CN107266654A - A kind of ultraviolet light solidification hyper-branched polyester polyurethane acrylate resin and preparation method thereof - Google Patents
A kind of ultraviolet light solidification hyper-branched polyester polyurethane acrylate resin and preparation method thereof Download PDFInfo
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- CN107266654A CN107266654A CN201710456007.8A CN201710456007A CN107266654A CN 107266654 A CN107266654 A CN 107266654A CN 201710456007 A CN201710456007 A CN 201710456007A CN 107266654 A CN107266654 A CN 107266654A
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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
- 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
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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
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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
- C08G18/68—Unsaturated polyesters
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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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
Abstract
The invention discloses the preparation method that a kind of ultraviolet light solidifies hyper-branched polyester polyurethane acrylate resin, step is：(1) at room temperature, diisocyanate, catalyst, polymerization inhibitor are added in reaction bulb, dropping end hydroxy acrylate, drips and be warming up to 40~50 DEG C while stirring, reaction reaches half when starting reaction to measured nco value, that is, the isocyanate-monomer of half end-blocking is made；(2) in the reaction bulb of step (1), it is kept stirring for the mixed liquor that hyper-branched polyester and tetrahydrofuran is added dropwise in state, drip 1~8h of insulation reaction, then 40~90 DEG C are to slowly warm up to, 1~6h of stirring reaction, 60~100 DEG C are warming up to again, stirring reaction to measured nco value reaches theoretical value, remove solvent.Solidify hyper-branched polyester chlorinated polyethylene the invention also discloses the ultraviolet light as made from the above method.Raw material of the present invention is easy to get, simple to operate, and obtained resin wearability is good, solidification rate is fast.
Description
Technical field
The invention belongs to light-cured resin technical field, and in particular to a kind of ultraviolet light solidification hyper-branched polyester polyurethane third
Alkene acid ester resin and preparation method thereof.
Background technology
Ultraviolet light solidification refers to that under the irradiation of ultraviolet light light trigger is produced in free radical or cation, initiation system
Polymerisation occurs for the compound (polymer, prepolymer and monomer) with unsaturated double-bond or epoxide group, so that system exists
It is changed into the process of solid-state in the very short time by liquid.A kind of green curing technology that it has been developed rapidly since being nineteen sixty,
It has the advantages that 5E to more conventional curing method, i.e., economical (Economical), environment-friendly (Environmental), efficiently
(Efficient), energy-conservation (Energy Saving), wide adaptability (Enabling).
Dissaving polymer is the macromolecular with highly branched structure, with degree of functionality is high, intramolecular and it is intermolecular not
The advantages of occurring entanglement, the spherical three-dimensional structure of high degree of symmetry.Hyper-branched polyester is used as branched repetition using ester group (- COO-) group
Unit, in addition to highly branched structure and spherical molecular shape, also containing hydroxyl activity functional group, it is easy to right
Its end group carries out modification with modified to assign multifunctionality；Super branched polyurethane is made with carbamate (- NHCOO-) group
For branching repeat unit, the characteristics of with dissaving polymer in addition to, also with the preferable adhesive force of polyurethane resin, pliability
And the advantages of wearability, both, which combine, has excellent combination property.
But do not contain ultraviolet curing group in existing hyper-branched polyester, it is impossible to carry out ultraviolet light solidification.
The content of the invention
It is an object of the invention to provide the preparation side that a kind of ultraviolet light solidifies hyper-branched polyester polyurethane acrylate resin
Method, this method raw material is simple and easy to get, simple to operate.
It is a further object of the present invention to provide the ultraviolet light solidification hyper-branched polyester polyurethane third that the above method is prepared
Alkene acid ester resin, can carry out ultraviolet light solidification.
