CN109369462A - A kind of non-isocyanate polyurethane monomer and preparation method thereof - Google Patents
A kind of non-isocyanate polyurethane monomer and preparation method thereof Download PDFInfo
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- CN109369462A CN109369462A CN201811401182.8A CN201811401182A CN109369462A CN 109369462 A CN109369462 A CN 109369462A CN 201811401182 A CN201811401182 A CN 201811401182A CN 109369462 A CN109369462 A CN 109369462A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/38—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
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- Chemical & Material Sciences (AREA)
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- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of non-isocyanate polyurethane monomer and preparation method thereof, the non-isocyanate polyurethane monomer has the structure being shown below:Wherein, R is selected from saturated alkane, unsaturated alkane or aromatic hydrocarbon group；R1For methyl or hydrogen-based；R2For alkyl；R3For hydrogen or alkyl, there is the non-isocyanate polyurethane monomer double bond group to be readily formed polymer and copolymer, also there are non-isocyanate polyurethane specific groups, tool has good corrosion resistance, chemical resistance, hydrolytic resistance and permeability resistance, from the weak bonding structure compensated on molecular structure in conventional polyurethanes molecule, preparation process is exactly two amidation process, and preparation process is simple.
Description
Technical field
The present invention relates to chemical material field, in particular to a kind of non-isocyanate polyurethane monomer and preparation method thereof.
Background technique
Polyurethane is carbamate quasi polymer, and since its raw material variety is quite abundant, the production to come in every shape can be made
Product are described as " can cut " polymer by Chemical Engineer.In recent years with economic growth, demand of the people to polyurethane products is got over
Come bigger, and gets the nod and develop in the world, it is in recent years that industrialization product, which forms market with high speed,
Form market scale, and one of the bright spot product for the potentiality that still grow a lot.
The exploitation of non-isocyanate polyurethane (Nonisocyanate Polyurethane, NIPU) is polyurethane research
One important directions, at present.Non-isocyanate polyurethane refers generally to one made of being reacted as cyclic carbonate compound with polyamine
Kind of novel environment friendly polyurethane, non-isocyanate polyurethane is from the weak bond knot compensated in conventional polyurethanes molecule on molecular structure
Structure, and toxic polyisocyanates is eliminated in its preparation process, but raw material used be not it is moisture-sensitive, give raw material
Preservation and construction bring inconvenience, and can make because generating bubble material formation fault of construction.Due to various countries' environmental consciousness
Gradually reinforce, tradition is limited using isocyanates as the polyurethane of Material synthesis by application, and the World Health Organization provides isocyanic acid
Ester polymer free monomers content must control within 0.5%, and part American-European countries has put into effect relevant method law
Rule forbid isocyanates in the use in certain fields, and the thermal insulation material and packaging industry of European market gradually disable isocyanic acid
Ester starts using NIPU, therefore the application range of NIPU is very broad.
But the preparation condition of present NIPU especially monomer is harsh, expensive, this seriously hinders NIPU further to send out
Exhibition, the present invention proposes a kind of production raw material simple cheap and preparation process is simple, and conventional polyurethanes are compensated on molecular structure and are divided
There is weak bonding structure in son double bond group to be readily formed polymer and copolymer, corrosion resistance also with super strength, resistance toization
The property learned, hydrolytic resistance and permeability resistance.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of non-isocyanate polyurethane monomer and its systems
Preparation Method, makes raw material simple cheap and preparation process is simple, can obtain non-isocyanate by two amidation process
Urethane monomer compensates for the weak bonding structure in conventional polyurethanes molecule on molecular structure, and there is double bond group to be readily formed
Polymer and copolymer, corrosion resistance, chemical resistance, hydrolytic resistance and permeability resistance also with super strength.
The purpose of the present invention is achieved through the following technical solutions:
A kind of non-isocyanate polyurethane monomer, general structure are as follows:
Wherein, R is saturated alkane, unsaturated alkane or aromatic hydrocarbon group；R1For methyl or hydrogen-based；R2For alkyl；R3For hydrogen
Or alkyl.
