CN106496511A - Hyperbranched UV cured polyurethane acrylates of tong ma anhydride base and its preparation method and application - Google Patents
Hyperbranched UV cured polyurethane acrylates of tong ma anhydride base and its preparation method and application Download PDFInfo
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- CN106496511A CN106496511A CN201610897959.9A CN201610897959A CN106496511A CN 106496511 A CN106496511 A CN 106496511A CN 201610897959 A CN201610897959 A CN 201610897959A CN 106496511 A CN106496511 A CN 106496511A
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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
- C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
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- 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 belongs to UV solidification polymeric material fields, specifically disclose hyperbranched UV cured polyurethane acrylates of a kind of tong ma anhydride base and its preparation method and application.Present invention intermediate product I after additive reaction under UV illumination first by methyl eleostearate and maleic anhydride, adds trimethylolpropane to react 2～3h with intermediate product I high-temperature vacuums dehydration esterification, tong ma anhydride dissaving polymer is obtained；Add the dissaving polymer to obtain intermediate product II mixed liquor of the diisocyanate with its catalyst, finally 1.5～2.5h is reacted with hydroxyalkyl acrylate again with dilution dilution agent intermediate product II and obtain the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base.Methyl eleostearate is used for light-cured resin raw material by the present invention, has been widened renewable natural oil lipid products application and has been improved its added value content, has had great social and economic effects.
Description
Technical field
The invention belongs to UV solidification polymeric material fields, and in particular to a kind of hyperbranched UV of tong ma anhydride base solidifies poly- ammonia
Ester acrylate and its preparation method and application.
Background technology
Traditional aqueouss are with oil paint as solids content is typically more using linearly low with the dual restriction of working viscosity
The resin of molecular weight is film forming binder, and the performance such as some mechanics is often limited by the linearity molecular structure feature of film forming binder.
And dissaving polymer (Hyperbranched Polymer) has low viscosity, high rheological variation, multiterminal position functional group etc. a series of
Unique physicochemical characteristicss, can be widely applied to the fields such as coating, ink.With in the last few years for high-performance polymer grinds
That studied carefully gos deep into, and dissaving polymer is considered as one of most promising polymer, and common dissaving polymer is generally adopted
One-step synthesis, make the molecular structure of polymer that there is uncontrollability, constrain the large-scale production of dissaving polymer and push away
Wide use.
Modern chemistry product substantially set up the extension system in raw material based on fossil resource, and non-renewable fossil is provided
Source has obvious dependency, and current biomass resource is considered as the optimal alternative of fossil resource.It is widely present in dynamic
The biomass of thing and plant cause extensively being keen to for industry, biomass macromolecular material due to its recyclability and readily degradable
Even more one of emphasis problem of scientific research field.But the material for preparing the high using value of high-performance with biomass material remains section
Grind focus and the difficult point on boundary.
Curable urethane acrylate is that a class extensively applies cross-linking type resin.Due to its special molecular structure,
The features such as the higher tensile strength of existing polyurethane, excellent wearability；There are excellent adhesion, the weatherability of acrylate again
Etc. feature；The feature such as large arch dam, solidification rate in addition with light-cured resin are adjustable.
It is wooden that the Chinese invention patent application of publication number CN102206917A does not disclose a kind of tong ma anhydride methyl ester modification
The manufacture method of fiber, although also relate to prepare wood fibre with renewable natural plant resource paulownia horse acid methyl ester, but do not have
It is related to tong ma anhydride to prepare hyperbranched hydroxy resin and be used for the preparation of high-performance UV cured polyurethane acrylate.
Content of the invention
In order to overcome the shortcoming of above-mentioned prior art and deficiency, the primary and foremost purpose of the present invention to be to provide a kind of tong ma anhydride
The hyperbranched UV cured polyurethane acrylates of base.
Another object of the present invention is the preparation for providing the hyperbranched UV cured polyurethane acrylates of above-mentioned tong ma anhydride base
Method.
It is still another object of the present invention to provide the use of the hyperbranched UV cured polyurethane acrylates of above-mentioned tong ma anhydride base
On the way.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base, comprises the steps：
(1) methyl eleostearate and maleic anhydride of metering part are added in the reactor, is dissolved with solvent, is then added light-initiated
Agent so as to all dissolve and mix homogeneously；1～2h of photoreaction under UV light irradiations；After vacuum drying is evaporated solvent volatilization, plus
Enter a certain amount of detergent, and be filtered to remove unreacted maleic anhydride, obtain product I (tong ma anhydride)；
(2) product I (tong ma anhydride), trimethylolpropane and the catalyzing esterification for measuring is added in a kettle.
