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CN105037297B - It is a kind of containing carboxy-modified polycyclic amines and preparation method thereof and its application in polyfunctional acrylic ester - Google Patents

It is a kind of containing carboxy-modified polycyclic amines and preparation method thereof and its application in polyfunctional acrylic ester Download PDF

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CN105037297B
CN105037297B CN201510348618.1A CN201510348618A CN105037297B CN 105037297 B CN105037297 B CN 105037297B CN 201510348618 A CN201510348618 A CN 201510348618A CN 105037297 B CN105037297 B CN 105037297B
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modified
ester
polyfunctional acrylic
polycyclic amines
acrylic ester
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CN105037297A (en
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庞来兴
李志云
巫朝剑
汪慧
曾贤健
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Guangdong Boxing New Materials Technology Co ltd
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Guangdong Bossin Novel Materials Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
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    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
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    • C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
    • C07C273/1863—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety from urea
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    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/18—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings
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    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/62—Carboxylic acid esters

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Abstract

The present invention relates to a kind of containing carboxy-modified polycyclic amines and preparation method thereof and its application in polyfunctional acrylic ester, described is the polycyclic amines with least two ring structures formed with carbonic ester and alicyclic diamine through ammonolysis reaction containing carboxy-modified polycyclic amines；Wherein, the alicyclic diamine refers to the one or more in piperazine, IPD, Isosorbide-5-Nitrae hexamethylene diamine, the cyclohexanediamine of 1 methyl 2,4 and the cyclohexanediamine of N, N' dimethyl 1,2.By it is described be applied to containing carboxy-modified polycyclic amines in polyfunctional acrylic ester when, the solidification rate of polyfunctional acrylic ester can be significantly improved, reduces cure shrinkage and the hardness and resistance to elevated temperatures of polyfunctional acrylic ester can be significantly improved, while the characteristics of there is small smell, small amine migration and small xanthochromia containing carboxy-modified polycyclic amines polyfunctional acrylic ester of generation.

Description

One kind is containing carboxy-modified polycyclic amines and preparation method thereof with it in polyfunctional acrylic ester In application
Technical field
The present invention relates to the synthesis containing carboxy-modified polycyclic amines, and in particular to one kind contains carboxy-modified polycyclic amines and its preparation Method and its application in polyfunctional acrylic ester, more particularly to containing carboxy-modified polycyclic amines in polyfunctional acrylate monomer And（It is branched）Application in polyether acrylate.
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 effectively reduction oxygen inhibition 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 is tertiary-aminated to obtain Arrive, the reactive amines that such as TMPTA or TPGDA are modified, but such reactive amines are still suffered from that smell is big, easily occur amine migration and xanthochromia is tight Disadvantage, should not largely use in UV systems, be only capable of as a kind of aided initiating of outer addition again etc.；Therefore, still need to seek one Plant smell small, be not susceptible to amine migration and the small reactive amines aided initiating of xanthochromia；Or seeking one kind, there is tertiary amine to help initiation The low viscosity resin of active group to overcome that reactive amines aided initiating of the prior art consumption in UV systems is small, smell big, The problem of easily occurring amine migration and serious xanthochromia.
The content of the invention
Contain carboxy-modified polycyclic amines it is an object of the invention to overcome the deficiencies of the prior art and provide one kind, it is described to contain carbonyl Base is modified the polycyclic amines with least two ring structures that polycyclic amines are formed by carbonic ester and alicyclic diamine through ammonolysis reaction, will It is described when being applied to containing carboxy-modified polycyclic amines in polyfunctional acrylic ester, the solidification speed of polyfunctional acrylic ester can be significantly improved Rate, reduction cure shrinkage can simultaneously significantly improve the hardness and resistance to elevated temperatures of polyfunctional acrylic ester, while what is generated contains carbonyl Base is modified the characteristics of polycyclic amines polyfunctional acrylic ester has small smell, small amine migration and small xanthochromia.
Another object of the present invention is to provide the above-mentioned preparation method containing carboxy-modified polycyclic amines.
It is above-mentioned many in the preparation modification of polycyclic amines containing carbonyl containing carboxy-modified polycyclic amines another object of the present invention is to provide Application in functional acrylate.
