CN114957798A - Modified NaA molecular sieve and application thereof in polyurethane synthesis - Google Patents
Modified NaA molecular sieve and application thereof in polyurethane synthesis Download PDFInfo
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- CN114957798A CN114957798A CN202210620192.0A CN202210620192A CN114957798A CN 114957798 A CN114957798 A CN 114957798A CN 202210620192 A CN202210620192 A CN 202210620192A CN 114957798 A CN114957798 A CN 114957798A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a modified NaA molecular sieve and application thereof in polyurethane synthesis, wherein the NaA molecular sieve is added into absolute ethyl alcohol, heated and stirred, a silane coupling agent is added for reaction, and after the reaction is finished, the modified NaA molecular sieve is obtained through centrifugation, washing, drying and calcination; the modified NaA molecular sieve keeps the original skeleton structure of the NaA molecular sieve, the appearance is basically unchanged, the original appearance characteristics are kept, the modified NaA molecular sieve and polyurethane have good affinity and good dispersibility, the high water absorption capacity is kept, and the service life in a polyurethane system is prolonged.
Description
Technical Field
The invention belongs to the field of inorganic non-metallic materials, and particularly relates to a modified NaA molecular sieve and application thereof in polyurethane synthesis.
Background
Polyurethane materials have attracted extensive attention and developed for a long time due to their excellent properties and rapid and convenient molding processes. In recent years, with the general popularization of vehicles such as automobiles and trains, the demand of polyurethane foam materials in products such as seats and sun visors is increasing, and the polyurethane foam materials are widely applied to the furniture industry due to the advantages of good comfort, adjustable density in a certain range and the like. Meanwhile, polyurethane is also widely used for preparing products such as sealing glue, cross-linking agent, coating and the like. The basic polyurethane synthesis reaction is a reaction between polyamine, hydroxyl-terminated polyol and isocyanate, and the isocyanate is very active and is easy to react with trace moisture in the polyol and other components to generate carbon dioxide, so that the phenomena of pinholes, bubbles and the like appear on the surfaces of certain cured products. Therefore, in order to ensure the normal use of some polyurethane cured products, we should remove as little moisture as possible from the corresponding systems.
The molecular sieve is composed of TO 4 The three-dimensional four-connection framework formed by sharing vertexes among tetrahedrons is framework type aluminosilicate with a crystalline pore channel structure, is an ideal moisture inhibitor and is often used for eliminating redundant trace moisture in a polyurethane system. The small-particle-size NaA molecular sieve has a higher specific surface area and a regular pore channel structure, so that the small-particle-size NaA molecular sieve has extremely strong water adsorption capacity and can fully remove redundant water in a polyurethane system. Compared with other organic water scavengers, the molecular sieve has ideal environmental protection and economic value. The molecular sieve has high surface activity and is easy to agglomerate, and the molecular sieve is difficult to disperse in an organic medium due to the action of hydroxyl on the surface of the molecular sieve, so that the problems of high viscosity of slurry oil, short product pot life and the like are easily caused, therefore, the conventional molecular sieve is difficult to meet the requirement of developing a polyurethane formula, and the wide application of the molecular sieve in a polyurethane system is hindered.
Generally, the compatibility between organic and inorganic phases can be enhanced by using a coupling agent, a large number of hydroxyl groups on the surface of inorganic powder can perform dehydration condensation reaction with hydrophilic groups of the coupling agent, the surface polarity of the powder is reduced, and the bonding force and the compatibility between organic molecules and the powder are improved. He shuting et al utilizes different coupling agents to silicon dioxide (SiO) 2 ) Surface modification is carried out, and the modified nano SiO 2 The dispersibility is improved, thereby being better applied to polymer materials (He shuting, Liu Bao Chun, nanometer SiO) 2 Surface modification of (1) application chemical engineering, 2017, (4): 693-697). In the invention patent CN201610630647.1, a silane coupling agent is adopted to modify the surface of lignocellulose, and due to the existence of the silane coupling agent, a certain chemical crosslinking reaction can be generated among the components of the lignocellulose, so that the interface compatibility during precipitation is improved, the prepared gel material has a compact structure and rich pores, and the gel strength is greatly improved. The research of using silane coupling agent to modify the surface of NaA molecular sieve and applying the NaA molecular sieve to a polyurethane synthesis system has not been reported at present.
Disclosure of Invention
Aiming at the problems that in the prior art, a polyurethane synthesis system contains trace moisture, a NaA molecular sieve is easy to agglomerate, poor in dispersibility in an organic medium, easy to cause the viscosity of slurry to rise and short in product pot life, the invention provides the modified NaA molecular sieve and the application thereof in polyurethane synthesis.
The invention is realized by the following technical scheme:
a modified NaA molecular sieve is prepared through adding NaA molecular sieve to absolute alcohol, heating while stirring, adding silane as coupling agent, reaction, centrifugal separation, washing, drying and calcining.
Further, the particle size of the NaA molecular sieve is 250-500 nm.
Further, the silane coupling agent is more than one of 3-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
Further, the mass ratio of the NaA molecular sieve to the absolute ethyl alcohol is 1: 3; the adding amount of the silane coupling agent is 1-5% of the mass of the NaA molecular sieve and the absolute ethyl alcohol solution.
Further, the reaction temperature is 30-80 ℃, and the reaction time is 20-80 min.
Further, the calcining temperature is 350 ℃, and the calcining time is 1 h.
In the invention, the modified NaA molecular sieve is applied to polyurethane synthesis; the modified NaA molecular sieve is added in the polyurethane synthesis process, so that the dispersion performance is good, the higher water absorption capacity is kept, and the service life in a polyurethane system is prolonged.
The invention selects the NaA molecular sieve with small grain diameter of 250-500 nm, which has larger pore volume and porosity, short pore channel, small diffusion resistance in crystal, higher specific surface area and regular pore channel structure, so the NaA molecular sieve has strong capability of absorbing water.
The viscosity of the modified NaA molecular sieve prepared by the invention in castor oil can reach 9830 mPa.s, the modified NaA molecular sieve keeps the original skeleton structure of the NaA molecular sieve, the appearance is basically unchanged, the original appearance characteristics are kept, the modified NaA molecular sieve and polyurethane have better affinity and good dispersibility, the water absorption capacity is kept higher, and the service life in a polyurethane system is prolonged.
Advantageous effects
The method for preparing the modified NaA molecular sieve has simple process, not only maintains the higher water absorption capacity of the molecular sieve, but also prolongs the service life of the molecular sieve in a polyurethane system, provides an idea for solving the phenomena of pinholes, bubbles and the like on the surface of some polyurethane cured products, and promotes the wider application of inorganic modified materials.
Drawings
FIG. 1 is an XRD pattern of the modified NaA molecular sieve and NaA molecular sieve prepared in example 5;
FIG. 2 is an SEM photograph of the modified NaA molecular sieve and NaA molecular sieve prepared in example 5;
FIG. 3 is a graph of the pot life viscosity change of the modified NaA molecular sieve prepared in example 5 and the NaA molecular sieve in a polyurethane system.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and the described embodiments are only some embodiments, but not all embodiments, of the present invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative work belong to the protection scope of the present invention.
Example 1
(1) Preparing a modified NaA molecular sieve: adding a NaA molecular sieve with the average particle size of 300nm and absolute ethyl alcohol (the mass ratio of the NaA molecular sieve to the absolute ethyl alcohol is 1: 3) into a four-neck flask, uniformly stirring, placing into a heating jacket at 30 ℃, mechanically stirring while adding a silane coupling agent 3-aminopropyl triethoxysilane (KH-550) with the mass of the NaA molecular sieve and the absolute ethyl alcohol being 1%, reacting for 30min, centrifuging, washing, drying, calcining the product in a 350 ℃ box-type resistance furnace for 1h, and cooling to obtain the modified NaA molecular sieve;
(2) synthesis of a polyurethane prepolymer: weighing 160 g of LEP-330N, adding into a four-mouth bottle, adding TDI while stirring at 80 ℃, and reacting for 6 hours to obtain a prepolymer with the viscosity of 4000 mPa.s; and (2) adding 10 g of the modified NaA molecular sieve prepared in the step (1) into a four-mouth bottle containing 100g of prepolymer, and stirring at 35 ℃ for 192 h.
Example 2
(1) Preparing a modified NaA molecular sieve: adding a NaA molecular sieve with the average particle size of 400nm and absolute ethyl alcohol (the mass ratio of the NaA molecular sieve to the absolute ethyl alcohol is 1: 3) into a four-neck flask, uniformly stirring, placing into a heating jacket at 40 ℃, mechanically stirring while adding a silane coupling agent gamma- (methacryloyloxy) propyl trimethoxy silane (KH-570) with the mass of the NaA molecular sieve and the absolute ethyl alcohol being 1%, reacting for 50min, centrifuging, washing, drying, calcining the product in a 350 ℃ box-type resistance furnace for 1h, and cooling to obtain the modified NaA molecular sieve;
(2) synthesis of a polyurethane prepolymer: weighing 160 g of LEP-330N, adding into a four-mouth bottle, adding TDI while stirring at 80 ℃, and reacting for 6 hours to obtain a prepolymer with the viscosity of 4000 mPa.s; and (2) adding 10 g of the modified NaA molecular sieve prepared in the step (1) into a four-mouth bottle containing 100g of prepolymer, and stirring at 35 ℃ for 192 h.
Example 3
(1) Preparing a modified NaA molecular sieve: adding a NaA molecular sieve with the average particle size of 500nm and absolute ethyl alcohol (the mass ratio of the NaA molecular sieve to the absolute ethyl alcohol is 1: 3) into a four-neck flask, uniformly stirring, placing into a heating jacket at 50 ℃, mechanically stirring while adding a silane coupling agent KH-550 with the mass of the NaA molecular sieve and the absolute ethyl alcohol being 2%, reacting for 20min, centrifuging, washing, drying, placing the product into a 350 ℃ box-type resistance furnace, calcining for 1h, and cooling to obtain the modified NaA molecular sieve;
(2) synthesis of a polyurethane prepolymer: weighing 160 g of LEP-330N, adding into a four-mouth bottle, adding TDI while stirring at 80 ℃, and reacting for 6 hours to obtain a prepolymer with the viscosity of 4000 mPa.s; and (2) adding 10 g of the modified NaA molecular sieve prepared in the step (1) into a four-mouth bottle containing 100g of prepolymer, and stirring at 35 ℃ for 192 h.
Example 4
(1) Preparing a modified NaA molecular sieve: adding a NaA molecular sieve with the average particle size of 250nm and absolute ethyl alcohol (the mass ratio of the NaA molecular sieve to the absolute ethyl alcohol is 1: 3) into a four-neck flask, uniformly stirring, placing into a heating jacket at 30 ℃, mechanically stirring while adding a silane coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH-560) with the mass of the NaA molecular sieve and the absolute ethyl alcohol being 1%, reacting for 40min, centrifuging, washing, drying, calcining the product in a 350 ℃ box-type resistance furnace for 1h, and cooling to obtain the modified NaA molecular sieve;
(2) synthesis of a polyurethane prepolymer: weighing 160 g of LEP-330N, adding into a four-mouth bottle, adding TDI while stirring at 80 ℃, and reacting for 6 hours to obtain a prepolymer with the viscosity of 4000 mPa.s; and (2) adding 10 g of the modified NaA molecular sieve prepared in the step (1) into a four-mouth bottle containing 100g of prepolymer, and stirring at 35 ℃ for 192 h.
Example 5
(1) Preparing a modified NaA molecular sieve: adding a NaA molecular sieve with the average particle size of 250nm and absolute ethyl alcohol (the mass ratio of the NaA molecular sieve to the absolute ethyl alcohol is 1: 3) into a four-neck flask, uniformly stirring, placing into a heating jacket at 70 ℃, mechanically stirring while adding a silane coupling agent KH-560 with the mass of the NaA molecular sieve and the absolute ethyl alcohol being 4%, reacting for 20min, centrifuging, washing, drying, placing the product into a box-type resistance furnace at 350 ℃, calcining for 1h, and cooling to obtain the modified NaA molecular sieve;
(2) the synthesis application of the polyurethane prepolymer comprises the following steps: weighing 160 g of LEP-330N, adding into a four-mouth bottle, adding TDI while stirring at 80 ℃, and reacting for 6 hours to obtain a prepolymer with the viscosity of 4000 mPa.s; and (2) adding 10 g of the modified NaA molecular sieve prepared in the step (1) into a four-mouth bottle containing 100g of prepolymer, and stirring at 35 ℃ for 192 h.