Agent, vacuum stirring and be warming up to 140～160 DEG C reaction 2～3h after, that is, obtain the hyperbranched hydroxy resin of tong ma anhydride base；
(3) at 20～30 DEG C, the mixture of diisocyanate and its catalyst is instilled the paulownia horse obtained by step (2)
In the hyperbranched hydroxy resin of anhydride, notice that adjusting rate of addition control drips off in 30～60min, heat up 60～90 DEG C of stirring reactions
After 1.5～3h, that is, obtain product II；
(4) product II that step (3) is obtained is diluted with a certain amount of reactive diluent, Deca a certain amount of (methyl)
Hydroxyalkyl acrylate and polymerization inhibitor, after 60～78 DEG C of 1.5～2.5h of reaction of control temperature, that is, obtain the hyperbranched UV of tong ma anhydride base
Cured polyurethane acrylate.
Methyl eleostearate of the present invention according to Publication No. CN105254499A Chinese patent application disclosed in system
Prepared by the method for standby eleostearate (methyl eleostearate is the one kind in eleostearate).
Methyl eleostearate described in step (1) is 1 with the mol ratio of maleic anhydride:1.2；Suddenly the solvent described in (1) is
Acetone, butanone, dimethylbenzene, at least one of ethyl acetate；In terms of 100 parts of weight of methyl eleostearate, described solvent is 300～
500 weight portions.
Light trigger described in step (1) be diphenylethan, α, α-diethoxy acetophenone, benzoin ethyl ether, peace
In the fragrant butyl ether of breath, phenyl double (2,4,6- trimethylbenzoyls) phosphine oxides and the chloro- 4- propoxyl group thioxanthones of 1- at least one
Kind, in terms of 100 parts of weight of methyl eleostearate, described light trigger is 3～5 weight portions.
Detergent described in step (1) is hexamethylene, normal hexane, heptane, one kind of octane；With 100 parts of methyl eleostearate
Weight meter, described detergent are 100～300 weight portions.
The mol ratio 3 of product I and trimethylolpropane described in step (2):7, esterification catalyst is N, N'- bis-
Diisopropylcarbodiimide, dicyclohexylcarbodiimide, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, to first
At least one in benzenesulfonic acid and butyl titanate；Its consumption for the mole of trimethylolpropane 2～4%.
Diisocyanate described in step (3) is aromatic series and/or aliphatic isocyanates, preferably isophorone two
Isocyanates, toluene di-isocyanate(TDI), PPDI, XDI and dicyclohexyl hexane two are different
At least one in cyanate；In terms of initial methyl eleostearate molal quantity, described diisocyanate is 2.0 moles (i.e. eleostearic acid
Methyl ester is 1 with diisocyanate mol ratio：2).
Catalyst described in step (3) is dibutyl tin laurate, solidifies poly- ammonia with the hyperbranched UV of tong ma anhydride base
100 weight portion meter of ester acrylate, the catalyst are 0.20～0.50 weight portion.
Reactive diluent described in step (4) be (methyl) isobornyl acrylate, 1,6 hexanediol diacrylate,
At least one in trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate and double pentaerythritol methacrylate；
In terms of hyperbranched 100 weight portion of UV cured polyurethane acrylates of tong ma anhydride base, the reactive diluent is 20～40 weight
Part.
(methyl) hydroxyalkyl acrylate described in step (4) is 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, metering system
Sour hydroxyl ethyl ester, Hydroxypropyl methacrylate, at least one of pentaerythritol triacrylate, described (methyl) acrylic acid hydroxyl alkane
Ester is 1 with the mol ratio of initial methyl eleostearate:2.5～1:3.0.Compared with the amount of remaining isocyano, (methyl) acrylic acid
Hydroxyalkyl is excessive slightly, to guarantee to be reacted with hydroxyl completely, does not remain isocyano, remaining in addition (methyl) acrylic acid hydroxyl alkane
Ester carries out photocuring together with activated monomer.