The preparation method of polyfunctional acrylic ester is modified another object of the present invention is to provide above-mentioned polycyclic amines containing carbonyl.
Another object of the present invention is to provide a kind of polycyclic amines containing carbonyl to be modified polyfunctional acrylic ester.
To achieve the above object, the present invention is adopted the following technical scheme that：
One kind contains carboxy-modified polycyclic amines, and described is through ammonolysis with carbonic ester and alicyclic diamine containing carboxy-modified polycyclic amines React the polycyclic amines with least two ring structures formed；Wherein, the alicyclic diamine refers to piperazine, isophorone two One or more in amine, 1,4- hexamethylene diamines, 1- methyl -2,4- cyclohexanediamine and N, N'- dimethyl -1,2- cyclohexanediamine.
What the present invention was provided has at least two ring structures containing carboxy-modified polycyclic amines, changes what the present invention was provided containing carbonyl Property polycyclic amines when applying in polyfunctional acrylic ester, the solidification rate of polyfunctional acrylic ester can be significantly improved, reduce solidification Shrinkage factor and the hardness and resistance to elevated temperatures that polyfunctional acrylic ester can be significantly improved, while containing for generation is carboxy-modified polycyclic The characteristics of amine polyfunctional acrylic ester has small smell, small amine migration and small xanthochromia.
Preferably, the carbonic ester is dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, carbonic acid two One or more in butyl ester, ethylene carbonate and propene carbonate.
The above-mentioned preparation method containing carboxy-modified polycyclic amines, specifically includes following steps：Carbonic ester and alicyclic diamine are pressed Mol ratio is 1:1~2 ratio reacts 3~12h under the conditions of 60~120 DEG C, and vacuum distillation removes the anti-of accessory substance and excess Thing is answered to produce.
A kind of polycyclic amines containing carbonyl are modified polyfunctional acrylic ester, and the polycyclic amines containing carbonyl are modified polyfunctional acrylic ester Contain carboxy-modified polycyclic amines with polyfunctional acrylic ester through Michael addition reaction by above-mentioned, in the part of polyfunctional acrylic ester Polycyclic tertiary amine structure is introduced in double bond.
In the present invention, above-mentioned polyfunctional acrylic ester include polyfunctional acrylate monomer and（It is branched）Polyoxyalkylene acrylate Ester, the polyfunctional acrylate monomer is diacrylate -1,6 hexylene glycol ester, trimethylolpropane trimethacrylate, two contractings threePropane diolsTwoAcrylate, one or more in pentaerythritol triacrylate；It is described（It is branched）Polyether acrylate is by gathering Ethoxylated polyhydric alcohol or branch polyether polyatomic alcohol with（Methyl）Acrylate carries out ester exchange reaction and obtained；The PPG or branch The degree of functionality for changing PPG is 3~12, and relative molecular mass is 400~5000；
Wherein, the branch polyether polyatomic alcohol is obtained by trihydroxylic alcohol and/or tetrahydroxylic alcohol through catalyzing and condensing, or passes through epoxy again Propane and/or oxirane are obtained after carrying out chain extension.
In the present invention, the degree of functionality of the PPG or branch polyether polyatomic alcohol refers to PPG 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 through catalyzing and condensing, more specifically Ground, can be condensed to yield by more than two trihydroxylic alcohols and/or tetrahydroxylic alcohol.
It is highly preferred that the branch polyether polyatomic alcohol is condensed to yield by the trihydroxylic alcohol and/or tetrahydroxylic alcohol of more than three.Invention People has been surprisingly found that the PPG 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.
