CN107603551B - Silane modified polyurea and preparation method thereof - Google Patents
Silane modified polyurea and preparation method thereof Download PDFInfo
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- CN107603551B CN107603551B CN201710724897.6A CN201710724897A CN107603551B CN 107603551 B CN107603551 B CN 107603551B CN 201710724897 A CN201710724897 A CN 201710724897A CN 107603551 B CN107603551 B CN 107603551B
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Abstract
The present invention provides a silane-modified polyurea having a structure represented by the following general formula (1), wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms; x is a divalent residue obtained after removal of two amine groups from the polyetheramine; y is a divalent residue obtained after removing two isocyanate groups from a polyisocyanate. In addition, the invention also provides a preparation method for the silane modified polyurea. According to the technical scheme, the silane modified polyurea with improved physical properties is provided, and when the silane modified polyurea prepared by the method is synthesized into the sealant, the obtained sealant has excellent physical properties such as elongation at break, tensile strength and the like, and also has excellent weather resistance and aging resistance.
Description
Technical Field
The invention relates to the field of components for building sealants, in particular to silane modified polyurea and a preparation method thereof.
Background
The sealant is a material for filling the gap, and the most used sealants include asphalt, oily caulking compound, and the like. However, when used in gaps that are subject to shock and thermal expansion and contraction, elastomeric sealants must be used.
In order to integrate the performances of the silicone sealant and the polyurethane sealant, the silane modified polyurethane sealant can be widely applied as a new generation of sealant product once being put into the market. The main chain of the sealant is of a polyurethane structure, and the end group of the sealant is of a silicone structure, so that the preparation method of the sealant comprises the step of performing crosslinking curing by adopting a curing mechanism of the silicone sealant, and the product integrates the performances of the silicone sealant and the polyurethane sealant. The product has excellent adhesion and aging resistance, can be coated on the surface, has good elasticity, high curing speed, water resistance and oil resistance, has no bubbles in a cured product, and is particularly suitable for occasions requiring good weather resistance, no pollution and dual adhesion. The silane modified polyurethane sealant does not contain silicone components and solvents, so that the product is safer and more environment-friendly. In addition, the silane modified polyurethane sealing adhesive has elasticity, can absorb and compensate dynamic load, uniformly transmits stress, prevents the material from being fatigued prematurely, and can realize the bonding among various base materials. However, the commercial silane modified polyurethane sealant has the defects of low physical property, poor surface gloss and the like, which limits the application range and development of the silane modified polyurethane sealant to a certain extent.
Therefore, there is a strong need in the art to develop a new silane-modified polyurea and a preparation method thereof to improve the physical and chemical properties of the sealant.
Disclosure of Invention
In view of the technical problems set forth above, the present invention aims to provide a novel silane-modified polyurea and a preparation method thereof, so as to solve the defects in the prior art, and when the silane-modified polyurea prepared by the method is synthesized into a sealant, the obtained sealant has excellent physical properties such as elongation at break, tensile strength and the like, and also has excellent weather resistance and aging resistance.
The present inventors have made intensive studies and completed the present invention.
According to one aspect of the present invention, there is provided a silane-modified polyurea having a structure represented by the following general formula (1):
wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms; x is a divalent residue obtained after removal of two amine groups from the polyetheramine; y is a divalent residue obtained after removing two isocyanate groups from a polyisocyanate.
According to certain preferred embodiments of the present invention, R is methyl, ethyl, butyl or phenyl.
According to certain preferred embodiments of the present invention, the polyetheramine is selected from one or more of polyetheramines having an amine functionality of 2 or 3 and a number average molecular weight of 230 to 5000.
According to certain preferred embodiments of the present invention, the polyisocyanate is an aliphatic polyisocyanate.
According to certain preferred embodiments of the present invention, the polyisocyanate is a diisocyanate.
According to certain preferred embodiments of the present invention, the polyisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate trimer.
According to certain preferred embodiments of the present invention, the silane-modified polyurea has a number average molecular weight in the range of 1300-6700.