Further, the method for preparing non-isocyanate polyurethane monomer as described in claim 1, using compound A,
Compound B and compound C obtains the non-isocyanate polyurethane monomer by amidation process twice；
The general structure of the compound A is as follows:
The general structure of the compound B is as follows:
The general structure of the compound C is as follows:
Wherein, R is saturated alkane, unsaturated alkane or aromatic hydrocarbon group；R1For methyl or hydrogen-based；R2For alkyl；R3For hydrogen
Or alkyl.
The preparation method of the non-isocyanate polyurethane monomer, the compound A are propene carbonate, compound B
For ethylenediamine, compound C is acrylic acid, specifically includes the following steps:
S11, by propene carbonate and ethylenediamine in molar ratio 1:1~1.5 distinguish uniform dissolution to 50~70ml solvent
In obtain carbonic allyl ester solution and ethylenediamine solution, under conditions of 0~90 DEG C of temperature, by carbonic allyl ester solution according to drop
Speed be 1~10ml/min be added dropwise to reacted 10~15 hours in ethylenediamine solution after obtain mixed solution, be measured to the mixing
It after propene carbonate fully reacting in solution, reuses Rotary Evaporators and solvent and remaining ethylenediamine is removed, obtain the
One reaction intermediate, specific reaction equation are as follows:
S12, take the first reaction intermediate 0.01mol obtained in acrylic acid 0.01mol~0.02mol and step S11~
0.02mol is added dropwise in the solvent of 50~70ml according to for 1~6ml/min simultaneously, is reacted 10~12 hours at normal temperature, is used
Rotary Evaporators remove solvent, obtain the non-isocyanate polyurethane monomer, and specific reaction equation is as follows:
Further, the molar ratio of the propene carbonate and ethylenediamine is 1:1.5.
Further, the preparation method of the non-isocyanate polyurethane monomer, the compound A are propylene carbonate
Ester, compound B are ethylenediamine, and compound C is acrylic acid, specifically includes the following steps:
S21, by ethylenediamine and acrylic acid compound represented in molar ratio 1:1~1.1.5 distinguish uniform dissolution to 50~
Obtain ethylenediamine solution and acrylic acid solution in the solvent of 70ml, under conditions of 0~90 DEG C of temperature, by acrylic acid solution according to
Drop speed be 1~10ml/min be added dropwise to react 10~15 hours in ethylenediamine solution after obtain mixed solution, be measured to it is described mix
After closing the acrylic acid fully reacting in solution, reuses Rotary Evaporators and solvent and remaining ethylenediamine are removed, obtain second
Reaction intermediate, specific reaction equation are as follows:
S22, the second reaction intermediate obtained in propene carbonate 0.01mol~0.02mol and step S21 is taken
0.01mol~0.02mol is added dropwise in the solvent of 50~70ml according to for 1~6ml/min simultaneously, reacts 10~12 at normal temperature
Hour, solvent is removed using Rotary Evaporators, obtains the non-isocyanate polyurethane monomer, specific reaction equation is such as
Under:
Further, the molar ratio of the acrylic acid and diamine sum is 1:1.5.
Further, measure whether propene carbonate or acrylic acid have reacted using online infrared or nuclear-magnetism method
Entirely.
Further, the solvent is acetonitrile, ethyl alcohol, methanol, 1- propyl alcohol, 2- propyl alcohol, benzene, toluene, furans, benzene first
The one of which of ether, chloroform, methylene chloride, monochloro methane.
The beneficial effects of the present invention are:
The present invention both instead of conventional urethane by the synthesis technology of polyisocyanates and polyol reaction, also instead of
Epoxide and carbon dioxide react when nonisocyanate polyurethane synthesized:
1) the production raw material simple cheap and preparation process of monomer of the invention are simple, significantly reduce Product formation
Cost, synthetic method are also simple: synthetic method is mainly the amidation process for passing through two carboxylic acids and primary amine, reaction condition temperature
With of less demanding to consersion unit, monomer has from weak bonding structure in conventional polyurethanes molecule is compensated for again on molecular structure
Double bond group is easy to self-polymerization or is copolymerized to form polymer and copolymer with other monomers, obtained polymer or copolymerization
Object has an excellent physical and chemical properties of non-isocyanate polyurethane, corrosion resistance also with super strength, chemical resistance, water-fast
Solution property and permeability resistance.
