CN104892928B - Polycyclic amine modified (branched) polyether acrylate and preparation method thereof - Google Patents
Polycyclic amine modified (branched) polyether acrylate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to polycyclic amine modified (branched) polyether acrylate and a preparation method and application thereof. The polycyclic amine modified (branched) polyether acrylate is prepared by taking heteropolycyclic amine with diphenyl ketone and polycyclic tertiary amide structure as a modifier for Michael addition reaction and introducing the polycyclic tertiary amide structure into part of double bonds of (branched) polyether acrylate. The polycyclic amine modified (branched) polyether acrylate is low in viscosity and curing shrinkage rate and high in curing speed, overcomes the defect that conventional active amine is large in smell, prone to amide migration and yellowing and is a photocuring material having great prospect.
Description
Technical field
The present invention relates to radiation curable material technical field, and in particular to a kind of polycyclic amines are modified（It is branched）Polyethers propylene
Acid esters and its preparation method and application.
Background technology
It is well known that aliphatic tertiary amine can be as a kind of aided initiating, with hydrogen-capture-type light initiator benzophenone（BP）Or
Heterocycle arone constitutes composite initiator, and collaboration under ultraviolet light promotes the generation of living radical and effective oxygen inhibition that reduces to make
With so as to improve UV solidification rates, contributing to being fully cured for deep layer and top layer.But existing reactive amines are mostly with small molecule amine
Class, such as diethylamine, di-n-propylamine, di-n-butylamine, by Michael addition reaction, make the partial double bond of many official's monomers tertiary-aminated
Arrive, the reactive amines that such as TMPTA or TPGDA is modified, but such reactive amines are still suffered from, and abnormal smells from the patient is big, amine migration easily occurs and xanthochromia is tight
Again etc. disadvantage, should not in a large number use in UV systems, be only capable of as a kind of aided initiating of outer addition.
Many researchs find that many polysubstituted derivant of benzophenone has the light effect of drawing.At present, comparative maturity has
Cadelle ketone（MK）Series and 44 '-two phenoxy benzophenones（DPBP）Deng compared to BP, the maximum of the derivant of benzophenone
Absorbing wavelength has a certain degree of Red Shift Phenomena, and light initiation polymerization is in hgher efficiency, especially with BP or reactive amines compatibility after, light
Efficiency of initiation is greatly improved, but due to defects such as toxicity is larger, easy xanthochromias, or even part is identified as carcinogen so as to apply
Popularization is subject to certain restrictions；Therefore, exploitation possesses the benzophenone derivatives light initiation system of good combination property, becomes this
The bottleneck of technology development.
Polyether acrylate has low viscosity, low-shrinkage and lower-price characteristic, meets very much UV ink-jets, 3D printing
Etc. eager demand of the industry to material；But due to acting on relatively weak between ehter bond, its solidification after interchain agglomeration power it is slightly worse, solidification
Film mechanical strength is relatively low, and cure shrinkage is larger, and has that curing rate is slightly slowly etc. not enough, and this is also current urgent need to resolve
Technical barrier.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of polycyclic amines are modified（It is branched）Polyoxyalkylene acrylate
Ester, the polycyclic amines are modified（It is branched）Polyether acrylate by the miscellaneous polycyclic amines with benzophenone and multi-ring tertiary amine structure with
（It is branched）Polyether acrylate Jing Michael addition reactions are prepared, and polycyclic amines are modified（It is branched）Polyether acrylate have compared with
Low cure shrinkage, curing rate is fast, and viscosity is low and overcomes big regular activated amine abnormal smells from the patient, easy amine migration and easy xanthochromia
Deficiency, be the very promising photo-curing material of a class.
Another object of the present invention is to provide above-mentioned polycyclic amines be modified（It is branched）The preparation method of polyether acrylate.
