CN100537684C - End-amido polyaspartic ester and method of manufacturing the same - Google Patents
End-amido polyaspartic ester and method of manufacturing the same Download PDFInfo
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- CN100537684C CN100537684C CNB2005100305941A CN200510030594A CN100537684C CN 100537684 C CN100537684 C CN 100537684C CN B2005100305941 A CNB2005100305941 A CN B2005100305941A CN 200510030594 A CN200510030594 A CN 200510030594A CN 100537684 C CN100537684 C CN 100537684C
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Abstract
The invention discloses a making method of end-amino polyether polyaspartate ester, which comprises the following steps: (1) reacting small molecule amine and excessive dicarboxylic acid ester to generate the mixture with first polyaspartate ester and surplus dicarboxylic acid ester; (2) dripping the mixture in the first step into polyalkylene ether polyamine to obtain the product through catalyzing reaction. The polyurea paint with polyether polyaspartate ester possesses long gel time, which is convenient to operate.
Description
Technical field
The present invention relates to make a kind of component and the manufacture method thereof that polyurethane coating is used, specifically, relate to a kind of manufacturing spray polyurea type coating component, i.e. end-amido polyaspartic ester and manufacture method thereof.
Background technology
Polyisocyanate component and the amine component that isocyanic ester has a reactive behavior cooperatively interacted to make the coating of various performances.This based composition can form high-quality coating, and this coating can possess multiple performances such as rigidity, elasticity, corrosion-resistant and anti-solvent, UV resistant.The traditional Amino Terminated polyether(ATPE) and the reactive behavior of polyisocyanates are too big, and operational difficulty must adopt special two-pack high pressure collision type spray gun to construct.The polyaspartate that develops out recent years has following structure:
Because nitrogen-atoms is subjected to the effect of the electronic induction effect and the steric hindrance shielding effect of huge shielding group in the molecular structure, the reactive behavior of polyaspartate is reduced, the reaction of it and aliphatic HDI tripolymer can be obtained the extraordinary novel aliphatics polyureas coating of weathering resistance, as long as change the gel time that the structure of X in the following formula just can be adjusted itself and the trimerical reaction of HDI.The gel time of now commercial polyaspartate polyurea formulation for coating material is generally 2～20min, and the polyaspartates that adopt based on the small molecules amine more, though verified already it can be used as useful reactive components in the polyurea composition, can make high solid coating and solventless coatings, but prepared coating presents rigidity and lacks flexibility thus, elongation at break generally is not more than 10%, this is because small molecule amine belongs to chainextender, and the molecular chain internal rotation is difficulty relatively.
Based on the preparation of the poly aspartic acid ester mixture of small molecule amine and polyoxypropylene polyamine or the polynary amine of polyoxyethylene, can form by their synthetic separately merging then.United States Patent (USP) 5236741 and 5623045 all discloses the scheme that a kind of single stage method is produced such polyaspartate.They all are with maleic acid ester or fumarate and primary amine reaction, preferably have an olefinic double bonds corresponding to each primary amine group, and excessive starting raw material is gone out by distillation after reaction.But these two patents are not all discussed the time that the polyaspartate productive rate reaches required cost in 100% o'clock.Thereby these methods are difficult to accomplish to make the polyaspartate that obtains in time to supply to the client.For example, use two (4-aminocyclohexyl) methane synthesizing polyaspartic acid ester to need six months just can reach 95% productive rate, need 12-～8 month just can reach complete reaction.Though United States Patent (USP) 5243012 has been mentioned the synthetic of Amino Terminated polyether(ATPE) ether type polyaspartate, do not mention that transformation efficiency reached for synthetic 100% required time fully.
Chinese patent CN1362946A discloses a kind of polyaspartate preparation process of mixture, though this method can reach 100% productive rate in the time in week.But used raw material all is the small molecule amine quasi-molecule, do not relate to the application in polyaspartate is synthetic of polyoxypropylene polyamine or polyoxyethylene polyamine, and the physicals of the elongation at break of gel time when also not mentioning the reaction of the poly aspartic acid ester mixture for preparing with this method and isocyanic ester and the polyurea materials made etc.
Summary of the invention
Purpose of the present invention is exactly at above-mentioned weak point, provide both contain the method that Amino Terminated polyether(ATPE) type polyaspartate also contains the polyaspartate of small molecule amine a kind of can the preparation at short notice, utilization the inventive method, this two classes material need not separately preparation separately, and the poly aspartic acid ester composition of preparation thus can directly be used as the resin Composition of carbamide paint.