In the present invention, when the polyfunctional acrylic ester is polyfunctional acrylate monomer, above-mentioned reaction is generated A kind of polyfunctional acrylate monomer containing carboxy-modified polycyclic amine structure, i.e., a kind of reactive amines aided initiating, reactive amines are helped The characteristics of initiator has small smell, small amine migration and small xanthochromia, which overcomes the deficiency of regular activated amine aided initiating, The polyfunctional acrylate monomer containing carboxy-modified polycyclic amine structure has higher solidification rate, less solidification simultaneously Shrinkage factor and more excellent hardness and resistance to elevated temperatures；
When the polyfunctional acrylic ester is（It is branched）During polyether acrylate, above-mentioned reaction generates one kind and changed containing carbonyl The polycyclic amine structure of property（It is branched）Polyether acrylate, it is described containing carboxy-modified polycyclic amine structure（It is branched）Polyether acrylate It is a kind of low viscosity resin for having and helping and triggering group, it has higher solidification rate, less cure shrinkage, more excellent Hardness and resistance to elevated temperatures, the gas that brings after reactive amines aided initiating is added into resin of the prior art while overcoming Taste is big, easily occur amine migration and the serious deficiency of xanthochromia；In addition, described containing carboxy-modified polycyclic amine structure（It is branched）Polyethers third Olefin(e) acid ester can largely be used in the formula of light-cured resin because viscosity is relatively low as a kind of resin, without the need for extra Reactive amines are added, this avoids the deficiency of reactive amines of the prior art.
Preferably, the degree of functionality of the PPG is 3~6, and relative molecular mass is 700~2000；It is described branched The degree of functionality of PPG is 5~9, and relative molecular weight is 400~3000.
Preferably, the acrylate is methyl acrylate, ethyl acrylate, methyl methacrylate or methacrylic acid One or more in ethyl ester.
In the present invention, the PPG or branch polyether polyatomic alcohol with（Methyl）The ester exchange reaction of acrylate Carried out under conditions of solidification enzyme and efficient accelerator, 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 sulfonic acid Salt.
The present invention is first using lanthanide rare sulfonate as the efficient accelerator of enzymatic ester exchange reaction, applied to preparation （It is branched）The catalysis that polyether acrylate, solidification enzyme and efficient accelerator synergy greatly improve solidification enzyme catalyst is lived 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, 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 production The concentration of thing, purifying products processing 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 It is one or more of；The efficient accelerator that the present invention is used can be bought or be made by oneself by market, 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, Make water-insoluble sulfonic acid lanthanum Precipitation, dry.
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 glycerine or trimethylolpropane；The tetrahydroxylic alcohol can be pentaerythrite.
It is above-mentioned（It is branched）The preparation method of polyether acrylate includes ester exchange reaction and the big step of purification process two, specifically It is as follows：
S1：Ester exchange reaction：By PPG 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 therefroms are filtered, methanol or ethanol that reaction is generated is distilled off in filtrate decompression And excessive（Methyl）Acrylate, produces final product.
Preferably,（It is branched）The preparation method of polyether acrylate is as follows：
S1：Ester exchange reaction：By PPG or branch polyether polyatomic alcohol, excessive（Methyl）Acrylate, antioxygen After agent and polymerization inhibitor are uniformly dispersed, solidification enzyme catalyst and efficient accelerator is added, reaction 3 under being stirred at 30~80 DEG C~ 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 therefroms are filtered, methanol or ethanol that reaction is generated is distilled off in filtrate decompression And excessive（Methyl）Acrylate, produces final product.
In the present invention, the addition of polymerization inhibitor can be prevented（Methyl）Acrylic double bond polymerize, it is ensured that handed 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 the long and good polymerization inhibitor of stability, it is further preferred that the polymerization inhibitor be cupric oxide, copper sulphate, ferrous sulfate, to benzene two One or more in phenol, MEHQ, 2,6 di tert butyl 4 methyl phenol and phenthazine；In order to avoid polymerization inhibitor Content is excessive, influences the light-cured performance of final products, and the consumption of the polymerization inhibitor has certain restriction, is 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 TBHQ, four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythrite Ester, β-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester of propionic acid, Wytox 312 or diphosphites One or more in the different certain herbaceous plants with big flowers ester of pentaerythrite two.
The preparation method of the above-mentioned polyfunctional acrylic ester containing carboxy-modified polycyclic amine structure, specifically includes following steps： Catalyst is added into the polyfunctional acrylic ester, is added dropwise under the conditions of 20~80 DEG C described containing carboxy-modified polycyclic amines, perseverance Temperature 3~12h of reaction, produces product.
