CN107805207A - A kind of preparation method of polyaspartic ester - Google Patents
A kind of preparation method of polyaspartic ester Download PDFInfo
- Publication number
- CN107805207A CN107805207A CN201710970681.8A CN201710970681A CN107805207A CN 107805207 A CN107805207 A CN 107805207A CN 201710970681 A CN201710970681 A CN 201710970681A CN 107805207 A CN107805207 A CN 107805207A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ester
- primary amine
- reaction
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- KDVGIHBJJVATGC-UHFFFAOYSA-N CCCCOC(CC(C(OCCCC)=O)NCCCC(C)CNC(CC(OCCCC)=O)C(OCCCC)=O)=O Chemical compound CCCCOC(CC(C(OCCCC)=O)NCCCC(C)CNC(CC(OCCCC)=O)C(OCCCC)=O)=O KDVGIHBJJVATGC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a kind of method for synthesizing polyaspartic ester, using tetra-alkyl ammonium hydroxide as catalyst, organic primary amine reacts to obtain with unsaturated dibasic acid ester.Tetra-alkyl ammonium hydroxide can significantly improve the Michael addition reactions activity of primary amine and butene dioic acid ester as organic alkali, after the completion of reaction by simply heat can complete Removal of catalyst, will not have a negative impact to product downstream application.The method of the invention has the advantages that catalytic activity is high, and primary amine high conversion rate, product colourity is low, and no catalyst remains.
Description
Technical field
The present invention relates to a kind of preparation method of polyaspartic ester, and in particular to one kind is urged in tetra-alkyl ammonium hydroxide
Under change effect, the method for high efficiency synthesis polyaspartic ester.
Background technology
Polyaspartic ester (Polyaspartic Ester, PAE) is as a kind of special steric hindrance type secondary amine, due to ester
The steric hindrance and inductive effect of base, the gel time with low viscosity isocyanate curing agent can be at several minutes between a few hours
It is adjusted.
The PAE of formula 1 synthetic reaction signal formula
PAE is synthesized by the Michael addition reactions of organic primary diamine and butene dioic acid diester.Because PAE is boiling point
Up to more than 500 DEG C of middle low viscosity liquid, therefore can not be purified by modes such as rectifying or crystallizations；If butylene two is remained in product
Volatile matter smell is larger when acid diesters can excessively cause to construct, and damages the machinery of PAE polyureas films due to its plasticization effect
Performance；Primary amine group is remained in product then can substantially shorten the gelation time of PAE polyureas.Thus, raw material conversion is improved as far as possible
Rate is one of key factor for improving PAE product quality.
Document (Advanced Materials Research.Vol 875-877,2014, pp 165-170.) reports
The Michael addition reactions series for synthesizing PAE is 3 grades.Well known in the art, PAE synthetic reaction later stage speed is very slow, room temperature
Place half a year or even can be only achieved satisfied reaction conversion ratio in more than 1 year, greatly reduce product supply of material efficiency.Pass through heating
Conversion ratio is improved with the reaction time is extended, causes accessory substance to increase, amine high-temperature oxydation colourity increases suddenly, influences product condition.Selection
Suitable catalyst is one of effective approach, but screening of catalyst standard is strict, it is necessary to meet：1. accelerate reaction；2.
Product colourity will not be increased；3. the reaction on PAE and isocyanate curing agent does not influence；4. film performance will not be damaged.
In order to improve feed stock conversion, patent US005821326A is reported using nitrogenous five-ring heterocycles, such as 1,2,4-
Triazole, 3,5- dimethyl -1,2,4- triazoles, 3,5- dimethyl pyrazoles catalysis PAE synthetic reaction.Liu Pei gifts et al. are in periodical
《Polyurethane industrial》 2005,20(4):16-19,《The preparation and research of Polyaspartic Polyurea》Report and add in one text
0.05wt% tertiary amine catalyst can is added to significantly improve conversion ratio.Catalyst choosing in patent CN201310448660
With pyridine, 2,4,6- tri- (dimethylamino methyl) phenol, triethylamine, triphenylphosphine.Arylamine is used in CN200610026565.2
For catalyst synthesizing polyether amine type PAE, 20~30h is reacted in 100 DEG C of high temperature above, room temperature is placed 3~4 months and can be only achieved
100% conversion ratio.These catalyst major part catalytic effects reported in the literature are unsatisfactory, and do not remove residual
In the product, downstream application may be adversely affected, including gel time, storage stability, film performance etc..Patent
CN201110115396 reports the method using loading type alkali metal fluoride-catalyzed synthesis PAE, and reaction rate has been lifted,
Heterogeneous catalysis can be removed by centrifugal filtration, but need to add tertiary carbonic acid glycidyl ester, could further be improved and be turned
Rate, and obtain being modified PAE compounds.