According to another aspect of the present invention, there is provided a method for preparing a silane-modified polyurea, the method comprising the steps of:
a) mixing and reacting polyetheramine, polyisocyanate and a solvent to obtain a polyetheramine prepolymer terminated at both ends by the polyisocyanate;
b) reacting equimolar amounts of 3-aminopropyltriethoxysilane with a dicarboxylic ester to obtain 3-aminopropyltriethoxysilane terminated at one end by said dicarboxylic ester; and
c) mixing and heating the polyether amine prepolymer obtained in step a) with the 3-aminopropyltriethoxysilane terminated at one end by the dicarboxylate obtained in step b) to obtain the silane-modified polyurea.
According to certain preferred embodiments of the present invention, the polyetheramine is selected from one or more of polyetheramines having an amine functionality of 2 or 3 and a number average molecular weight of 230 to 5000.
According to certain preferred embodiments of the present invention, the polyisocyanate is an aliphatic polyisocyanate.
According to certain preferred embodiments of the present invention, the polyisocyanate is a diisocyanate.
According to certain preferred embodiments of the present invention, the polyisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate trimer.
According to certain preferred embodiments of the present invention, the silane-modified polyurea has a number average molecular weight in the range of 1300-6700.
According to certain preferred embodiments of the present invention, the dicarboxylic acid ester has a structure represented by the following general formula (2):
wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms.
According to certain preferred embodiments of the present invention, R is methyl, ethyl, butyl or phenyl.
According to certain preferred embodiments of the present invention, the dicarboxylic acid ester is selected from one or more of dimethyl maleate, diethyl maleate, dibutyl maleate and diphenyl maleate.
According to certain preferred embodiments of the present invention, the solvent is selected from one or more of ethyl acetate, acetone, xylene and ethylene glycol dimethyl ether.
According to certain preferred embodiments of the present invention, in step a), the ratio of the number of moles of the polyisocyanate to the number of moles of the polyetheramine is from 1.0 to 1.1.
According to certain preferred embodiments of the present invention, in step a), the ratio of the weight of the solvent to the weight of the polyetheramine is from 0.1 to 1.0.
According to certain preferred embodiments of the present invention, in step c), the ratio of the number of moles of the polyetheramine prepolymer employed to the number of moles of the 3-aminopropyltriethoxysilane terminated at one end by the dicarboxylate is from 0.9 to 1.
According to certain preferred embodiments of the present invention, the process for preparing the silane-modified polyurea comprises:
a) slowly dripping polyether amine into a mixture of polyisocyanate and a solvent at the temperature of 0-10 ℃, and reacting at normal temperature for 0.5-1.0 hour after dripping to obtain a polyether amine prepolymer with two ends capped by the polyisocyanate;
b) dripping 3-aminopropyltriethoxysilane into equimolar dicarboxylic ester at 0-10 ℃ for reaction, and continuing the reaction for 0.5-1.0 hour after dripping to obtain 3-aminopropyltriethoxysilane of which one end is capped by the dicarboxylic ester; and
c) mixing the polyether amine prepolymer obtained in step a) with the 3-aminopropyltriethoxysilane terminated at one end by the dicarboxylic ester obtained in step b) and heating to 30 to 50 ℃ for 0.5 to 2.0 hours, followed by removing the solvent by distillation under reduced pressure to obtain the silane-modified polyurea.
Compared with the prior art in the field, the invention has the advantages that:
1) the silane modified polyurea synthesized by the method is a pure polyurea system, so that the physical properties of the silane modified polyurea sealant, such as elongation at break, tensile strength and the like, are improved;
2) the molecular structure of the silane modified polyurea synthesized by the method contains dicarboxylic ester groups, so that the viscosity of the silane modified polyurea is reduced, and the weather resistance of the silane modified polyurea sealant is improved;
3) the method for synthesizing the silane modified polyurea has simple process and short required time; and
4) the molecular structure of the silane modified polyurea synthesized by the method of the invention contains carbamido, thereby improving the content of hard segment in the silane modified polyurea sealant.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. It will be appreciated that other embodiments are contemplated and may be made without departing from the scope or spirit of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense.
