CN114276508A - Preparation method of organic silicon modified polyurea - Google Patents
Preparation method of organic silicon modified polyurea Download PDFInfo
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Abstract
The invention discloses an organic silicon modified polyurea material and a preparation method thereof, belonging to the technical field of high polymer materials. The method specifically comprises the following steps: firstly, adopting disiloxane coupling agent as a chain extender, carrying out block copolymerization with hydroxyl silicone oil, and introducing amino; and then, carrying out prepolymerization reaction on an isocyanate monomer and polyaspartic acid ester to obtain an isocyanate-terminated prepolymer, adding modified hydroxyl silicone oil, and reacting amino and isocyanate groups to obtain the organic silicon-polyurea composite material. The invention provides a brand new preparation method of organic silicon modified polyurea, and the prepared organic silicon-polyurea composite material effectively improves the adhesive force to base surfaces such as cement mortar, concrete and the like, and prolongs the service life of the organic silicon-polyurea composite material.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a preparation method of organic silicon modified polyurea.
Background
The special microstructure of the polyurea molecules endows the polyurea material with a plurality of excellent performances, and compared with other polymer materials, the polyurea material has the characteristics of aging resistance, corrosion resistance, abrasion resistance, high temperature resistance, radiation resistance and the like, and also has higher strength, good elongation at break and thermal stability, and can be used for a long time in a severe environment; however, polyurea also has some disadvantages, and the application of polyurea is always restricted by the problems of general water resistance, low adhesion to base materials and the like.
In order to improve the water resistance and the surface hydrophobicity of a coating film of a polyurea material, researchers often modify the polyurea material by using hydroxyl silicone oil (PDMS) with excellent water resistance, heat resistance and chemical resistance, but the modified polyurea has good water resistance but poor mechanical properties, or has good mechanical properties but poor water resistance, and in order to make the advantages of the modified polyurea and the polyurea complementary, the modified polyurea is often modified by crosslinking to form a polysiloxane-polyurea copolymer, so that the performance of the polyurea material is improved, and the application range of the polysiloxane and the polyurea material is expanded.
Chinese patent CN107298930A discloses an organosilicon-polyurea self-layering coating and a use method thereof, wherein the application number is 201611115377.7, the application date is 2016.12.07, the preparation method of the organosilicon-polyurea self-layering coating comprises two parts, namely organosilicon modified polyurethane curing agent component preparation and silicon-containing resin component preparation, when in use, the organosilicon modified polyurethane curing agent component and the silicon-containing resin component are prepared into a coating according to the mass ratio of 2:1, the coating is uniformly coated on an as-cast finish concrete base surface or a treated as-cast finish concrete base surface, a gradual transition layer is formed in the coating curing process by using the organosilicon resin component and a polyurea base material, a polyurea chain segment is gathered on a membrane inner layer, and an organosilicon-polyurea chain segment is gathered on a membrane outer layer, so that the organosilicon-polyurea self-layering protective coating with excellent base layer bonding force and comprehensive weather resistance is obtained; although silicone-polyurea materials are disclosed in the prior art, they have poor adhesion, resulting in easy release.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of organic silicon modified polyurea; the invention provides a brand new preparation method of organic silicon modified polyurea, and the prepared organic silicon-polyurea composite material effectively improves the adhesive force of the organic silicon-polyurea composite material to base surfaces such as cement mortar, concrete and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, firstly polymerizing hydroxyl silicone oil and NaOH at 80 ℃, then adding a coupling agent for modification, adjusting the pH value to be neutral after the reaction is finished, then heating to the temperature of 100 ℃ and 110 ℃, heating for 30min, and cooling to the room temperature to obtain modified hydroxyl silicone oil;
(2) preparation of the silicone-polyurea composite material:
pre-polymerizing polyaspartic acid ester and an isocyanate monomer for 10min to obtain a prepolymer, adding the modified hydroxyl silicone oil obtained in the step (1), uniformly stirring, continuously reacting for 10min, adding an isocyanate curing agent, and continuously stirring for 0.5-2min to obtain an organic silicon-polyurea composite material;
wherein, the mol ratio of NCO in the isocyanate monomer to NH in the polyaspartic acid ester is 0.1-0.3; the molar ratio of NCO of the isocyanate curing agent to NH in the prepolymer is 1.05-1.15.