In summary, while PAE synthetic technology difficult point is that reaction rate improves, avoid to product quality and downstream
Using adversely affecting.
The content of the invention
It is an object of the invention to overcome above the deficiencies in the prior art, there is provided one kind is urged using tetra-alkyl ammonium hydroxide
It is combined to PAE method, this method has that production efficiency is high, easy to operate, product quality is high, is easy to industrialized feature.
For achieving the above object, the present invention uses following technical scheme：
A kind of method for catalyzing and synthesizing PAE, comprises the following steps：
(1) organic primary amine is reacted to obtain product with unsaturated dibasic acid ester under catalyst；
(2) the product removal catalyst for obtaining step (1), obtains polyaspartic ester product.
Preferably, in step (1), the device used in the reaction is equipped with mechanical agitation oar, thermometer, constant pressure addition leakage
Struggle against, be connected with N2Three mouthfuls of reactors of gas circuit pipe, bubbler, such as three-necked flask.
In step (1), the course of reaction is：Under inert gas atmosphere, unsaturated dibasic acid ester is added drop-wise to organic primary
Amine, catalyst mixture in, heat up, react after being added dropwise, reach and stop reaction, the inert gas after target conversion
It is preferred that nitrogen.
In step (1), the time that the reaction is passed through inert gas is 10~30min, and whipping temp is 10~40 DEG C, is risen
Temperature is 30~70 DEG C after temperature, and the reaction time is 1~12h.
In step (1), described organic primary amine be selected from 2 methyl pentamethylenediamine, 4,4 '-diamino-dicyclohexyl methane, 3,
One or more in 3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane, IPD, polyetheramine.
In step (1), the catalyst is tetra-alkyl ammonium hydroxide catalyst, preferably TMAH, tetrem
Base ammonium hydroxide, TPAOH, hydrate, the aqueous solution of TBAH and these tetra-alkyl ammonium hydroxides
In one or more, more preferably TMAH.In step (1), with the molar amount of primary amine group in organic primary amine,
The dosage of the catalyst is 0.005~0.5%, preferably the 0.01~0.1% of primary amine group mole.
In step (1), the one kind or more of described unsaturated dibasic acid ester in maleic acid diester, dimethyl ester
Kind.
Described dimethyl ester is selected from diethyl fumarate, fumaric acid dipropyl, dibutyl fumarate and fumaric acid first
One or more in base propyl diester；Described maleic acid diester is selected from diethyl maleate, dipropyl maleate, maleic acid two
One or more in butyl ester, methyl propyl diester.Unsaturated dibasic acid ester and the rate of charge of organic primary amine are unsaturation
The mol ratio of C=C and primary amine group in organic primary amine is 1 in dibasic acid ester:1.
In step (1), described reaction can be carried out in the presence of solvent-free or solvent, solvent be selected from methanol, ethanol,
One or more in propyl alcohol, the tert-butyl alcohol, acetone, tetrahydrofuran, acetonitrile, calculated with the gross mass of reactant and solvent, it is described
The dosage of solvent is 0~90wt%, in view of post-reaction treatment and the simplification and low cost of three-protection design, preferably solvent-free bar
Part reacts.
Product polyaspartic ester described in step (1) has following architectural feature：
Wherein x represents organic group, R1And R2For identical or different alkyl group, n represents the secondary of polyaspartic ester
Amine degree of functionality, it is >=2 integer.
In step (2), the method for the Removal of catalyst is that will stop reacted reaction unit heating, nitrogen stream, water
Pumping carries Removal of catalyst.In step (2), the temperature of Removal of catalyst is 90~130 DEG C, removing gauge pressure is 0.001~
0.02MPa, extraction times are 20~40min.