Polymerization inhibitor described in step (4) is MEHQ or hydroquinone；With (methyl) hydroxyalkyl acrylate 100
Weight portion meter, the polymerization inhibitor are 0.05～1.5 weight portion.
Preferably, in step (3) and (4), the speed of Deca solution is 1～15ml/min.
Product I of the hyperbranched UV cured polyurethane acrylates building-up process of tong ma anhydride base of the present invention, arrive paulownia
The hyperbranched hydroxy resin of horse anhydride group, product II, final product (the hyperbranched UV curing polyurethane acroleic acids of castor oil-base
Ester) structural formula such as following formula (1), (2), (3), shown in (4)：
The multistep processes synthesis terminal hydroxy group that the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base of the invention are adopted surpasses
Hyperbranched compounds improve the controllability of dissaving polymer reaction；Adopt eleostearic acid methyl ester many for initiation material synthesis of super branched
Hydroxy resin has widened the use range of biological material significantly.The hyperbranched UV of tong ma anhydride base prepared by the present invention solidifies poly- ammonia
Ester acrylate has excellent film performance, can be used as protecting metallic surface coating, the preferred film forming base of woodwork coating finish paint
Material.
The present invention is had the following advantages and beneficial effect relative to existing synthetic technology：
(1) eleostearic acid methyl ester is used for preparing the hyperbranched UV cured polyurethane acrylates oligomer of high-performance by the present invention
Raw material, alleviates the dependency to petrochemicals, has widened the range of application of renewable biomass raw material.Eleostearic acid first
Tong ma anhydride after ester and maleic anhydride photoreaction is still retained two carbon-carbon double bonds and can be provided and drawn with the further light of reactive diluent
Send out the avtive spot of additive reaction, in addition the hyperbranched polyhydroxy oligomer after tong ma anhydride and trihydroxymethylpropanyl ester with rear
Continuous urethane acrylate reacts to form double avtive spot, and the double space cross-linked structure enhances polymer coating film
Mechanical property afterwards and hydrolytic Resistance.
(2) the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base prepared by the present invention, compare common UV solidifications
Polyurethane acrylate resin, the UV cured polyurethane acrylates have higher adhesive force and hardness, and its curing performance is excellent
Good.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
(1) metering part methyl eleostearate and maleic anhydride (methyl eleostearate and maleic anhydride are sequentially added in transparency reactor
Mol ratio be 1:1.2), with acetone solution (consumption for methyl eleostearate quality 300%), then add diphenylethan and (use
Measure for methyl eleostearate quality 3%) so as to all dissolving mix homogeneously.Open UV ray machines, photoreaction under UV light irradiations
2h.After vacuum drying is evaporated acetone volatilization, hexamethylene (consumption for methyl eleostearate quality 100%) is added, and is filtered to remove
Unreacted maleic anhydride, obtains product I；
(2) product I, trimethylolpropane (product I and the three hydroxyl first for measuring are sequentially added in a kettle.
The mol ratio 3 of base propane:7) and N, N'- DIC the 2% of trimethylolpropane mole (consumption for), vacuum
After stirring and being warming up to 140 DEG C of reaction 3h, that is, obtain the hyperbranched hydroxy resin of tong ma anhydride base；
(3) in 20 DEG C of constant temperature oil baths, by isophorone diisocyanate, (consumption is the 2 of initial methyl eleostearate mole
Times) and dibutyl tin laurate (consumption is the 0.2% of the hyperbranched UV cured polyurethane acrylates weight of paulownia horse acid butt)
Mixture instill in the hyperbranched hydroxy resin of tong ma anhydride obtained by step (2), notes that adjusting rate of addition controls to exist
30min is dripped off, and after 90 DEG C of stirring reactions 1.5h that heat up, that is, obtains product II；
(4) (consumption is paulownia horse acid butt for all product II isobornyl acrylate dilutions for obtaining step (3)
20%), (consumption is initial methyl eleostearate mole to Deca 2-(Acryloyloxy)ethanol to hyperbranched UV cured polyurethane acrylates weight
250%) with MEHQ the 1.5% of 2-(Acryloyloxy)ethanol weight (consumption for), after control temperature 60 C reaction 2.5h,
Tong ma anhydride base hyperbranched UV cured polyurethane acrylate is obtained.