Unless otherwise indicated, all numbers expressing feature sizes, quantities, and physical and chemical characteristics used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
The present invention provides a silane-modified polyurea having a structure represented by the following general formula (1):
wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms; x is a divalent residue obtained after removal of two amine groups from the polyetheramine; y is a divalent residue obtained after removing two isocyanate groups from a polyisocyanate. Preferably, R is a straight chain alkyl group having 1 to 4 carbon atoms. Preferably, R is methyl, ethyl, butyl or phenyl.
The polyetheramines according to the present invention have the meaning generally known in the art, i.e., polyetheramines are a class of polymers having a polyether structure in the main chain and amine groups as terminal reactive functional groups. According to certain embodiments of the present invention, the polyetheramine is selected from one or more of polyetheramines having an amine functionality of 2 or 3 and a number average molecular weight of 230 to 5000. Specific examples of polyetheramines that can be used in the present invention include Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine T-3000, and Jeffamine T-5000, which are manufactured by Huntsman Chemical Company.
Preferably, the polyisocyanate used in the present invention is an aliphatic polyisocyanate. Preferably, the polyisocyanate is a diisocyanate. According to certain embodiments of the present invention, the polyisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate trimer.
According to certain embodiments of the present invention, the number average molecular weight of the silane-modified polyurea is in the range of 1300-. When the silane-modified polyurea having the number average molecular weight within the above range is used for preparing a sealant by a curing reaction, the resulting sealant has excellent physical properties such as elongation at break and tensile strength.
In addition, the invention also provides a preparation method of the silane modified polyurea, which comprises the following steps:
a) mixing and reacting polyetheramine, polyisocyanate and a solvent to obtain a polyetheramine prepolymer terminated at both ends by the polyisocyanate;
b) reacting equimolar amounts of 3-aminopropyltriethoxysilane with a dicarboxylic ester to obtain 3-aminopropyltriethoxysilane terminated at one end by said dicarboxylic ester; and
c) mixing and heating the polyether amine prepolymer obtained in step a) with the 3-aminopropyltriethoxysilane terminated at one end by the dicarboxylate obtained in step b) to obtain the silane-modified polyurea.
The polyetheramines according to the present invention have the meaning generally known in the art, i.e., polyetheramines are a class of polymers having a polyether structure in the main chain and amine groups as terminal reactive functional groups. According to certain embodiments of the present invention, the polyetheramine is selected from one or more of polyetheramines having an amine functionality of 2 or 3 and a number average molecular weight of 230 to 5000. Specific examples of polyetheramines that can be used in the present invention include Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine T-3000, and Jeffamine T-5000, which are manufactured by Huntsman Chemical Company.
Preferably, the polyisocyanate used in the present invention is an aliphatic polyisocyanate. Preferably, the polyisocyanate is a diisocyanate. According to certain embodiments of the present invention, the polyisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate trimer.
According to certain embodiments of the present invention, the number average molecular weight of the silane-modified polyurea is in the range of 1300-. When the silane-modified polyurea having the number average molecular weight within the above range is used for preparing a sealant by a curing reaction, the resulting sealant has excellent physical properties such as elongation at break and tensile strength.
According to certain embodiments of the present invention, the dicarboxylic acid ester has a structure represented by the following general formula (2):
wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms. Preferably, R is a straight chain alkyl group having 1 to 4 carbon atoms. Preferably, R is methyl, ethyl, butyl or phenyl.
According to certain embodiments of the present invention, the dicarboxylic acid ester is selected from one or more of dimethyl maleate, diethyl maleate, dibutyl maleate and diphenyl maleate.
The solvent used in the technical solution according to the present invention is not particularly limited as long as it can dissolve or disperse the respective components and can be removed by distillation under reduced pressure at the end of the preparation process. According to certain embodiments of the present invention, the solvent is selected from one or more of ethyl acetate, acetone, xylene and ethylene glycol dimethyl ether.
According to certain embodiments of the present invention, in step a), the ratio of the number of moles of the polyisocyanate to the number of moles of the polyetheramine is from 1.0 to 1.1, preferably from 1.0 to 1.08, more preferably from 1.0 to 1.05. The reaction of polyisocyanate with polyetheramine makes it possible to obtain polyetheramine prepolymers terminated with the polyisocyanate in different structures, for example, polyetheramine prepolymers terminated with the polyisocyanate at one end, polyetheramine prepolymers terminated with the polyisocyanate at both ends, or a mixture of polyetheramine prepolymers terminated with the polyisocyanate at one end and polyetheramine prepolymers terminated with the polyisocyanate at both ends, and the like. However, by specifically selecting the ratio of the number of moles of the polyisocyanate to the number of moles of the polyether amine within the above range, it is possible to efficiently and selectively preferentially synthesize a polyether amine prepolymer terminated at both ends with the polyisocyanate.