Example 6
(1) Preparing a modified NaA molecular sieve: adding a NaA molecular sieve with the average particle size of 350nm and absolute ethyl alcohol (the mass ratio of the NaA molecular sieve to the absolute ethyl alcohol is 1: 3) into a four-neck flask, uniformly stirring, placing into a heating jacket at 70 ℃, mechanically stirring while adding a silane coupling agent KH-560 with the mass of the NaA molecular sieve and the absolute ethyl alcohol being 3%, reacting for 20min, centrifuging, washing, drying, placing the product into a 350 ℃ box-type resistance furnace, calcining for 1h, and cooling to obtain the modified NaA molecular sieve;
(2) the synthesis application of the polyurethane prepolymer comprises the following steps: weighing 160 g of LEP-330N, adding into a four-mouth bottle, adding TDI while stirring at 80 ℃, and reacting for 6 hours to obtain a prepolymer with the viscosity of 4000 mPa.s; and (2) adding 10 g of the modified NaA molecular sieve prepared in the step (1) into a four-mouth bottle containing 100g of prepolymer, and stirring at 35 ℃ for 192 h.
In example 5 of the present invention, the XRD spectrum of the modified NaA molecular sieve prepared in the step (1) and the raw material NaA molecular sieve thereof are shown in fig. 1, and the SEM photo is shown in fig. 2, which show from fig. 1 and 2 that the NaA molecular sieve before and after modification maintains the original framework structure of the NaA molecular sieve, the morphology is not changed substantially, and the original appearance characteristics are maintained.
And (3) viscosity testing:
(1) 20 g of the modified NaA molecular sieve and 20 g of castor oil were added to a beaker, stirred for 15 min with an electric stirrer to form a slurry, which was put into a viscometer to measure the viscosity, and the viscosity of the slurry consisting of the modified NaA molecular sieve and castor oil prepared in examples 1 to 6 was as shown in the following Table 1:
TABLE 1 viscosity of slurries of modified NaA molecular sieves and Castor oil
(2) The working life of the modified NaA molecular sieve in a polyurethane system is reflected by intermittently testing the viscosity change of the prepolymer. The time consumed when the viscosity of the prepolymer reaches 50000 mPa.s is taken as the pot life of the modified NaA molecular sieve. The pot life of the modified NaA molecular sieve prepared in examples 1-6 in a polyurethane system is shown in Table 2 below, the pot life viscosity change diagram of the modified NaA molecular sieve prepared in example 5 and the raw material NaA molecular sieve thereof in the polyurethane system is shown in FIG. 3, the modified NaA molecular sieve and polyurethane have better affinity and good dispersibility, and not only higher water absorption capacity is maintained, but also the pot life in the polyurethane system is prolonged;
table 2 pot life of modified NaA molecular sieves in polyurethane systems
Claims (8)
1. A modified NaA molecular sieve is characterized by being prepared by the following method, adding a NaA molecular sieve into absolute ethyl alcohol, heating and stirring, adding a silane coupling agent for reaction, and after the reaction is finished, centrifuging, washing, drying and calcining to obtain the modified NaA molecular sieve.
2. The modified NaA molecular sieve of claim 1, wherein the particle size of the NaA molecular sieve is 250-500 nm.
3. The modified NaA molecular sieve of claim 1, wherein the silane coupling agent is at least one of 3-aminopropyltriethoxysilane, γ - (2, 3-glycidoxy) propyltrimethoxysilane, and γ - (methacryloyloxy) propyltrimethoxysilane.
4. The modified NaA molecular sieve of claim 1, wherein the mass ratio of the NaA molecular sieve to the absolute ethyl alcohol is 1: 3; the adding amount of the silane coupling agent is 1-5% of the mass of the NaA molecular sieve and the absolute ethyl alcohol solution.
5. The modified NaA molecular sieve of claim 1, wherein the reaction temperature is 30-80 ℃ and the reaction time is 20-80 min.
6. The modified NaA molecular sieve of claim 1, wherein the calcination temperature is 350 ℃ and the calcination time is 1 h.
7. Use of the modified NaA molecular sieve of any one of claims 1 to 6 in polyurethane synthesis.
8. The use according to claim 7, characterized in that the modified NaA molecular sieve is added during the polyurethane synthesis.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634317A (en) * | 2012-04-28 | 2012-08-15 | 南京理工大学常熟研究院有限公司 | Preparation method of polyurethane/molecular sieve composite adhesive |
| CN103819944A (en) * | 2014-03-03 | 2014-05-28 | 上海绿强新材料有限公司 | Preparation method for molecular sieve reactive powder suitable for polyurethane system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634317A (en) * | 2012-04-28 | 2012-08-15 | 南京理工大学常熟研究院有限公司 | Preparation method of polyurethane/molecular sieve composite adhesive |
| CN103819944A (en) * | 2014-03-03 | 2014-05-28 | 上海绿强新材料有限公司 | Preparation method for molecular sieve reactive powder suitable for polyurethane system |
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