2) the production raw material for the monomer invented not is moisture-sensitive, and the preservation and construction to raw material are brought conveniently, and
Material will not be made to form fault of construction because generating bubble.
Specific embodiment
Below in conjunction with embodiment, technical solution of the present invention is clearly and completely described, it is clear that described
Embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field
Technical staff's every other embodiment obtained under the premise of not making the creative labor belongs to what the present invention protected
Range.
The present invention provides a kind of technical solution:
A kind of non-isocyanate polyurethane monomer, general structure are as follows:
Wherein, R is saturated alkane, unsaturated alkane or aromatic hydrocarbon group；R1For methyl or hydrogen-based；R2For alkyl；R3For hydrogen
Or alkyl.
Further, the method for preparing non-isocyanate polyurethane monomer as described in claim 1, using compound A,
Compound B and compound C obtains the non-isocyanate polyurethane monomer by amidation process twice；
The general structure of the compound A is as follows:
The general structure of the compound B is as follows:
The general structure of the compound C is as follows:
Wherein, R is saturated alkane, unsaturated alkane or aromatic hydrocarbon group；R1For methyl or hydrogen-based；R2For alkyl；R3For hydrogen
Or alkyl.
The carbonate products A can be carbonate products, propene carbonate may be selected, compound B can be second two
Amine or propane diamine, compound C can be also (methyl) propylene or acryloyl chloride or acrylic acid.
The preparation method of the non-isocyanate polyurethane monomer, the compound A select propene carbonate, compound B
Ethylenediamine is selected, compound C selects acrylic acid, and steps are as follows:
Embodiment 1
The preparation non-isocyanate polyurethane monomer, first method, specifically includes the following steps:
S11, by propene carbonate and ethylenediamine, uniform dissolution obtains 1:1 into the solvent acetonitrile of 50ml respectively in molar ratio
Carbonic allyl ester solution and ethylenediamine solution, it is under conditions of 0 DEG C of temperature, carbonic allyl ester solution is fast for 1ml/ according to drop
Min is added dropwise to reacted 10 hours in ethylenediamine solution after obtain mixed solution, if being measured to institute using online infrared or nuclear-magnetism
After stating the propene carbonate fully reacting in mixed solution, reuses Rotary Evaporators and solvent acetonitrile and remaining ethylenediamine are gone
It removes, obtains the first reaction intermediate, specific reaction equation is as follows:
S12, take the first reaction intermediate 0.01mol obtained in acrylic acid 0.01mol and step S1 simultaneously according to for
1ml/min is added dropwise in the solvent acetonitrile of 50ml, reacts 10 hours, solvent acetonitrile is gone at normal temperature using Rotary Evaporators
It removes, obtains the non-isocyanate polyurethane monomer, specific reaction equation is as follows:
Non-isocyanate polyurethane monomer is prepared, second method can carry out in accordance with the following steps:
S21, by ethylenediamine and acrylic acid, according to molar ratio 1:1, uniform dissolution obtains second into the solvent acetonitrile of 50ml respectively
Acrylic acid solution is added dropwise to second according to drop speed under conditions of 0 DEG C of temperature for 1ml/min by diamine solution and acrylic acid solution
Mixed solution is obtained after reacting 10 hours in diamine solution, if being measured in the mixed solution using online infrared or nuclear-magnetism
Acrylic acid fully reacting after, reuse Rotary Evaporators and solvent acetonitrile and remaining ethylenediamine removed, obtain the second reaction
Intermediate, specific reaction equation are as follows:
S22, take the second reaction intermediate 0.01mol obtained in propene carbonate 0.01mol and step S1 simultaneously according to
It is added dropwise in the solvent acetonitrile of 50ml for 1ml/min, reacts 10 hours, solvent acetonitrile is gone at normal temperature using Rotary Evaporators
It removes, obtains the non-isocyanate polyurethane monomer, specific reaction equation is as follows:
The solvent can also be ethyl alcohol, methanol, 1- propyl alcohol, 2- propyl alcohol, benzene, toluene, furans, methyl phenyl ethers anisole, chloroform, dichloro
The one of which of methane, monochloro methane.