Another object of the present invention is to provide above-mentioned polycyclic amines be modified（It is branched）Polyether acrylate is in leather finish, UV
Application in ink-jet or 3D printing material.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of polycyclic amines are modified（It is branched）Polyether acrylate, the polycyclic amines are modified（It is branched）Polyether acrylate be with
Miscellaneous polycyclic amines with benzophenone and multi-ring tertiary amine structure as modified body, Jing Michael addition reactions,（It is branched）Polyethers
Multi-ring tertiary amine structure is introduced in the partial double bond of acrylate；
The low viscosity（It is branched）Polyether acrylate by polyether polyol or branch polyether polyatomic alcohol with（Methyl）Propylene
Acid esters carries out ester exchange reaction and obtains；The degree of functionality of the polyether polyol or branch polyether polyatomic alcohol is 3～12, average molecular
Quality is 400～5000；
Wherein, the branch polyether polyatomic alcohol is obtained by trihydroxylic alcohol and/or tetrahydroxylic alcohol Jing catalyzing and condensings, or again through epoxy
Propane and/or oxirane carry out being obtained after chain extension.
In the present invention, the degree of functionality of the polyether polyol or branch polyether polyatomic alcohol refers to polyether polyol or branched poly-
The number of the hydroxyl contained in ethoxylated polyhydric alcohol.
In the present invention, the branch polyether polyatomic alcohol is obtained by trihydroxylic alcohol and/or tetrahydroxylic alcohol Jing catalyzing and condensings, more specifically
Ground, can be condensed to yield by plural trihydroxylic alcohol and/or tetrahydroxylic alcohol.
It is highly preferred that the branch polyether polyatomic alcohol by more than three trihydroxylic alcohol and/or tetrahydroxylic alcohol be condensed to yield.Invention
People has been surprisingly found that the polyether polyol with this branched structure when being prepared into branch polyether acrylate of the present invention, is removed
Have outside low viscosity, have also obtained higher curing rate.
What the present invention was provided（It is branched）Polyether acrylate has the characteristics of esterification degree is high, viscosity is low, curing rate is fast,
Amine is carried out on the basis of it to be modified, and has been obtained a kind of amine and has been modified（It is branched）Polyether acrylate, amine is modified（It is branched）Polyethers third
The solidification rate of olefin(e) acid ester is higher, and cure shrinkage has obtained significant reduction, while still having relatively low viscosity；This
The amine of bright offer is modified（It is branched）Polyether acrylate can effectively reduce gas compared with the reactive amines that TMPTA or TPGDA is modified
Taste and reduce amine animal migration, and with xanthochromia it is little the characteristics of.
Preferably, the miscellaneous polycyclic amines are that 4,4'- difluoro benzophenones are prepared with alicyclic diamine nucleo philic substitution reaction
Obtain；The nucleophilic substitution is carried out in a solvent or under melting condition；The alicyclic diamine is piperazine, isophorone two
One or more in amine, 1,4- hexamethylene diamines, 1- methyl -2,4- cyclohexanediamine and N, N'- dimethyl -1,2- cyclohexanediamine.
Preferably, the degree of functionality of the polyether polyol is 3～6, and relative molecular mass is 700～2000；It is described branched
The degree of functionality of polyether polyol is 5～9, and relative molecular weight is 400～3000.
Preferably, the miscellaneous polycyclic amines with it is described（It is branched）The mol ratio of polyether acrylate is 1：1～1：2.
Preferably, it is described（Methyl）Acrylate is acrylic acid methyl ester., ethyl acrylate, methyl methacrylate or methyl
One or more in ethyl acrylate.
In the present invention, polyether polyol or branch polyether polyatomic alcohol with（Methyl）The ester exchange reaction of acrylate is solid
Change is carried out under conditions of enzyme and efficient accelerator, and the solidification enzyme is esterase（E.C.3.1.1.1）, lipase（E.C.3.1.1.3）
Or protease（E.C.3.4.-.-）In one or more；The efficient accelerator is lanthanide rare sulfonate.
The present invention is applied to prepare first using lanthanide rare sulfonate as the efficient accelerator of enzyme catalysiss ester exchange reaction
（It is branched）Polyether acrylate, solidifies enzyme and efficient accelerator synergism greatly improves the catalysis work of solidification enzyme catalyst
Property, improve the esterification yield of product；In addition, compared with prior art, the present invention is carried out under low temperature condition of no solvent, and low temperature is anti-
Degraded and the double-bond polymerization of ehter bond should be advantageously reduced, product purity is high；Solvent-free system is conducive to improving reaction substrate and product
The concentration of thing, purifying products process is simple, step is few, without catalyst residual.