Preferably, the molar ratio of NCO in the isocyanate monomer of the step (2) to NH in the polyaspartic ester is 0.1; the molar ratio of NCO in the isocyanate curing agent to NH in the prepolymer was 1.05.
Preferably, the polymerization reaction time in the step (1) is 0-60min, and the modification reaction time is 0-2 h.
Preferably, the polymerization reaction time in the step (1) is 5-30min, and the modification reaction time is 0.5-1 h.
Preferably, in the step (1), the mass ratio of the hydroxyl silicone oil to the coupling agent is 30-60: 1, the mass ratio of NaOH to hydroxyl silicone oil is 0.017-0.3: 100.
preferably, the mass ratio of the hydroxyl silicone oil to the coupling agent in the step (1) is 30: 1, the mass ratio of NaOH to hydroxyl silicone oil is 0.033-0.067: 100.
preferably, the coupling agent of step (1) is selected from gamma-aminopropylmethyldiethoxysilane or N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
Preferably, the mass ratio of the modified hydroxyl silicone oil to the polyaspartic acid ester in the step (2) is 5-40: 100.
preferably, the mass ratio of the modified hydroxyl silicone oil to the polyaspartic acid ester in the step (2) is 5-20: 100.
preferably, the isocyanate monomer in step (2) is selected from hexamethylene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate; the isocyanate curing agent is selected from HDI tripolymer HT-100 or N3390; the polyaspartic acid ester is selected from one of F420, NH1420, F524, XP7068, F520 and NH 1520.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a brand-new preparation method of organic silicon modified polyurea, which comprises the following steps: firstly, adopting disiloxane coupling agent as a chain extender, carrying out block copolymerization with hydroxyl silicone oil, and introducing amino; and then, carrying out prepolymerization reaction on an isocyanate monomer and polyaspartic acid ester to obtain an isocyanate-terminated prepolymer, then adding modified hydroxyl silicone oil, and reacting amino and isocyanate groups to obtain the organic silicon-polyurea composite material.
2. Compared with the preparation method in the prior art, the preparation method disclosed by the application does not need a solvent and only needs NaOH as a catalyst, so that the cost is greatly improved compared with the prior art; in addition, in the application, the molar ratio of NCO in an isocyanate monomer to NH in polyaspartic ester is 0.1-0.3, and the preparation method of the application has no solvent, so that if the ratio is too high, the viscosity of a prepolymerization system is increased, and the subsequent organic silicon modification cannot be carried out.
3. Compared with the organic silicon-polyurea composite material disclosed by the prior art, the organic silicon-polyurea composite material prepared by the invention has more excellent mechanical property, the adhesive force to a concrete base surface is effectively improved to a certain extent after the organic silicon-polyurea composite material is applied to concrete, the adhesive force of the organic silicon-polyurea composite material disclosed by the prior art is about 2.0Mpa, the adhesive force of the organic silicon-polyurea composite material disclosed by the prior art is about 4.0Mpa, and the tensile strength can reach more than 20 Mpa; it can be seen that the differences in the preparation methods lead to the differences in the properties of the same material, and the properties of the silicone-polyurea composite material prepared by the method are significantly superior to those of the prior art.
Drawings
FIG. 1 is a graph showing the mechanical properties of organosilicon-polyurea composites of examples 1-4 of the invention after standing for 7 days at different reaction times for coupling agents;
FIG. 2 is a graph of the mechanical properties of silicone-polyurea composites of different NaOH quality in examples 5-10 of the invention after standing for 7 days;
FIG. 3 is the mechanical properties of the silicone-polyurea composite material with different polymerization times of the hydroxyl silicone oil in examples 11-16 of the present invention after being left for 7 days;
FIG. 4 is the mechanical properties of silicone-polyurea composites of different hydroxyl silicone oil contents in examples 2, 10, and 17-21 of the present invention after standing for 7 days;
FIG. 5 is a graph showing the water absorption rate of silicone-polyurea composites with different hydroxy silicone oil contents in examples 2, 10 and 17 to 21 of the present invention.
Detailed Description
The following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental methods described in the examples of the present invention are all conventional methods unless otherwise specified.