The polyaspartic ester product colourity prepared by the process conditions can reach 30 below Hazen, product primary
Amine conversion ratio reach 97% and more than, and without catalyst remain so that the construction with isocyanate curing agent formulated coatings is applicable
Phase is better than having reported result.
The present invention is had the following advantages and beneficial effect relative to existing PAE synthetic methods：
(1) tetra-alkyl ammonium hydroxide catalyst of the present invention, compared to other organic homogeneous catalysts, it is strong to have benefited from its
Alkalescence, catalytic activity is higher, and easily removes, pollution-free to PAE products.
(2) tetra-alkyl ammonium hydroxide catalyst of the present invention, compared to inorganic heterogeneous catalysis, metal will not be introduced
Ion, PAE product colourities are more excellent.
(3) tetra-alkyl ammonium hydroxide catalyst of the present invention, the PAE productions of high primary amine conversion ratio can be obtained in a short time
Product, gel time are considerably longer than comparative example product.
Brief description of the drawings
Fig. 1 is that 4,4 '-diamino-dicyclohexyl methane and the PAE products of diethyl maleate synthesis exist in embodiment 5
CDCl3In reagent1H NMR spectras, wherein having no that catalyst remains appearance.
Embodiment
The following examples will be further described to method provided by the present invention, but the invention is not restricted to listed
The embodiment gone out, it should also be included in other any known changes in interest field of the presently claimed invention.
Calculate conversion ratio：PAE products are carried out using Bruker 400MHz NMRs1H NMR are characterized, such as Fig. 1 institutes
Show, the double bond appearance of unreacted diethyl fumarate (dialkyl is isomerized to fumaric acid dialkyl in the presence of amine) exists
Unimodal σ 6.85, the peak of the newly-generated methine being connected with secondary amine appears in σ 3.5-3.8, and the peak of scope is subordinate to from 4.3 to 4.0
Belong in product and unreacted diethyl fumarate the methylene being connected with oxygen atom in ester group, we set its area integral
For 8, the calculation formula of the conversion ratio of diethyl maleate：C=1-A/4.
Determine gel time：At 25 DEG C, by gained PAE, (NCO contains low viscous HDI trimer curing agent N3600 with Cohan wound
23%) amount is 1 in NCO and NH mol ratios:It is well mixed under 1 proportioning, gel point is judged by fiber elongation method, surveyed with manual time-keeping
Determine gel time.
Colour measurement：By BYK model LCS IV chromascopes, sample Hazen colourities are measured with quartz sample pool.
Medicine information：2 methyl pentamethylenediamine is more than 98% reagent from TCI production purity；Diethyl maleate is resistance to from pacifying
Lucky purity is more than 99% reagent；Dibutyl maleate is more than 99.5% reagent using Aladdin purity；Diethyl fumarate
It is more than 98.5% reagent from Aladdin purity；4,4 '-diamino-dicyclohexyl methane selects the purity of ten thousand magnificent chemical productions
HMDA products more than 99.5%；3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane is more than 99% from TCI production purity
Reagent；Polyetheramine D-2000 uses Hensel Man trade mark Jeffamine D-2000 industry standards；Tetramethyl hydroxide
Ammonium and its pentahydrate are more than 99% technical grade product from the purity of the grand safe great achievement commerce and trade Co., Ltd in Jinan；Tetraethyl hydrogen
The aqueous solution of amine-oxides 25% selects Aladdin company reagent.
Embodiment 1
(1) 174.31g (1.5mol) 2 methyl pentamethylenediamines and 0.137g (1.5mmol) TMAH are catalyzed
Agent, which adds, to be equipped with mechanical agitation oar, thermometer, constant pressure funnel, is connected with N2The 1L three-necked flasks of gas circuit pipe, bubbler
In, 516.54g (3.0mol) diethyl maleate is added in constant pressure funnel, N is passed through in system220min, replacement
Air in system；Diethyl maleate is slowly dropped under 25 DEG C of stirring conditions, after dripping off, 40 DEG C of reaction 2h is warming up to, stops
Reaction.