According to the present invention, described amino end group polyether-type polyaspartate is by after small molecule amine and the reaction of excessive dicarboxylic esters, again by forming with the reaction of polyalkylene ether polyamine.Described small component amine is selected from molecular weight less than 500 two functional groups or trifunctional amine; Described dicarboxylic esters is selected from maleic acid ester or fumarate; Described polyalkylene ether polyamine is selected from the polyoxyethylene polyamine or the polyoxypropylene polyamine of two functionality or three-functionality-degree.
The present invention is based on following discovery: by small molecule amine and excessive dicarboxylic esters, the first poly aspartic acid ester mixture that is maleic acid ester or fumarate prepared in reaction can be used as the catalyzer for preparing polyoxypropylene polyamine or polyoxyethylene polyamine polyaspartate, and can form compound system, thereby finish 100% reaction in the required usually time being less than with suitable catalyzer.Prepared small molecules polyaspartate not only can be used as the catalyzer of preparation polyoxypropylene polyamine or polyoxyethylene polyamine polyaspartate, and itself also can be used as polyaspartate and participate in reaction with polyisocyanates, at this moment, the small molecules polyaspartate plays the effect of chainextender, produce the hardness of increase material and the effect of tensile strength, and polyoxypropylene polyamine or polyoxyethylene polyamine polyaspartate mainly play the increase elastic properties of materials and material is corrosion-resistant, the effect of performances such as anti-solvent, this is mainly owing to the structure of its molecule, polyoxypropylene polyamine or polyoxyethylene polyamine intramolecularly contain ehter bond, the intramolecularly rotation is more prone to, thereby has increased the elasticity of material.By rational formulating of recipe, can prepare various materials such as rigid material very big and excellent corrosion-resistant, anti-solvent from the big rubber type of material of elasticity to hardness.
Further analyze and find, shielding group huge on the end group nitrogen-atoms has played very big restraining effect for the reactive behavior that reduces amine molecule and polyisocyanates, this mainly is because the electronic induction effect of shielding group and the influence of steric hindrance shielding effect common, and in polyoxypropylene polyamine or polyoxyethylene polyamine poly aspartic acid ester molecule, hydrogen atom on the nitrogen can form hydrogen bond with ehter bond on polyoxypropylene polyamine or the polyoxyethylene polyamine, has further reduced the reactive behavior of itself and isocyanic ester.
That is to say that Amino Terminated polyether(ATPE) type polyaspartate of the present invention is two step method preparation as described below:
(1) a kind of small molecule amine and the reaction of excessive dicarboxylic esters are generated contains first polyaspartate and because of the mixture of excessive and remaining unreacted dicarboxylic esters;
(2) mixture that above-mentioned steps (1) is obtained is added drop-wise in the polyalkylene ether polyamine and obtains final product through catalyzed reaction---Amino Terminated polyether(ATPE) type polyaspartate.
Described here " small molecule amine " is meant that molecular weight is less than 500 and contain the amine that at least one is connected the primary amine group on the cyclic group, for example a kind of amine that is connected on the secondary ring carbon atom." polyoxypropylene polyamine or polyoxyethylene polyamine " is meant the amine that is connected with primary amine group on this class polyoxypropylene or polyoxyethylated ehter bond.This type of amine component is selected from two functional groups that can realize target of the present invention or small molecule amine and the polyoxypropylene polyamine or the polyoxyethylene polyamine of trifunctional usually.Suitable small molecules two functional group's amine comprise ring pentamethylene diamine, two (3-dimethyl-4-hexahydroaniline), two (3-diethyl-4-encircles amine), 3,3 '-dimethyl-4,4 '-diamino, two cyclohexyl methane, diformazan sulfenyl tolylene diamine.Two suitable functional group's polypropyleneoxide diamine or polyethyleneoxide diamine comprise the commodity that Huntsman chemical company produces: Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, JeffamineEDR-148, Jeffamine EDR-192, Jeffamine ED-600, Jeffamine ED-900 and Jeffamine ED-2000 etc.; Suitable three-functionality-degree polyoxypropylene amine or the polynary amine of polyoxyethylene comprise the commodity that Huntsman chemical company produces: Jeffamine T-403, Jeffamine T-3000, Jeffamine T-5000 etc.
The dicarboxylic esters that is suitable for is selected from maleic acid ester or fumarate, be dialkyl maleate or dialkyl fumarate, comprise ethyl maleate, dipropyl maleate, dibutyl maleinate, toxilic acid methyl-propyl ester etc. and DEF, fumaric acid dipropyl, dibutyl fumarate, fumaric acid methyl-propyl ester etc.Can select their wherein a kind of or several for use.
As mentioned above, the first step of the inventive method is the mixture that small molecule amine and excessive fumarate or maleic acid ester reaction is contained the first polyaspartate component and excessive unreacted fumarate or maleic acid ester with generation.At this moment, maleic acid ester or fumarate and small molecules polyamines mol ratio should be greater than 1:1, preferred 1.5:1～5:1, more preferably 2:1～3:1.In general, employed maleic acid ester or fumarate are many more, react fast more.For example when maleic acid ester or fumarate and small molecule amine mol ratio were 3:1, the reaction times was less than 10 hours.Concrete practical ratio can be determined by routine test according to actual needs.
Second step of the inventive method is that the first polyaspartate component that the first step noted earlier is obtained and the mixture of excessive unreacted fumarate or maleic acid ester are added dropwise in polyoxypropylene polyamine or the polyoxyethylene polyamine, make this polyoxypropylene polyamine or polyoxyethylene polyamine and excessive fumarate or maleic acid ester reaction, generate the second polyaspartate component.At this moment, the preferred 0.5:1～4:1 of mol ratio of polyoxypropylene polyamine or polyoxyethylene polyamine and small molecule amine, more preferably 1:1～2:1.
Reaction is carried out under 0～100 ℃ temperature usually.Can under solvent-free or the situation that has appropriate solvent to exist, carry out the mixture of solvent such as methyl alcohol, ethanol, propyl alcohol, ethyl acetate or butylacetate, toluene and these solvents.Reaction pressure is normal atmosphere normally.Catalyzer can be hydrochloric acid, sulfuric acid, nitric acid, tosic acid, phenylformic acid, aluminum oxide, silicon oxide, zinc sulfate, copper sulfate, dibutyl tin laurate etc.Especially serve as effective to adopt the composite form of multiple catalyzer.
Match with polyisocyanates with the present invention's end-amido polyaspartic ester it is compared with the polyaspartate of general merchandiseization, the gel time of material of the present invention is 50～90min (28 ℃), elongation at break is 148～180%, and this two indexes of commercial product is respectively 1.5～40min (22 ℃) and 4～6%.As seen, the reactive behavior of material of the present invention is significantly less than existing commercialization polyaspartate, then obviously is better than the latter with the elasticity of the coating of material preparation of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, but the present invention never is limited to these embodiment.The per-cent that all provide among the embodiment all is weight percentage except as otherwise noted.
Embodiment 1
There-necked flask fit on agitator, well heater, feed hopper and nitrogen inlet.With 3 of 73.3 grams (0.700 equivalent), 3 '-dimethyl-4,4 '-diamino, two cyclohexyl methane install in the flask, under logical nitrogen protection, add 446.9 gram (1.96 equivalent) dibutyl maleinates by feed hopper in 1 hour in flask.Because exothermic heat of reaction, the temperature of reaction mixture rises to 40 ℃, and after this temperature kept 7 hours at 60 ℃, this moment 3, and 3 '-dimethyl-4,4 '-diamino, two cyclohexyl methane 100% are converted into polyaspartate.This mixture was joined in 45 minutes in the reaction flask that 144.9 gram D-230 (1.26 equivalent) are housed, and reaction is heated to 60 ℃ to be carried out 12 hours, and be converted into polyaspartate this moment 90%, and after one month, reaction 100% is finished.
Embodiment 2
There-necked flask fit on agitator, well heater, feed hopper and nitrogen inlet.With 3 of 86.87 grams (0.730 equivalent), 3 '-dimethyl-4,4 '-diamino, two cyclohexyl methane install in the flask, under logical nitrogen protection, add 499.3 gram (2.19 equivalent) dibutyl maleinates by feed hopper in 1 hour in flask.Because exothermic heat of reaction, the temperature of reaction mixture rises to 40 ℃, and after this temperature kept 7 hours at 60 ℃, this moment 3, and 3 '-dimethyl-4,4 '-diamino, two cyclohexyl methane 100% are converted into polyaspartate.This mixture was joined in 45 minutes in the reaction flask that 229.9 gram T-403 (1.46 equivalent) are housed, and reaction is heated to 70 ℃ to be carried out 12 hours, and be converted into polyaspartate this moment 90%, and afterreaction 100% was finished in one month.
Embodiment 3
There-necked flask fit on agitator, well heater, feed hopper and nitrogen inlet.With 3 of 90.57 grams (0.761 equivalent), 3 '-dimethyl-4,4 '-diamino, two cyclohexyl methane install in the flask, under logical nitrogen protection, add 542.64 gram (2.38 equivalent) dibutyl maleinates by feed hopper in 1 hour in flask.Because exothermic heat of reaction, the temperature of reaction mixture rises to 40 ℃, and after this temperature kept 7 hours at 60 ℃, this moment 3, and 3 '-dimethyl-4,4 '-diamino, two cyclohexyl methane 100% are converted into polyaspartate.This mixture was joined in 45 minutes in the reaction flask that 323.8 gram D-400 (1.62 equivalent) are housed, and reaction is heated to 70 ℃ to be carried out 12 hours, and be converted into polyaspartate this moment 90%, and afterreaction 100% was finished in one month.