Reagents for experiments: polyaspartic acid ester F420, Shenzhen flying Jun research New materials GmbH; isocyanate curing agent HDI trimer (HT-100), Hexamethylene Diisocyanate (HDI), Vanhua chemical group Co., Ltd; gamma-aminopropylmethyldiethoxysilane (KH902), Shenzhen, Excellent Changhao science and technology Limited; hydroxyl silicone oil (PDMS, viscosity 30 mPas), Shenzhen, Excellent Changhao science and technology Limited; alpha, omega-dihydroxy polysiloxane (107 silicone rubber, viscosity 1000 mPas), Shenzhen, Jipeng, silicofluoride materials, Inc.; hydroxyl silicone oil (PDMS, viscosity 1000 mPas), Shenzhen Shenpeng silicon fluoride materials Limited; sodium hydroxide, Shanghai Michelin Biochemical technology, Inc.
The experimental instrument: a digital display constant temperature magnetic stirrer (85-2A), a Town Xinrui instrument factory of gold Tan city; a full-automatic digital display tension method adhesion tester (BGD 500/S), Dage precision instruments (Guangzhou) Inc.; universal tensile tester (UTM5305), shenzhen mitsui longitudinal and transverse science and technology ltd.
The prepolymerization R values in the embodiment of the invention are all as follows: the molar ratio of NCO in the isocyanate monomer to NH in the polyaspartic acid ester is 0.1-0.3.
Example 1
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.09g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 0min (wherein 0min means that acetic acid is added for neutralization immediately after the coupling agent KH902 is added), finally adding acetic acid for neutralizing NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 10% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 2
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.09g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 10% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 3
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.09g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 60min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 10% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 4
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.09g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 120min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 10% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 5
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.005g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 20% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 6
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.01g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 20% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 7
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.02g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 20% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 8
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.05g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 20% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 9
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.07g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 20% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 10
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.09g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 20% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 11
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.02g of NaOH into a round-bottom flask, reacting for 0min at 80 ℃, then adding 1g of coupling agent KH902, reacting for 30min, (wherein the 0min means that after the hydroxyl silicone oil is heated to 80 ℃, NaOH is immediately added, then the coupling agent KH902 is immediately added), finally adding acetic acid to neutralize the NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 20% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 12
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.02g of NaOH into a round-bottom flask, reacting at 80 ℃ for 10min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 20% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 13
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.02g of NaOH into a round-bottom flask, reacting at 80 ℃ for 20min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 20% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 14
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.02g of NaOH into a round-bottom flask, reacting at 80 ℃ for 40min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 20% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 15
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.02g of NaOH into a round-bottom flask, reacting for 50min at 80 ℃, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain hydroxyl silicone oil modified liquid for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 20% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 16
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.02g of NaOH into a round-bottom flask, reacting at 80 ℃ for 60min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 20% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 17
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.09g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 5% (based on the mass of the F420) of hydroxy silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 18
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.09g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI) for prepolymerization for 10min, then adding 15% (based on the mass of the F420) of the hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 19
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.09g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI) for prepolymerization for 10min, then adding 25% (based on the mass of the F420) of the hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 20
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.09g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI), pre-polymerizing for 10min, then adding 30% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 21
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 30g of hydroxyl silicone oil and 0.09g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 110 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 0.9152g of Hexamethylene Diisocyanate (HDI) for prepolymerization for 10min, then adding 40% (based on the mass of the F420) of hydroxy silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 15g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 22
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, adding 50g of hydroxyl silicone oil and 0.0085g of NaOH into a round-bottom flask, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 105 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 1.8303g of Hexamethylene Diisocyanate (HDI) for prepolymerization for 10min, then adding 40% (based on the mass of the F420) of hydroxy silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 17.74g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Example 23
A preparation method of organic silicon modified polyurea comprises the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
adding 60g of hydroxyl silicone oil and 0.04g of NaOH into a round-bottom flask under a vacuum condition, reacting at 80 ℃ for 30min, then adding 1g of coupling agent KH902, reacting for 30min, finally adding acetic acid to neutralize NaOH to neutrality, heating to 100 ℃, stopping heating after 30min, and cooling to room temperature to obtain a hydroxyl silicone oil modified solution for later use;
(2) preparation of the silicone-polyurea composite material:
adding 30g of polyaspartic acid ester (F420) into a beaker, adding 1.8303g of Hexamethylene Diisocyanate (HDI) for prepolymerization for 10min, then adding 40% (based on the mass of the F420) of hydroxyl silicone oil modified solution, stirring uniformly, continuing to react for 10min, then adding 16.69g of isocyanate curing agent HDI trimer (HT-100), quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the organic silicon-polyurea composite material.
