CN110819033A - A kind of nanometer polymer material and preparation method thereof - Google Patents

Abstract

The invention discloses a nano-polymer material and a preparation method thereof, belonging to the technical field of materials. The raw materials of the material, in parts by weight, include the following components: 40-55 parts of polyvinyl chloride resin and 10-20 parts of acrylic hydroxyl resin , 5-8 parts of nano aluminum hydroxide, 1-2 parts of micron magnesium hydroxide, 7-12 parts of modified carbon nanotubes, 3-5 parts of chlorinated paraffin, 2-4 parts of tetrapropylene titanate, phthalate 5-6 parts of dioctyl formate, 9-11 parts of tris(2-chloroethyl) phosphate, 1-2 parts of antimony trioxide, 3-5 parts of zinc water borate, 8-13 parts of modified polyether, 1-3 parts of coupling agent; the material is non-absorbent, non-flammable, wear-resistant, simple in process, good in dimensional stability, good in compression creep resistance, suitable for mechanized production lines, low in price, with an oxygen index of 54.7% and a smoke density of 33.52 , has excellent fire resistance and has broad application prospects.

Description

A kind of nanometer polymer material and preparation method thereof

technical field

The invention relates to the technical field of materials, in particular to a nano-polymer material and a preparation method thereof.

Background technique

The polymer material is the abbreviation of the material based on the polymer compound. Polymer materials are materials composed of compounds with relatively high molecular weight, including rubber, plastic and polymer matrix composite materials. Polymer materials are divided into natural, semi-synthetic (modified natural polymer materials) and synthetic polymer materials according to their sources. Polymer materials are divided into ordinary polymer materials and functional polymer materials according to their uses. In addition to the general mechanical functions, insulating properties and thermal properties of polymers, functional polymer materials also have special functions such as the conversion, transmission and storage of matter, energy and information. At present, there are polymer information conversion materials, polymer transparent materials, biodegradable polymer materials, polymer shape memory materials, and medical and pharmaceutical polymer materials. Due to the excellent physical and chemical properties of polymer materials, they have been widely used in the main fields of the national economy such as construction, transportation, agriculture, electrical and electronic industries, and in the fields of daily life such as automobiles, furniture, and home furnishing.

However, because most of the materials are flammable, the fire scene becomes the source of smoke, toxic gas and heat. This not only brings great fire hazards to people's safety and quality of life and property, but also greatly limits the application in special fields with high fire protection requirements (such as public places, commercial places, entertainment, educational places and other personnel-intensive places) venue furniture materials). For example, the fire in the Shijingshan Home Furnishing Mall in Beijing was caused by the spontaneous combustion of furniture materials and the rapid burning of fire, so that a small-scale fire quickly spread into a large-scale fire until it was finally out of control, causing casualties and great economic losses to the people of the country.

Therefore, the problem to be solved urgently for polymer materials at present is the improvement of fire rating.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a nano-polymer material and a preparation method thereof, so as to solve the problems existing in the above-mentioned prior art.

For achieving the above object, the present invention provides the following scheme:

The present invention provides a nano-polymer material, in parts by weight, the raw material includes the following components:

40-55 parts of polyvinyl chloride resin, 10-20 parts of acrylic hydroxyl resin, 5-8 parts of nano aluminum hydroxide, 1-2 parts of micron magnesium hydroxide, 7-12 parts of modified carbon nanotubes, 3-chlorinated paraffin 5 parts, 2-4 parts of tetrapropylene titanate, 5-6 parts of dioctyl phthalate, 9-11 parts of tris(2-chloroethyl) phosphate, 1-2 parts of antimony trioxide, water 3-5 parts of zinc borate, 8-13 parts of modified polyether, 1-3 parts of coupling agent.

As a further improvement of the present invention, the polyvinyl chloride resin is SG-3 type resin; the chlorinated paraffin is chlorinated paraffin-52.

As a further improvement of the present invention, the average particle size of the nano aluminum hydroxide is less than or equal to 100 nm, the initial weight loss temperature is 340-370° C., and the weight loss rate is 48-52%.

As a further improvement of the present invention, the average particle size of the micron magnesium hydroxide is 1-8 μm.

As a further improvement of the present invention, the modified carbon nanotubes are prepared by using the following methods: carbon nanotubes with a mass fraction of 1:0.6-1.2:200-300, acid binding agent and organic solvent ultrasonic treatment, power 350-400W, frequency 40-50kHz, time 1-2h, under the condition of -20-10℃, slowly add phenylphosphonyl dichloride, 4,4'-diaminodiphenylmethane, the carbon nanotubes, phenylphosphine The mass ratio of acid dichloride and 4,4'-diaminodiphenylmethane is 1:1:1.2-2.3, the temperature is raised to 110°C, and the reaction is carried out for 12h.

As a further improvement of the present invention, the acid binding agent is triethylamine or ammonium carbonate; the organic solvent is tetrahydrofuran, toluene, acetone, methanol, ethanol or acetonitrile.

As a further improvement of the present invention, the modified polyether is prepared by the following method: aluminum fluoride, propylene oxide, catalyst, and polytetrafluoroethylene whose mass fractions are 1:0.9:1.3:1.3, respectively, at temperature Under the reaction conditions of 520-600°C, pressure 60-75MPa, and voltage of 1.2-15,000 volts, it can be obtained after 2-4 hours of reaction; preferably, it is obtained under the reaction conditions of temperature of 560°C, pressure of 75MP, and voltage of 15,000 volts, after 3 hours The reaction is obtained.