Preferably, the mol ratio containing carboxy-modified polycyclic amines and the polyfunctional acrylic ester is 1:1~1:2.
Compared with prior art, the present invention has the advantages that：
（1）The present invention by adjust carbonic ester and alicyclic diamine with when synthesis condition, products therefrom has a variety of Structure, now can be modified intermediate containing carboxy-modified polycyclic amines as a kind of wider reactive amines of applicability, by its with it is multifunctional Acrylate monomer is after Michael addition reaction, and the resulting polyfunctional acrylate monomer of polycyclic amines containing carbonyl is used as one Plant reactive amines and overcome big regular activated amine smell, easy xanthochromia, the deficiency for easily occurring amine migration；
（2）The present invention will contain carboxy-modified polycyclic amines and apply（It is branched）When in polyether acrylate, one kind one has been synthesized Plant with the low viscosity resin for helping initiation group, there should be the low viscosity resin for helping initiation group that there is higher solidification rate, Less cure shrinkage, more excellent hardness and resistance to elevated temperatures, are added while overcoming into resin of the prior art Amine migration and the serious deficiency of xanthochromia greatly, easily occur for the smell brought after reactive amines；
（3）The present invention contains carboxy-modified polycyclic amines, technique letter using alicyclic diamine as raw material through carbonate-modified formed Single, raw material is cheap and easy to get.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this. Unless stated otherwise, material involved in embodiment, method are material commonly used in the art and method.
A kind of ring polyamines 1 containing carbonyl two of synthesis example 1
177.2g diethyl carbonates and 258.4g are added in the three-necked flask equipped with rectifier unit, thermometer and agitator Piperazine anhydrous；After stirring, 80 DEG C are gradually heating to, isothermal reaction 6h, rectifying mouthful temperature control is treated at 60~70 DEG C or so Substantially after being separated without rectifying liquid, 90~100 DEG C of vacuum distillations is warming up to and remove low-boiling by-products and impurity, obtain clear, colorless production Thing 350.2g（Actual recovery 95.5%）.
A kind of polycyclic oligomeric polyamines 2 containing carbonyl of synthesis example 2
162.0g dimethyl carbonates and 194.6g are added in the three-necked flask equipped with rectifier unit, thermometer and agitator Piperazine anhydrous；After stirring, be gradually heating to 80 DEG C, isothermal reaction 12h, rectifying mouthful temperature control at 60~70 DEG C or so, After being separated substantially without rectifying liquid, it is warming up to 90~100 DEG C of vacuum distillations and removes low-boiling by-products and impurity, obtain clear, colorless Product 290.2g（Actual recovery 95.9%）.
A kind of ring polyamines 3 containing carbonyl two of synthesis example 3
97.0g ethylene carbonates and 374.7g are added in the three-necked flask equipped with rectifier unit, thermometer and agitator IPD；After stirring, 80 DEG C of reaction 6h are gradually heating to, rectifying mouthful temperature control is treated at 60~70 DEG C or so Substantially after being separated without rectifying liquid, 90~100 DEG C of vacuum distillations is warming up to and remove low-boiling by-products and impurity, obtain clear, colorless production Thing 385.2g（Actual recovery 95.5%）.
The polyether acrylate 1 of synthesis example 4（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 MEHQs, after being uniformly dispersed, add 6g solidification enzyme LVK-F100 and 0.1g lanthanum methanesulfonates, the stirring reaction 24h at 40 DEG C；
A. purification process：After mixture filtering obtained by upper step, filtrate carries out vacuum rotary steam, eliminates the methanol of reaction generation With excessive methyl acrylate, clear, colorless carboxylate 463.0g is obtained（Solid content 99.5%, 105mPas/25 DEG C of viscosity, ester Rate is 97.1%）.
