CN107151306A - A kind of hydrolysis resistant polyester resin of UV-curable and preparation method thereof - Google Patents
A kind of hydrolysis resistant polyester resin of UV-curable and preparation method thereof Download PDFInfo
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- CN107151306A CN107151306A CN201710483008.1A CN201710483008A CN107151306A CN 107151306 A CN107151306 A CN 107151306A CN 201710483008 A CN201710483008 A CN 201710483008A CN 107151306 A CN107151306 A CN 107151306A
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
- C08G18/2835—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds having less than 5 ether groups
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a kind of hydrolysis resistant polyester resin of UV-curable and preparation method thereof, by adding the monomer with epoxy functionality and (methyl) acrylic ester monomer containing fluorine atom during polyester resin free radical solution polymerization, the hydrolysis resistant polyester resin of above-mentioned UV-curable is obtained.Using above-mentioned technical proposal, light trigger is added in obtained polyester resin to be sprayed on ABS/PC plates after film-forming, carries out the impact strength of film before and after hydrothermal aging experiment, test hydrothermal aging, glossiness and hardness, can greatly promote the hydrolytic resistance of polyester resin.
Description
Technical field
The present invention relates to a kind of preparation method of the polyester resin of the UV-curable for woodcare paint industry, and in particular to one
Plant the preparation method of the hydrolysis resistant polyester resin of UV-curable.
Background technology
Ultraviolet light (UV) curing technology has the advantages that rapid curing, low energy consumption, high efficiency, pollution-free, complies fully with
" 5E " principle, is a kind of environment-friendly green technology.One of advantage of ultraviolet light solidification is that it is free of solvent, so as to disappear significantly
Pollution except organic volatile part VOC to environment.But, due to main component used be the oligomer of low molecule amount generally
With higher viscosity, monomer i.e. reactive diluent is must be added to when in use, to adjust its viscosity and rheological characteristic.These activity
Diluent still contains VOC, and also different degrees of toxicity and excitatory.On the other hand, water paint turns into coating
One of Main way of development, its low viscosity easily adjusted and extremely low VOC make it suitable for spraying, UV solidified aqueous coatings
Both advantages are combined, are closely being developed faster during the last ten years；But UV solidified aqueous coatings also have the shortcomings that its own,
I.e. hydrolytic resistance is poor, and the problem of water resistance is poor limits its broader purposes, and the present invention mainly solves to be used for coating
The hydrolytic resistance problem of the polyester resin of the UV-curable of industry.
The content of the invention
In order to solve the above technical problems, containing epoxide group by being added during polyester resin free radical solution polymerization
Monomer and (methyl) acrylic ester monomer containing fluorine atom, the hydrolysis resistant polyester resin of UV-curable is made.
The present invention provides a kind of hydrolysis resistant polyester resin of UV-curable, and its structural formula is shown below：
Wherein,
Wherein n=10~20, m=10~25, p=0~10, q=0~5, and p, q are not simultaneously 0.
Herein, B represents the basic group in amine nertralizer；ECA represents end-capping reagent.
The present invention also provides a kind of preparation method of the hydrolysis resistant polyester resin of above-mentioned UV-curable, its technical scheme simultaneously
For：
Step (1)：According to the mass fraction, by 10~15 parts of acrylic acid, 9~15 parts of acrylic ester monomers, 4~6 part third
Olefin(e) acid hydroxyl esters monomer, 3~20 parts of (methyl) acrylic ester monomers containing fluorine atom, 0.5~0.7 part of peroxide draw
Send out agent, 0.1~0.3 part of molecular weight regulator, 100~110 parts of solvents to add in reaction vessel, the free radical at 100~110 DEG C
Polymerisation 4~5 hours, temperature is down to 65~75 DEG C, and 4~7 parts of acrylic acid containing epoxide group are added into above-mentioned solution
Esters monomer, 0.5~0.7 part of quaternary ammonium salt catalyst, continue to react untill epoxy peak disappears, obtain acrylic polyester tree
Fat；
Step (2)：By 8~11 parts of IPDIs, 20~25 parts of polyethylene glycol, 12~16 parts of polyethylene glycol
Monomethyl ether, 0.05~0.15 part of catalyst dibutyltin dilaurylate are added in above-mentioned reaction vessel, are reacted at 65~75 DEG C
Untill nco value reaches predetermined value, polyurethane resin prepolymer is made；
Step (3)：It is made after acrylic acid polyester resin and polyurethane resin prepolymer, is added into above-mentioned reaction vessel
3.5~5 parts of end-capping reagents, temperature control is at 65~75 DEG C, and stirring reaction is for a period of time until nco value is zero, and then temperature is dropped to
45~50 DEG C, high-speed stirred adds 3~4 parts of amine nertralizers, obtains band blue light translucent polyester resin emulsion.