Embodiment 2
(1) metering part methyl eleostearate and maleic anhydride (methyl eleostearate and maleic anhydride are sequentially added in transparency reactor
Mol ratio be 1:1.2), with the dissolving of a certain amount of butanone (consumption for methyl eleostearate quality 500%), then add quantitative
α, α-diethoxy acetophenone (consumption for methyl eleostearate quality 5%) so as to all dissolve and mix homogeneously.Open UV light
Machine, photoreaction 1h under UV light irradiations.After vacuum drying is evaporated butanone volatilization, (consumption is to add a certain amount of normal hexane
Methyl eleostearate quality 300%), and be filtered to remove unreacted maleic anhydride, obtain product I；
(2) product I, trimethylolpropane (product I and the three hydroxyl first for measuring are sequentially added in a kettle.
The mol ratio 3 of base propane:7) with dicyclohexylcarbodiimide (consumption for trimethylolpropane mole 4%), vacuum stirring
And after being warming up to 160 DEG C of reaction 2h, that is, obtain the hyperbranched hydroxy resin of tong ma anhydride base；
(3) in 30 DEG C of constant temperature oil baths by toluene di-isocyanate(TDI) (consumption is 2 times of initial methyl eleostearate mole) and
The mixing of dibutyl tin laurate (consumption is the 0.2% of the hyperbranched UV cured polyurethane acrylates weight of paulownia horse acid butt)
Thing is instilled in the hyperbranched hydroxy resin of tong ma anhydride obtained by step (2), notes adjusting rate of addition control in 60min drops
Complete, after 60 DEG C of stirring reactions 3.0h that heat up, that is, obtain product II；
(4) (consumption is the acid of paulownia horse for all product II isobornyl methacrylate dilutions for obtaining step (3)
40%), (consumption rubs Deca Hydroxypropyl acrylate the hyperbranched UV cured polyurethane acrylates weight of butt for initial methyl eleostearate
Your amount 300%) with hydroquinone the 0.5% of Hydroxypropyl acrylate weight (consumption for), after 78 DEG C of reaction 1.5h of control temperature,
Tong ma anhydride base hyperbranched UV cured polyurethane acrylate is obtained.
Embodiment 3
(1) metering part methyl eleostearate and maleic anhydride (methyl eleostearate and maleic anhydride are sequentially added in transparency reactor
Mol ratio be 1:1.2), with a certain amount of xylene soluble (consumption for methyl eleostearate quality 320%), then add quantitative
Benzoin ethyl ether (consumption for methyl eleostearate quality 4%) so as to all dissolve and mix homogeneously.UV ray machines are opened, in UV light
The lower photoreaction 1.5h of irradiation.After vacuum drying is evaporated dimethylbenzene volatilization, (consumption is methyl eleostearate matter to add a certain amount of heptane
Amount 200%), and be filtered to remove unreacted maleic anhydride, obtain product I；
(2) product I, trimethylolpropane (product I and the three hydroxyl first for measuring are sequentially added in a kettle.
The mol ratio 3 of base propane:7) (consumption is trihydroxy methyl third with 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides
Alkane mole 3%), vacuum stirring and be warming up to 150 DEG C reaction 2.5h after, that is, obtain the hyperbranched hydroxyl tree of tong ma anhydride base
Fat；
(3) in 25 DEG C of constant temperature oil baths by PPDI (consumption is 2 times of initial methyl eleostearate mole) and
The mixing of dibutyl tin laurate (consumption is the 0.3% of the hyperbranched UV cured polyurethane acrylates weight of paulownia horse acid butt)
Thing is instilled in the hyperbranched hydroxy resin of tong ma anhydride obtained by step (2), notes adjusting rate of addition control in 40min drops
Complete, after 70 DEG C of stirring reactions 2.0h that heat up, that is, obtain product II；
(4) 1,6 hexanediyl esters of all product II that step (3) is obtained dilute (consumption be paulownia horse
30%), (consumption is initial eleostearic acid to Deca hydroxyethyl methylacrylate to the hyperbranched UV cured polyurethane acrylates weight of sour butt
Methyl ester mole 270%) with MEHQ the 1.0% of hydroxyethyl methylacrylate weight (consumption for), control temperature
After 66 DEG C of reaction 2.5h, that is, obtain the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base.
