CN110564005B

CN110564005B - Anion additive

Info

Publication number: CN110564005B
Application number: CN201910804170.8A
Authority: CN
Inventors: 丛穆; 张宇璇; 张斌; 郑虹; 任晓珊; 张明远; 滕腾; 周宇飞; 刘宏宇; 任书伯
Original assignee: FAW Group Corp
Current assignee: FAW Group Corp
Priority date: 2019-08-28
Filing date: 2019-08-28
Publication date: 2021-04-09
Anticipated expiration: 2039-08-28
Also published as: CN110564005A

Abstract

The invention discloses an anion additive, which belongs to the technical field of automobile interior materials and is used for being added into a synthetic leather material, because the dispersion and dispersion stability of anion powder directly influence the final quality and various properties of an anion product, the higher the dispersion uniformity, the better the quality property, and meanwhile, the anion additive cannot bring negative influence on the production process. The invention designs and prepares a negative ion additive which is suitable for production systems of polyurethane coatings and polyurethane synthetic leather. The anion additive is a tourmaline @13X molecular sieve with a core-shell structure, the tourmaline in the raw material is powder with the grain diameter of 6-20 microns, the grain diameter of the final product is 8-20 microns, the tourmaline is basically uniformly dispersed in polyurethane,the prepared negative ion polyurethane leather has the advantages that the surface quality is free of defects, the mechanical properties such as breaking strength, breaking elongation and the like are kept unchanged, and the negative ion emission is more than or equal to 3000/cm³。

Description

Anion additive

Technical Field

The invention belongs to the technical field of automotive interior materials.

Background

The anion powder, namely tourmaline powder has the characteristics of a permanent electrode, and can cause potential difference under the condition of slight change of temperature and pressure, so that air is ionized, and free electrons can be attached to gaseous water and oxygen molecules and converted into air anions.

Because the anion has the advantages of purifying air, eliminating peculiar smell and harmful gas in the air, relieving fatigue, promoting metabolism of human body and the like, if the synthetic leather capable of releasing the negative oxygen ions is developed, the anion generating agent is mainly used for narrow closed spaces such as airplanes and the like, is beneficial to improving the environment of the narrow spaces and improves the sense organ experience of drivers and passengers.

Generally, the product with the anion function is prepared by directly preparing anion powder into superfine powder by mechanical force and then adding the superfine powder into production raw materials. This results in that the dispersibility and stability of the tourmaline powder in the high molecular polymer matrix cannot meet the requirements of practical application. The reason is that the surface energy of tourmaline powder is large, the surface activity of ultrafine negative ion powder particles is very high, and single particles cannot exist stably and are often agglomerated by mutual attraction, thereby reducing the surface energy thereof to form a stable state. Furthermore, after agglomeration, the properties of the ultrafine powder are deteriorated, which is not favorable for the performance of the anion powder. In application, the difference between the surface properties of the tourmaline powder and the high molecular polymer is large, so that the tourmaline powder is not easy to uniformly disperse and stably exist in a non-polar polymer, and if the tourmaline powder is directly filled in an organic matter, certain properties of the material are easy to reduce, so that the overall comprehensive performance of the composite material is influenced.

At present, aiming at the development of negative ion functional products, particularly negative ion synthetic leather and other composite materials, tourmaline powder and other materials are basically and completely adopted, and are processed into superfine powder and then directly added into a polyurethane synthesis system so as to obtain a negative ion generating effect. However, this process is currently problematic: the surface energy of the tourmaline powder is large, the surface activity of the ultrafine negative ion powder particles is very high, and single particles cannot exist stably and are often agglomerated by mutual attraction, so that the surface energy of the tourmaline powder is reduced to form a stable state. And after agglomeration, the performance of the ultrafine powder is deteriorated, the performance of the negative ion powder is not reflected, and the product quality problem is easy to occur. In application, the difference between the surface properties of the tourmaline powder and the high molecular polymer is large, so that the tourmaline powder is not easy to uniformly disperse and stably exist in a non-polar polymer, and if the tourmaline powder is directly filled in an organic matter, certain properties of the material are easy to reduce, so that the overall comprehensive performance of the composite material is influenced.

Disclosure of Invention

Because the final quality and various performances of the anion product are directly influenced by the dispersion and dispersion stability of the anion powder, the higher the dispersion uniformity, the better the quality performance, and meanwhile, the anion additive can not bring negative influence on the production process. The invention designs and prepares the anion additive which is suitable for production systems of polyurethane coatings and polyurethane synthetic leather. The anion additive is a tourmaline @13X molecular sieve with a core-shell structure, and the preparation method comprises the following steps:

a) the tourmaline is made into powder A with the grain diameter of 6-20 microns through mechanical shearing;

b) mixing sodium metaaluminate, sodium hydroxide, sodium silicate and water according to the following molar ratio of SiO₂:Al₂O₃＝3～5:1、Na₂O:SiO₂1-1.5: 1 and H₂O:Na₂O is 35-65: 1, and sol B is obtained after uniform mixing;

c) adding the powder A into the sol B, wherein the mass ratio of A to B is 3-5%, continuously stirring uniformly, and standing at room temperature for 3-8 h;

d) placing the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and standing the mixture for 5 to 14 hours at the temperature of 98 +/-2 ℃;

e) washing the product with deionized water, filtering and drying to obtain the tourmaline @13X molecular sieve composite material.