(2) 90 DEG C are heated to, nitrogen stream, water pump extracting 20min removing TMAHs are urged under 0.001MPa pressure
Agent, polyaspartic ester PAE-1 is produced, its structure is shown below：
(3) phenetic analysis result, diethyl maleate conversion ratio 99.7%, Hazen colourities 25, gel time 5min,
X is 2- methyl isophthalic acids in PAE-1,5- pentyls, R1=R2For ethyl, n=2.
Embodiment 2
(1) by 174.31g (1.5mol) 2 methyl pentamethylenediamines and the tetraethyl hydroxides of 0.044g (0.075mmol) 25%
Aqueous ammonium, which adds, to be equipped with mechanical agitation oar, thermometer, constant pressure funnel, is connected with N2The 1L tri- of gas circuit pipe, bubbler
In mouth flask, 516.54g (3.0 mol) diethyl maleate is added in constant pressure funnel, N is passed through in system210min,
The hollow gas of displacement system；Diethyl maleate is slowly dropped under 10 DEG C of stirring conditions, after dripping off, is warming up to 30 DEG C of reactions
6h, stop reaction.
(2) 130 DEG C are heated to, nitrogen stream, water pump extracting 40min removing tetraethyl ammonium hydroxides are urged under 0.02MPa pressure
Agent and moisture, produce polyaspartic ester PAE-1.
(3) phenetic analysis result, diethyl maleate conversion ratio 99%, Hazen colourities 28, gel time 4min, PAE-1
Middle X is 2- methyl isophthalic acids, 5- pentyls, R1=R2For ethyl, n=2.
Embodiment 3
(1) 174.31g (1.5mol) 2 methyl pentamethylenediamines and 0.685g (7.5mmol) TMAH are catalyzed
Agent, which adds, to be equipped with mechanical agitation oar, thermometer, constant pressure funnel, is connected with N2The 1L three-necked flasks of gas circuit pipe, bubbler
In, 516.54g (3.0mol) diethyl fumarate is added in constant pressure funnel, N is passed through in system215min, replacement
Air in system；Diethyl fumarate is slowly dropped under 40 DEG C of stirring conditions, after dripping off, 70 DEG C of reaction 1h is warming up to, stops
Reaction.
(2) 120 DEG C are heated to, nitrogen stream, water pump extracting 30min removing TMAHs are urged under 0.01MPa pressure
Agent, produce polyaspartic ester PAE-1.
(3) phenetic analysis result, diethyl fumarate conversion ratio 98.5%, Hazen colourities 29, gel time 4min,
X is 2- methyl isophthalic acids in PAE-1,5- pentyls, R1=R2For ethyl, n=2.
Embodiment 4
(1) by 174.31g (1.5mol) 2 methyl pentamethylenediamines and the water of 0.272g (1.5mmol) TMAH five
Compound, which adds, to be equipped with mechanical agitation oar, thermometer, constant pressure funnel, is connected with N2Tri- mouthfuls of burnings of 1L of gas circuit pipe, bubbler
In bottle, 684.78g (3.0mol) dibutyl maleate is added in constant pressure funnel, N is passed through in system220min, displacement
Air in system；Dibutyl maleate is slowly dropped under 20 DEG C of stirring conditions, after dripping off, 40 DEG C of reaction 12h is warming up to, stops
Only react.
(2) it is heated to 120 DEG C, nitrogen stream, water pump extracting 30min removing TMAHs five under 0.01MPa pressure
Hydrate, polyaspartic ester PAE-2 is produced, its structure is shown below：
(3) phenetic analysis result, dibutyl maleate conversion ratio 99%, Hazen colourities 24, gel time 20min, PAE-
X is 2- methyl isophthalic acids in 1,5- pentyls, R1=R2For butyl, n=2.
Embodiment 5
(1) by 315.54g (1.5mol) 4,4 '-diamino-dicyclohexyl methanes and 0.137 g (1.5mmol) tetramethyl hydrogen
Amine-oxides catalyst, which adds, to be equipped with mechanical agitation oar, thermometer, constant pressure funnel, is connected with N2Gas circuit pipe, bubbler
In 1L three-necked flasks, 516.54g (3.0mol) diethyl maleate is added in constant pressure funnel, N is passed through in system2
20min, replace the hollow gas of system；Diethyl maleate is slowly dropped under 25 DEG C of stirring conditions, after dripping off, is warming up to 50 DEG C
7h is reacted, stops reaction.