Preferably, the solidification enzyme is lipase（E.C.3.1.1.3）, it is further preferred that the commodity board of the solidification enzyme
Number be Novozyme 435 or LVK-F100.
Preferably, the efficient accelerator is in lanthanum methanesulfonate, trifluoromethane sulfonic acid lanthanum or dodecyl sodium sulfonate lanthanum
One or more；The efficient accelerator that the present invention is used can be buied by market or be made by oneself, lanthanum methanesulfonate and dodecyl sulphur
Sour lanthanum can be prepared via a method which to obtain：Lanthana is soluble in water with water-soluble sulfonate, pH is adjusted at a certain temperature,
Water-insoluble sulfonic acid lanthanum Precipitation is made, is dried.
Preferably, the consumption of the solidification enzyme catalyst is the 0.5%～2.0% of gross mass, the consumption of the accelerator
To solidify the 1%～2% of enzyme quality.
Trihydroxylic alcohol of the present invention, tetrahydroxylic alcohol can be ternary well known in the art or quaternary small molecule polyol, preferably
Ground, the trihydroxylic alcohol can be glycerol or trimethylolpropane；The tetrahydroxylic alcohol can be tetramethylolmethane.
In the present invention, it is described（It is branched）The preparation method of polyether acrylate includes ester exchange reaction and purification process two
Big step, it is specific as follows：
S1：Ester exchange reaction：By polyether polyol or branch polyether polyatomic alcohol, excessive（Methyl）Acrylate, antioxygen
Agent and polymerization inhibitor carry out ester exchange reaction under the conditions of 30～80 DEG C after being uniformly dispersed, 3～48h of sustained response obtains product standby
With；
S2：Purification process：Step S1 products therefrom is filtered, filtrate decompression is distilled off reacting methanol or the ethanol for generating
And excess（Methyl）Acrylate, obtains final product final product.
Preferably, it is described（It is branched）The preparation method of polyether acrylate is as follows：
S1：Ester exchange reaction：By polyether polyol or branch polyether polyatomic alcohol, excessive（Methyl）Acrylate, antioxygen
After agent and polymerization inhibitor are uniformly dispersed, add solidification enzyme catalyst and efficient accelerator, under 30～80 DEG C of stirrings reaction 3～
48h, obtains that product is standby, and the consumption of the solidification enzyme catalyst is the 0.5%～2.0% of gross mass, the consumption of the accelerator
To solidify the 1%～2% of enzyme quality；
S2：Purification process：Step S1 products therefrom is filtered, filtrate decompression is distilled off reacting methanol or the ethanol for generating
And excess（Methyl）Acrylate, obtains final product final product.
In the present invention, the addition of polymerization inhibitor can be prevented（Methyl）Acrylic double bond is polymerized, it is ensured that hand in ester
Change the stability in the stages such as course of reaction, purification process, Product transport and storage；The present invention preferentially from it is of light color, inhibition when
Between long and good stability polymerization inhibitor, it is further preferred that the polymerization inhibitor be copper oxide, copper sulfate, ferrous sulfate, to benzene two
One or more in phenol, MEHQ, 2,6 di tert butyl 4 methyl phenol and phenothiazine；In order to avoid polymerization inhibitor
Content is excessive, affects the light-cured performance of final products, the consumption of the polymerization inhibitor to have certain restriction, be usually no more than total matter
The 1.0% of amount.
The addition of antioxidant can be effectively improved low viscosity（It is branched）The outward appearance of polyether acrylate product, to keeping producing
The permanent performance of product also has certain effect, the antioxidant be mainly Hinered phenols or/andPhosphorous acidEsters auxiliary is anti-
Oxygen agent, specifically can from tert-butyl hydroquinone, four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] tetramethylolmethane
Ester, β-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester of propanoic acid, Wytox 312 or diphosphites
One or more in the different certain herbaceous plants with big flowers ester of tetramethylolmethane two.