Further, the structure such as following formula of (methyl) acrylic ester monomer containing fluorine atom described in step (1)
It is shown：
Wherein p=0~10, q=0~5, and p, q are not simultaneously 0.
Further, the acrylic ester monomer described in step (1) is methyl acrylate, ethyl acrylate or acrylic acid
Butyl ester.
Further, the acrylic hydroxy ester monomer described in step (1) is hydroxy-ethyl acrylate or hydroxypropyl acrylate.
Further, the peroxide type initiators described in step (1) are benzoyl peroxide, benzoyl peroxide uncle
Butyl ester or methyl ethyl ketone peroxide.
Further, the molecular weight regulator described in step (1) selects n-dodecyl mercaptan.
Further, the solvent described in step (1) be glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether,
One kind in propylene glycol monomethyl ether, propylene-glycol ethyl ether or diethylene glycol dimethyl ether.
Further, the quaternary ammonium salt catalyst described in step (1) selects TBAB.
Further, the acrylic ester monomer containing epoxide group described in step (1) is Glycidyl methacrylate
Glyceride.
Further, the nertralizer described in step (3) is ammoniacal liquor, triethylamine or triethanolamine.
Further, (methyl) acrylic ester monomer containing fluorine atom described in step (1) is with containing epoxy radicals
The quality summation of the acrylic ester monomer of group accounts for the 8.0%~25% of reaction monomers gross mass, specifically, reaction monomers are step
Suddenly acrylic acid, acrylic ester monomer, acrylic hydroxy ester monomer, (methyl) esters of acrylic acid containing fluorine atom in (1)
Monomer, the acrylic ester monomer containing epoxide group and the IPDI in step (2), polyethylene glycol,
Pentaerythritol triacrylate in poly glycol monomethyl ether and step (3).
Further, (methyl) acrylic ester monomer containing fluorine atom described in step (1) contains ring with described
The mass ratio of the acrylic ester monomer of oxygen groups is (3~1):1.
Using above-mentioned technical proposal, because fluorocarbons has extremely low surface tension, so incorporating fluorine atoms into poly-
It is that, in order to obtain low-surface-energy, surface can be low, and hydrophobicity is strong, and water absorption rate substantially reduces to improve hydrolysis in ester resin
Property；The another monomer containing epoxy functionality, makes polyester resin by the compound containing active hydrogen and epoxy ring-opening chaining
Property modify, in resin film forming improve film hardness and weatherability, so as to improve hydrolytic resistance.
Embodiment
With reference to specific embodiment, the present invention is furture elucidated.
Embodiment 1
Step (1)：According to the mass fraction, by 15 parts of acrylic acid, 12 parts of butyl acrylates, 6 parts of hydroxypropyl acrylates, 4 parts
Trifluoroethyl methacrylate, 0.6 part of benzoyl peroxide, 0.2 part of n-dodecyl mercaptan, 100 parts of diethylene glycol dimethyl ethers
Add in reaction vessel, Raolical polymerizable 5 hours at 110 DEG C, temperature is down to 70 DEG C, 4 parts are added into above-mentioned solution
GMA, 0.6 part of TBAB, continue to react untill epoxy peak disappears, and obtain acrylic acid and gather
Ester resin；
Step (2)：By 10.5 parts of IPDIs, 25 parts of polyethylene glycol, 15 parts of poly glycol monomethyl ethers,
0.1 part of catalyst dibutyltin dilaurylate is added in above-mentioned reaction vessel, is reacted at 70 DEG C to nco value and is reached that predetermined value is
Only, polyurethane resin prepolymer is made；
Wherein n=10~20, m=10~25.