(2) 100 DEG C are heated to, nitrogen stream, water pump extracting 30min removing TMAHs are urged under 0.01MPa pressure
Agent, polyaspartic ester PAE-3 is produced, its structure is shown below：
(3) phenetic analysis result, diethyl maleate conversion ratio 99%, Hazen colourities 20, gel time 90min, PAE-
X is 4 in 3,4 '-dicyclohexyl methyl hydride, R1=R2For ethyl, n=2.
Embodiment 6
(1) by 357.62g (1.5mol) 3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane and 0.137g
(1.5mmol) TMAH catalyst, which adds, to be equipped with mechanical agitation oar, thermometer, constant pressure funnel, is connected with
N2Gas circuit pipe, bubbler 1L three-necked flasks in, by 516.54g (3.0mol) diethyl maleate add constant pressure funnel
In, N is passed through in system220min, replace the hollow gas of system；Diethyl maleate is slowly dropped under 25 DEG C of stirring conditions, is dripped
After complete, 70 DEG C of reaction 10h are warming up to, stop reaction.
(2) 100 DEG C are heated to, nitrogen stream, water pump extracting 30min removing TMAHs are urged under 0.01MPa pressure
Agent, polyaspartic ester PAE-4 is produced, its structure is shown below：
(3) phenetic analysis result, diethyl maleate conversion ratio 97%, Hazen colourities 23, gel time 10h, PAE-4
Middle X is 3,3 '-dimethyl -4,4 '-dicyclohexyl methyl hydride, R1=R2For ethyl, n=2.
Embodiment 7
(1) by 3000g (1.5mol) polyetheramine D-2000 and 0.884g (1.5mmol) 25% tetraethyl ammonium hydroxide water
Solution, which adds, to be equipped with mechanical agitation oar, thermometer, constant pressure funnel, is connected with N2The three-necked flask of gas circuit pipe, bubbler
In, 516.54g (3.0mol) diethyl maleate is added in constant pressure funnel, N is passed through in system220min, replacement
Air in system；Diethyl maleate is slowly dropped under 25 DEG C of stirring conditions, after dripping off, 50 DEG C of reaction 12h is warming up to, stops
Reaction.
(2) 100 DEG C are heated to, nitrogen stream, water pump extracting 30min removing tetraethyl ammonium hydroxides are urged under 0.01MPa pressure
Agent and moisture, polyaspartic ester PAE-5 is produced, its structure is shown below：
(3) phenetic analysis result, diethyl maleate conversion ratio 98%, Hazen colourities 30, gel time 11h, PAE-5
Middle X is the propylene oxide polyether of mean molecule quantity 2000 or so, R1=R2For ethyl, n=2.
Comparative example 1
(1) by 357.62g (1.5mol) 3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane and 2.07g
(2mol%) 1,2,4- triazoles catalyst, which adds, to be equipped with mechanical agitation oar, thermometer, constant pressure funnel, is connected with N2Gas circuit
Manage, in the 1L three-necked flasks of bubbler, 516.54g (3.0mol) diethyl maleate is added in constant pressure funnel, system
In be passed through N220min, replace the hollow gas of system；Diethyl maleate is slowly dropped under 25 DEG C of stirring conditions, after dripping off,
70 DEG C of reaction 24h are warming up to, stop reaction.
(2) phenetic analysis result, diethyl maleate conversion ratio 85%, Hazen colourities 96, gel time 4h.
Claims (10)
1. a kind of method for synthesizing polyaspartic ester, comprises the following steps：
(1) organic primary amine is reacted to obtain product with unsaturated dibasic acid ester under catalyst；
(2) the product removal catalyst for obtaining step (1), obtains polyaspartic ester product.
2. according to the method for claim 1, it is characterised in that in step (1), the process of the reaction is：Inert gas
Under atmosphere, by unsaturated dibasic acid ester be added drop-wise to organic primary amine, catalyst mixture in, after being added dropwise heat up, react, reach
Stop reaction, the preferred nitrogen of inert gas after to target conversion.