Above-mentioned polycyclic amines are modified（It is branched）The preparation method of polyether acrylate, specifically includes following steps：
S1：The synthesis of miscellaneous polycyclic amines
By 4,4 '-difluoro benzophenone and alicyclic diamine in the presence of Anhydrous potassium carbonate and organic solvent, reacting by heating 6
～24h, cooling is washed, filters, is dried；
S2：Polycyclic amines are modified（It is branched）Polyether acrylate
The miscellaneous polycyclic amines of step S1 gained, plus catalyst are taken, after being warming up to 20～80 DEG C described in Deca（It is branched）Polyethers propylene
Acid esters, reacts 3～12h, and cooling obtains final product product.
Preferably, the polycyclic amines are modified（It is branched）The preparation method of polyether acrylate can adopt following steps：
S1：The synthesis of miscellaneous polycyclic amines
Mol ratio is sequentially added in the four-hole bottle equipped with condensing tube, thermometer and agitator for 1:The 4,4 ' of 2-difluoro two
Benzophenone and alicyclic diamine, Anhydrous potassium carbonate and appropriate organic solvent；Under nitrogen protection, 100 DEG C of 6～24h of reaction are warming up to；
When being cooled to 80 DEG C, filtered while hot, filtrate adds anhydrous sodium sulfate drying Jing after washing 2～3 times, after filtering again, decompression
Solvent is distilled off, you can obtain miscellaneous multi-ring semi-finished product；
S2：Polycyclic amines are modified（It is branched）Polyether acrylate
Take above-mentioned miscellaneous polycyclic amines to add in there-necked flask, add a small amount of DBU catalyst（Account for the 3% of gross mass）, gradually rise
Temperature is to 20～80 DEG C；Start Deca under stirring（It is branched）Polyether acrylate, controls rate of addition, it is to avoid heat release is too fast；Drop
Plus completely after, continue 3～12h of isothermal reaction, cooling discharging obtains colourless or micro- yellowing transparency liquid.
Compared with prior art, the present invention has the advantages that：
（1）The polycyclic amines that the present invention is provided are modified（It is branched）Polyether acrylate has that viscosity is low, cure shrinkage is little, Gu
Change fireballing feature, suitably use in a large number in formula；In addition, the polycyclic amines of the present invention are modified（It is branched）Polyether acrylate
Strand in introduce miscellaneous multiring structure so that the rigidity increase of segment, improve the intensity of polyether acrylate and heat-resisting
Property；In the composite can be widely applied to various UV coating and ink formulations；
（2）The polycyclic amines that the present invention is provided are modified（It is branched）The characteristics of polyether acrylate has xanthochromia little, with TMPTA
Or the reactive amines aided initiating that TPGDA is modified is compared, can effectively reduce abnormal smells from the patient and reduce amine animal migration；
（3）The polycyclic amines of the present invention are modified（It is branched）Benzophenone photosensitive structure in the strand of polyether acrylate and
Tertiary amine helps initiating group synergism between the two, greatly improves light-initiated efficiency, and the presence of various groups causes to work as
There is more preferably intermiscibility with other compositions when the present invention is applied in light-cured resin.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Unless stated otherwise, material involved in embodiment, method are material commonly used in the art and method.
The polyether acrylate 1 of synthesis example 1（Mn ≈ 862, degree of functionality is 3）
A kind of polyethers triacrylate and preparation method thereof, including following two steps：
A. ester exchange reaction：Take 400g polyether-tribasic alcohols (Mn ≈ 700, Tao Shi VOANOL 2070), 343.2g acrylic acid second
Ester, 1.2g Wytox 312s, 0.2g 2,6- di-tert-butyl-4-methy phenols after being uniformly dispersed, add 5g solidifications
Enzyme Novozyme 435 and 0.1g dodecyl sodium sulfonate lanthanums, stirring reaction 24h at 40 DEG C；
B. purification process：After upper step gained mixture is filtered, filtrate carries out vacuum rotary steam, eliminates the ethanol that reaction is generated
With excessive metering system acetic acid, clear, colorless carboxylate 490.2g is obtained（Solid content 99.2%, viscosity 85mPas/25 DEG C,
Esterification yield（The substrate on the basis of polyether polyol, similarly hereinafter）For 97.4%）.
