CN114773593B - Synthesis method and application of large-steric-hindrance secondary amine polyurea resin - Google Patents
Synthesis method and application of large-steric-hindrance secondary amine polyurea resin Download PDFInfo
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- CN114773593B CN114773593B CN202110510458.1A CN202110510458A CN114773593B CN 114773593 B CN114773593 B CN 114773593B CN 202110510458 A CN202110510458 A CN 202110510458A CN 114773593 B CN114773593 B CN 114773593B
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- 229920002396 Polyurea Polymers 0.000 title claims abstract description 46
- 229920005989 resin Polymers 0.000 title claims abstract description 43
- 239000011347 resin Substances 0.000 title claims abstract description 43
- 238000001308 synthesis method Methods 0.000 title claims abstract description 16
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 title abstract description 18
- -1 vinyl dicarbonyl compound Chemical class 0.000 claims abstract description 39
- 150000004985 diamines Chemical class 0.000 claims abstract description 34
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical group N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 20
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 8
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims 1
- 229920001228 polyisocyanate Polymers 0.000 abstract description 8
- 239000005056 polyisocyanate Substances 0.000 abstract description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007259 addition reaction Methods 0.000 abstract description 4
- 239000011976 maleic acid Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 150000003141 primary amines Chemical class 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 238000004448 titration Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 108010064470 polyaspartate Proteins 0.000 description 6
- 229920000805 Polyaspartic acid Polymers 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 241000234427 Asparagus Species 0.000 description 3
- 235000005340 Asparagus officinalis Nutrition 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 125000004989 dicarbonyl group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/02—Polyureas
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
Abstract
The invention relates to the field of polyureas, in particular to a synthesis method and application of a large-steric-hindrance secondary amine polyurea resin. Comprising the following steps: the molar ratio is (2-3): 1 and diamine, and distilling under reduced pressure to obtain the polyurea resin. The inventor finds that by selecting a suitable vinyl dicarbonyl compound and diamine to perform an addition reaction, compared with a commonly used maleic acid ester or monocarbonyl vinyl compound, the C=CHR structure in the compound and two primary amine groups in the diamine are favorable to be added to obtain a diimine structure, and when the diimine structure is cured with polyisocyanate, R groups, R' groups in the middle of the diimine structure, carbonyl groups and the like can be effectively controlled and controlled to react with the polyisocyanate, so that a coating film with high gel time is obtained. And the inventor finds that the crystallization in the curing process can be reduced by selecting a proper diimine structure and a high-polarity carbonyl structure around the diimine structure, so that the improvement of mechanical strength is promoted.
Description
Technical Field
The invention relates to the field of polyureas, in particular to a synthesis method and application of a large-steric-hindrance secondary amine polyurea resin.
Background
Polyaspartic acid esters are a new class of sterically hindered amines developed in recent years. The curing reaction of the polyaspartate with the polyisocyanate may form a polyurea resin. The gel time of the curing reaction of the polyaspartic acid ester and the polyisocyanate depends on the structure of the polyaspartic acid ester, and the polyaspartic acid ester derivatives with different reaction speeds and different physical properties can be obtained by adopting substituents with different structures, and the coating film of the derivatives has excellent yellowing resistance, ultraviolet aging resistance and wear resistance, thus being an important polyurea polymer material.
The general synthesis method of polyaspartic acid ester is that a binary primary amine and two equivalents of maleic acid ester are subjected to Michael addition reaction, wherein the steric hindrance effect of an ester bond on a maleic acid ester group and the steric hindrance effect on the binary primary amine greatly influence the performance of the asparaguse polyurea resin. However, the limited change of substituents on the prior primary dibasic amine and maleate greatly limits the gel time of the asparaguses, and the prior asparaguses have shorter gel time and can not fully meet the requirements of some constructions. Therefore, it is necessary to synthesize a novel polyurea resin which has a longer gel time and which has properties satisfying the requirements of asparaguses.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides a method for synthesizing a large-steric-secondary-amine polyurea resin, comprising: the molar ratio is (2-3): 1 reacting a vinyl dicarbonyl compound with diamine, and distilling under reduced pressure to obtain the polyurea resin;
the structural formula of the vinyl dicarbonyl compound is shown as a formula (1):
R 1 one or more selected from alkyl, alkoxy, aryl, cycloalkyl and aryloxy groups;
R 2 one or more selected from alkyl, alkoxy, aryl, cycloalkyl and aryloxy groups;
and R is selected from one or more of alkyl, cycloalkyl and aryl.
As a preferable technical scheme of the invention, R 1 The number of carbon atoms of not more than 6, R 2 The number of carbon atoms of (2) is 6 or less.
In a preferred embodiment of the present invention, R has 6 or less carbon atoms.
As a preferable technical scheme of the invention, the structural formula of the diamine is shown as formula (2):
r' is selected from one or more of chain alkyl, chain ether, secondary amino and cyclic alkyl.
As a preferable technical scheme of the invention, the structural formula of the chain alkyl is shown as a formula (3):
m is 2-30.
As a preferable technical scheme of the invention, the structural formula of the chain ether group is shown as formula (4):
p is 2 to 30, R' is a C1 to C5 alkyl group or a hydrogen atom.
As a preferable technical scheme of the invention, the structural formula of the secondary amine group is shown as a formula (5):
q is 1 to 20.
As a preferable technical scheme of the invention, the number of the cyclic alkyl groups is 1-3, and when the number of the cycloalkyl groups is 2-3, the cycloalkyl groups are connected through methylene, O, S or NH;
the hydrogen atom on the cycloalkyl group may be substituted with alkyl, alkoxy, hydroxy.
As a preferable technical scheme of the invention, the reaction temperature is 40-100 ℃.
The second aspect of the invention provides an application of the polyurea resin prepared by the synthesis method of the large-steric-hindrance secondary amine polyurea resin in a coating.
Compared with the prior art, the invention has the following beneficial effects:
(1) The inventor finds that by selecting a suitable vinyl dicarbonyl compound and diamine to perform an addition reaction, compared with a commonly used maleic acid ester or monocarbonyl vinyl compound, the addition of the C=CHR structure in the compound and two primary amine groups in the diamine is facilitated, the diimine structure of CHRNHR 'NHRCH is obtained, and when the diimine compound is cured with polyisocyanate, R' groups in the middle of the diimine structure, carbonyl groups and the like can be effectively regulated and controlled to react with the polyisocyanate, so that a coating film with high gel time is obtained. And the inventor finds that the selection of a suitable CHRNHR 'NHRCH structure and a high-polarity carbonyl structure around the CHRNHR' NHRCH structure can reduce crystallization in the curing process and promote the improvement of mechanical strength.
(2) In addition, the inventor found that when the reaction is performed by using the vinyl dicarbonyl compound and the diamine, in order to ensure that the primary amine groups are completely reacted, an excessive amount of the vinyl dicarbonyl compound needs to be added, and because of the existence of dicarbonyl groups in the vinyl dicarbonyl compound, the electron withdrawing effect is obvious, and when the vinyl dicarbonyl compound reacts with the diamine, partial vinyl dicarbonyl compound possibly exists to be connected on the same nitrogen atom to form a tertiary amine structure.
(3) And in order to remove the excess of the vinyldicarbonyl compound, reduced pressure distillation is required, which is accompanied by productionLoss of species, the present invention uses R by controlling the temperature of the reaction and the structure of the two reactants, on the one hand, and the molecular weight and substituent species of the vinyl dicarbonyl compound, on the other hand 1 、R 2 The substituents having 6 or less carbon atoms, particularly alkyl groups, alkoxy groups, and the like, promote the improvement and stabilization of the yield after distillation.
Detailed Description
The contents of the present invention can be more easily understood by referring to the following detailed description of preferred embodiments of the present invention and examples included. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
The singular forms include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or event may or may not occur, and that the description includes both cases where the event occurs and cases where the event does not.
Approximating language, in the specification and claims, may be applied to modify an amount that would not limit the invention to the specific amount, but would include an acceptable portion that would be close to the amount without resulting in a change in the basic function involved. Accordingly, the modification of a numerical value with "about", "about" or the like means that the present invention is not limited to the precise numerical value. In some examples, the approximating language may correspond to the precision of an instrument for measuring the value. In the present specification and claims, the range limitations may be combined and/or interchanged, such ranges including all the sub-ranges contained therein if not expressly stated.
Furthermore, the indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirements of the number of elements or components (i.e. the number of occurrences). Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component also includes the plural reference unless the amount is obvious to the singular reference.
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The first aspect of the invention provides a method for synthesizing a large-steric-hindrance secondary amine polyurea resin, which comprises the following steps: the molar ratio is (2-3): 1 and diamine, and distilling under reduced pressure to obtain the polyurea resin.
In a preferred embodiment, the molar ratio of the vinyl dicarbonyl compound to diamine according to the invention is (2-3): examples of 1 include 2: 1. 2.1: 1. 2.2: 1. 2.3: 1. 2.4: 1. 2.5: 1. 2.6: 1. 2.7: 1. 2.8: 1. 2.9: 1. 3:1. preferably (2 to 2.8): 1.
vinyl dicarbonyl compound
In one embodiment, the vinyl dicarbonyl compound has a structural formula shown in formula (1):
R 1 one or more selected from alkyl, alkoxy, aryl, cycloalkyl and aryloxy groups; alkyl and alkoxy groups are preferred.
R 2 One or more selected from alkyl, alkoxy, aryl, cycloalkyl and aryloxy groups; alkyl and alkoxy groups are preferred.
R is selected from one or more of alkyl, cycloalkyl and aryl, preferably alkyl.
As examples of alkyl groups, methyl Me, ethyl Et, n-propyl n-Pr, isopropyl i-Pr, n-butyl n-Bu, isobutyl i-Bu, t-butyl t-Bu, sec-butyl s-Bu may be cited. As examples of alkoxy groups, methoxy OMe, ethoxy OEt, n-propoxy On-Pr, isopropoxy Oi-Pr, n-butoxy On-Bu, isobutoxy Oi-Bu, t-butoxy Ot-Bu, sec-butoxy Os-Bu may be cited.
Preferably, R 1 The number of carbon atoms of not more than 6, R 2 The number of carbon atoms of (2) is 6 or less, and examples thereof include 6, 5, 4, 3, 2 and 1, and preferably 1 to 4; the number of carbon atoms of R is 6 or less, and examples thereof include 6, 5, 4, 3, 2 and 1, and preferably 3 to 6.
Diamine (diamine)
In one embodiment, the structural formula of the diamine is shown in formula (2):
r' is selected from one or more of chain alkyl, chain ether, secondary amino and cyclic alkyl.
Preferably, the structural formula of the chain alkyl is shown as formula (3):
m is 2 to 30, and examples thereof include 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 20, 22, 25, 27, and 30, preferably 2 to 10, and more preferably 2 to 5.
More preferably, the structural formula of the chain ether group is shown as formula (4):
p is 2 to 30, and examples thereof include 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 20, 22, 25, 27, and 30, preferably 2 to 10, and more preferably 2 to 5. R' is a C1-C5 alkyl group or a hydrogen atom, and examples thereof include methyl Me, ethyl Et, n-propyl n-Pr, isopropyl i-Pr, n-butyl n-Bu, isobutyl i-Bu, t-butyl t-Bu, sec-butyl s-Bu, and preferably methyl or hydrogen atom.
Further preferably, the structural formula of the secondary amine group is shown as formula (5):
q is 1 to 20, and examples thereof include 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 20, 22, 25, 27, and 30, preferably 2 to 10, and more preferably 2 to 5..
Still more preferably, the number of cycloalkyl groups in the cyclic alkyl group is 1 to 3, and when the number of cycloalkyl groups is 2 to 3, the cycloalkyl groups are connected through methylene, O, S or NH; preferably, the cycloalkyl groups are linked by methyl groups.
The hydrogen atom on the cycloalkyl group may be substituted with an alkyl group, an alkoxy group or a hydroxyl group, and preferably, the hydrogen atom on the cycloalkyl group may be substituted with a C1-C5 alkyl group or a C1-C5 alkoxy group. The hydrogen atom in the cycloalkyl group in the cyclic alkyl group of the present invention may be substituted with other groups or may not be substituted, is not particularly limited, and the number of hydrogen atoms substituted is not limited. Cycloalkyl in the cyclic alkyl is C3-C6 cycloalkyl, such as cyclohexane, cyclopropane, cyclopentane and cyclobutane.
Examples of cyclic alkyl groups include, but are not limited to:
in one embodiment, the reaction temperature of the present invention is 40 to 100 ℃. The reaction temperature of the present invention is preferably higher than the melting points of the vinyl dicarbonyl compound and diamine, preferably 60 to 90℃and more preferably 70 to 80 ℃. Because of the electron withdrawing effect of 2 carbonyl groups in the vinyl dicarbonyl compound, NH of vinyl and diamine 2 Addition reactions tend to occur and even grafting 3 or 4 vinyl groups on the diamine, which can affect the yield of polyurea resin and can also affect the subsequent curing of the polyisocyanate. The inventor discovers that when the vinyl dicarbonyl compound with a proper structure and diamine are used for reaction at a certain temperature, the completion of the addition reaction can be promoted, the losses in overaddition and reduced pressure distillation are avoided, and the purity and the yield of the product are improved. The reaction of the invention was judged by TLC and primary amine titration, when the primary amine reaction was stopped completely.
The second aspect of the invention provides an application of the polyurea resin prepared by the synthesis method of the large-steric-hindrance secondary amine polyurea resin in a coating.
Examples
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of further illustration and are not to be construed as limitations on the scope of the invention, as will be apparent to those skilled in the art in light of the foregoing disclosure.
Example 1
The example provides a synthesis method of a large-steric-hindrance secondary amine polyurea resin, which comprises the following steps: 228 g of vinyl dicarbonyl compound and 30 g of diamine are reacted under the condition of introducing nitrogen into a four-mouth reaction flask, the temperature is increased to 80 ℃, the reaction condition is monitored by TLC and primary amine titration, when the reaction is completed, unreacted raw materials are removed by reduced pressure distillation, 250 g of polyurea resin is obtained, and the yield is 96.9%.
The structural formula of the vinyl dicarbonyl compound is shown as follows:
r is nBu, R 1 Is OEt, R 2 Is OEt.
The structural formula of diamine is shown as follows:
r' is-CH 2 CH 2 -。
Example 2
The example provides a synthesis method of a large-steric-hindrance secondary amine polyurea resin, which comprises the following steps: 296 g of a vinyl dicarbonyl compound and 52 g of diamine were introduced into a four-necked reaction flask under nitrogen atmosphere, the temperature was raised to 80 ℃, the reaction was monitored by TLC and primary amine titration, and when the reaction was completed, unreacted raw materials were removed by distillation under reduced pressure, 300 g of polyurea resin was obtained in a yield of 96.8%.
The structural formula of the vinyl dicarbonyl compound is shown as follows:
r is nBu, R 1 Is OEt, R 2 Is OEt.
The structural formula of diamine is shown as follows:
r' is-CH 2 CH 2 OCH 2 CH 2 -。
Example 3
The example provides a synthesis method of a large-steric-hindrance secondary amine polyurea resin, which comprises the following steps: 400 g of a vinyl dicarbonyl compound and 170 g of diamine are introduced into a four-necked reaction flask under the condition of introducing nitrogen, the temperature is increased to 80 ℃, the reaction condition is monitored by TLC and primary amine titration, and when the reaction is completed, unreacted raw materials are removed by reduced pressure distillation, 440 g of polyurea resin is obtained, and the yield is 92.1%.
The structural formula of the vinyl dicarbonyl compound is shown as follows:
r is iPr, R 1 Is Me, R 2 Me.
The structural formula of diamine is shown as follows:
r' is->
Example 4
The example provides a synthesis method of a large-steric-hindrance secondary amine polyurea resin, which comprises the following steps: 484 g of vinyl dicarbonyl compound and 210 g of diamine are introduced into a four-necked reaction flask under the condition of introducing nitrogen, the temperature is raised to 80 ℃, the reaction condition is monitored by TLC and primary amine titration, and when the reaction is completed, unreacted raw materials are removed by reduced pressure distillation, 550 g of polyurea resin is obtained, and the yield is 94.5%.
The structural formula of the vinyl dicarbonyl compound is shown as follows:
r is iPr, R 1 Is OMe, R 2 OMe.
The structural formula of diamine is shown as follows:
r' is->
Example 5
The example provides a synthesis method of a large-steric-hindrance secondary amine polyurea resin, which comprises the following steps: 547.2 g of a vinyl dicarbonyl compound and 238 g of diamine are introduced into a four-necked reaction flask under the condition of introducing nitrogen, the temperature is raised to 80 ℃, the reaction condition is monitored by TLC and primary amine titration, and when the reaction is completed, unreacted raw materials are removed by reduced pressure distillation, 650 g of polyurea resin is obtained, and the yield is 93.5%.
The structural formula of the vinyl dicarbonyl compound is shown as follows:
r is sBu, R 1 Is OEt, R 2 Is OEt.
The structural formula of diamine is shown as follows:
r' is->
Example 6
The example provides a synthesis method of a large-steric-hindrance secondary amine polyurea resin, which comprises the following steps: 442 g of a vinyl dicarbonyl compound and 210 g of diamine are introduced into a four-necked reaction flask under the condition of introducing nitrogen, the temperature is increased to 80 ℃, the reaction condition is monitored by TLC and primary amine titration, and when the reaction is completed, unreacted raw materials are removed by reduced pressure distillation, 540 g of polyurea resin is obtained, and the yield is 93.4%.