A kind of ultraviolet light solidifies the preparation method of hyper-branched polyester polyurethane acrylate resin, comprises the following steps：
(1) at room temperature, diisocyanate, catalyst, polymerization inhibitor are added in dry reaction bulb, dripped under stirring
Plus terminal hydroxy group acrylate, it was added dropwise to complete in 0.5~2 hour, drips and be warming up to 35~50 DEG C, is reacted to measured different
Cyanic acid ester group (- NCO) value reaches half when starting reaction, that is, the isocyanate-monomer of half end-blocking is made；Two described isocyanides
The mol ratio of acid ester monomer and described terminal hydroxy group acrylate is 1：1~1.1：1；
Described diisocyanate is selected from IPDI, hexamethylene diisocyanate, diphenyl methane
One or more mixtures in diisocyanate, toluene di-isocyanate(TDI), hydrogenated diphenyl methane diisocyanate；
Described terminal hydroxy group acrylate is selected from hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, first
One or more mixtures in base hydroxypropyl acrylate, polycaprolactone acrylate；
(2) in the reaction bulb of step (1), it is kept stirring under state that superbrnaching end-hydroxy polyester and tetrahydrofuran is added dropwise
Mixed liquor, was added dropwise to complete in 0.5~2 hour, dripped insulation reaction 1~8 hour；Then 40~90 DEG C are to slowly warm up to,
Stirring reaction 1~6 hour；It is warming up to 60~100 DEG C again, stirring reaction to measured-nco value reaches theoretical value；Decompression is removed
After solvents tetrahydrofurane, that is, ultraviolet light solidification hyper-branched polyester polyurethane acrylate resin is made；It is different that described half blocks
The mol ratio of-NCO and hydroxyl (- OH) in described hyper-branched polyester is 1 in cyanate ester monomer：1~1：1.2；
The mean molecule quantity of described superbrnaching end-hydroxy polyester is 200~4000g/mol.
It is preferred that, described superbrnaching end-hydroxy polyester be selected from hydroxyl quantity on each super branched molecule be 4 or 8 or 16 or
One or more mixtures in 32 or 64 or 128 superbrnaching end-hydroxy polyester.
Further, same to step (1) identical catalyst and polymerization inhibitor are added in step (2), reactivity is improved.
It is preferred that, described catalyst is selected from dibutyl tin laurate or stannous iso caprylate.
It is preferred that, described polymerization inhibitor is selected from BHT or p methoxy phenol.
Wherein, the assay method of described NCO (- NCO) content is di-n-butylamine back titration method.
The present invention also provides a kind of ultraviolet light solidification hyper-branched polyester polyurethane acrylate resin, and it is by above-mentioned preparation side
Method is made, and the resin is the dissaving polymer simultaneously containing carbamate groups, alkyl, ester group and terminal acrylate base.
The present invention introduces carbamate groups and acrylate group by the terminal reactive group of hyper-branched polyester, enters
One step is modified to hyper-branched polyester, so as to obtain more preferable wearability, pliability and more efficient solidification rate.It is modified
Dissaving polymer there is excellent dissolubility, low viscosity and substantial amounts of unsaturated double-bond, the occasions such as coating, ink should
Used time occupies higher proportion, can reduce the consumption of diluent and acrylic monomers, and then reduces pollution to environment and human body
Harm.
The ultraviolet light that the present invention is provided solidifies the preparation method of hyper-branched polyester polyurethane acrylate resin, and this method makes
Raw material is simple and easy to get, and solvents tetrahydrofurane low boiling point, post-processes simple to operation.
Brief description of the drawings
Fig. 1 is the synthetic route of the isocyanate-monomer partly blocked；
Fig. 2 is the synthetic route that ultraviolet light solidifies hyper-branched polyester polyurethane acrylate resin.
Embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
(1) at room temperature, by 1.2mol IPDIs (IPDI), 0.05wt% dibutyl tin laurates,
0.2wt%2,6- BHT are added in dry reaction bulb, and 1.2mol polycaprolactones third are added dropwise under stirring
Olefin(e) acid ester (CA), time for adding 1 hour drips and is warming up to 35 DEG C, reacts to measured-nco value and reaches when starting reaction
Half, that is, the isocyanates IPDI-CA monomers of half end-blocking are made, synthetic route is as shown in Figure 1；
(2) in the reaction bulb of step (1), 0.05wt% dibutyl tin laurates, 0.2wt%2, the tertiary fourths of 6- bis- are added
Base paracresol, is kept stirring for being added dropwise superbrnaching end-hydroxy polyester and tetrahydrochysene that hydroxyl value on each super branched molecule is 8 under state
The mixed liquor (tetrahydrofuran consumption is defined by all dissolving hyper-branched polyester) of furans, time for adding 1 hour drips insulation anti-
Answer 1 hour；Then 40~50 DEG C, stirring reaction 1 hour are to slowly warm up to；It is warming up to 65~75 DEG C again, stirring reaction is to being surveyed
- nco value reaches theoretical value；Decompression is removed after solvents tetrahydrofurane, obtains ultraviolet light solidification hyper-branched polyester polyurethane acroleic acid
Ester resin, synthetic route is as shown in Figure 2.Wherein, in the isocyanates IPDI-CA monomers of half end-blocking-NCO with it is each hyperbranched point
- OH mol ratio is 1 in the hyper-branched polyester that hydroxyl value is 8 on son：1.