3. according to the method for claim 2, it is characterised in that described to react the time for being passed through inert gas in step (1)
For 10~30min, whipping temp is 10~40 DEG C, and temperature is 30~70 DEG C after heating, and the reaction time is 1~12h.
4. according to the method described in claim any one of 1-3, it is characterised in that in step (1), the choosing of described organic primary amine
From 2 methyl pentamethylenediamine, 4,4 '-diamino-dicyclohexyl methane, 3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane, different
One or more in isophoronediamine, polyetheramine.
5. according to the method described in claim any one of 1-4, it is characterised in that in step (1), the catalyst is four alkane
Base ammonium hydroxide, preferably TMAH, tetraethyl ammonium hydroxide, TPAOH, TBAH with
And the one or more in the hydrates of these tetra-alkyl ammonium hydroxides, the aqueous solution, more preferably TMAH.
6. according to the method described in claim any one of 1-5, it is characterised in that in step (1), described unsaturated binary
One or more of the acid esters in maleic acid diester, dimethyl ester；Described dimethyl ester be selected from diethyl fumarate,
One or more in fumaric acid dipropyl, dibutyl fumarate and fumaric acid methyl-prop base ester；Described maleic acid diester choosing
One or more from diethyl maleate, dipropyl maleate, dibutyl maleate, methyl propyl diester.
7. according to the method described in claim any one of 1-6, it is characterised in that in step (1), with primary amine groups in organic primary amine
The molar amount of group, the dosage of the catalyst are the 0.005~0.5%, preferably 0.01~0.1% of primary amine group, unsaturated
The dosage of dibasic acid ester is that the mol ratio of C=C and primary amine group is 1 in unsaturated dibasic acid ester:1.
8. according to the method described in claim any one of 1-7, it is characterised in that in step (1), described reaction is solvent-free
Or carried out in the presence of solvent, one kind in methanol, ethanol, propyl alcohol, the tert-butyl alcohol, acetone, tetrahydrofuran, acetonitrile of solvent or
A variety of, preferably condition of no solvent reacts.
9. according to the method described in claim any one of 1-8, it is characterised in that in step (2), the temperature of Removal of catalyst is
90~130 DEG C, removing pressure is 0.001~0.02MPa, and extraction times are 20~40min.
10. according to the method described in claim any one of 1-9, it is characterised in that in step (2), the poly- Tianmen of described product
Winter propylhomoserin ester has following architectural feature：
Wherein X represents organic group, R1And R2For identical or different alkyl group, n represents the secondary amine official of polyaspartic ester
Energy degree, n >=2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710970681.8A CN107805207B (en) | 2017-10-18 | 2017-10-18 | Preparation method of polyaspartic aspartate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710970681.8A CN107805207B (en) | 2017-10-18 | 2017-10-18 | Preparation method of polyaspartic aspartate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107805207A true CN107805207A (en) | 2018-03-16 |
| CN107805207B CN107805207B (en) | 2020-01-31 |
Family
ID=61584518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710970681.8A Active CN107805207B (en) | 2017-10-18 | 2017-10-18 | Preparation method of polyaspartic aspartate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107805207B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109020859A (en) * | 2018-07-23 | 2018-12-18 | 万华化学集团股份有限公司 | A kind of water-soluble cationic polyaspartic ester and its preparation method and application |
| CN109320681A (en) * | 2018-11-05 | 2019-02-12 | 深圳飞扬兴业科技有限公司 | A kind of preparation method of polyaspartic ester resin |