The branch polyether acrylate 2 of synthesis example 2（Mn ≈ 1022, degree of functionality is 9）
A kind of branch polyether acrylate and preparation method thereof, comprises the following steps that：
（1）The synthesis of branch polyether polyatomic alcohol
With glycerol as raw material, in acid condition, the steps of Jing mono- are condensed to form branch polyether polyatomic alcohol（Mn ≈ 536, degree of functionality
For 9, the degree of branching is 0.72）；
（2）Enzyme catalysiss ester exchange reaction, including following two steps：
A. ester exchange reaction：Take above-mentioned branch polyether polyatomic alcohol 300g, 550.0g acrylic acid methyl ester., the nonyl of 1.8g phosphorous acid three
Base phenylester, 0.25g MEHQ, after being uniformly dispersed, add 8g solidification enzymes Novozyme 435 and 0.1g dodecyls
Sulfonic acid lanthanum, stirring reaction 24h at 50 DEG C；Chemical equation is as follows
B. purification process：After upper step gained mixture is filtered, filtrate carries out vacuum rotary steam, eliminates the methanol that reaction is generated
With excessive acrylic acid methyl ester., clear, colorless carboxylate 553.0g is obtained（Solid content 99.3%, viscosity 65mPas/25 DEG C, ester
Rate is 96.7%）.
The polyether acrylate 3 of synthesis example 3（Mn ≈ 1162, degree of functionality is 3）
A kind of polyethers triacrylate and preparation method thereof, including following two steps：
A. ester exchange reaction：Take 400g polyether-tribasic alcohols (Mn ≈ 1000, VOANOL CP-1055), 384.4g acrylic acid first
Ester, 3.2g Wytox 312s, 0.4g MEHQ, after being uniformly dispersed, add 6g solidification enzyme LVK-F100 and
0.1g lanthanum methanesulfonates, stirring reaction 24h at 40 DEG C；
A. purification process：After upper step gained mixture is filtered, filtrate carries out vacuum rotary steam, eliminates the methanol that reaction is generated
With excessive acrylic acid methyl ester., clear, colorless carboxylate 463.0g is obtained（Solid content 99.5%, viscosity 105mPas/25 DEG C, ester
Rate is 97.1%）.
The branch polyether acrylate 4 of synthesis example 4（Mn ≈ 2340, degree of functionality is 5）
A kind of branch polyether（Mn≈2000）Acrylate and preparation method thereof, comprises the following steps that：
（1）The synthesis of branch polyether polyatomic alcohol
With trimethylolpropane as raw material, in acid condition a step is condensed to form branch polyether polyatomic alcohol, and with PO and
A small amount of EO carries out chain extension, the macromolecule branch polyether polyatomic alcohol of formation（Mn ≈ 2000, degree of functionality is 5）.
（2）Enzyme catalysiss ester exchange reaction, including following two steps：
A. ester exchange reaction：Take above-mentioned macromolecule branch polyether polyatomic alcohol 500g, 300.0g methyl methacrylate,
1.2g Wytox 312s, 0.2g MEHQ, after being uniformly dispersed, add the Hes of 8g solidification enzymes Novozyme 435
0.1g dodecyl sodium sulfonate lanthanums, stirring reaction 24h at 50 DEG C；Chemical equation is as follows：
B. purification process：After upper step gained mixture is filtered, filtrate carries out vacuum rotary steam, eliminates the methanol that reaction is generated
With excessive methyl methacrylate, clear, colorless carboxylate 558.8g is obtained（Solid content 99.4%, viscosity 150mPas/25
DEG C, esterification yield is 95.5%）.
The polycyclic amines modified polyether acrylate 1 of embodiment 1
（1）The synthesis of miscellaneous polycyclic amines
218.2g 4 is sequentially added in the four-hole bottle equipped with condensing tube, thermometer and agitator, 4 '-difluoro benzophenone,
175.0g Piperazine anhydrous, 150.0g Anhydrous potassium carbonates and 300ml dimethyl sulfoxide；Under the protection of logical nitrogen, 100 DEG C are warming up to instead
Answer 12h；When being cooled to 80 DEG C, filtered while hot, filtrate adds anhydrous sodium sulfate drying Jing after washing 2 times, after filtering again,
Vacuum distillation removes solvent, obtains miscellaneous multi-ring semi-finished product 345.0g, yield 87.7%；Reaction equation is as follows：
（2）The preparation of polycyclic amines modified polyether acrylate 1
Take step（1）Obtained miscellaneous polycyclic amines 35.1g (0.1mol) is added in there-necked flask, adds 0.6g DBU catalyst,
It is gradually heating to 60 DEG C；Start Deca 172.4g (0.2mol) polyether acrylate 1 under stirring（Mn ≈ 862, degree of functionality is 3）,
Deca completely, continues isothermal reaction 6h in 1h, and cooling discharging obtains colourless transparent liquid 207.5g（Solid content is 99.5%, is glued
Spend for 100mPas/25 DEG C）.