Embodiment 2
(1) at room temperature, by 1.1mol hexamethylene diisocyanates (HDI), 0.05wt% dibutyl tin laurates,
0.2wt%2,6- BHT are added in dry reaction bulb, and 1.0mol polycaprolactones third are added dropwise under stirring
Olefin(e) acid ester (CA), time for adding 0.5 hour drips and is warming up to 45 DEG C, reacts to measured-nco value and reaches and start reaction
When half, that is, the isocyanates HDI-CA monomers of half end-blocking are made；
(2) in the reaction bulb of step (1), it is 8 to be kept stirring for being added dropwise hydroxyl value on each super branched molecule under state
The mixed liquor of superbrnaching end-hydroxy polyester and tetrahydrofuran, time for adding 1 hour, drips insulation reaction 2 hours；Then it is slow
It is warming up to 50~60 DEG C, stirring reaction 2 hours；It is warming up to 70~80 DEG C again, stirring reaction to measured-nco value reaches reason
By value；Decompression is removed after solvents tetrahydrofurane, obtains ultraviolet light solidification hyper-branched polyester polyurethane acrylate resin.Wherein, half seal
- NCO and hydroxyl value on each super branched molecule rub for-OH in 8 hyper-branched polyester in the isocyanates HDI-CA monomers at end
You are than being 1：1.05.
Embodiment 3
(1) at room temperature, by 1.5mol IPDIs (IPDI), 0.05wt% dibutyl tin laurates,
0.2wt%2,6- BHT are added in dry reaction bulb, and 1.5mol acrylic acid hydroxyl second is added dropwise under stirring
Ester (HEA), time for adding 1.5 hours drips and is warming up to 40 DEG C, reacts to measured-nco value and reaches when starting reaction
Half, that is, be made the isocyanates IPDI-HEA monomers of half end-blocking；
(2) in the reaction bulb of step (1), it is 8 to be kept stirring for being added dropwise hydroxyl value on each super branched molecule under state
The mixed liquor of superbrnaching end-hydroxy polyester and tetrahydrofuran, time for adding 2 hours, drips insulation reaction 4 hours；Then it is slow
It is warming up to 60~70 DEG C, stirring reaction 4 hours；It is warming up to 80~90 DEG C again, stirring reaction to measured-nco value reaches reason
By value；Decompression is removed after solvents tetrahydrofurane, obtains ultraviolet light solidification hyper-branched polyester polyurethane acrylate resin.Wherein, half seal
- NCO and hydroxyl value on each super branched molecule are-OH in 8 hyper-branched polyester in the isocyanates IPDI-HEA monomers at end
Mol ratio is 1：1.1.
Embodiment 4
(1) at room temperature, by 1.5mol IPDIs (IPDI), 0.05wt% dibutyl tin laurates,
0.2wt%2,6- BHT are added in dry reaction bulb, and 1.4mol methacrylic acids are added dropwise under stirring
Hydroxyl ethyl ester (HEMA), time for adding 1 hour drips and is warming up to 50 DEG C, reacts to measured-nco value and reaches and start reaction
When half, that is, the isocyanates IPDI-HEMA monomers of half end-blocking are made；
(2) in the reaction bulb of step (1), it is 64 to be kept stirring for being added dropwise hydroxyl value on each super branched molecule under state
The mixed liquor of superbrnaching end-hydroxy polyester and tetrahydrofuran, time for adding about 2 hours, drips insulation reaction 3 hours；Then delay
Slowly 80~90 DEG C, stirring reaction 3 hours are warming up to；It is warming up to 95~100 DEG C again, stirring reaction to measured-nco value reaches
Theoretical value；Decompression is removed after solvents tetrahydrofurane, obtains ultraviolet light solidification hyper-branched polyester polyurethane acrylate resin.Wherein, half
In the isocyanates IPDI-HEMA monomers of end-blocking on-NCO and each super branched molecule hydroxyl value in 64 hyper-branched polyester-
OH mol ratio is 1：1.1.
