C) mixture obtained by b step is continued to be heated to 160-190 DEG C, heat time 0.5-2 hour, insulation reaction 2-4 hours,
Then proceed to be heated to 190-230 DEG C, heat time 0.5-2 hour, insulation reaction 2-5 hours；
D) mixture obtained by step c is carried out slow cooling, epoxy modifying agent is added when temperature is down to 110-140 DEG C, and protect
Temperature reaction 2-4 hours；
E) mixture obtained by Step d is carried out slow cooling, nertralizer, and insulation reaction is added when temperature is down to 50-90 DEG C
0.5-1 hours；
F) toward deionized water is slowly added dropwise in mixture obtained by step e, persistently stir 0.5-1 hours, then go out while dropwise addition
Material can obtain the aqueous polyester resin of water boiling resistance excellent performance.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109354980A (en) * | 2018-10-31 | 2019-02-19 | 苏州巨峰电气绝缘系统股份有限公司 | A kind of water-base epoxy impregnating varnish and its preparation method and application |
| CN109721717A (en) * | 2017-10-31 | 2019-05-07 | 万华化学（广东）有限公司 | A kind of waterborne epoxy modified saturated polyester resin and its preparation method and application |
| CN112759720A (en) * | 2021-01-11 | 2021-05-07 | 广东锐涂精细化工有限公司 | Boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin and preparation method and application thereof |
| CN112794999A (en) * | 2020-12-30 | 2021-05-14 | 长兴化学（天津）有限公司 | Epoxy modified polyester emulsion and preparation method and application thereof |
| CN113403853A (en) * | 2021-07-29 | 2021-09-17 | 东台市东驰服装有限公司 | Waterproof and moisture permeable radiation-proof fabric and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5101009A (en) * | 1990-03-02 | 1992-03-31 | Polyplastics Co., Ltd. | Copolyester resins and methods of making the same |
| JPH1180336A (en) * | 1997-09-12 | 1999-03-26 | Teijin Ltd | Block copolyester and its production |
| CN101735431A (en) * | 2009-12-25 | 2010-06-16 | 广州擎天实业有限公司 | Weather resistant polyester resin with excellent water-boiling resisting performance and method for preparing same |
| CN103304789A (en) * | 2013-06-06 | 2013-09-18 | 广东伊诗德新材料科技有限公司 | 6:4 type polyester resin with good water boiling resistance and preparation method thereof |
| CN105504252A (en) * | 2016-01-12 | 2016-04-20 | 湖北乾兴化工有限公司 | Preparation method for polyester resin for water-based baking paint |
-
2017
- 2017-06-21 CN CN201710474842.4A patent/CN107099024A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5101009A (en) * | 1990-03-02 | 1992-03-31 | Polyplastics Co., Ltd. | Copolyester resins and methods of making the same |
| JPH1180336A (en) * | 1997-09-12 | 1999-03-26 | Teijin Ltd | Block copolyester and its production |
| CN101735431A (en) * | 2009-12-25 | 2010-06-16 | 广州擎天实业有限公司 | Weather resistant polyester resin with excellent water-boiling resisting performance and method for preparing same |
| CN103304789A (en) * | 2013-06-06 | 2013-09-18 | 广东伊诗德新材料科技有限公司 | 6:4 type polyester resin with good water boiling resistance and preparation method thereof |
| CN105504252A (en) * | 2016-01-12 | 2016-04-20 | 湖北乾兴化工有限公司 | Preparation method for polyester resin for water-based baking paint |
Non-Patent Citations (1)
| Title |
|---|
| 徐航: "环氧改性水性聚酯树脂合成及应用", 《广州化工》 * |
Cited By (9)
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| CN109721717A (en) * | 2017-10-31 | 2019-05-07 | 万华化学（广东）有限公司 | A kind of waterborne epoxy modified saturated polyester resin and its preparation method and application |
| CN109721717B (en) * | 2017-10-31 | 2021-12-10 | 万华化学（广东）有限公司 | Waterborne epoxy modified saturated polyester resin and preparation method and application thereof |
| CN109354980A (en) * | 2018-10-31 | 2019-02-19 | 苏州巨峰电气绝缘系统股份有限公司 | A kind of water-base epoxy impregnating varnish and its preparation method and application |
| CN109354980B (en) * | 2018-10-31 | 2021-01-29 | 苏州巨峰电气绝缘系统股份有限公司 | Water-based epoxy impregnating varnish and preparation method and application thereof |
| CN112794999A (en) * | 2020-12-30 | 2021-05-14 | 长兴化学（天津）有限公司 | Epoxy modified polyester emulsion and preparation method and application thereof |
| CN112794999B (en) * | 2020-12-30 | 2022-08-16 | 长兴化学（天津）有限公司 | Epoxy modified polyester emulsion and preparation method and application thereof |
| CN112759720A (en) * | 2021-01-11 | 2021-05-07 | 广东锐涂精细化工有限公司 | Boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin and preparation method and application thereof |
| CN113403853A (en) * | 2021-07-29 | 2021-09-17 | 东台市东驰服装有限公司 | Waterproof and moisture permeable radiation-proof fabric and preparation method thereof |
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