The modified branch polyether acrylate 2 of the polycyclic amines of embodiment 2
（1）The synthesis of miscellaneous polycyclic amines（Synthetic method is with embodiment 1（1））
（2）The preparation of the modified branch polyether acrylate 2 of polycyclic amines
Take step（1）Obtained miscellaneous polycyclic amines 35.1g (0.1mol) is added in there-necked flask, adds 0.4g DBU catalyst,
It is gradually heating to 60 DEG C；Start Deca 102.2g (0.1mol) branch polyether acrylate 2 under stirring（Mn ≈ 1022, degree of functionality
For 9, the degree of branching is 0.72）, Deca completely, continues isothermal reaction 6h in 1h, and cooling discharging obtains colourless transparent liquid 136.5g
（Solid content is 99.5%, and viscosity is 85mPas/25 DEG C）.
The polycyclic amines modified polyether acrylate 3 of embodiment 3
（1）The synthesis of miscellaneous polycyclic amines
218.2g 4 is sequentially added in the four-hole bottle equipped with condensing tube, thermometer and agitator, 4 '-difluoro benzophenone,
214.5g isophorone diamine, 150.0g Anhydrous potassium carbonates and 400ml mixed solvents（Toluene and N,N-dimethylformamide each
Half）；Under the protection of logical nitrogen, 100 DEG C of reaction 12h are warming up to；When being cooled to 80 DEG C, filtered while hot, filtrate Jing is washed 2 times
Afterwards, anhydrous sodium sulfate drying is added, after filtering again, vacuum distillation removes solvent, obtains miscellaneous multi-ring semi-finished product 390.2g, yield
90.2%.
（2）The preparation of polycyclic amines modified polyether acrylate 3
Take step（1）Obtained miscellaneous polycyclic amines 39.3g (0.1mol) is added in there-necked flask, adds 0.5g DBU catalyst,
It is gradually heating to 60 DEG C；Start Deca 116.2g (0.1mol) polyether acrylate 3 under stirring（Mn ≈ 1162, degree of functionality is 3）,
Deca completely, continues isothermal reaction 6h in 1h, and cooling discharging obtains colourless transparent liquid 155.1g（Solid content is 99.3%, is glued
Spend for 120mPas/25 DEG C）.
The modified branch polyether acrylate 4 of the polycyclic amines of embodiment 4
（1）The synthesis of miscellaneous polycyclic amines
218.2g 4 is sequentially added in the four-hole bottle equipped with condensing tube, thermometer and agitator, 4 '-difluoro benzophenone,
288.4g N, N'- dimethyl -1,2- cyclohexanediamine, 150.0g Anhydrous potassium carbonates and 400ml toluene；Under the protection of logical nitrogen, rise
Temperature to 100 DEG C are reacted 18h；When being cooled to 80 DEG C, filtered while hot, filtrate adds anhydrous sodium sulfate drying Jing after washing 2 times,
After filtering again, vacuum distillation removes solvent, obtains miscellaneous multi-ring semi-finished product 457.5g, yield 90.3%.
（2）The preparation of the modified branch polyether acrylate 4 of polycyclic amines
Take step（1）Obtained miscellaneous polycyclic amines 46.7g (0.1mol) is added in there-necked flask, adds 0.9g DBU catalyst,
It is gradually heating to 60 DEG C；Start Deca 232.4g (0.1mol) branch polyether acrylate 4 under stirring（Mn ≈ 2432, degree of functionality
For 5）, Deca completely, continues isothermal reaction 6h in 1h, and cooling discharging obtains colourless transparent liquid 277.1g（Solid content is
99.3%, viscosity is 180 mPas/25 DEG C）.