Comparative example 1
The same experiment parameters as in the step (2) of the example are obtained, except that the hydroxy silicone oil modifier is not added.
Comparative example 2
The experimental procedure and experimental parameters were the same as those of example 11 except that the hydroxy silicone oil was changed to 107 silicone rubber.
Comparative example 3
The experimental procedure and experimental parameters were the same as those of example 11 except that the hydroxy silicone oil was changed to a high hydrogen-containing silicone oil.
Comparative example 4
The experimental procedure and experimental parameters were the same as those of example 11 except that the hydroxy silicone oil (30 mPas) was changed to the hydroxy silicone oil (1000 mPas).
Testing and characterization
(1) And testing tensile strength and elongation at break. According to GB/T528-050mm, width d of test portion010mm and 4mm in depth), testing by using an electronic universal tensile testing machine UTM5305, setting the loading speed to be 50mm/min, testing 3 sample bars of the same sample, and taking the time for calculationAverage of 3 sample data. The calculation formula is as follows:
①
②
(2) and (3) testing water resistance: before testing, the dry polyurea tensile bars were weighed to mass m0(ii) a Soaking the sample strip in deionized water for 7 days, taking out the sample strip, immediately wiping off the water on the surface by using dry filter paper, and weighing the mass m of the sample strip1The water absorption of the sample was calculated as follows:
(3) and (3) testing the adhesive force performance: according to GB/T5210-2006, an adhesion tester adopting a full-automatic digital display pull-open method is adopted for testing.
Results and discussion
1. Influence of the reaction time of the coupling agent on the mechanical properties of the organic silicon-polyurea composite material:
the mechanical properties of the composite material of the coupling agent in different reaction times are shown in figure 1 and table 1, and it can be seen from figure 1 and table 1 that the tensile strength of the composite material is reduced in sequence along with the increase of the reaction time; although the tensile strength of the composite material is highest when the reaction time is 0h, the coupling agent is not grafted to the hydroxyl silicone oil at the moment, and the aim of modification is not achieved; when the reaction time is 0.5h and 1h, the modification effect of the composite material is almost the same, so that the reaction time is selected to be 0.5h in consideration of saving time and cost on the premise of achieving the modification purpose.
TABLE 1 mechanical Properties data sheet of composite materials with different reaction times of coupling agent
2. Influence of the content of catalyst NaOH on the mechanical property of the organic silicon-polyurea composite material:
in order to investigate the influence of the NaOH content on the mechanical properties of the silicone-polyurea composite material. The polymerization time of the fixed hydroxyl silicone oil is 30min, 6g of the modified hydroxyl silicone oil in the composite material is taken, and the influence of the NaOH content on the mechanical property of the organic silicon-polyurea composite material is shown in figure 2 and table 2. It can be seen from the graph that as the mass of NaOH increases, the tensile strength of the composite increases and then decreases and then approaches no change. The reason is that when the NaOH has low mass, the reaction speed of the hydroxyl silicone oil is slow, the chain length of the modified hydroxyl silicone oil is short in the same modification time, and then the modified hydroxyl silicone oil is compounded with polyurea to generate more oligomers, so that the crosslinking degree of the composite material is reduced, and the mechanical property of the composite material is further reduced. On the other hand, the quality of NaOH cannot be too high, and the mechanical property of the composite material is also reduced. Therefore, the mass of NaOH in the modification process is preferably 0.02 g.
TABLE 2 mechanical property data table of composite materials with different NaOH qualities
3. Influence of the polymerization time of the hydroxyl silicone oil on the mechanical properties of the organic silicon-polyurea composite material:
the effect of the polymerization time of the hydroxyl silicone oil on the mechanical properties of the silicone-polyurea composite is shown in fig. 3 and table 3. It can be seen from the graph that the tensile strength of the composite increases and then decreases as the polymerization time increases.
TABLE 3 mechanical property data table of composite material of hydroxy silicone oil with different polymerization time
| Polymerization time (min) | Tensile Strength (MPa) | Elongation at Break (%) | Examples |
| 0 | 34.685 | 18.4 | Example 11 |
| 10 | 37.614 | 20.13 | Example 12 |
| 20 | 34.11 | 18.9 | Example 13 |
| 30 | 33.486 | 17.61 | Example 7 |
| 40 | 33.017 | 21.4 | Example 14 |
| 50 | 28.418 | 17.63 | Example 15 |
| 60 | 26.417 | 15.97 | Example 16 |
4. Influence of the content of hydroxyl silicone oil on the silicone-polyurea composite:
4.1 mechanical Properties
According to different mass ratios of the organic silicon resin hydroxyl silicone oil and the polyaspartic ester F420, the content of the hydroxyl silicone oil is changed, the hydroxyl silicone oil and the polyurea are compounded respectively, and the mechanical properties of the hydroxyl silicone oil and the polyurea are measured, and the results are shown in a table 4 and a figure 4. As can be seen from the graph, as the silicone resin content increases, the tensile strength of the composite material tends to decrease, and there are two possible reasons for this phenomenon. (1) The compatibility of the hydroxyl silicone oil and the hard segment in the polyurethane/polyurea is poor, when the content of the hydroxyl silicone oil is higher, the mechanical property of the composite material is reduced, and (2) the acting force between Si-O chain segments does not have van der Waals force with large hydrogen bonds, so that the intermolecular acting force of the modified polyurea is reduced, and the tensile strength is reduced. Therefore, the content of the hydroxyl silicone oil should be controlled to be about 20 percent.
TABLE 4 mechanical property data table of composite material with different hydroxy silicone oil contents
4.2 adhesion Properties
In order to investigate the influence of the hydroxyl silicone oil on the adhesive force performance of the composite material, the content of the hydroxyl silicone oil was changed according to different mass ratios of the organic silicon resin hydroxyl silicone oil and the polyaspartic ester F420, the hydroxyl silicone oil was respectively compounded with polyurea, and the adhesive force performance of the polyurea and the cement mortar was measured, and the results are shown in Table 5. It can be seen that the adhesive force of the composite material added with the hydroxyl silicone oil and the cement mortar is superior to that of the pure polyurea material and the cement mortar.
TABLE 5 adhesion performance data table of composite material with different hydroxy silicone oil contents and cement mortar
| Hydroxyl silicone oil content (in F420 mass fraction (%)) | Cement mortar adhesion (MPa) | Examples |
| 0 | 3.57 | Comparative example 1 |
| 5(1.5g) | 4.05 | Example 17 |
| 10(3.0g) | 4.42 | Example 2 |
| 15(4.5g) | 4.20 | Example 18 |
| 20(6.0g) | 4.68 | Example 10 |
| 25(7.5g) | 3.95 | Example 19 |
| 30(9.0g) | 4.71 | Example 20 |
| 40(12g) | 4.87 | Example 21 |
4.3 Water resistance
In order to investigate the influence of the content of the hydroxyl silicone oil on the water resistance of the composite material, the composite materials with different contents of the hydroxyl silicone oil were soaked in water, and the water absorption of the composite materials was measured after 7 t. FIG. 5 is a graph of water absorption of composites with different hydroxy silicone oil content. As can be seen from FIG. 5, the water absorption of the composite material is in a downward trend as the mass fraction of the hydroxyl silicone oil is increased. The reason is that in the molecular chain of the polyurea modified by the hydroxyl silicone oil, the interaction force between polysiloxane and water is weak, the hydrophobicity of the composite material is increased, the process of water molecules entering the composite material is slowed, and the resin is difficult to associate with the water molecules, so that the water absorption of the composite material is reduced.
5. Influence of organosilicon species on mechanical properties of organosilicon-polyurea composites:
in order to investigate the influence of the types of organic silicon on the mechanical properties of the composite material, four different organic silicon resins were selected to be compounded with polyurea respectively and the mechanical properties were measured, and the results are shown in table 6. As can be seen from the table, the mechanical property of the high hydrogen-containing silicone oil-polyurea composite material is poor, and the performance of the composite material obtained by modifying 107 silica gel is optimal.
Table 6 mechanical property data table of different organosilicon composite materials
| Organosilicon type | Tensile Strength (MPa) | Elongation at break | Examples |
| Hydroxy silicone oil (30 mPa. s) | 34.685 | 20.078 | Example 11 |
| 107 silicon rubber | 36.758 | 21.112 | Comparative example 2 |
| High hydrogen-containing silicone oil | 25.3581 | 17.499 | Comparative example 3 |
| Hydroxy silicone oil (1000 mPa. s) | 36.176 | 20.766 | Comparative example 4 |
According to the invention, hydroxyl silicone oil, hexamethylene diisocyanate, polyaspartic acid ester F420 and HDI tripolymer are used as raw materials, the preparation conditions of modified hydroxyl silicone oil such as different polymerization time of the hydroxyl silicone oil, the quality of a catalyst NaOH, the reaction time of adding a coupling agent and the like are explored, and a series of organic silicon-polyurea composite materials with different hydroxyl silicone oil contents are prepared.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A preparation method of organic silicon modified polyurea is characterized by comprising the following steps:
(1) preparation of amino coupling agent modified hydroxyl silicone oil:
under the vacuum condition, firstly polymerizing hydroxyl silicone oil and NaOH at 80 ℃, then adding a coupling agent for modification, adjusting the pH value to be neutral after the reaction is finished, then heating to the temperature of 100 ℃ and 110 ℃, heating for 30min, and cooling to the room temperature to obtain modified hydroxyl silicone oil;
(2) preparation of the silicone-polyurea composite material:
pre-polymerizing polyaspartic acid ester and an isocyanate monomer for 10min to obtain a prepolymer, adding the modified hydroxyl silicone oil obtained in the step (1), uniformly stirring, continuously reacting for 10min, adding an isocyanate curing agent, and continuously stirring for 0.5-2min to obtain an organic silicon-polyurea composite material;
wherein, the mol ratio of NCO in the isocyanate monomer to NH in the polyaspartic acid ester is 0.1-0.3; the molar ratio of NCO of the isocyanate curing agent to NH in the prepolymer is 1.05-1.15.
2. The method for preparing organosilicon-modified polyurea according to claim 1, wherein in step (2), the molar ratio of NCO in the isocyanate monomer and NH in the polyaspartate is 0.1; the molar ratio of NCO in the isocyanate curing agent to NH in the prepolymer was 1.05.
3. The method for preparing organosilicon modified polyurea according to claim 1, wherein the polymerization time in step (1) is 0-60min, and the modification time is 0-2 h.
4. The method for preparing organosilicon modified polyurea according to claim 3, wherein in step (1), the polymerization reaction time is 5-30min, and the modification reaction time is 0.5-1 h.
5. The method for preparing the organosilicon-modified polyurea according to claim 1, wherein in the step (1), the mass ratio of the hydroxyl silicone oil to the coupling agent is 30-60: 1, the mass ratio of NaOH to hydroxyl silicone oil is 0.017-0.3: 100.
6. the method for preparing the organosilicon modified polyurea of claim 5, wherein the mass ratio of the hydroxyl silicone oil to the coupling agent in the step (1) is 30: 1, the mass ratio of NaOH to hydroxyl silicone oil is 0.033-0.067: 100.
7. the method for preparing organosilicon modified polyurea according to claim 1, wherein the coupling agent in step (1) is selected from γ -aminopropylmethyldiethoxysilane or N- (β aminoethyl) - γ -aminopropylmethyldimethoxysilane.
8. The method for preparing the organosilicon modified polyurea according to claim 1, wherein the mass ratio of the modified hydroxyl silicone oil to the polyaspartic acid ester in the step (2) is 5-40: 100.
9. the method for preparing the organosilicon modified polyurea of claim 8, wherein the mass ratio of the modified hydroxyl silicone oil to the polyaspartic acid ester in the step (2) is 5-20: 100.
10. the method for preparing organosilicon modified polyurea according to claim 1, wherein in step (2), the isocyanate monomer is selected from hexamethylene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate; the isocyanate curing agent is selected from HDI tripolymer HT-100 or N3390; the polyaspartic acid ester is selected from one of F420, NH1420, F524, XP7068, F520 and NH 1520.
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