The invention has the beneficial effects that:

the excellent characteristics of the tourmaline @13X molecular sieve composite material as the negative ion additive are derived from the material characteristics: the shell is a 13X molecular sieve framework with negative charges, and micropores can adsorb water molecules and carbon dioxide, so that free electrons generated by tourmaline are transferred to air molecules, and negative ions are more easily formed; meanwhile, the surface of the material contains silicon hydroxyl and aluminum hydroxyl, the material can react with TDI (toluene diisocynate) which is a polyurethane synthesis raw material, after molecular sieve particles are added into polyurethane, the polyurethane is a continuous phase, and the molecular sieve particles are dispersed in the polyurethane to form a sea-island structure. Meanwhile, because the surface charge of the molecular sieve particles is not uniformly distributed, the crystal form of the hard chain segment of the polyurethane is changed to form a small and more hard segment crystal wafer layer which is dispersed in the soft segment, the surface area of the fine crystal is large and is connected with the soft segment by chemical bonds, and the physical crosslinking is increased and the stress distribution is changed. In addition, micropores of the molecular sieve can adsorb carbon dioxide gas and moisture, so that micro-bubble pores in the polyurethane/molecular sieve composite material are reduced, and the performance of the polyurethane/tourmaline @13X molecular sieve composite material is improved.

Therefore, the tourmaline powder disclosed by the invention solves the compatibility problem of tourmaline powder and a polyurethane system, and can be used as a negative ion additive of polyurethane coating and polyurethane synthetic leather.

Drawings

FIG. 1 is an XRD spectrum of a tourmaline @13X molecular sieve composite material;

FIG. 2 is an SEM photograph of tourmaline powder;

FIG. 3 is an SEM photograph of a tourmaline @13X molecular sieve composite material

FIG. 4 is a photograph showing the dispersion of the tourmaline @13X molecular sieve composite material in a PU system,

Detailed Description

Example 1

a) The tourmaline is made into powder A (shown in figure 2) with the grain diameter of 6-20 microns through mechanical shearing;

As shown in figure 1, diffraction peaks of the tourmaline @13X molecular sieve composite material correspond to those of tourmaline and 13X molecular sieve respectively.

As shown in fig. 3, the SEM photograph of the tourmaline @13X molecular sieve composite material is shown, and the particle size of the tourmaline @13X molecular sieve composite material is 8-20 microns. Comparing fig. 2 and fig. 3, it can be seen that a layer of new granular material is attached to the outer surface of the granule, so that the particle size is increased, and thus it can be seen that the product in fig. 3 has a core-shell structure.

Example 2

Adding polyester Polyol (PEA) or polyether Polyol (PTMG) or a mixture of the polyester Polyol (PEA) and the PTMG which are measured according to a certain proportion into a three-necked bottle provided with a stirrer and a thermometer, adding the tourmaline @13X molecular sieve composite material prepared in the example 1 after vacuum drying for 9 hours at 150 ℃, starting a vacuum pump and the stirrer, and dehydrating for 2-3 hours under the conditions that the vacuum degree is 0.09MPa and the temperature is about 120 ℃. Cooling to 40 ℃, adding measured TDI, stirring, slowly heating to 80 ℃, carrying out heat preservation reaction for 2h at 80-85 ℃, standing at room temperature for 4-5 h to enable the TDI to fully react with the TDI, carrying out vacuum defoaming for about 0.5h to prepare a prepolymer, adding measured chain extension crosslinking agent 3,3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA), uniformly stirring, pouring into a preheated mold, vulcanizing at 120 ℃ for 10min on a flat plate vulcanizing machine, demolding, and curing at 100 ℃ for 24 h. The mixture was left at room temperature for 7 days.

The composition metering ratio is as follows:

the stoichiometric ratio of polyol and TDI is calculated according to the ratio of NCO/OH between 1.3 and 1.4; MOCA according to-NH₂The proportion of the added/NCO is 0.9, and the added tourmaline @13X molecular sieve accounts for 3 percent of the mass of the polyurethane.

As can be seen from fig. 4, the tourmaline @13X molecular sieve composite material is dispersed in polyurethane substantially uniformly, and has a small proportion of the individual particles, although the individual particles are agglomerated. The tourmaline @13X molecular sieve composite material has good dispersibility in a polyurethane system.

Example 3

The surface layer sizing agent of the anion polyurethane resin for leather comprises the following components in parts by mass:

aqueous polyurethane resin (kesichu: Bayhydrol a 2601): 100 portions of

Water: 20 to 40 portions of

Water-based ink (BASF: Joncryl 678): 10 to 30 portions of

Anion additive (namely tourmaline @13X molecular sieve composite material): 3-5 parts.

Compounding the negative ion polyurethane resin surface layer slurry onto base cloth by a dry method facing process at the speed of: 8m/min, surface layer thickness100 mu m and the oven temperature is 102 ℃; the prepared negative ion polyurethane leather has the advantages that the surface quality is free of defects, the mechanical properties such as breaking strength, breaking elongation and the like are kept unchanged (shown in the table below), and the negative ion emission is more than or equal to 3000/cm³。

Claims

1. The anion additive is characterized in that the anion additive is a tourmaline @13X molecular sieve with a core-shell structure, the shell is a 13X molecular sieve, the tourmaline is 6-20 microns powder, and the tourmaline @13X molecular sieve is 8-20 microns granular powder.

2. The method for preparing the anion additive according to claim 1, which comprises the following steps:

b) mixing sodium metaaluminate, sodium hydroxide, sodium silicate and water according to the following molar ratio of SiO₂:Al₂O₃=3~5:1、Na₂O:SiO₂= 1-1.5: 1 and H₂O:Na₂O = 35-65: 1, and sol B is obtained after uniform mixing;

c) adding the powder A into the sol B, wherein the mass ratio of A to B = 3-5%, continuously stirring uniformly, and standing at room temperature for 3-8 h;