Embodiment 4
(1) metering part methyl eleostearate and maleic anhydride (methyl eleostearate and maleic anhydride are sequentially added in transparency reactor
Mol ratio be 1:1.2), with the dissolving of a certain amount of ethyl acetate (consumption for methyl eleostearate quality 400%), it is fixed then to add
Double (2,4,6- trimethylbenzoyl) phosphine oxides of amount phenyl (consumption for methyl eleostearate quality 3.5%) so as to all dissolve
And mix homogeneously.UV ray machines are opened, and 1.8h is reacted under UV light irradiation light.After vacuum drying is evaporated ethyl acetate volatilization, plus
Enter a certain amount of octane (consumption for methyl eleostearate quality 150%), and be filtered to remove unreacted maleic anhydride, reacted
Product I；
(2) product I, trimethylolpropane (product I and the three hydroxyl first for measuring are sequentially added in a kettle.
The mol ratio 3 of base propane:7) with p-methyl benzenesulfonic acid (consumption for trimethylolpropane mole 2.5%), vacuum stirring simultaneously rises
Temperature obtains the hyperbranched hydroxy resin of tong ma anhydride base to 145 DEG C of reaction 3h；
(3) in 22 DEG C of constant temperature oil baths, by XDI, (consumption is the 2 of initial methyl eleostearate mole
Times) and dibutyl tin laurate (consumption is the 0.4% of the hyperbranched UV cured polyurethane acrylates weight of paulownia horse acid butt)
Mixture instill in the hyperbranched hydroxy resin of tong ma anhydride obtained by step (2), notes that adjusting rate of addition controls to exist
50min is dripped off, and after 80 DEG C of stirring reactions 2.5h that heat up, that is, obtains product II；
(4) (consumption is paulownia for all product II trimethylolpropane trimethacrylate dilutions for obtaining step (3)
35%), (consumption is initial paulownia to Deca Hydroxypropyl methacrylate to the hyperbranched UV cured polyurethane acrylates weight of horse acid butt
Sour methyl ester mole 260%) with hydroquinone the 1.3% of Hydroxypropyl methacrylate weight (consumption for), control temperature 69
DEG C reaction 2.3h after, that is, obtain the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base.
Embodiment 5
(1) metering part methyl eleostearate and maleic anhydride (methyl eleostearate and maleic anhydride are sequentially added in transparency reactor
Mol ratio be 1:1.2), with a certain amount of acetone solution (consumption for methyl eleostearate quality 380%), then add quantitative 1-
Chloro- 4- propoxyl group thioxanthone (consumption for methyl eleostearate quality 4.5%) so as to all dissolve and mix homogeneously.Open UV
Ray machine, photoreaction 1.2h under UV light irradiations.After vacuum drying is evaporated acetone volatilization, a certain amount of normal hexane (consumption is added
For methyl eleostearate quality 150%), and be filtered to remove unreacted maleic anhydride, obtain product I；
(2) product I, trimethylolpropane (product I and the three hydroxyl first for measuring are sequentially added in a kettle.
The mol ratio 3 of base propane:7) with butyl titanate (consumption for trimethylolpropane mole 2.3%), vacuum stirring simultaneously rises
Temperature obtains the hyperbranched hydroxy resin of tong ma anhydride base to 148 DEG C of reaction 2.7h；
(3) in 22 DEG C of constant temperature oil baths, by dicyclohexyl hexane diisocyanate, (consumption is initial methyl eleostearate mole
2 times) and dibutyl tin laurate (consumption is the paulownia horse acid hyperbranched UV cured polyurethane acrylates weight of butt
0.35%) mixture is instilled in the hyperbranched hydroxy resin of tong ma anhydride obtained by step (2), notes regulation rate of addition control
System is dripped off in 50min, after 80 DEG C of stirring reactions 2.0h that heat up, that is, obtains product II；
(4) (consumption is the acid of paulownia horse for all product II tetramethylol methane tetraacrylate dilutions for obtaining step (3)
35%), (consumption is initial eleostearic acid to Deca pentaerythritol triacrylate to the hyperbranched UV cured polyurethane acrylates weight of butt
Methyl ester mole 280%) with hydroquinone the 0.7% of 2-(Acryloyloxy)ethanol weight (consumption for), the 72 DEG C of reactions of control temperature
After 2.0h, that is, obtain the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base.