According to certain embodiments of the present invention, in step a), the ratio of the weight of the solvent to the weight of the polyetheramine is from 0.1 to 1.0, preferably from 0.2 to 1.0, more preferably from 0.2 to 0.5. When the concentration of the solvent is controlled within the above range, the reaction can be promoted while selectively generating a polyether amine prepolymer terminated at both ends with the polyisocyanate.
According to certain embodiments of the present invention, in step c), the ratio of the number of moles of the polyetheramine prepolymer employed to the number of moles of the 3-aminopropyltriethoxysilane terminated at one end by the dicarboxylate is from 0.9 to 1, preferably from 0.95 to 1, more preferably from 0.98 to 1. By controlling the ratio of the number of moles of the polyetheramine prepolymer employed in step c) to the number of moles of the 3-aminopropyltriethoxysilane terminated at one end by the dicarboxylic ester within the above range, a silane-modified polyurea having a structure according to the general formula (1) can be preferentially obtained.
Specifically, the preparation method of the silane modified polyurea comprises the following steps:
a) slowly dripping polyether amine into a mixture of polyisocyanate and a solvent at the temperature of 0-10 ℃, and reacting at normal temperature for 0.5-1.0 hour after dripping to obtain a polyether amine prepolymer with two ends capped by the polyisocyanate;
b) dripping 3-aminopropyltriethoxysilane into equimolar dicarboxylic ester at 0-10 ℃ for reaction, and continuing the reaction for 0.5-1.0 hour after dripping to obtain 3-aminopropyltriethoxysilane of which one end is capped by the dicarboxylic ester; and
c) mixing the polyether amine prepolymer obtained in step a) with the 3-aminopropyltriethoxysilane terminated at one end by the dicarboxylic ester obtained in step b) and heating to 30 to 50 ℃ for 0.5 to 2.0 hours, followed by removing the solvent by distillation under reduced pressure to obtain the silane-modified polyurea.
The synthetic route of the preparation method of the silane modified polyurea is as follows:
step a)
Step b)
Step c)
Wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms; x is a divalent residue obtained after removal of two amine groups from the polyetheramine; y is a divalent residue obtained after removing two isocyanate groups from a polyisocyanate.
Wherein, as mentioned above, in step a), the polyetheramine is selected from one or more polyetheramines having an amine functionality of 2 or 3 and a number average molecular weight of 230 to 5000. The polyisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate trimer. The solvent is selected from one or more of ethyl acetate, acetone, xylene and ethylene glycol dimethyl ether.
Wherein, as mentioned above, in step b), the dicarboxylic acid ester is selected from one or more of dimethyl maleate, diethyl maleate, dibutyl maleate and diphenyl maleate.
In step a), the ratio of the weight of the solvent to the weight of the polyetheramine is from 0.1 to 1.0, preferably from 0.2 to 1.0, more preferably from 0.2 to 0.5. Furthermore, in step c), the ratio of the number of moles of the polyetheramine prepolymer employed to the number of moles of the 3-aminopropyltriethoxysilane terminated at one end by the dicarboxylate is from 0.9 to 1, preferably from 0.95 to 1, more preferably from 0.98 to 1.
The present invention will be described in more detail with reference to examples. It should be noted that the description and examples are intended to facilitate the understanding of the invention, and are not intended to limit the invention. The scope of the invention is to be determined by the claims appended hereto.
Examples
In the present invention, unless otherwise indicated, all reagents used were commercially available products and were used without further purification treatment. Further, "%" mentioned is "% by weight", and "parts" mentioned is "parts by weight".
Test method
Measurement of viscosity of silane-modified polyurea
The viscosity of each of the silane-modified polyureas obtained in examples 1 to 5 below was measured according to the viscosity measurement method specified in GB/T12008.8-1992.
Measurement of physical Properties of films formed from sealants prepared from silane-modified polyureas
100g of the silane-modified polyurea prepared according to any one of examples 1 to 5 below was mixed with 3g of dibutyltin dilaurate under sufficient stirring under reaction conditions at 25 ℃ to react for 0.1 to 0.5 hours to obtain a liquid mixture. The mixture was coated on a polytetrafluoroethylene sheet having dimensions of 350mm × 320mm so that the final coating film thickness was 1.5 ± 0.2 mm. The teflon plate coated with the coating film was dried at room temperature for 2 days. Followed by 4 days at a temperature of 23 ℃ and a humidity of 50%. The resulting coating films were then tested for tensile strength and elongation at break according to the test methods specified in GB/T528-2009.
Example 1
In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, 22.2 g of isophorone diisocyanate and 30 g of ethylene glycol dimethyl ether were charged, and nitrogen gas was introduced. 100g of polyether amine Jeffamine D-2000 with functionality of 2 and molecular weight of 2000 is slowly dropped into the mixture under the condition of water bath cooling at 5 ℃, and the mixture containing polyether amine prepolymer and ethylene glycol dimethyl ether is obtained after the dropping is finished and stirred for 0.5 hour at 25 ℃.
17.2 g of diethyl maleate were placed in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, and nitrogen gas was introduced thereinto. 22.1 g of 3-aminopropyltriethoxysilane was slowly dropped in a water bath under cooling, and the reaction was continued for 1.0 hour after the dropping to obtain 3-aminopropyltriethoxysilane one end of which was capped with diethyl maleate.
And mixing the mixture of the polyether amine prepolymer and the ethylene glycol dimethyl ether with 3-aminopropyl triethoxysilane with one end capped by diethyl maleate, heating to 50 ℃ for reaction for 2.0 hours, and removing the ethylene glycol dimethyl ether by reduced pressure distillation to obtain the silane modified polyurea with the viscosity of 6500MPa & s. The coating film formed from the silane-modified polyurea after curing measured by the above method had a tensile strength of 9.8MPa and an elongation at break of 630%.
Example 2
In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, 16.8 g of hexamethylene diisocyanate and 50 g of ethyl acetate were placed, and nitrogen gas was introduced. 200 g of Jeffamine D-4000 with functionality of 2 and molecular weight of 4000 are slowly dropped into the mixture under the condition of water bath cooling at 5 ℃, and the mixture containing polyether amine prepolymer and ethyl acetate is obtained after the dropping is finished and stirred for 1.0 hour at 25 ℃.
In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, 14.4 g of dimethyl maleate was charged, and nitrogen gas was introduced. 22.1 g of 3-aminopropyltriethoxysilane was slowly dropped under the cooling condition of water bath, and the reaction was continued for 1.0 hour after the dropping to obtain 3-aminopropyltriethoxysilane one end of which was capped with dimethyl maleate.
And (3) mixing the mixture of the polyether amine prepolymer and ethyl acetate with 3-aminopropyltriethoxysilane of which one end is terminated by dimethyl maleate, heating to 50 ℃ for reaction for 1.5 hours, and removing the ethyl acetate by reduced pressure distillation to obtain the silane modified polyurea with the viscosity of 8600MPa & s. The coating film formed from the silane-modified polyurea after curing measured by the above method had a tensile strength of 4.5MPa and an elongation at break of 750%.
Example 3
In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, 22.2 g of isophorone diisocyanate and 80 g of acetone were charged, and nitrogen was introduced. 167 g of Jeffamine T-5000 with functionality of 3 and molecular weight of 5000 was slowly dropped in under the condition of water bath cooling at 10 ℃, and after dropping, stirred at 25 ℃ for 1.0 hour to obtain a mixture containing polyether amine prepolymer and acetone.
In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, 22.8 g of dibutyl maleate was charged, and nitrogen gas was introduced. 22.1 g of 3-aminopropyltriethoxysilane was slowly dropped under cooling in a water bath, and the reaction was continued for 1.0 hour after the dropping to obtain 3-aminopropyltriethoxysilane having one end capped with dibutyl maleate.