To synthesis example 1～4（It is branched）Polycyclic amines prepared by polyether acrylate, embodiment 1～4 are modified（It is branched）Polyethers
The performances such as viscosity, shrinkage factor, the curing rate of acrylate are tested, and the branch polyether third obtained with the synthesis of synthesis example 4
The scheme that olefin(e) acid ester 4 is used cooperatively with commercially available reactive amines CN371 as a comparison case 1, test result is as shown in table 1.
The performance test contrast of each polyether acrylate of table 1.
Note：Solidification rate test condition：Add 3% 1173,25 μm of wet films, 200mJ/ cm2；To be fully cured linear speed
Degree（Unit：m/s）Solidification rate is represented, linear velocity is more big then to illustrate that solidification rate is faster；"-" represents that the performance is not deposited in table 1
.
As shown in Table 1, the present invention is prepared（It is branched）Polyether acrylate has relatively low viscosity and solid faster
Change speed, in can be widely applied to 3D printing photo-curing material；It is described（It is branched）Polyether acrylate Jing polycyclic amines are modified to be obtained
The polycyclic amines for arriving are modified（It is branched）The solidification rate of polyether acrylate is further enhanced, and shrinkage factor is significantly reduced, almost
Without xanthochromia, and Jing amine is modified（It is branched）Polyether acrylate still has（It is branched）The low spy of the viscosity of polyether acrylate
Point；
Comparative example 1 is that the branch polyether acrylate 4 obtained with the synthesis of synthesis example 4 makes with the cooperation of commercially available reactive amines CN371
Scheme, embodiment 4 is the product modified with miscellaneous polycyclic amines of branch polyether acrylate 4, from comparative example 1, with reality
Apply example 4 to compare, after with the addition of commercially available reactive amines CN371, the viscosity of branch polyether acrylate 4 is basically unchanged, solidification rate
Have a certain upgrade, but the addition of reactive amines CN371 the cure shrinkage of branch polyether acrylate 4 can be caused to have increased,
Easy xanthochromia；And the present invention introduces tertiary amine structure by Michael addition reaction in the double bond of branch polyether acrylate 4
Initiating group is helped, its own has the active group for helping initiation so that reactive amines need not be added in photocurable formulation is prepared
Composition, so as to avoid the generation of xanthochromia and amine migration, in addition, the modified branch polyether third of the polycyclic amines obtained in embodiment 4
Olefin(e) acid ester has relatively low viscosity, can in a large number use in photocurable formulation as a kind of low viscosity resin, it follows that this
The polycyclic amines of bright offer are modified（It is branched）Polyether acrylate and existing reactive amines aided initiating and existing propylene
Acid ester resin is compared with more excellent performance.
Claims (10)
1. a kind of modified branch polyether acrylate of polycyclic amines or polyether acrylate, it is characterised in that the polycyclic amines are modified
Branch polyether acrylate or polyether acrylate are using the miscellaneous polycyclic amines with benzophenone and multi-ring tertiary amine structure as changing
Gonosome, Jing Michael addition reactions introduce multi-ring uncle in the partial double bond of branch polyether acrylate or polyether acrylate
Amine structure；
The branch polyether acrylate or polyether acrylate are by polyether polyol or branch polyether polyatomic alcohol and (methyl) third
Olefin(e) acid ester carries out ester exchange reaction and obtains；The degree of functionality of the polyether polyol or branch polyether polyatomic alcohol is 3～12, relative point
Protonatomic mass is 400～5000；
Wherein, the branch polyether polyatomic alcohol is obtained by trihydroxylic alcohol and/or tetrahydroxylic alcohol Jing catalyzing and condensings, or again through expoxy propane
And/or oxirane carries out being obtained after chain extension.
2. the modified branch polyether acrylate of polycyclic amines or polyether acrylate according to claim 1, it is characterised in that institute
State miscellaneous polycyclic amines to obtain with piperazine or alicyclic diamine nucleo philic substitution reaction for 4,4'- difluoro benzophenones；It is described alicyclic
Diamidogen is the one kind or several in isophorone diamine, 1- methyl -2,4- cyclohexanediamine and N, N'- dimethyl -1,2- cyclohexanediamine
Kind.