| CN110183335A (en) * | 2019-06-10 | 2019-08-30 | 万华化学集团股份有限公司 | A method of preparing polyaspartic ester |
| CN110981741A (en) * | 2019-11-20 | 2020-04-10 | 万华化学集团股份有限公司 | Method for preparing polyaspartic acid ester |
| CN111187566A (en) * | 2020-02-24 | 2020-05-22 | 顺缔高新材料江苏有限公司 | Solvent-free self-leveling polyurethane wear-resistant material and preparation method thereof |
| CN111303368A (en) * | 2020-04-22 | 2020-06-19 | 深圳飞扬骏研新材料股份有限公司 | Water-based polyaspartic acid ester resin and preparation method thereof |
| CN111454413A (en) * | 2020-04-09 | 2020-07-28 | 万华化学集团股份有限公司 | Multifunctional polyaspartic acid ester mixture and preparation method and application thereof |
| CN112409560A (en) * | 2019-08-21 | 2021-02-26 | 万华化学（北京）有限公司 | High-resilience polyurethane foam and preparation method thereof |
| US10968165B2 (en) * | 2017-09-19 | 2021-04-06 | Covestro Deutschland Ag | Polyaspartic acid ester compositions and method for purification |
| CN112920068A (en) * | 2021-01-26 | 2021-06-08 | 深圳飞扬兴业科技有限公司 | Synthetic method and application of polyaspartic acid ester |
| CN114316250A (en) * | 2021-12-30 | 2022-04-12 | 深圳飞扬骏研新材料股份有限公司 | Polyether family secondary amine ester resin and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4871822A (en) * | 1984-04-04 | 1989-10-03 | Hoechst Ag | Reaction product of olefinically unsaturated compounds with compounds containing active hydrogen, processes for their preparation and 2-component lacquers based thereon HOE 85/F O36J |
| US5821326A (en) * | 1996-07-02 | 1998-10-13 | Bayer Aktiengesellschaft | Process for preparing mono and polyaspartates |
| CN1934143A (en) * | 2004-01-21 | 2007-03-21 | 阿拉巴马耐科塔医药公司 | Method of preparing propionic acid-terminated polymers |
| CN102250343A (en) * | 2011-05-05 | 2011-11-23 | 西安交通大学 | Method for synthesizing polyaspartic ester in presence of supported alkali metal fluoride serving as catalyst |
-
2017
- 2017-10-18 CN CN201710970681.8A patent/CN107805207B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4871822A (en) * | 1984-04-04 | 1989-10-03 | Hoechst Ag | Reaction product of olefinically unsaturated compounds with compounds containing active hydrogen, processes for their preparation and 2-component lacquers based thereon HOE 85/F O36J |
| US5821326A (en) * | 1996-07-02 | 1998-10-13 | Bayer Aktiengesellschaft | Process for preparing mono and polyaspartates |
| CN1934143A (en) * | 2004-01-21 | 2007-03-21 | 阿拉巴马耐科塔医药公司 | Method of preparing propionic acid-terminated polymers |
| CN102250343A (en) * | 2011-05-05 | 2011-11-23 | 西安交通大学 | Method for synthesizing polyaspartic ester in presence of supported alkali metal fluoride serving as catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 刘培: "高附着力的室温快速固化胶粘剂的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 孙世刚 等: "聚天门冬氨酸酯的合成及其在聚脲中的应用", 《TOTAL CORROSION CONTROL》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10968165B2 (en) * | 2017-09-19 | 2021-04-06 | Covestro Deutschland Ag | Polyaspartic acid ester compositions and method for purification |
| CN109020859A (en) * | 2018-07-23 | 2018-12-18 | 万华化学集团股份有限公司 | A kind of water-soluble cationic polyaspartic ester and its preparation method and application |
| CN109320681B (en) * | 2018-11-05 | 2021-04-16 | 深圳飞扬骏研新材料股份有限公司 | Preparation method of polyaspartic acid ester resin |
| CN109320681A (en) * | 2018-11-05 | 2019-02-12 | 深圳飞扬兴业科技有限公司 | A kind of preparation method of polyaspartic ester resin |
| CN110183335A (en) * | 2019-06-10 | 2019-08-30 | 万华化学集团股份有限公司 | A method of preparing polyaspartic ester |
| CN110183335B (en) * | 2019-06-10 | 2022-07-12 | 万华化学集团股份有限公司 | Method for preparing polyaspartic acid ester |
| CN112409560A (en) * | 2019-08-21 | 2021-02-26 | 万华化学（北京）有限公司 | High-resilience polyurethane foam and preparation method thereof |
| CN110981741A (en) * | 2019-11-20 | 2020-04-10 | 万华化学集团股份有限公司 | Method for preparing polyaspartic acid ester |