Embodiment 2
The preparation non-isocyanate polyurethane monomer, first method, specifically includes the following steps:
S1, by propene carbonate and ethylenediamine, 1:1.5 distinguishes uniform dissolution into the solvent acetonitrile of 70ml in molar ratio
To carbonic allyl ester solution and ethylenediamine solution, under conditions of 90 DEG C of temperature, it is according to drop speed by carbonic allyl ester solution
10ml/min is added dropwise to reacted 15 hours in ethylenediamine solution after obtain mixed solution, if online infrared or nuclear-magnetism is used to measure
To after the propene carbonate fully reacting in the mixed solution, Rotary Evaporators are reused solvent acetonitrile and remaining second two
Amine removal, obtains the first reaction intermediate, specific reaction equation is as follows:
S2, take the first reaction intermediate 0.02mol obtained in acrylic acid 0.02mol and step S1 simultaneously according to for 6ml/
Min is added dropwise in the solvent acetonitrile of 70ml, reacts 12 hours at normal temperature, solvent acetonitrile is removed using Rotary Evaporators, is obtained
To the non-isocyanate polyurethane monomer, specific reaction equation is as follows:
Non-isocyanate polyurethane monomer is prepared, second method can carry out in accordance with the following steps:
S1, by ethylenediamine and acrylic acid, according to molar ratio 1:1.5, uniform dissolution is obtained into the solvent acetonitrile of 70ml respectively
Ethylenediamine solution and acrylic acid solution instill acrylic acid solution according to drop speed under conditions of 90 DEG C of temperature for 10ml/min
Mixed solution is obtained after reacting 15 hours into ethylenediamine solution, if it is molten to be measured to the mixing using online infrared or nuclear-magnetism
After acrylic acid fully reacting in liquid, reuses Rotary Evaporators and solvent acetonitrile and remaining ethylenediamine are removed, obtain second
Reaction intermediate, specific reaction equation are as follows:
S2, take the second reaction intermediate 0.02mol obtained in propene carbonate 0.02mol and step S1 simultaneously according to for
6ml/min is added dropwise in the solvent acetonitrile of 70ml, reacts 12 hours, solvent acetonitrile is gone at normal temperature using Rotary Evaporators
It removes, obtains the non-isocyanate polyurethane monomer, specific reaction equation is as follows:
The solvent can also be ethyl alcohol, methanol, 1- propyl alcohol, 2- propyl alcohol, benzene, toluene, furans, methyl phenyl ethers anisole, chloroform, dichloro
The one of which of methane, monochloro methane.