3. the modified branch polyether acrylate of polycyclic amines or polyether acrylate according to claim 1, it is characterised in that institute
The degree of functionality for stating polyether polyol is 3～6, and relative molecular mass is 700～2000；The degree of functionality of the branch polyether polyatomic alcohol
For 5～9, relative molecular weight is 400～3000.
4. the modified branch polyether acrylate of polycyclic amines or polyether acrylate according to claim 1, it is characterised in that institute
It is 1 that polycyclic amines are stated with the mol ratio of the branch polyether acrylate or polyether acrylate：1～1：2.
5. the modified branch polyether acrylate of polycyclic amines or polyether acrylate according to claim 1, it is characterised in that institute
(methyl) acrylate is stated in acrylic acid methyl ester., ethyl acrylate, methyl methacrylate or ethyl methacrylate
Plant or several.
6. the modified branch polyether acrylate of polycyclic amines or polyether acrylate according to claim 1, it is characterised in that institute
State ester exchange reaction is carried out under conditions of solidification enzyme and efficient accelerator, and the solidification enzyme is esterase E.C.3.1.1.1, lipase
One or more in E.C.3.1.1.3 or protease E.C.3.4.-.-；The efficient accelerator is lanthanide rare sulfonate.
7. the modified branch polyether acrylate of polycyclic amines or polyether acrylate according to claim 6, it is characterised in that institute
The consumption for stating solidification enzyme catalyst is the 0.5%～2.0% of gross mass, and the consumption of the accelerator is solidify enzyme quality 1%
～2%.
8. the modified branch polyether acrylate of the polycyclic amines according to any one of claim 1～7 or polyether acrylate, it is special
Levy and be, the preparation method of the branch polyether acrylate or polyether acrylate includes ester exchange reaction and purification process two
Big step, it is specific as follows：
S1：Ester exchange reaction：By polyether polyol or branch polyether polyatomic alcohol, excessive (methyl) acrylate, antioxidant
Ester exchange reaction is carried out under the conditions of 30～80 DEG C after being uniformly dispersed with polymerization inhibitor, 3～48h of sustained response obtains product standby；
S2：Purification process：Step S1 products therefrom is filtered, filtrate decompression is distilled off reacting methanol or ethanol and the mistake for generating
(methyl) acrylate of amount, obtains final product final product.
9. the modified branch polyether acrylate of polycyclic amines described in any one of claim 1～8 or polyether acrylate are applied in leather
Application in decorations, UV ink-jets or 3D printing material.
10. the preparation side of the modified branch polyether acrylate of polycyclic amines described in any one of claim 1～8 or polyether acrylate
Method, it is characterised in that specifically include following steps：
S1：The synthesis of polycyclic amines
By 4,4 '-difluoro benzophenone and piperazine or alicyclic diamine in the presence of Anhydrous potassium carbonate and organic solvent, heating is anti-
6～24h is answered, is cooled down, washed, filter, be dried；
S2：The modified branch polyether acrylate of polycyclic amines or polyether acrylate
Take step S1 gained polycyclic amines, plus catalyst, branch polyether acrylate described in Deca or poly- after being warming up to 20～80 DEG C
Ether acrylate, reacts 3～12h, and cooling obtains final product product.
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| CN104893224B (en) * | 2015-06-23 | 2019-01-11 | 广东博兴新材料科技有限公司 | Application of the low viscosity light-cured resin in 3D printing material |
| CN107286337B (en) * | 2017-06-21 | 2019-04-09 | 大连理工大学 | A kind of piperazine functionalized polyphenylene oxide alkaline anion-exchange membrane and preparation method thereof |
| CN110294978A (en) * | 2019-07-02 | 2019-10-01 | 惠州市至上新材料有限公司 | A kind of radium-shine illusion-colour anti-forgery ink of UV silk-screen and its preparation method and application |
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Effective date of registration: 20170419 Address after: 210000 Nanjing Province, Liuhe District, Xiong State Street, Chen Lu Road, No. 21, No. Patentee after: Nanjing Jiu Tai new Mstar Technology Ltd Address before: 510000 Haizhuqu District, Guangzhou, Xingang East Road, No. East Street, sea floor, room 8, No. 801 Patentee before: GUANGDONG BOSSIN NOVEL MATERIALS TECHNOLOGY CO., LTD. |