| CN110981741B (en) * | 2019-11-20 | 2023-01-13 | 万华化学集团股份有限公司 | Method for preparing polyaspartic acid ester |
| CN111187566A (en) * | 2020-02-24 | 2020-05-22 | 顺缔高新材料江苏有限公司 | Solvent-free self-leveling polyurethane wear-resistant material and preparation method thereof |
| CN111454413B (en) * | 2020-04-09 | 2022-02-18 | 万华化学集团股份有限公司 | Multifunctional polyaspartic acid ester mixture and preparation method and application thereof |
| CN111454413A (en) * | 2020-04-09 | 2020-07-28 | 万华化学集团股份有限公司 | Multifunctional polyaspartic acid ester mixture and preparation method and application thereof |
| CN111303368B (en) * | 2020-04-22 | 2021-09-17 | 深圳飞扬骏研新材料股份有限公司 | Water-based polyaspartic acid ester resin and preparation method thereof |
| CN111303368A (en) * | 2020-04-22 | 2020-06-19 | 深圳飞扬骏研新材料股份有限公司 | Water-based polyaspartic acid ester resin and preparation method thereof |
| CN112920068A (en) * | 2021-01-26 | 2021-06-08 | 深圳飞扬兴业科技有限公司 | Synthetic method and application of polyaspartic acid ester |
| CN112920068B (en) * | 2021-01-26 | 2023-09-22 | 深圳飞扬骏研新材料股份有限公司 | Synthesis method and application of polyaspartic acid ester |
| CN114316250A (en) * | 2021-12-30 | 2022-04-12 | 深圳飞扬骏研新材料股份有限公司 | Polyether family secondary amine ester resin and preparation method thereof |
| CN114316250B (en) * | 2021-12-30 | 2024-06-18 | 深圳飞扬骏研新材料股份有限公司 | Polyether secondary amine ester resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107805207B (en) | 2020-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107805207A (en) | A kind of preparation method of polyaspartic ester | |
| CN104130390B (en) | Polyether-type polyaspartate and preparation method thereof | |
| CN105001389A (en) | Polyurethane material and preparation method thereof | |
| CN101585906A (en) | Curing agents for epoxy resins | |
| AU2001282733B2 (en) | Dendritic macromolecule with improved polyether polyol solubility and process for production thereof | |
| JP2014524468A (en) | Cyclic carbonate monomers and polymers prepared therefrom | |
| CN104744670B (en) | A kind of epoxy acrylic ester prepolymer and its application | |
| JP2011524448A (en) | Method for producing polyol | |
| CN104447350A (en) | Method for preparing C14 diamine and long carbon chain nylon PA1414 | |
| CN105622933A (en) | Preparation method of novel polyaspartic ester and polyurea coating | |
| CN103204876B (en) | A kind of preparation method of oligomeric Organophosphonate | |
| CN109651955B (en) | Preparation method of acetoacetate-based modified castor oil cured coating | |
| US8822625B2 (en) | Method for providing higher molecular weight natural oil polyols without loss of functionality | |
| CN107652443A (en) | A kind of surface and the internal hyperbranched poly (ester amine) containing functional group and preparation method thereof | |
| CN112661788A (en) | Phosphorus-containing polyaspartic acid ester and preparation method and application thereof | |
| KR102579270B1 (en) | Method for producing polyester polyol | |
| CN113072674B (en) | Heat-sensitive tertiary amine catalyst, quaternized derivative thereof, preparation and application | |
| US10072178B2 (en) | Biobased cyclic carbonate functional resins and polyurethane thermosets therefrom | |
| CN113563564B (en) | Grease-based latent resin, and preparation method and application thereof | |
| CN113004514B (en) | Low-hygroscopicity PA5T and synthesis method thereof | |
| CN114958296A (en) | Preparation method of organic silicon glue | |
| CN107548392B (en) | Cyclic carbonates | |
| CN111138616B (en) | Amine chain extender, preparation method thereof and polyurethane foam | |
| JPH02174750A (en) | Secondary polyetheramine,preparation thereof and preparationof polyurehtnane therefrom in the absence of catalyst | |
| US8933191B1 (en) | Method for synthesizing high molecular weight natural oil polyols |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |