CN114989036A - Secondary amine modified asparagus resin, preparation method thereof and polyurea material - Google Patents

Abstract

The invention relates to C07C, in particular to a secondary amine modified aspartic resin, a preparation method thereof and a polyurea material. The aspartic resin is prepared from an aspartic ester compound and a multi-acrylate compound. The invention provides secondary amine modified aspartic resin and a preparation method thereof, and the inventor surprisingly finds that when the aspartic ester compound and the polybasic acrylic ester compound provided by the invention are used for reaction, the aspartic ester compound and the primary amine are acted by two adjacent ester groups, so that the primary amine is acted by electron-withdrawing or intramolecular/intermolecular hydrogen bonds in the reaction process, the cross-linking and molecular chain growth caused by over-fast reaction are avoided, the reaction stability is improved, the primary amine is prevented from being shielded by gel, the yield is improved, and the primary amine residue is reduced.

Description

A kind of secondary amine modified aspartic resin and preparation method thereof, polyurea material

technical field

The present invention relates to CO7C, and more particularly, the present invention relates to a secondary amine modified aspartic resin, a preparation method thereof, and a polyurea material.

Background technique

Aspartic polyurea, that is, polyaspartate polyurea, is prepared by curing aspartic resin and curing agent, such as polyisocyanate. CN112079740A and CN112079740A provide synthesis methods of aspartic resin. Among them, amine groups, such as primary amine groups and polyisocyanates, have a high reaction rate and are prone to gel, which affects the mechanical properties, surface smoothness and gloss of polyurea materials, as well as solvent resistance, acid and alkali resistance and other properties.

Therefore, the synthesis of secondary amines is generally carried out by the method of primary amine and excess maleate. On the one hand, the primary amine is difficult to react completely, and the yield is difficult to reach 90% and above, which makes it easy to form gelation in the subsequent curing process. On the one hand, in order to improve the yield, the method of adding maleate or other compounds in batches is generally used to synthesize secondary amines, which causes the complex preparation method and also makes the amount of maleate or other compounds added too much, Difficult to remove later.

Therefore, it is necessary to provide a new structure and preparation method of secondary amine-modified aspartic resin, so as to simplify the process and dosage, while improving the yield of aspartic resin and avoiding the residue of primary amine.

SUMMARY OF THE INVENTION

A first aspect of the present invention provides a secondary amine modified aspartic resin, the aspartic resin is prepared from an aspartate compound and a polyacrylate compound.

aspartate compound

In one embodiment, the structural formula of the aspartate compound of the present invention is shown in formula (1):

R is a C1-C10 alkyl group, and examples thereof include a methyl group, an ethyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, and the like, and preferably a C1-C4 alkyl group.

再根据CN108440494A将二元酸和醇，如乙醇、甲醇等在硫酸等催化剂的催化下制备得到，不对天冬氨酸酯化合物的制备方法做具体限定。The aspartate compound of the present invention can first obtain the structure of dibasic acid by reacting maleic acid with ammonia water according to RO 126760 AO

According to CN108440494A, dibasic acids and alcohols, such as ethanol, methanol, etc., are prepared under the catalysis of catalysts such as sulfuric acid, and the preparation method of the aspartate compound is not specifically limited.

Polyacrylate Compounds

In one embodiment, the number of vinyl groups in the polyvalent acrylate compound of the present invention is 2 to 5, preferably 2 to 4, and more preferably 2 to 3.

Preferably, the polyacrylate compound of the present invention is a chain polyacrylate compound and/or a cyclic polyacrylate compound.

More preferably, when the number of vinyl groups of the polyvalent acrylate compound of the present invention is 2, the structural formula of the polyvalent acrylate compound is as shown in formula (2) or formula (3):

m is 2-30, preferably 2-20, more preferably 2-10, and R ₁ is H or methyl;

p is 0-30, preferably 0-20, more preferably 0-10, more preferably 0-5;

X is selected from one of C1-C30 alkyl, C1-C30 cycloalkyl, C1-C30 alkyl derivatives, and C1-C30 cycloalkyl derivatives, preferably C1-C20 alkyl, C1-C20 cycloalkane C1-C20 alkyl derivatives, C1-C20 cycloalkyl derivatives, more preferably C1-C10 alkyl, C4-C10 cycloalkyl, C1-C10 alkyl derivatives, C4-C10 cycloalkyl derivatives compounds, more preferably C1-C5 alkyl, C4-C6 cycloalkyl, C1-C5 alkyl derivatives, C4-C6 cycloalkyl derivatives;

R ₂ is H or methyl.

Further preferably, when the number of vinyl groups of the polybasic acrylate compound of the present invention is 3 or 4, the structural formula of the polybasic acrylate compound is shown in formula (4):

n is 3 or 4;

Y is selected from one of C1-C30 alkyl, C1-C30 cycloalkyl, C1-C30 alkyl derivatives, and C1-C30 cycloalkyl derivatives, preferably C1-C20 alkyl, C1-C20 cycloalkane C1-C20 alkyl derivatives, C1-C20 cycloalkyl derivatives, more preferably C1-C10 alkyl, C4-C10 cycloalkyl, C1-C10 alkyl derivatives, C4-C10 cycloalkyl derivatives compounds, more preferably C1-C5 alkyl, C4-C6 cycloalkyl, C1-C5 alkyl derivatives, C4-C6 cycloalkyl derivatives;

_R3 is H or methyl, and R' is H or alkyl.

More preferably, when n is 3, R' is H or C1-C5 alkyl; when n is 4, R' is H.

In a preferred embodiment, the structural formula of the cyclic polyacrylate compound of the present invention is shown in formula (5):

为芳基或环烷基，优选为苯基、萘基、环己基、环戊基。q is 2-5, f is 0-30, preferably 0-20, more preferably 0-10, more preferably 0-5;

It is an aryl group or a cycloalkyl group, preferably a phenyl group, a naphthyl group, a cyclohexyl group, and a cyclopentyl group.

Z is selected from one of C1-C30 alkyl, C1-C30 cycloalkyl, C1-C30 alkyl derivatives, and C1-C30 cycloalkyl derivatives, preferably C1-C20 alkyl, C1-C20 cycloalkane C1-C20 alkyl derivatives, C1-C20 cycloalkyl derivatives, more preferably C1-C10 alkyl, C4-C10 cycloalkyl, C1-C10 alkyl derivatives, C4-C10 cycloalkyl derivatives compounds, more preferably C1-C5 alkyl, C4-C6 cycloalkyl, C1-C5 alkyl derivatives, C4-C6 cycloalkyl derivatives;

R ₄ is H or methyl;

R₄为H或甲基，q为2～5。like

R ₄ is H or methyl, and q is 2-5.

In a more preferred embodiment, the C1-C30 alkyl derivative of the present invention is that the hydrogen atoms in C1-C30 are substituted by ether group, carbonyl group, ester group, nitrile group or mercapto group. The C1-C30 alkyl group in the present invention can be a straight-chain alkyl group or a branched-chain alkyl group, which is not specifically limited, such as methyl, ethyl, isopropyl, propyl, butyl and the like.

In a further preferred embodiment, the C1-C30 cycloalkyl derivative of the present invention is that the hydrogen atoms in C1-C30 are substituted by ether group, carbonyl group, ester group, nitrile group or mercapto group.

R₄为H或甲基，q为2～5。Examples of polyacrylate compounds include, but are not limited to,

R ₄ is H or methyl, and q is 2-5.

In one embodiment, the molar ratio of the amino group of the aspartate compound of the present invention to the vinyl group of the polyvalent acrylate compound is 1:(0.9-1.3), preferably 1:(0.9-1.2), More preferably, it is 1:(0.9-1.11).

In one embodiment, the raw material for the preparation of the aspartic resin of the present invention further includes a polymerization inhibitor.

Polymerization inhibitor

Examples of the polymerization inhibitor include, but are not limited to, hydroquinone, hydroxyanisole, tert-butylhydroquinone, butylated hydroxyanisole (BHA), and di-tert-butylhydroquinone. In one embodiment, the polymerization inhibitor accounts for 0.1 to 1 wt % of the total weight of the aspartate compound and the polyacrylate compound, for example, 0.1 wt %, 0.2 wt %, 0.3 wt %, 0.4 wt % wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt %, 1 wt %.

The second aspect of the present invention provides a method for preparing the above-mentioned secondary amine-modified aspartic resin, comprising: reacting an aspartate compound and a polyacrylate compound at 50-80° C. to obtain a secondary amine-modified aspartic resin. Asparagus resin. The endpoint of the reaction was monitored by TLC.

In one embodiment, the preparation method of the secondary amine modified aspartic resin according to the present invention includes: dropping the aspartate compound into the polyacrylate compound, adding a polymerization inhibitor, and raising the temperature to 50-80° C. Reaction to obtain secondary amine modified aspartic resin.

In one embodiment, after the reaction described in the present invention, an organic solvent is added, washed and dried to obtain the secondary amine modified aspartic resin. Described organic solvent is selected from a kind of in esters, ketones, ethers, can enumerate is, ethyl acetate, methyl acetate, propyl acetate, methyl butyrate, acetone, methyl ethyl ketone, methyl ethyl ketone, ether, Esters are preferred.

The washing of the present invention can be washed with water or an aqueous solution of an inorganic salt, and the aqueous solution of the inorganic salt can be exemplified as saturated aqueous sodium chloride solution, saturated aqueous sodium bicarbonate solution, saturated aqueous ammonium chloride solution, saturated aqueous sodium carbonate solution, etc., Preferably, the washing comprises successively washing with saturated aqueous sodium bicarbonate solution, saturated aqueous sodium chloride solution and water.

The drying described in the present invention is an operation of removing solvent and residual water, which is not specifically limited, such as drying under reduced pressure, drying with anhydrous sodium sulfate, or spray drying, heating drying, and the like.

A third aspect of the present invention provides a polyurea material, and the preparation raw materials of the polyurea material include the secondary amine modified aspartic resin as described above.

In one embodiment, the raw materials for preparing the polyurea material of the present invention further include isocyanate curing agents, such as HDI, MDI, HDI trimer, MDI trimer, IPDI, TDI, HMDI, LDI and the like.

In one embodiment, the molar ratio of the secondary amine group in the secondary amine modified aspartic resin of the present invention to the isocyanate group in the isocyanate curing agent is 1:(1-1.3).

Compared with the prior art, the present invention has the following beneficial effects:

(1) The present invention provides a secondary amine modified aspartic resin and a preparation method thereof, wherein the inventors found that because of the primary amine and the polyacrylate compound, especially the polyacrylate with electron-withdrawing ester group adopted in the present invention The reaction rate of the compound is relatively fast. In the direct reaction process, the reaction is too fast, and gel is easily formed, which affects the improvement of the yield and the subsequent curing performance. The inventor unexpectedly found that when using the aspartate compound provided by the present invention. When reacting with a polyacrylate compound, due to the action of the aspartate compound and the two adjacent ester groups of the primary amine, during the reaction process, the primary amine is subjected to electron withdrawing or intramolecular/intermolecular hydrogen bonding to avoid The cross-linking and molecular chain growth caused by the excessively fast reaction are avoided, the reaction stability is improved, the shielding of the primary amine by the gel is avoided, the yield is increased, and the primary amine residue is reduced.

(2) In addition, the inventor found that because of the stabilizing effect of the aspartate compound, it is necessary to rationally design the structure of the polyacrylate compound to further improve the reaction of the primary amine, and the inventor found that when using 2 to 5 Vinyl compounds of vinyl groups, especially vinyl compounds with 2 to 3 vinyl groups, and controlling the chain length between different vinyl groups in the vinyl compounds are beneficial to improve the performance of aspartate and polyacrylate compounds. Reactivity and rate, resulting in higher yields of resin and easier washout of residual primary amines. And the inventor found that when the number of vinyl groups is 1 or more, such as more than 6, when the number of vinyl groups is small, it is difficult to complete the reaction, and when the number of vinyl groups is large, the addition of vinyl compounds to aspartic acid is also increased. The resistance of the acid ester compound is thus also detrimental to the yield and the complete washout of amine residues.

(3) In addition, the inventor found that, using the method provided by the invention, while reducing the excess amount of the reaction raw materials, the method of one-step heating can directly obtain a resin with high yield, no primary amine residue and excessive cross-linking. During the curing process of polyurea material, no gelation occurs, which improves the construction performance and pot life of the resin.

Detailed ways

Example

Example 1

This example provides a secondary amine modified aspartic resin. The aspartic resin is prepared from diethyl aspartate and a polyacrylate compound. The structural formula of the aspartate compound is as follows:

R为乙基；

R is ethyl;

The structural formula of the polyacrylate compound is as follows:

This example also provides the above-mentioned preparation method of the secondary amine modified aspartic resin, comprising: under the protection of nitrogen, 189 grams of diethyl aspartate was added dropwise to the The flask was added with 0.3 wt % hydroquinone relative to the total weight of diethyl aspartate and polyacrylate compounds, and the temperature was raised to 60° C. to react, and the reaction end point was monitored by TLC. After the reaction was completed, ethyl acetate was added, washed with saturated aqueous sodium bicarbonate solution, saturated sodium chloride solution, and double distilled water, evaporated the solvent under reduced pressure, and dried by adding anhydrous sodium sulfate. No gel was obtained during the reaction, and 280 g of light yellow oily liquid was obtained, with a yield of 97.2%.

Example 2

This example provides a secondary amine modified aspartic resin. The aspartic resin is prepared from diethyl aspartate and a polyacrylate compound. The structural formula of the aspartate compound is as follows:

R为乙基；

R is ethyl;

The structural formula of the polyacrylate compound is as follows:

This example also provides the above-mentioned preparation method of secondary amine modified aspartic resin, comprising: under the protection of nitrogen gas, 189 grams of diethyl aspartate was added dropwise to a tetramethyl acrylate containing 143 grams of polyacrylate compound. A flask was added, and 0.3 wt% hydroquinone relative to the total weight of diethyl aspartate and polyacrylate compounds was added as a polymerization inhibitor, the temperature was raised to 70° C. to react, and the reaction end point was monitored by TLC. After the reaction was completed, ethyl acetate was added, washed with saturated aqueous sodium bicarbonate solution, saturated sodium chloride solution, and double distilled water, evaporated the solvent under reduced pressure, and dried by adding anhydrous sodium sulfate. There was no gel during the reaction, and 302 g of a yellow oily liquid was obtained with a yield of 91%.

Example 3

This example provides a secondary amine modified aspartic resin, the aspartic resin is prepared from dimethyl aspartate and a polyacrylate compound, and the structural formula of the aspartate compound is as follows:

R为甲基；

R is methyl;

The structural formula of the polyacrylate compound is as follows:

This example also provides the above-mentioned preparation method of the secondary amine modified aspartic resin, comprising: under the protection of nitrogen gas, 161 grams of dimethyl aspartate is added dropwise to the A flask was added, and 0.3 wt% hydroquinone relative to the total weight of dimethyl aspartate and polyacrylate compounds was added as a polymerization inhibitor, and the temperature was raised to 60 °C to react, and the reaction end point was monitored by TLC. After the reaction was completed, ethyl acetate was added, washed with saturated aqueous sodium bicarbonate solution, saturated sodium chloride solution, and double distilled water, evaporated the solvent under reduced pressure, and dried by adding anhydrous sodium sulfate. There was no gel during the reaction, and 280 g of light yellow oily liquid was obtained, with a yield of 96.6%.

Example 4

This example provides a secondary amine modified aspartic resin. The aspartic resin is prepared from diethyl aspartate and a polyacrylate compound. The structural formula of the aspartate compound is as follows:

R为乙基；

R is ethyl;

The structural formula of the polyacrylate compound is as follows:

This example also provides the above-mentioned preparation method of secondary amine modified aspartic resin, comprising: under the protection of nitrogen gas, 283.5 grams of diethyl aspartate is added dropwise to a tetramethyl acrylate compound containing 148.2 grams of polyacrylate compound. The flask was added with 0.5 wt % hydroquinone as a polymerization inhibitor relative to the total weight of diethyl aspartate and polyacrylate compounds, and the temperature was raised to 65°C for the reaction, and the reaction end point was monitored by TLC. After the reaction was completed, ethyl acetate was added, washed with saturated aqueous sodium bicarbonate solution, saturated sodium chloride solution, and double distilled water, evaporated the solvent under reduced pressure, and dried by adding anhydrous sodium sulfate. There was no gel during the reaction, and 400 g of light yellow oily liquid was obtained, with a yield of 92.7%.

Performance evaluation

The aspartate resin and HDI provided by the examples are cured according to the mol ratio of secondary amine group and isocyanate group as 1:1.1, the gloss is carried out according to GB/T9754-1988, and the adhesion (measured (pulled open) is carried out in GB/T5210-2006. method) test, GB/T6739-1986 for pencil hardness test, GB/T23446-2009 for gel time test, the results are shown in Table 1.

Table 1 Performance Characterization Test

As can be seen from the above test results, the present invention can prepare high-yield aspartate resin through aspartate compound and polyacrylate compound, promote the complete reaction of primary amine, reduce the residual of primary amine, and can be used for polyurea material. , and by adjusting the structure of the aspartic resin, the gel time can be regulated, and during the curing process, there is no local gelation, which also shows that the raw materials and methods provided by the present invention can avoid the residue of primary amines.

Claims (10)

1. a secondary amine modified aspartic resin is characterized in that, described aspartic resin is prepared by aspartic acid ester compound and polybasic acrylate compound, and the structural formula of described aspartic acid ester compound is such as formula (1 ) as shown:

R is a C1-C10 alkyl group. 2 . The secondary amine modified aspartic resin according to claim 1 , wherein the number of acrylate groups in the polyvalent acrylate compound is 2 to 5. 3 . 3 . The secondary amine modified aspartic resin according to claim 2 , wherein the polyacrylate compound is a chain polyacrylate compound and/or a cyclic polyacrylate compound. 4 . 4. secondary amine modified aspartic resin according to claim 3, is characterized in that, when the vinyl number of described polybasic acrylate compound is 2, the structural formula of described polybasic acrylate compound is as formula (2) Or as shown in formula (3):

m is 2-30, R ₁ is H or methyl;

p is 0-30, X is selected from one of C1-C30 alkyl, C1-C30 cycloalkyl, C1-C30 alkyl derivatives, C1-C30 cycloalkyl derivatives, R ₂ is H or methyl . 5. secondary amine modified aspartic resin according to claim 3, is characterized in that, when the vinyl number of described polybasic acrylate compound is 3 or 4, the structural formula of described polybasic acrylate compound is such as formula ( 4) shown:

n is 3 or 4, Y is selected from one of C1-C30 alkyl, C1-C30 cycloalkyl, C1-C30 alkyl derivatives, C1-C30 cycloalkyl derivatives, R ₃ is H or methyl , R' is H or alkyl. 6. secondary amine modified aspartic resin according to claim 3 is characterized in that, the structural formula of described cyclic polyacrylate compound is as shown in formula (5):

q is 2-5, f is 0-30, Z is selected from one of C1-C30 alkyl, C1-C30 cycloalkyl, C1-C30 alkyl derivative and C1-C30 cycloalkyl derivative, R ₄ is H or methyl. 7. The secondary amine-modified aspartic resin according to any one of claims 4 to 6, wherein the C1-C30 alkyl derivative is a hydrogen atom in the C1-C30 that is replaced by an ether group, a carbonyl group, an ester group group, nitrile group or mercapto group. 8 . The secondary amine modified aspartic resin according to claim 1 , wherein the molar ratio of the amino group of the aspartate compound to the vinyl group of the polyacrylate compound is 1:(0.9～1.3 ). 9. A preparation method of the secondary amine modified aspartic resin according to any one of claims 1 to 8, characterized in that, comprising: The aspartic acid ester compound and the polyvalent acrylate compound are reacted at 50 to 80° C. to obtain a secondary amine modified aspartic resin. 10 . A polyurea material, wherein the raw materials for preparing the polyurea material comprise the secondary amine modified aspartic resin according to any one of claims 1 to 8 .