And mixing the mixture of the polyether amine prepolymer and acetone with 3-aminopropyltriethoxysilane with one end capped with dibutyl maleate, heating to 40 ℃ for reaction for 2.0 hours, and carrying out reduced pressure distillation to remove the acetone to obtain the silane modified polyurea with the viscosity of 9800MPa & s. The coating film formed from the silane-modified polyurea after curing measured by the above method had a tensile strength of 10.6MPa and an elongation at break of 420%.
Example 4
In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, 26.2 g of dicyclohexylmethane diisocyanate and 50 g of xylene were charged, and nitrogen was introduced. 100g of Jeffamine T-3000 with functionality of 3 and molecular weight of 3000 is slowly dropped in water bath cooling condition at 5 ℃, and stirred for 0.5 hour at 25 ℃ after dropping, thus obtaining a mixture containing polyether amine prepolymer and dimethylbenzene.
17.2 g of diethyl maleate were placed in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, and nitrogen gas was introduced thereinto. 22.1 g of 3-aminopropyltriethoxysilane was slowly dropped in a water bath under cooling, and the reaction was continued for 1.0 hour after the dropping to obtain 3-aminopropyltriethoxysilane one end of which was capped with diethyl maleate.
And mixing the mixture of the polyether amine prepolymer and xylene with 3-aminopropyltriethoxysilane with one end capped with diethyl maleate, heating to 30 ℃ for reaction for 2.0 hours, and removing the xylene through reduced pressure distillation to obtain the silane modified polyurea with the viscosity of 7400MPa & s. The coating film formed from the silane-modified polyurea after curing measured by the above method had a tensile strength of 12.0MPa and an elongation at break of 380%.
Example 5
In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, 13.1 g of dicyclohexylmethane diisocyanate, 11.1 g of isophorone diisocyanate and 50 g of xylene were charged, and nitrogen gas was introduced. 100g of polyether amine Jeffamine D-2000 with functionality of 2 and molecular weight of 2000 is slowly dropped into the mixture under the condition of water bath cooling at 0 ℃, and the mixture containing polyether amine prepolymer and xylene is obtained after the dropping is finished and stirred for 0.5 hour at 25 ℃.
In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, 8.6 g of diethyl maleate and 11.4 g of dibutyl maleate were charged, and nitrogen gas was introduced. 22.1 g of 3-aminopropyltriethoxysilane was slowly dropped under cooling in a water bath, and the reaction was continued for 1.0 hour after the dropping to obtain a mixture of 3-aminopropyltriethoxysilane having one end capped with diethyl maleate and 3-aminopropyltriethoxysilane having one end capped with dibutyl maleate.
And (2) mixing the mixture of the polyether amine prepolymer and the xylene with a mixture of 3-aminopropyltriethoxysilane with one end capped by diethyl maleate and 3-aminopropyltriethoxysilane with one end capped by dibutyl maleate, heating to 50 ℃ for reaction for 1.0 hour, and carrying out reduced pressure distillation to remove the xylene to obtain the silane modified polyurea with the viscosity of 7100MPa & s. The coating film formed from the silane-modified polyurea after curing measured by the above method had a tensile strength of 11.0MPa and an elongation at break of 750%.
Examples 1-5 above demonstrate that when the silane modified polyurea prepared by this process is synthesized into a sealant, the resulting sealant has excellent elongation at break and tensile strength.
The embodiments of the present invention are described only for the preferred embodiments of the present invention, and not for the purpose of limiting the spirit and scope of the present invention, and various modifications and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall within the protection scope of the present invention, and the technical contents of the present invention as claimed are all described in the claims.
Claims (20)
1. A sealant comprising a silane-modified polyurea having a structure represented by the following general formula (1):
wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms; x is a divalent residue obtained after removal of two amine groups from the polyetheramine; y is a divalent residue obtained after removing two isocyanate groups from a polyisocyanate.
2. The sealant of claim 1 wherein R is methyl, ethyl, butyl or phenyl.
3. The sealant of claim 1 wherein the polyetheramine is selected from one or more of polyetheramines having an amine functionality of 2 or 3 and a number average molecular weight of 230 to 5000.