The structural formula of the vinyl dicarbonyl compound is shown as follows:
r is iPr, R 1 Is Me, R 2 Is OEt.
The structural formula of diamine is shown as follows:
r' is->
Example 7
The example provides a synthesis method of a large-steric-hindrance secondary amine polyurea resin, which comprises the following steps: 556 g of a vinyl dicarbonyl compound and 114 g of diamine are introduced into a four-necked reaction flask under the condition of introducing nitrogen, the temperature is raised to 80 ℃, the reaction condition is monitored by TLC and primary amine titration, and when the reaction is completed, unreacted raw materials are removed by reduced pressure distillation, 500 g of polyurea resin is obtained, and the yield is 92.6%.
The structural formula of the vinyl dicarbonyl compound is shown as follows:
r is tBu, R 1 Is OEt, R 2 Is OEt.
The structural formula of diamine is shown as follows:
the obtained polyurea resin is subjected to nuclear magnetic characterization, and the result is that: 1 H NMR(500 MHz,CDCl 3 )δ4.13(q,J＝11.9 Hz,8H),4.05(s,2H),3.84(dd,J＝2.3,1.0 Hz,2H),3.29(dd,J＝2.3,1.0 Hz,2H),2.94–2.80(m,2H),1.72–1.48(m,2H),1.35(s,2H),1.21(s,13H),1.11(s,2H),0.96(s,18H)。 13 C NMR(125 MHz,CDCl 3 )δ167.44(s),67.15(s),61.74(s),57.55(s),51.06(s),34.01(s),30.90(s),26.89(s),25.02(s),14.68(s)。
comparative example 1
This example provides a polyurea resin F420 from Shenzhen fly Jun research New Material Co., ltd.
Evaluation of Performance
The coatings obtained by mixing the polyurea resin and the HDI trimer provided in the examples and comparative examples at a ratio of 1:1.1 were applied to polished tinplate, cured at room temperature, and the properties are shown in Table 1.
Table 1 performance characterization test
The test result shows that the synthesis method provided by the invention can be used for synthesizing the polyurea resin, has high yield and purity, and the polyurea resin prepared by the invention can be used in a coating, and can be cured with polyisocyanate to obtain a coating film, so that the construction requirement is met, and the comprehensive performance of the coating film is improved. And the inventor finds that when the polyurea resin provided by the invention is used, the polyurea resin can be used in an environment with higher humidity, and interlayer foaming can not occur in a longer gel time, so that the performance of a coating film is affected.
The foregoing examples are illustrative only and serve to explain some features of the method of the invention. The appended claims are intended to claim the broadest possible scope and the embodiments presented herein are merely illustrative of selected implementations based on combinations of all possible embodiments. It is, therefore, not the intention of the applicant that the appended claims be limited by the choice of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within which variations in these ranges should also be construed as being covered by the appended claims where possible.
Claims (3)
1. A method for synthesizing polyurea resin, comprising: the molar ratio is (2-3): 1 with diamine to obtain a diimine structure of CHRNHR' NHRCH by reduced pressure distillation, and HDI trimer with 1:1.1, mixing and proportioning to obtain the polyurea resin;
the structural formula of the vinyl dicarbonyl compound is shown as a formula (1):
（1）；
R 1 one or more selected from alkyl, alkoxy, aryl, cycloalkyl and aryloxy groups;
R 2 one or more selected from alkyl, alkoxy, aryl, cycloalkyl and aryloxy groups;
r is selected from one or more of alkyl, cycloalkyl and aryl;
R、R 1 、R 2 carbon atoms of 6 or less;
the structural formula of the diamine is shown as formula (2):
（2）；
r' is selected fromWherein m is one or more of 2-30, substituted or unsubstituted cyclic alkyl;
the reaction temperature is 70-80 ℃.
2. The method for synthesizing a polyurea resin according to claim 1, wherein the number of cyclic alkyl groups in the cyclic alkyl group is 1 to 3, and when the number of cyclic alkyl groups is 2 to 3, the cyclic alkyl groups are connected to each other through a methylene group.
3. Use of the polyurea resin prepared by the synthesis method of the polyurea resin according to any one of claims 1 to 2 in a coating.
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