The branch polyether acrylate 2 of synthesis example 5（Mn ≈ 1022, degree of functionality is 9）
A kind of branch polyether acrylate and preparation method thereof, is comprised the following steps that：
（1）The synthesis of branch polyether polyatomic alcohol
Using glycerine as raw material, in acid condition, it is condensed to form branch polyether polyatomic alcohol through a step（Mn ≈ 536, degree of functionality For 9, the degree of branching is 0.72）；
（2）Enzymatic ester exchange reaction, including following two steps：
A. ester exchange reaction：Take above-mentioned branch polyether polyatomic alcohol 300g, 550.0g methyl acrylate, the nonyl of 1.8g phosphorous acid three Base phenylester, 0.25g MEHQs, after being uniformly dispersed, add 8g solidification enzymes Novozyme 435 and 0.1g dodecyls Sulfonic acid lanthanum, the stirring reaction 24h at 50 DEG C；Chemical equation is as follows
B. purification process：After mixture filtering obtained by upper step, filtrate carries out vacuum rotary steam, eliminates the methanol of reaction generation With excessive methyl acrylate, clear, colorless carboxylate 553.0g is obtained（Solid content 99.3%, 65mPas/25 DEG C of viscosity, ester Rate is 96.7%）.
A kind of ring modified polyamine TMPTA monomers 1 containing carbonyl two of embodiment 1
Take the commercially available TMPTA monomers of 59.3g (0.2mol) to be placed in there-necked flask, add 0.16g DBU catalyst, gradually heat up To 60 DEG C；Start that the ring polyamines 1 containing carbonyl two that 19.8g (0.1mol) synthesis example 1 is prepared is added dropwise under stirring, dripped in 1h Add entirely, continue isothermal reaction 6h, cooling discharging obtains colourless transparent liquid 75.6g（Solid content is 99.3%, and viscosity is 100mPa·s/25℃）.
A kind of ring modified polyamine polyether acrylate 2 containing carbonyl two of embodiment 2
232.4g (0.2mol) synthesis example 4 is taken to synthesize obtained polyether acrylate 1（Mn ≈ 1162, degree of functionality is 3）, It is placed in there-necked flask, adds 0.4g DBU catalyst, be gradually heating to 60 DEG C；Start to be added dropwise 0.1mol under stirring by synthesis example 2 The ring polyamines 2 containing carbonyl two prepared, is added dropwise completely in 1h, continues isothermal reaction 6h, cooling discharging obtains water white transparency liquid Body 235.1g（Solid content is 99.5%, and viscosity is 120 mPas/25 DEG C）.
A kind of ring modified polyamine branch polyether acrylate 3 containing carbonyl two of embodiment 3
The branch polyether acrylate 2 for taking 102.2g (0.1mol) synthesis example 5 to prepare（Mn ≈ 1022, degree of functionality is 9）Add in there-necked flask, add 0.3g DBU catalyst, be gradually heating to 60 DEG C；Start to be added dropwise 0.1mol under stirring by synthesis example The 3 ring polyamines 3 containing carbonyl two prepared, are added dropwise completely in 1h, continue isothermal reaction 6h, cooling discharging obtains water white transparency Liquid 121.1g（Solid content is 99.4%, and viscosity is 80mPas/25 DEG C）.
A kind of urethane-modified TMPTA monomers containing single ring architecture of comparative example 1
（1）A kind of synthesis of the carbamate containing single ring architecture
177.2g diethyl carbonates and 129.2g are added in the three-necked flask equipped with rectifier unit, thermometer and agitator Piperazine anhydrous；After stirring, 80 DEG C are gradually heating to, isothermal reaction 3h, rectifying mouthful temperature control is treated at 60~70 DEG C or so Substantially after being separated without rectifying liquid, 90~100 DEG C of vacuum distillations is warming up to and remove low-boiling by-products and impurity, obtain clear, colorless production Thing 233.8g（Actual recovery 98.5%）.
（2）The synthesis of urethane-modified TMPTA monomers containing single ring architecture
Take the commercially available TMPTA monomers of 59.3g (0.2mol) to be placed in there-necked flask, add 0.16g DBU catalyst, gradually heat up To 60 DEG C；Start that 0.2mol steps are added dropwise under stirring（1）The carbamate containing single ring architecture prepared, drips in 1h Add entirely, continue isothermal reaction 6h, cooling discharging obtains colourless transparent liquid 90.4g（Solid content is 99.5%, and viscosity is 95 mPa·s/25℃）.
A kind of urethane-modified branch polyether acrylate containing single ring architecture of comparative example 2
（1）The synthesis of carbamate containing single ring architecture
Synthetic method is with comparative example 1（1）；
（2）The synthesis of urethane-modified branch polyether acrylate containing single ring architecture
The branch polyether acrylate 2 for taking 102.2g (0.1mol) synthesis example 5 to prepare（Mn ≈ 1022, degree of functionality is 9）Add in there-necked flask, add 0.3g DBU catalyst, be gradually heating to 60 DEG C；Start that 0.1mol steps are added dropwise under stirring（1） The carbamate containing single ring architecture prepared, is added dropwise completely in 1h, continues isothermal reaction 6h, cooling discharging obtains nothing The g of color transparency liquid 116.6（Solid content is 98.8 %, and viscosity is 90 mPas/25 DEG C）.
The synthesis of embodiment 1 is obtained respectively synthesizes what is obtained containing the ring modified polyamine TMPTA monomers of carbonyl two, comparative example 1 Urethane-modified TMPTA monomers containing single ring architecture are added in photocurable formulation as additive, then to photocuring The performance such as the viscosity of formula and the xanthochromia of shaped article, cure shrinkage, solidification rate and hardness is tested, test knot Fruit is as shown in table 1：
Table 1：Partial properties are contrasted
Note：Solidification rate test condition：1173,25 μm of wet films of addition 3%, 200mJ/ cm2；So that linear speed is fully cured Degree（Unit：m/s）Solidification rate is represented, linear velocity is more big, illustrates that solidification rate is faster.
Embodiment 1 in table 1 is a kind of ring modified polyamine TMPTA monomers containing carbonyl two, and it can be used as a kind of reactive amines Aided initiating, it is inhibited from yellowing when being used in photocurable formulation, be not susceptible to amine migration, it is tasteless, overcome conventional reactive amines Deficiency, in addition, the shaped article prepared using it as the photocuring system of reactive amines aided initiating have higher solidification Speed, less cure shrinkage and more excellent hardness, have broad application prospects；By contrast, comparative example 1 is through surveying Examination, urethane-modified TMPTAs containing single ring architecture of the TMPTA through being obtained after urethane-modified containing single ring architecture Although viscosity is smaller, its solidification rate is not high, and has that shrinkage factor is larger and deficiency of slight xanthochromia；As can be seen here, Polycyclic amines containing carbonyl are much more desirable as the modification intermediate of active amine monomer.
It is 2-in-1 to embodiment into the obtained ring modified polyamine containing carbonyl two respectively（It is branched）Polyether acrylate and comparative example 2-in-1 viscosity and the xanthochromia of shaped article into the obtained urethane-modified branch polyether acrylate containing single ring architecture The performance such as property, cure shrinkage, solidification rate and hardness is tested, and with branch polyether acrylate 2 and commercially available reactive amines The scheme as a comparison case 3 that CN371 coordinates, test result is as shown in table 2：
Table 2：Partial properties are contrasted
Note：Solidification rate test condition：1173,25 μm of wet films of addition 3%, 200mJ/ cm2；So that linear speed is fully cured Degree（Unit：m/s）Solidification rate is represented, linear velocity is more big, illustrates that solidification rate is faster.
Embodiment 2 and 3 is to form one kind after being reacted containing carboxy-modified polycyclic amines and branch polyether acrylate With the resin for helping the low viscosity for triggering group, comparative example 2 is the urethane-modified branch polyether propylene containing single ring architecture The product that acid esters is obtained, comparative example 3 is the scheme that branch polyether acrylate 2 and commercially available reactive amines CN371 coordinate, with existing skill Reactive amines are added in resin in art is compared（I.e. compared with comparative example 3）, contain carbonyl in embodiments of the invention 2 and 3 Modified polycyclic amines branch polyether acrylate itself, which possesses, helps initiation group, and described containing carboxy-modified polycyclic amines branch polyether Acrylate is not susceptible to xanthochromia, overcomes the deficiency of the regular activated easy xanthochromia of amine aided initiating；In addition, described containing carboxy-modified Polycyclic amines branch polyether acrylate possesses the low characteristic of viscosity, can as a kind of low viscosity resin in photocurable formulation it is a large amount of Use；And the shaped article prepared using it as photocuring raw material also has higher solidification rate, less solidification is received Shrinkage, and more excellent hardness have greatly widened its application；By contrast, comparative example 2 after tested, branch polyether propylene Though the solidification rate of acid esters is higher, still suffer from that shrinkage factor is larger, the deficiency of slight xanthochromia.As can be seen here, polycyclic amines containing carbonyl More suitably acrylate is modified.