Embodiment 6
(1) metering part methyl eleostearate and maleic anhydride (methyl eleostearate and maleic anhydride are sequentially added in transparency reactor
Mol ratio be 1:1.2), with a certain amount of xylene soluble (consumption for methyl eleostearate quality 450%), then add quantitative
Diphenylethan (consumption for methyl eleostearate quality 3.7%) so as to all dissolve and mix homogeneously.UV ray machines are opened, in UV
Photoreaction 1.9h under light irradiation.After vacuum drying is evaporated dimethylbenzene volatilization, (consumption is methyl eleostearate to add a certain amount of heptane
Quality 170%), and be filtered to remove unreacted maleic anhydride, obtain product I；
(2) product I, trimethylolpropane (product I and the three hydroxyl first for measuring are sequentially added in a kettle.
The mol ratio 3 of base propane:7) with p-methyl benzenesulfonic acid (consumption for trimethylolpropane mole 3.3%), vacuum stirring simultaneously rises
Temperature obtains the hyperbranched hydroxy resin of tong ma anhydride base to 155 DEG C of reaction 2.3h；
(3) in 26 DEG C of constant temperature oil baths, by isophorone diisocyanate, (consumption is the 2 of initial methyl eleostearate mole
Times) and dibutyl tin laurate (consumption is the 0.23% of the hyperbranched UV cured polyurethane acrylates weight of paulownia horse acid butt)
Mixture instill in the hyperbranched hydroxy resin of tong ma anhydride obtained by step (2), notes that adjusting rate of addition controls to exist
35min is dripped off, and after 80 DEG C of stirring reactions 2.5h that heat up, that is, obtains product II；
(4) (consumption is paulownia horse for all product II double pentaerythritol methacrylate dilutions for obtaining step (3)
27%), (consumption is initial methyl eleostearate to Deca 2-(Acryloyloxy)ethanol to the hyperbranched UV cured polyurethane acrylates weight of sour butt
Mole 290%) with MEHQ the 1.2% of 2-(Acryloyloxy)ethanol weight (consumption for), the 71 DEG C of reactions of control temperature
After 1.7h, that is, obtain the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base.
Embodiment 7
(1) metering part methyl eleostearate and maleic anhydride (methyl eleostearate and maleic anhydride are sequentially added in transparency reactor
Mol ratio be 1:1.2), with the dissolving of a certain amount of ethyl acetate (consumption for methyl eleostearate quality 480%), it is fixed then to add
Amount α, α-diethoxy acetophenone (consumption for methyl eleostearate quality 4.3%) so as to all dissolve and mix homogeneously.Open UV
Ray machine, photoreaction 1.4h under UV light irradiations.After vacuum drying is evaporated ethyl acetate volatilization, a certain amount of octane is added (to use
Measure for methyl eleostearate quality 240%), and be filtered to remove unreacted maleic anhydride, obtain product I；
(2) product I, trimethylolpropane (product I and the three hydroxyl first for measuring are sequentially added in a kettle.
The mol ratio 3 of base propane:7) with butyl titanate (consumption for trimethylolpropane mole 2.7%), vacuum stirring simultaneously rises
Temperature obtains the hyperbranched hydroxy resin of tong ma anhydride base to 147 DEG C of reaction 2.7h；
(3) in 26 DEG C of constant temperature oil baths by toluene di-isocyanate(TDI) (consumption is 2 times of initial methyl eleostearate mole) and
Dibutyl tin laurate (consumption is the 0.44% of the paulownia horse acid hyperbranched UV cured polyurethane acrylates weight of butt) mixed
Compound is instilled in the hyperbranched hydroxy resin of tong ma anhydride obtained by step (2), notes adjusting rate of addition control in 48min drops
Complete, after 70 DEG C of stirring reactions 1.8h that heat up, that is, obtain product II；
(4) (consumption is paulownia for all product II trimethylolpropane trimethacrylate dilutions for obtaining step (3)
38%), (consumption is initial to Deca pentaerythritol triacrylate to the hyperbranched UV cured polyurethane acrylates weight of horse acid butt
Methyl eleostearate mole 250%) with hydroquinone the 0.9% of 2-(Acryloyloxy)ethanol weight (consumption for), control 68 DEG C of temperature
After reaction 1.9h, that is, obtain the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base.