Embodiment 5
(1) at room temperature, by 1.5mol methyl diphenylene diisocyanates (MDI), 0.05wt% stannous iso caprylates,
0.2wt% p methoxy phenols are added in dry reaction bulb, and 1.5mol hydroxyethyl methacrylates are added dropwise under stirring
(HEMA), time for adding 1 hour, drips and is warming up to 35 DEG C, reacts to measured-nco value one reached when starting reaction
Half, that is, the isocyanates MDI-HEMA monomers of half end-blocking are made；
(2) in the reaction bulb of step (1), 0.05wt% stannous iso caprylates, 0.2wt% p methoxy phenols are added, is protected
Hold the mixing that superbrnaching end-hydroxy polyester and tetrahydrofuran that hydroxyl value on each super branched molecule is 16 are added dropwise under stirring
Liquid, time for adding about 2 hours, drips insulation reaction 1 hour；Then 40~50 DEG C, stirring reaction 1 hour are to slowly warm up to；
It is warming up to 65~75 DEG C again, stirring reaction to measured-nco value reaches theoretical value；Decompression is removed after solvents tetrahydrofurane, obtains purple
Outer photocuring hyper-branched polyester polyurethane acrylate resin.Wherein ,-NCO in the isocyanates MDI-HEMA monomers of half end-blocking
Material amount and each super branched molecule on hydroxyl value be 16 hyper-branched polyester in-OH the ratio between the amount of material be 1：1.2.
Embodiment 6
(1) at room temperature, by 1.5mol hydrogenated diphenyl methane diisocyanates (HMDI), 0.05wt% stannous iso caprylates,
0.2wt% p methoxy phenols are added in dry reaction bulb, and 1.5mol hydroxy-ethyl acrylates are added dropwise under stirring
(HEA), time for adding 1.2 hours, drip and are warming up to 35 DEG C, react to measured-nco value one reached when starting reaction
Half, that is, the isocyanates HMDI-HEA monomers of half end-blocking are made；
(2) in the reaction bulb of step (1), it is 32 to be kept stirring for being added dropwise hydroxyl value on each super branched molecule under state
The mixed liquor of superbrnaching end-hydroxy polyester and tetrahydrofuran, time for adding about 2 hours, drips insulation reaction 8 hours；Then delay
Slowly 40~50 DEG C, stirring reaction 2 hours are warming up to；It is warming up to 65~75 DEG C again, stirring reaction to measured-nco value reaches
Theoretical value；Decompression is removed after solvents tetrahydrofurane, obtains ultraviolet light solidification hyper-branched polyester polyurethane acrylate resin.Wherein, half
- NCO and hydroxyl value on each super branched molecule are-OH in 32 hyper-branched polyester in the isocyanates HMDI-HEA monomers of end-blocking
Mol ratio be 1：1.
Embodiment 7
(1) at room temperature, by 1.5mol toluene di-isocyanate(TDI)s (TDI), 0.05wt% stannous iso caprylates, 0.2wt% to first
Epoxide phenol is added in dry reaction bulb, and 1.5mol hydroxypropyl acrylates (HPA), time for adding 2 are added dropwise under stirring
Hour, drip and be warming up to 40 DEG C, react to measured-nco value and reach half when starting reaction, that is, half end-blocking is made
Isocyanates TDI-HPA monomers；
(2) in the reaction bulb of step (1), it is 4 to be kept stirring for being added dropwise hydroxyl value on each super branched molecule under state
The mixed liquor of superbrnaching end-hydroxy polyester and tetrahydrofuran, time for adding about 2 hours, drips insulation reaction 6 hours；Then delay
Slowly 40~50 DEG C, stirring reaction 6 hours are warming up to；It is warming up to 65~75 DEG C again, stirring reaction to measured-nco value reaches
Theoretical value；Decompression is removed after solvents tetrahydrofurane, obtains ultraviolet light solidification hyper-branched polyester polyurethane acrylate resin.Wherein, half
- NCO and hydroxyl value on each super branched molecule are-OH in 4 hyper-branched polyester in the isocyanates TDI-HPA monomers of end-blocking
Mol ratio is 1：1.2.