Step (3)：It is made after acrylic acid polyester resin and polyurethane resin prepolymer, is added into above-mentioned reaction vessel
4.5 parts of end-capping reagent pentaerythritol triacrylates, temperature control is at 70 DEG C, and stirring reaction is for a period of time until nco value is zero, so
Temperature drops to 50 DEG C afterwards, and high-speed stirred adds 3.8 parts of triethylamine aqueous solutions, obtains band blue light translucent polyester resin emulsion.
Wherein n=10~20, m=10~25.
The above-mentioned homemade polyester resin emulsions of 35g, 10g deionized waters, 0.5g defoamer EFKA2721,0.5g levellings is taken to help
Agent BYK-348,0.5g wetting agent BYK168,1g adhesion promoter DH7340,1.2g light trigger one
The BASFIRGACURE 2959 of BASFIRGACURE184,1.3g light trigger two, is stirred at room temperature mixing 0.5 hour, is made
Coating.
Embodiment 2
Step (1)：According to the mass fraction, by 13.7 parts of acrylic acid, 11 parts of butyl acrylates, 5.6 parts of hydroxypropyl acrylates,
10 parts of methacrylic acid octafluoro pentyl esters, 0.6 part of benzoyl peroxide, 0.2 part of n-dodecyl mercaptan, 100 parts of diethylene glycols two
Methyl ether is added in reaction vessel, and Raolical polymerizable 5 hours at 110 DEG C, temperature is down to 70 DEG C, is added into above-mentioned solution
5 parts of GMAs, 0.6 part of TBAB, continue to react untill epoxy radicals disappears, obtain acrylic acid
Polyester resin；
Step (2)：By 9.5 parts of IPDIs, 22.5 parts of polyethylene glycol, 14.5 parts of polyethyleneglycol first
Ether, 0.1 part of catalyst dibutyltin dilaurylate are added in above-mentioned reaction vessel, reacted at 70 DEG C to nco value reach it is predetermined
Untill value, polyurethane resin prepolymer is made；
Step (3)：It is made after acrylic acid polyester resin and polyurethane resin prepolymer, is added into above-mentioned reaction vessel
4.2 parts of end-capping reagent pentaerythritol triacrylates, temperature control is at 70 DEG C, and stirring reaction is for a period of time until nco value is zero, so
Temperature drops to 50 DEG C afterwards, and high-speed stirred adds 3.8 parts of triethylamine aqueous solutions, obtains band blue light translucent polyester resin emulsion.
The above-mentioned homemade polyester resin emulsions of 35g, 10g deionized waters, 0.5g defoamer EFKA2721,0.5g levellings is taken to help
Agent BYK-348,0.5g wetting agent BYK168,1g adhesion promoter DH7340,1.2g light trigger one
The BASFIRGACURE 2959 of BASFIRGACURE184,1.3g light trigger two, is stirred at room temperature mixing 0.5 hour, is made
Coating.
Embodiment 3
Step (1)：According to the mass fraction, by 12 parts of acrylic acid, 9.7 parts of butyl acrylates, 4.9 parts of hydroxypropyl acrylates,
18.6 parts of trifluoroethyl methacrylates, 0.6 part of benzoyl peroxide, 0.2 part of n-dodecyl mercaptan, 100 parts of diethylene glycols
Dimethyl ether is added in reaction vessel, and Raolical polymerizable 5 hours at 110 DEG C, temperature is down to 70 DEG C, is added into above-mentioned solution
Enter 6.2 parts of GMAs, 0.6 part of TBAB, continue to react untill epoxy peak disappears, obtain third
Olefin(e) acid polyester resin；
Step (2)：By 8.5 parts of IPDIs, 20 parts of polyethylene glycol, 12.5 parts of poly glycol monomethyl ethers,
0.1 part of catalyst dibutyltin dilaurylate is added in above-mentioned reaction vessel, is reacted at 70 DEG C to nco value and is reached that predetermined value is
Only, polyurethane resin prepolymer is made；
Step (3)：It is made after acrylic acid polyester resin and polyurethane resin prepolymer, is added into above-mentioned reaction vessel
3.6 parts of end-capping reagent pentaerythritol triacrylates, temperature control is at 70 DEG C, and stirring reaction is for a period of time until nco value is zero, so
Temperature drops to 50 DEG C afterwards, and high-speed stirred adds 3.8 parts of triethylamine aqueous solutions, obtains band blue light translucent polyester resin emulsion.