Embodiment 8
(1) metering part methyl eleostearate and maleic anhydride (methyl eleostearate and maleic anhydride are sequentially added in transparency reactor
Mol ratio be 1:1.2), with the dissolving of a certain amount of butanone (consumption for methyl eleostearate quality 390%), then add quantitative
Benzoin isobutyl ether (consumption for methyl eleostearate quality 3.8%) so as to all dissolve and mix homogeneously.UV ray machines are opened, in UV
Photoreaction 1.7h under light irradiation.After vacuum drying is evaporated butanone volatilization, (consumption is eleostearic acid first to add a certain amount of hexamethylene
Ester quality 270%), and be filtered to remove unreacted maleic anhydride, obtain product I；
(2) product I, trimethylolpropane (product I and the three hydroxyl first for measuring are sequentially added in a kettle.
The mol ratio 3 of base propane:7) with dicyclohexylcarbodiimide (consumption for trimethylolpropane mole 3.2%), vacuum is stirred
After mixing and being warming up to 153 DEG C of reaction 2.3h, that is, obtain the hyperbranched hydroxy resin of tong ma anhydride base；
(3) in 25 DEG C of constant temperature oil baths by PPDI (consumption is 2 times of initial methyl eleostearate mole) and
Dibutyl tin laurate (consumption is the 0.38% of the paulownia horse acid hyperbranched UV cured polyurethane acrylates weight of butt) mixed
Compound is instilled in the hyperbranched hydroxy resin of tong ma anhydride obtained by step (2), notes adjusting rate of addition control in 52min drops
Complete, after 75 DEG C of stirring reactions 1.6h that heat up, that is, obtain product II；
(4) (consumption is paulownia for all product II trimethylolpropane trimethacrylate dilutions for obtaining step (3)
38%), (consumption is initial to Deca pentaerythritol triacrylate to the hyperbranched UV cured polyurethane acrylates weight of horse acid butt
Methyl eleostearate mole 300%) with hydroquinone the 0.9% of 2-(Acryloyloxy)ethanol weight (consumption for), control 68 DEG C of temperature
After reaction 1.9h, that is, obtain the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base.
Each embodiment product all-round property testing
By hyperbranched for tong ma anhydride base obtained in the various embodiments described above UV cured polyurethane acrylates be added into isodose,
Congener light trigger makes UV cured coating films；
Hardness analysis, according to the hardness that GB/T 6739-1996 determine paint film；
Film body Analysis of tensile strength, determines photocuring according to GB13022-91 using UTM4204 type universal electricals testing machine
The mechanical property of thin film.Each embodiment test result is shown in Table 1.
Resistance to water is characterized by water absorption rate, is tested according to the method for GB/T1733 93；The measure of adhesive force is according to GB/
The method test of T9286 1998.
Coating film gloss is tested, and will determine its light with Elcometer406 gloss meters after resin coating film on the glass sheet UV solidifications
Pool, fixed angles are 60 degree, take three points at random respectively and are measured, and take the glossiness that their meansigma methodss are film.
1 each embodiment all-round property testing result of table
Can be seen from 1 data of table, the hyperbranched UV cured polyurethane acrylates of the tong ma anhydride base prepared by the present invention are applied
Film hardness is relatively mono-component aqueous or oleoresin film is high, and after film, mechanical property is more excellent, can make multiple protection finish paints
First-selection.The PUA performed polymers tensile strength is big, and water absorption rate is low, and adhesive force grade is high, and film coated surface glossiness is high, can be used as gold
Metal surface protective coating, the preferred film forming binder of woodwork coating finish paint.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, other any spirit without departing from the present invention and the change, modification, replacement that is made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. the preparation method of the hyperbranched UV cured polyurethane acrylates of a kind of tong ma anhydride base, it is characterised in that including as follows
Step：
(1) methyl eleostearate and maleic anhydride of metering part are added in the reactor, are dissolved with solvent, is then added light trigger,
Make its all dissolving mix homogeneously；1～2h of photoreaction under UV light irradiations；After vacuum drying, detergent is added, and is filtered excessively
Unreacted maleic anhydride is removed, product I is obtained；
(2) product I, trimethylolpropane and the esterification catalyst for measuring, vacuum stirring is added simultaneously to rise in a kettle.