Claims (6)

1. a kind of polycyclic amines containing carbonyl are modified polyfunctional acrylic ester, it is characterised in that the polycyclic amines containing carbonyl are modified many officials Can acrylate by containing carboxy-modified polycyclic amines and polyfunctional acrylic ester through Michael addition reaction, in polyfunctional acrylic ester Partial double bond in introduce polycyclic tertiary amine structure, the polyfunctional acrylic ester is polyfunctional acrylate monomer, polyethers propylene Acid esters or branch polyether acrylate；The polyfunctional acrylate monomer is the hexylene glycol of diacrylate -1,6 ester, trihydroxy methyl One or more in propane triacrylate, tri (propylene glycol) diacrylate, pentaerythritol triacrylate；It is described poly- Ether acrylate carries out ester exchange reaction by PPG and methacrylate and obtained；The branch polyether acrylate by Branch polyether polyatomic alcohol carries out ester exchange reaction with methacrylate and obtained；The PPG or branch polyether polyatomic alcohol Degree of functionality be 3~12, relative molecular mass be 400~5000；
Described is to have at least two rings through what ammonolysis reaction was formed with carbonic ester and alicyclic diamine containing carboxy-modified polycyclic amines The polycyclic amines of structure；Wherein, the alicyclic diamine refers to piperazine, IPD, Isosorbide-5-Nitrae-hexamethylene diamine, 1- methyl -2,4- One or more in cyclohexanediamine and N, N'- dimethyl -1,2- cyclohexanediamine；The carbonic ester is dimethyl carbonate, carbonic acid One or more in diethylester, methyl ethyl carbonate, dipropyl carbonate, dibutyl carbonate, ethylene carbonate and propene carbonate.
2. polycyclic amines containing carbonyl are modified polyfunctional acrylic ester according to claim 1, it is characterised in that described to change containing carbonyl It by the carbonic ester and alicyclic diamine is 1 in molar ratio that the preparation method of property polycyclic amines, which is,:1~2 ratio is in 60~120 DEG C Under the conditions of react 3~12h, vacuum distillation remove accessory substance and excess reactant produce.
3. polycyclic amines containing carbonyl are modified polyfunctional acrylic ester according to claim 1, it is characterised in that the ester exchange is anti- It should be carried out under conditions of solidification enzyme and efficient accelerator, 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.
4. polycyclic amines containing carbonyl are modified polyfunctional acrylic ester according to claim 1, it is characterised in that the polyethers propylene The preparation method of acid esters or branch polyether acrylate includes ester exchange reaction and the big step of purification process two, specific as follows：
S1：Ester exchange reaction：By PPG or branch polyether polyatomic alcohol, excessive methacrylate, antioxidant and Polymerization inhibitor carries out ester exchange reaction under the conditions of 30~80 DEG C after being uniformly dispersed, 3~48h of sustained response obtains product standby；
S2：Purification process：Step S1 products therefroms are filtered, methanol or ethanol and the mistake that reaction is generated is distilled off in filtrate decompression The polyfunctional acrylic ester of amount, produces final product.
5. polycyclic amines containing carbonyl described in Claims 1 to 4 any claim are modified the preparation method of polyfunctional acrylic ester, its It is characterised by, DUB catalyst is added into the polyfunctional acrylic ester, changes under the conditions of 20~80 DEG C described in dropwise addition containing carbonyl Property polycyclic amines, 3~12h of isothermal reaction produces product.
6. preparing the multifunctional acrylic acid of the modification of polycyclic amines containing carbonyl containing carboxy-modified polycyclic amines described in Claims 1 to 4 is any Application in ester.
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