The above-mentioned homemade polyester resin emulsions of 35g, 10g deionized waters, 0.5g defoamer EFKA2721,0.5g levellings is taken to help
Agent BYK-348,0.5g wetting agent BYK168,1g adhesion promoter DH7340,1.2g light trigger one
The BASFIRGACURE 2959 of BASFIRGACURE184,1.3g light trigger two, is stirred at room temperature mixing 0.5 hour, is made
Coating.
Comparative example
Step (1)：According to the mass fraction, by 15 parts of acrylic acid, 12 parts of butyl acrylates, 6 parts of hydroxypropyl acrylates, 8 parts
Methyl methacrylate, 0.6 part of benzoyl peroxide, 0.2 part of n-dodecyl mercaptan, 100 parts of diethylene glycol dimethyl ethers are added
In reaction vessel, Raolical polymerizable 5 hours at 110 DEG C, temperature is down to 70 DEG C, adds 0.6 part of TBAB, obtains
To acrylic acid polyester resin；
Step (2)：By 10.5 parts of IPDIs, 25 parts of polyethylene glycol, 15 parts of poly glycol monomethyl ethers,
0.1 part of catalyst dibutyltin dilaurylate is added in above-mentioned reaction vessel, is reacted at 70 DEG C to nco value and is reached that predetermined value is
Only, polyurethane resin prepolymer is made；
Step (3)：It is made after acrylic acid polyester resin and polyurethane resin prepolymer, is added into above-mentioned reaction vessel
4.5 parts of end-capping reagent pentaerythritol triacrylates, temperature control is at 70 DEG C, and stirring reaction is for a period of time until nco value is zero, so
Temperature drops to 50 DEG C afterwards, and high-speed stirred adds 3.8 parts of triethylamine aqueous solutions, obtains band blue light translucent polyester resin emulsion.
The above-mentioned homemade polyester resin emulsions of 35g, 10g deionized waters, 0.5g defoamer EFKA2721,0.5g levellings is taken to help
Agent BYK-348,0.5g wetting agent BYK168,1g adhesion promoter DH7340,1.2g light trigger one
The BASFIRGACURE 2959 of BASFIRGACURE184,1.3g light trigger two, is stirred at room temperature mixing 0.5 hour, is made
Coating.
Respectively by coating made from embodiment 1, embodiment 2, embodiment 3 and comparative example, it is sprayed on ABS/PC base materials,
After UV solidifications, it is put into after damp heat test ageing oven, 40 DEG C of temperature, humidity 98%, aging 120h, the resistance to punching surveyed before and after ginkgo seeds
Hit intensity (height 60cm, weight 2kg), 60 DEG C of glossiness and hardness, test result are as follows：
It can be seen that from form, carry out the impact strength of film before and after hydrothermal aging experiment, test hydrothermal aging, gloss
Degree and hardness, it is found that the monomer with epoxy functionality and (methyl) acrylic ester monomer containing fluorine atom can be carried significantly
Rise the hydrolytic resistance of polyester resin.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (8)
1. a kind of hydrolysis resistant polyester resin of UV-curable, it is characterised in that its structural formula is shown below：
Wherein,
Wherein n=10~20, m=10~25, p=0~10, q=0~5, and p, q are not simultaneously 0.