Embodiment 8
(1) at room temperature, by 1.5mol IPDIs (IPDI), 0.05wt% tin dilaurate diisobutyls
Tin, 0.2wt% p methoxy phenols are added in dry reaction bulb, and 1.4mol methacrylic acid hydroxypropyls are added dropwise under stirring
Ester (HPMA), time for adding 1 hour drips and is warming up to 40 DEG C, reacts to measured-nco value and reaches when starting reaction
Half, that is, be made the isocyanates IPDI-HPMA monomers of half end-blocking；
(2) in the reaction bulb of step (1), it is 128 to be kept stirring for being added dropwise hydroxyl value on each super branched molecule under state
Superbrnaching end-hydroxy polyester and tetrahydrofuran mixed liquor, time for adding about 2 hours drips insulation reaction 2 hours；Slowly
It is warming up to 50~60 DEG C, stirring reaction 2 hours；It is warming up to 75~85 DEG C again, stirring reaction to measured-nco value reaches reason
By value；Decompression is removed after solvents tetrahydrofurane, obtains ultraviolet light solidification hyper-branched polyester polyurethane acrylate resin.Wherein, half seal
- NCO and hydroxyl value on each super branched molecule are-OH in 128 hyper-branched polyester in the isocyanates IPDI-HPMA monomers at end
Mol ratio be 1：1.1.
Comparative example (preparation of conventional modified urethane acrylate resin)：
(1) by 1.5mol IPDIs (IPDI), 0.05wt% tin dilaurate diisobutyls tin,
0.2wt% p methoxy phenols are added in dry reaction bulb, and 1.5mol hydroxy-ethyl acrylates are added dropwise under stirring
(HEA), time for adding about 1 hour, dropwise addition, which is reunited, is warming up to 35 DEG C, reacts to measured-nco value and reaches when starting reaction
Half, that is, be made the isocyanates IPDI-HEA monomers of half end-blocking；
(2) in the reaction bulb of step (1), 0.05wt% tin dilaurate diisobutyls tin, 0.2wt% are added to methoxyl group
Phenol, is kept stirring for being added dropwise the PTMG (molecular weight is 1000g/mol) of bifunctionality under state, time for adding is about
0.5 hour, drip insulation reaction 1 hour；Then 40~50 DEG C, stirring reaction 1 hour are to slowly warm up to；It is warming up to 65 again~
75 DEG C, stirring reaction to measured-nco value reaches theoretical value, obtains ultraviolet light solidification bifunctionality polyether-polyurethane acrylic acid
Ester resin.
Performance comparision
The viscosity of prepared resin is tested using NDJ-5S rotation viscometers, condition determination is rotating speed 60r/min, temperature
Room temperature, test result such as table 1：
Table 1
| Viscosity (mPa.s) | |
| Embodiment 1 | 3000 |
| Embodiment 2 | 3500 |
| Embodiment 3 | 2800 |
| Embodiment 4 | 8000 |
| Embodiment 5 | 5000 |
| Embodiment 6 | 7000 |
| Embodiment 7 | 1000 |
| Embodiment 8 | 12000 |
| Comparative example | 3000 |
By each 20 parts of the resin of embodiment 1, embodiment 5 and comparative example, with trimethylolpropane diacrylate (TMPTA)
40 parts, 2 parts of TPO photoinitiator, 1,6- hexanediyl ester (HDDA), 38 parts of mixing, are sprayed on PC substrates, ultraviolet light
Solidification obtains the film of 20 microns of thickness, gained film performance test result such as table 2：
Table 2
| Performance indications | Embodiment 1 | Embodiment 5 | Comparative example |
| Paper tape is wear-resisting (@175g) | 360 times | 530 times | 170 times |
| Case hardness (@1kg, PET) | 1H | 4H | 1B |
| Adhesive force (cross-cut methods) | 5B | 5B | 5B |
| Surface gloss (60 ° of@) | 92° | 95° | 90° |
| Curing rate | 250mJ/cm2(fast) | 150mJ/cm2(very fast) | 1000mJ/cm2(medium) |
As shown in Table 2, all it is significantly increased using the wearability, hardness, curing rate of the ester modified film of hyperbranched poly,
And hyperbranched degree is higher, the amplitude of raising is bigger.