4. The sealant of claim 1 wherein the polyisocyanate is an aliphatic polyisocyanate.
5. The sealant of claim 1 wherein the polyisocyanate is a diisocyanate.
6. The sealant of claim 1 wherein the polyisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate trimer.
7. The sealant of claim 1 wherein the silane-modified polyurea has a number average molecular weight in the range of 1300-6700.
8. A method of preparing a sealant comprising the silane-modified polyurea according to claim 1, the method comprising the steps of:
a) mixing and reacting polyetheramine, polyisocyanate and a solvent to obtain a polyetheramine prepolymer terminated at both ends by the polyisocyanate;
b) reacting equimolar amounts of 3-aminopropyltriethoxysilane with a dicarboxylic ester to obtain 3-aminopropyltriethoxysilane terminated at one end by said dicarboxylic ester; and
c) mixing and heating the polyether amine prepolymer obtained in step a) with the 3-aminopropyltriethoxysilane terminated at one end by the dicarboxylate obtained in step b) to obtain the silane-modified polyurea.
9. The method of preparing a sealant comprising a silane-modified polyurea according to claim 8, wherein the polyetheramine is selected from one or more polyetheramines having an amine functionality of 2 or 3 and a number average molecular weight of 230 to 5000.
10. The method of preparing a sealant comprising a silane-modified polyurea according to claim 8, wherein the polyisocyanate is an aliphatic polyisocyanate.
11. The method of preparing a sealant comprising a silane-modified polyurea according to claim 8, wherein the polyisocyanate is a diisocyanate.
12. The method of preparing a sealant comprising a silane-modified polyurea according to claim 8, wherein the polyisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate trimer.
13. The method of preparing a sealant comprising a silane-modified polyurea according to claim 8, wherein the silane-modified polyurea has a number average molecular weight in the range of 1300-6700.
14. The method of preparing a sealant comprising a silane-modified polyurea according to claim 8, wherein R is methyl, ethyl, butyl, or phenyl.
15. The method of claim 8, wherein the dicarboxylic acid ester is selected from one or more of dimethyl maleate, diethyl maleate, dibutyl maleate, and diphenyl maleate.
16. The method of preparing a sealant comprising a silane-modified polyurea according to claim 8, wherein the solvent is selected from one or more of ethyl acetate, acetone, xylene, and ethylene glycol dimethyl ether.
17. The method of preparing a sealant comprising a silane-modified polyurea of claim 8 wherein in step a) the ratio of the number of moles of the polyisocyanate to the number of moles of the polyetheramine is from 1.0 to 1.1.
18. The method of preparing a sealant comprising a silane-modified polyurea of claim 8 wherein in step a) the ratio of the weight of the solvent to the weight of the polyetheramine is from 0.1 to 1.0.
19. The method of preparing a sealant comprising silane-modified polyurea of claim 8 wherein in step c) the ratio of the number of moles of polyether amine prepolymer employed to the number of moles of 3-aminopropyltriethoxysilane terminated at one end by said dicarboxylate is from 0.9 to 1.
20. The method of preparing a sealant comprising a silane-modified polyurea according to claim 8, wherein the silane-modified polyurea is prepared by a method comprising:
a) slowly dripping polyether amine into a mixture of polyisocyanate and a solvent at the temperature of 0-10 ℃, and reacting at normal temperature for 0.5-1.0 hour after dripping to obtain a polyether amine prepolymer with two ends capped by the polyisocyanate;
b) dripping 3-aminopropyltriethoxysilane into equimolar dicarboxylic ester at 0-10 ℃ for reaction, and continuing the reaction for 0.5-1.0 hour after dripping to obtain 3-aminopropyltriethoxysilane of which one end is capped by the dicarboxylic ester; and
c) mixing the polyether amine prepolymer obtained in step a) with the 3-aminopropyltriethoxysilane terminated at one end by the dicarboxylic ester obtained in step b) and heating to 30 to 50 ℃ for 0.5 to 2.0 hours, followed by removing the solvent by distillation under reduced pressure to obtain the silane-modified polyurea.
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| US20090030161A1 (en) * | 2007-07-27 | 2009-01-29 | Bayer Materialscience Llc | Allophanate modified diphenylmethane diisocyanates, prepolymers thereof, and their use in the preparation of polyureas and polyurethanes |
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