Embodiment 3
The preparation non-isocyanate polyurethane monomer, first method, specifically includes the following steps:
S1, propene carbonate and ethylenediamine are distinguished into uniform dissolution into the solvent acetonitrile of 60ml according to molar ratio 1:1.25
Carbonic allyl ester solution and ethylenediamine solution are obtained, under conditions of temperature 50 C, is according to drop speed by carbonic allyl ester solution
5ml/min is added dropwise to reacted 12 hours in ethylenediamine solution after obtain mixed solution, if online infrared or nuclear-magnetism is used to measure
To after the propene carbonate fully reacting in the mixed solution, Rotary Evaporators are reused solvent acetonitrile and remaining second two
Amine removal, obtains the first reaction intermediate, specific reaction equation is as follows:
S2, take the first reaction intermediate 0.01mol obtained in acrylic acid 0.01mol and step S1 simultaneously according to for 3ml/
Min is added dropwise in the solvent acetonitrile of 60ml, reacts 12 hours at normal temperature, solvent acetonitrile is removed using Rotary Evaporators, is obtained
To the non-isocyanate polyurethane monomer, specific reaction equation is as follows:
Non-isocyanate polyurethane monomer is prepared, second method can carry out in accordance with the following steps:
S1, by ethylenediamine and acrylic acid, according to molar ratio 1:1.25, uniform dissolution is obtained into the solvent acetonitrile of 60ml respectively
Acrylic acid solution is added dropwise under conditions of temperature 50 C according to drop speed for 6ml/min by ethylenediamine solution and acrylic acid solution
Mixed solution is obtained after reacting 12 hours in ethylenediamine solution, if being measured to the mixed solution using online infrared or nuclear-magnetism
In acrylic acid fully reacting after, reuse Rotary Evaporators and solvent acetonitrile and remaining ethylenediamine removed, it is anti-to obtain second
Intermediate is answered, specific reaction equation is as follows:
S2, take the second reaction intermediate 0.01mol obtained in propene carbonate 0.01mol and step S1 simultaneously according to for
3ml/min is added dropwise in the solvent acetonitrile of 60ml, reacts 12 hours, solvent acetonitrile is gone at normal temperature using Rotary Evaporators
It removes, obtains the non-isocyanate polyurethane monomer, specific reaction equation is as follows:
The solvent can also be ethyl alcohol, methanol, 1- propyl alcohol, 2- propyl alcohol, benzene, toluene, furans, methyl phenyl ethers anisole, chloroform, dichloro
The one of which of methane, monochloro methane.
In the non-isocyanate polyurethane monomer that above-described embodiment generates:
Wherein, double bond group is readily formed polymer and copolymer, and non-isocyanate polyurethane specific groups have very
Good corrosion resistance, chemical resistance, hydrolytic resistance and permeability resistance, from being compensated on molecular structure in conventional polyurethanes molecule
Weak bonding structure.
The raw material of the production of the non-isocyanate polyurethane monomer: propene carbonate, diamine (ethylenediamine, propane diamine)
With acrylic acid (or acryloyl chloride), price is all very cheaply.
The first preparation process of above-described embodiment is related to following chemical general equation:
Second of preparation process of above-described embodiment is related to following chemical general equation:
The above is only a preferred embodiment of the present invention, it should be understood that the present invention is not limited to described herein
Form should not be regarded as an exclusion of other examples, and can be used for other combinations, modifications, and environments, and can be at this
In the text contemplated scope, modifications can be made through the above teachings or related fields of technology or knowledge.And those skilled in the art institute into
Capable modifications and changes do not depart from the spirit and scope of the present invention, then all should be in the protection scope of appended claims of the present invention
It is interior.
Claims (8)
1. a kind of non-isocyanate polyurethane monomer, which is characterized in that general structure is as follows:
Wherein, R is saturated alkane, unsaturated alkane or aromatic hydrocarbon group；R1For methyl or hydrogen-based；R2For alkyl；R3For hydrogen or alkane
Base.
2. the method for preparing non-isocyanate polyurethane monomer as described in claim 1, it is characterised in that: using compound A,
Compound B and compound C obtains the non-isocyanate polyurethane monomer by amidation process twice；
The general structure of the compound A is as follows:
The general structure of the compound B is as follows:
The general structure of the compound C is as follows:
Wherein, R is saturated alkane, unsaturated alkane or aromatic hydrocarbon group；R1For methyl or hydrogen-based；R2For alkyl；R3For hydrogen or alkane
Base.