2. a kind of preparation method of the hydrolysis resistant polyester resin of the UV-curable described in claim 1, it is characterised in that by with
Lower step is prepared：
Step (1)：According to the mass fraction, by 10~15 parts of acrylic acid, 9~15 parts of acrylic ester monomers, 4~6 parts of acrylic acid
Hydroxyl esters monomer, 3~20 parts of (methyl) acrylic ester monomers containing fluorine atom, 0.5~0.7 part of peroxide trigger
Agent, 0.1~0.3 part of molecular weight regulator, 100~110 parts of solvents are added in reaction vessel, the radical polymerization at 100~110 DEG C
Reaction 4~5 hours is closed, temperature is down to 65~75 DEG C, 4~7 parts of acrylate containing epoxide group are added into above-mentioned solution
Class monomer, 0.5~0.7 part of quaternary ammonium salt catalyst, continue to react untill epoxy peak disappears, obtain acrylic acid polyester resin；
Step (2)：By 8~11 parts of IPDIs, 20~25 parts of polyethylene glycol, 12~16 parts of polyethyleneglycol first
Ether, 0.05~0.15 part of catalyst dibutyltin dilaurylate are added in above-mentioned reaction vessel, are reacted at 65~75 DEG C to NCO
Untill value reaches predetermined value, polyurethane resin prepolymer is made；
Step (3)：It is made after acrylic acid polyester resin and polyurethane resin prepolymer, 3.5~5 is added into above-mentioned reaction vessel
Part end-capping reagent, temperature control is at 65~75 DEG C, and stirring reaction is for a period of time until nco value is zero, and then temperature drops to 45~50
DEG C, high-speed stirred adds 3~4 parts of amine nertralizers, obtains band blue light translucent polyester resin emulsion.
3. the preparation method of the hydrolysis resistant polyester resin of UV-curable as claimed in claim 2, it is characterised in that step (1)
Described in the structure of (methyl) acrylic ester monomer containing fluorine atom be shown below：
Wherein p=0~10, q=0~5, and p, q are not simultaneously 0.
4. the preparation method of the hydrolysis resistant polyester resin of UV-curable as claimed in claim 2, it is characterised in that step (1)
Described in acrylic ester monomer be methyl acrylate, ethyl acrylate or butyl acrylate, acrylic hydroxy ester monomer is
Hydroxy-ethyl acrylate or hydroxypropyl acrylate, peroxide type initiators are benzoyl peroxide, the benzoyl peroxide tert-butyl ester
Or methyl ethyl ketone peroxide, molecular weight regulator selects n-dodecyl mercaptan, and solvent is glycol monoethyl ether, ethylene glycol list second
One kind in ether, ethylene glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether or diethylene glycol dimethyl ether, quaternary ammonium salt catalyst
From TBAB.
5. the preparation method of the hydrolysis resistant polyester resin of UV-curable as claimed in claim 2, it is characterised in that step (1)
Described in the acrylic ester monomer containing epoxide group be GMA.
6. the preparation method of the hydrolysis resistant polyester resin of UV-curable as claimed in claim 2, it is characterised in that step (3)
Described in nertralizer be ammoniacal liquor, triethylamine or triethanolamine.
7. the preparation method of the hydrolysis resistant polyester resin of UV-curable as claimed in claim 2, it is characterised in that step (1)
Described in (methyl) acrylic ester monomer containing fluorine atom and the acrylic ester monomer containing epoxide group quality
Summation accounts for the 8.0%~25% of reaction monomers gross mass.
8. the preparation method of the hydrolysis resistant polyester resin of UV-curable as claimed in claim 2, it is characterised in that step (1)
Described in (methyl) acrylic ester monomer containing fluorine atom and the acrylic ester monomer containing epoxide group
Mass ratio is (3~1):1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710483008.1A CN107151306B (en) | 2017-06-22 | 2017-06-22 | Hydrolysis-resistant polyester resin capable of being cured by UV and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710483008.1A CN107151306B (en) | 2017-06-22 | 2017-06-22 | Hydrolysis-resistant polyester resin capable of being cured by UV and preparation method thereof |
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| Publication Number | Publication Date |
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| CN107151306A true CN107151306A (en) | 2017-09-12 |
| CN107151306B CN107151306B (en) | 2020-02-28 |
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| CN112029067A (en) * | 2020-09-08 | 2020-12-04 | 珠海市金团化学品有限公司 | Photo-curing water-based acrylic acid dispersion and preparation method and application thereof |
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