Claims (7)
1. a kind of ultraviolet light solidifies the preparation method of hyper-branched polyester polyurethane acrylate resin, it is characterised in that including such as
Lower step：
(1) at room temperature, diisocyanate, catalyst, polymerization inhibitor are added in dry reaction bulb, the dropping end under stirring
Hydroxy acrylate, was added dropwise to complete in 0.5~2 hour, drips and is warming up to 35~50 DEG C, reaction to measured isocyanic acid
Ester group value reaches half when starting reaction, that is, the isocyanate-monomer of half end-blocking is made；Described diisocyanate monomer with
The mol ratio of described terminal hydroxy group acrylate is 1：1~1.1：1；
It is different that described diisocyanate is selected from IPDI, hexamethylene diisocyanate, diphenyl methane two
One or more mixtures in cyanate, toluene di-isocyanate(TDI), hydrogenated diphenyl methane diisocyanate；
Described terminal hydroxy group acrylate is selected from hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, methyl-prop
One or more mixtures in olefin(e) acid hydroxypropyl acrylate, polycaprolactone acrylate；
(2) in the reaction bulb of step (1), it is kept stirring for being added dropwise the mixing of superbrnaching end-hydroxy polyester and tetrahydrofuran under state
Liquid, was added dropwise to complete in 0.5~2 hour, dripped insulation reaction 1~8 hour；Then 40~90 DEG C, stirring are to slowly warm up to
Reaction 1~6 hour；60~100 DEG C are warming up to again, and stirring reaction to measured isocyanates base value reaches theoretical value；Decompression
After solvents tetrahydrofurane, that is, ultraviolet light solidification hyper-branched polyester polyurethane acrylate resin is made；Half described end-blocking
The mol ratio of NCO and hydroxyl in described hyper-branched polyester is 1 in isocyanate-monomer：1~1：1.2；
The mean molecule quantity of described superbrnaching end-hydroxy polyester is 200~4000g/mol.
2. ultraviolet light according to claim 1 solidifies the preparation method of hyper-branched polyester polyurethane acrylate resin, its
It is characterised by, it is 4 or 8 or 16 or 32 or 64 that described superbrnaching end-hydroxy polyester, which is selected from hydroxyl quantity on each super branched molecule,
Or 128 superbrnaching end-hydroxy polyester in one or more mixtures.
3. ultraviolet light according to claim 1 solidifies the preparation method of hyper-branched polyester polyurethane acrylate resin, its
It is characterised by, same to step (1) identical catalyst and polymerization inhibitor is added in step (2).
4. ultraviolet light according to claim 1 solidifies the preparation method of hyper-branched polyester polyurethane acrylate resin, its
It is characterised by, described catalyst is selected from dibutyl tin laurate or stannous iso caprylate.
5. ultraviolet light according to claim 1 solidifies the preparation method of hyper-branched polyester polyurethane acrylate resin, its
It is characterised by, described polymerization inhibitor is selected from BHT or p methoxy phenol.
6. a kind of ultraviolet light solidifies hyper-branched polyester polyurethane acrylate resin, it is characterised in that it is by Claims 1 to 5
Preparation method described in any one is made.
7. ultraviolet light according to claim 6 solidifies hyper-branched polyester polyurethane acrylate resin, it is characterised in that should
Resin is the dissaving polymer simultaneously containing carbamate groups, alkyl, ester group and terminal acrylate base.
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| CN107759757A (en) * | 2017-10-30 | 2018-03-06 | 北京理工大学 | The preparation method and ultraviolet-curing paint of a kind of ultra-branched polyurethane acrylate |
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| CN112064169A (en) * | 2020-09-03 | 2020-12-11 | 邓生平 | Crease-resistant breathable suit fabric |
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