By embodiment 1,2 and 3 polyaspartate that obtains and the reactive behavior that presents after isocyanic ester cooperates and solidify the elasticity of back material and commercial polyaspartate at present more respectively shown in table 1 and table 2 and table 3 and table 4.
Table 1
Annotate: Desmodur N3390---HDI tripolymer, Bayer company produces, NCO content 19.5%, viscosity 550cps (25 ℃).
Table 2
Annotate: 1) Desmodur N7100---HDI tripolymer, Bayer company produces, NCO content 20.5%, viscosity 1000cps (25 ℃).
2) Desmophen NH 1520 grades are the trade name of the polyaspartate of Bayer company product.
Table 3
Table
Annotate: Desmodur N3300---HDI tripolymer, Bayer company produces, NCO content 21.5%, viscosity 3000cps (25 ℃).
Claims (9)
1, a kind of Amino Terminated polyether(ATPE) type polyaspartate is characterized in that, it by small molecule amine and the reaction of excessive dicarboxylic esters after, again by forming with the reaction of polyalkylene ether polyamine; Described dicarboxylic esters is selected from maleic acid ester or fumarate; Described small molecular weight amine is selected from molecular weight less than 500 two functional groups or trifunctional amine; Described polyalkylene ether polyamine is selected from the polyoxyethylene polyamine or the polyoxypropylene polyamine of two functionality or three-functionality-degree.
According to the manufacture method of the described Amino Terminated polyether(ATPE) type of claim 1 polyaspartate, it is characterized in that 2, this polyaspartate is made by two-step approach:
(1) a kind of small molecule amine and the reaction of excessive dicarboxylic esters are generated contains first polyaspartate and because of the mixture of excessive and remaining unreacted dicarboxylic esters;
(2) mixture that above-mentioned steps (1) is obtained is added drop-wise in the polyalkylene ether polyamine and obtains final product through catalyzed reaction---Amino Terminated polyether(ATPE) type polyaspartate.
3, the manufacture method of Amino Terminated polyether(ATPE) type polyaspartate according to claim 2 is characterized in that, described dicarboxylic esters is selected from a kind of in maleic acid ester or the fumarate.
4, the manufacture method of Amino Terminated polyether(ATPE) type polyaspartate according to claim 3, it is characterized in that described maleic acid ester is selected from a kind of in ethyl maleate, dipropyl maleate, dibutyl maleinate and the toxilic acid methyl-propyl ester or several mixture.
5, the manufacture method of Amino Terminated polyether(ATPE) type polyaspartate according to claim 3, it is characterized in that described fumarate is selected from a kind of in DEF, fumaric acid dipropyl, dibutyl fumarate and the fumaric acid methyl-propyl ester or several mixture.
6, the manufacture method of Amino Terminated polyether(ATPE) type polyaspartate according to claim 2, it is characterized in that described small molecule amine is selected from molecular weight less than 500 and contain at least one two functional groups that are connected the primary amine group on the cyclic group or trifunctional amine.
7, the manufacture method of Amino Terminated polyether(ATPE) type polyaspartate according to claim 2 is characterized in that, described polyalkylene ether polyamine is selected from the polyoxyethylene polyamine or the polyoxypropylene polyamine of two functionality or three-functionality-degree.
8, the manufacture method of Amino Terminated polyether(ATPE) type polyaspartate according to claim 2 is characterized in that, the mol ratio of dicarboxylic esters and small molecular weight amine reaction is 1.5:1～5:1 in step (1).
9, the manufacture method of Amino Terminated polyether(ATPE) type polyaspartate according to claim 2 is characterized in that, applied polyalkylene polyamine is 0.5:1～4:1 with respect to the mol ratio of small molecule amine in step (2).
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| EP3456755A1 (en) * | 2017-09-19 | 2019-03-20 | Covestro Deutschland AG | Polyaspartic acid ester compositions containing polyaspartic acid ester with primary amino groups and small amounts of fumaric acid dialkyl ester |
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Assignee: BEIJING BSS CORROSION PROTECTION INDUSTRY Co.,Ltd. Assignor: Shanghai Research Institute of Paint and Coatings Contract record no.: 2012310000021 Denomination of invention: End-amido polyaspartic ester and method of manufacturing the same Granted publication date: 20090909 License type: Exclusive License Open date: 20070425 Record date: 20120217 |
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Address after: 200052 Shanghai city Putuo District Yunling Road No. 345 Patentee after: Shanghai Coating Research Institute Co.,Ltd. Address before: 200062 Shanghai city Putuo District Yunling Road No. 345 Patentee before: Shanghai Research Institute of Paint and Coatings |
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