Temperature obtains the hyperbranched hydroxy resin of tong ma anhydride base to 140～160 DEG C of 2～3h of reaction；
(3) at 20～30 DEG C, the mixture of diisocyanate and its catalyst is instilled the tong ma anhydride obtained by step (2)
In hyperbranched hydroxy resin, control is dripped off in 30～60min, is heated up after 60～90 DEG C of 1.5～3h of stirring reaction, that is, is reacted
Product II；
(4) product II that step (3) is obtained reactive diluent dilution, Deca (methyl) hydroxyalkyl acrylate and inhibition
Agent, after 60～78 DEG C of 1.5～2.5h of reaction of control temperature, that is, obtains the hyperbranched UV curing polyurethane acroleic acids of tong ma anhydride base
Ester.
2. the preparation method of the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base according to claim 1, its are special
Levy and be, the methyl eleostearate described in step (1) is 1 with the mol ratio of maleic anhydride:1.2；Suddenly the solvent described in (1) is third
At least one of ketone, butanone, dimethylbenzene and ethyl acetate；In terms of 100 parts of weight of methyl eleostearate, described solvent is 300～
500 weight portions.
3. the preparation method of the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base according to claim 1, its are special
Levy and be, the light trigger described in step (1) is diphenylethan, α, α-diethoxy acetophenone, benzoin ethyl ether, rests in peace
At least one in double (2,4, the 6- trimethylbenzoyl) phosphine oxides of fragrant butyl ether, phenyl and the chloro- 4- propoxyl group thioxanthones of 1-,
In terms of 100 parts of weight of methyl eleostearate, described light trigger is 3～5 weight portions；
Detergent described in step (1) is at least one in hexamethylene, normal hexane, heptane and octane；With methyl eleostearate 100
Part weight meter, described detergent are 100～300 weight portions.
4. the preparation method of the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base according to claim 1, its are special
Levy and be, the mol ratio 3 of product I described in step (2) and trimethylolpropane:7；Esterification catalyst is N, N'- bis-
Diisopropylcarbodiimide, dicyclohexylcarbodiimide, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, to first
At least one in benzenesulfonic acid and butyl titanate, its consumption for the mole of trimethylolpropane 2～4%.
5. the preparation method of the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base according to claim 1, its are special
Levy and be, the diisocyanate described in step (3) is isophorone diisocyanate, toluene di-isocyanate(TDI), different to benzene two
At least one in cyanate, XDI and dicyclohexyl hexane diisocyanate；With initial eleostearic acid first
Ester molal quantity meter, described diisocyanate are 2.0 moles.
6. the preparation method of the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base according to claim 1, its are special
Levy and be, the catalyst described in step (3) is dibutyl tin laurate, polyurethane is solidified with the hyperbranched UV of tong ma anhydride base
100 weight portion meter of acrylate, the catalyst are 0.20～0.50 weight portion；
Reactive diluent described in step (4) is (methyl) isobornyl acrylate, 1,6 hexanediol diacrylate, three hydroxyls
At least one in propane tri, tetramethylol methane tetraacrylate and double pentaerythritol methacrylate；With paulownia
The hyperbranched 100 weight portion meter of UV cured polyurethane acrylates of horse anhydride group, the reactive diluent are 20～40 weight portions.
7. the preparation method of the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base according to claim 1, its are special
Levy and be, (methyl) hydroxyalkyl acrylate described in step (4) is 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, metering system
Sour hydroxyl ethyl ester, Hydroxypropyl methacrylate, at least one of pentaerythritol triacrylate, described (methyl) acrylic acid hydroxyl alkane
Ester is 1 with the mol ratio of initial methyl eleostearate:2.5～1:3.0.
8. the preparation method of the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base according to claim 1, its are special
Levy and be, the polymerization inhibitor described in step (4) is MEHQ or hydroquinone；With (methyl) hydroxyalkyl acrylate 100
Weight portion meter, the polymerization inhibitor are 0.05～1.5 weight portion.
9. hyperbranched UV cured polyurethane acrylates of a kind of tong ma anhydride base, it is characterised in which is by claim 1 to 8 times
The preparation method of the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base described in one is obtained.
10. the hyperbranched UV cured polyurethane acrylates of tong ma anhydride base described in claim 9 are applied as protecting metallic surface
The application of the film forming binder of material or woodwork coating finish paint.
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