3. the preparation method of non-isocyanate polyurethane monomer according to claim 2, which is characterized in that the compound
A is propene carbonate, and compound B is ethylenediamine, and compound C is acrylic acid, specifically includes the following steps:
S11, by propene carbonate and ethylenediamine, 1:1~1.5 distinguishes uniform dissolution into the solvent of 50~70ml in molar ratio
To carbonic allyl ester solution and ethylenediamine solution, under conditions of 0~90 DEG C of temperature, it is according to drop speed by carbonic allyl ester solution
1~10ml/min is added dropwise to reacted 10~15 hours in ethylenediamine solution after obtain mixed solution, be measured to the mixed solution
In propene carbonate fully reacting after, reuse Rotary Evaporators and solvent and remaining ethylenediamine removed, it is anti-to obtain first
Intermediate is answered, specific reaction equation is as follows:
S12, take the first reaction intermediate 0.01mol obtained in acrylic acid 0.01mol~0.02mol and step S11~
0.02mol is added dropwise in the solvent of 50~70ml according to for 1~6ml/min simultaneously, is reacted 10~12 hours at normal temperature, is used
Rotary Evaporators remove solvent, obtain the non-isocyanate polyurethane monomer, and specific reaction equation is as follows:
4. the preparation method of non-isocyanate polyurethane monomer according to claim 3, it is characterised in that: the carbonic acid
The molar ratio of acrylic ester and ethylenediamine is 1:1.5.
5. the preparation method of non-isocyanate polyurethane monomer according to claim 2, which is characterized in that the compound
A is propene carbonate, and compound B is ethylenediamine, and compound C is acrylic acid, specifically includes the following steps:
S21, by ethylenediamine and acrylic acid compound represented, 1:1~1.1.5 distinguishes uniform dissolution to 50~70ml in molar ratio
Solvent in obtain ethylenediamine solution and acrylic acid solution, under conditions of 0~90 DEG C of temperature, by acrylic acid solution according to drop speed
It is added dropwise to for 1~10ml/min after being reacted 10~15 hours in ethylenediamine solution and obtains mixed solution, it is molten to be measured to the mixing
After acrylic acid fully reacting in liquid, reuses Rotary Evaporators and solvent and remaining ethylenediamine are removed, obtain the second reaction
Intermediate, specific reaction equation are as follows:
S22, take the second reaction intermediate 0.01mol obtained in propene carbonate 0.01mol~0.02mol and step S21~
0.02mol is added dropwise in the solvent of 50~70ml according to for 1~6ml/min simultaneously, is reacted 10~12 hours at normal temperature, is used
Rotary Evaporators remove solvent, obtain the non-isocyanate polyurethane monomer, and specific reaction equation is as follows:
6. the preparation method of non-isocyanate polyurethane monomer according to claim 5, it is characterised in that: the propylene
The molar ratio of acid and diamine sum is 1:1.5.
7. according to the preparation method of the described in any item non-isocyanate polyurethane monomers of claim 3-6, it is characterised in that: make
Measured with online infrared or nuclear-magnetism method propene carbonate or acrylic acid whether fully reacting.
8. according to the preparation method of the described in any item non-isocyanate polyurethane monomers of claim 3-6, it is characterised in that: institute
The solvent stated is acetonitrile, ethyl alcohol, methanol, 1- propyl alcohol, 2- propyl alcohol, benzene, toluene, furans, methyl phenyl ethers anisole, chloroform, methylene chloride, a chlorine
The one of which of methane.
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| CN111285975A (en) * | 2020-03-18 | 2020-06-16 | 华南理工大学 | Polyurethane photosensitive resin for clinical customized medical instruments and preparation and application thereof |
| CN115322367A (en) * | 2022-08-23 | 2022-11-11 | 华南理工大学 | Polyurethane prepared based on urea and preparation method and application thereof |
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| CN106795281A (en) * | 2014-10-15 | 2017-05-31 | 阿科玛法国公司 | Simple function or polyfunctional urethane acrylate oligomer without isocyanates |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285975A (en) * | 2020-03-18 | 2020-06-16 | 华南理工大学 | Polyurethane photosensitive resin for clinical customized medical instruments and preparation and application thereof |
| CN111285975B (en) * | 2020-03-18 | 2021-06-08 | 华南理工大学 | Polyurethane photosensitive resin for clinical customized medical instruments and preparation and application thereof |
| CN115322367A (en) * | 2022-08-23 | 2022-11-11 | 华南理工大学 | Polyurethane prepared based on urea and preparation method and application thereof |
| CN115322367B (en) * | 2022-08-23 | 2023-09-29 | 华南理工大学 | Polyurethane prepared based on urea and preparation method and application thereof |
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