As a further improvement of the present invention, the reaction for preparing the modified polyether is carried out in a closed reaction vessel, the reaction vessel is filled with a non-oxidizing gas, and the non-oxidizing gas is in a mass ratio of 5:1:1:0.1 of helium, argon, carbon dioxide and carbon monoxide.

As a further improvement of the present invention, the catalyst includes the following components in parts by weight: 0.6-0.8 part of sodium hydrogen silicate, 0.3-0.5 part of methanol, and 0.1-0.2 part of silicone oil.

The present invention also provides a method for preparing the above-mentioned nano-polymer material, comprising the following steps:

(1) Under the condition of 70-85 ℃, mix the nano aluminum hydroxide, micron magnesium hydroxide, antimony trioxide and zinc borate evenly;

(2) Add coupling agent and acrylic hydroxyl resin, stir, add polyvinyl chloride resin, tetrapropylene titanate, tris(2-chloroethyl) phosphate, heat up to 105°C, add modified polyether, mix for 10min ;

(3) adding chlorinated paraffin, dioctyl phthalate, modified carbon nanotubes, stirring for 2min, cooling to 50-60°C, and stirring for 10min;

(4) Putting the material obtained in step (3) into a twin-screw extruder for extrusion to form a strip-shaped nano-polymer material.

The present invention discloses the following technical effects:

The nano-polymer material provided by the invention is non-absorbent, non-flammable, wear-resistant, simple in process, good in dimensional stability, good in compression creep resistance, suitable for mechanized production lines, low in price, has an oxygen index of 54.7%, and a smoke density grade of 33.52. It has excellent fire resistance and has broad application prospects.

The nano-polymer material of the present invention reaches the Class A fire protection standard of GB 50222-95 "The People's Republic of China National Standard Building Interior Decoration Design Fire Protection Code".

Flame retardant mechanism of nano-polymer materials:

Combustion of polymers is a very intense and complex thermal oxidation reaction characterized by thick smoke or fiery flames. The general process of combustion is that under the continuous heating of an external heat source, the polymer first undergoes a free radical chain degradation reaction with oxygen in the air to generate volatile combustibles, which will catch fire and burn when they reach a certain concentration and temperature. Part of the heat released supplies the degrading polymer, further aggravating its degradation, producing more flammable gas, and the flame will spread rapidly in a very short time, causing a large fire.

The combustion of PVC is divided into two steps. First, the hydrogen chloride gas and diolefins containing double bonds are decomposed by combustion at 240℃～340℃, and then carbon combustion occurs at 400～470℃.

In the pyrolysis process of PVC, HCl is first removed at about 240 °C to form a highly conjugated carbon skeleton. After the temperature continues to rise, the thermal degradation process intensifies the removal of HCl from PVC to form polyolefins with conjugated double bonds and further cracking to generate carbon content. High residues, gaseous saturated hydrocarbon mixtures and unsaturated hydrocarbon mixtures. The cracking intensifies at 400-470 °C, and when it reaches a certain concentration, it reacts with oxygen to form an open flame. Therefore, the incomplete combustion of combustible gas will generate aromatic or polymer compounds due to polymerization, and then polycondensate into graphite to generate carbon particles, thereby generating black smoke with a maximum smoke yield of 72%. It can be seen that reducing the concentration of PVC pyrolysis products will not generate a lot of smoke and open flames. The study found that when the concentration of PVC pyrolysis combustible products in the air is lower than 15%, there will be no open flame.

The invention uses zinc water borate to release crystal water at 300°C, and under the action of halogen compounds, generates boron halide and zinc halide, inhibits and captures free hydroxyl groups, and prevents the combustion chain reaction; at the same time, a solid phase covering layer is formed to isolate The surrounding oxygen prevents the flame from continuing to burn and has a smoke suppression effect.

When the chlorinated paraffin-52 is heated above a certain temperature (usually 120°C), it will slowly decompose and release hydrogen chloride gas, so when the polymer is decomposed, the chlorinated paraffin-52 also begins to decompose, and can capture the decomposition of the polymer material. Free radicals, thereby delaying or inhibiting the reaction of the combustion chain, and the released hydrogen chloride itself is a flame-retardant gas, which can cover the surface of the material and play a role in blocking and diluting the oxygen concentration. At the same time, the compound use of chlorinated paraffin-52 and antimony trioxide can significantly improve the flame retardant effect through coordination. In the presence of halides, antimony trioxide reacts with antimony trioxide to generate trichloride during combustion. Antimony oxychloride and antimony oxychloride, antimony oxychloride is decomposed by heat and endothermic to continue to generate antimony trichloride, the relative density of antimony halide such as antimony chloride is very large, covering the surface of the polymer to play a covering effect, and also in the gaseous state. Capture the role of free radicals, and the reaction of antimony oxychloride not only inhibits the formation of open flames, but also reduces the concentration of HCl, a suffocating gas. Moreover, zinc hydroborate and chlorinated paraffin-52 will also react to form zinc dichloride and boron trichloride, which can capture OH and Oxygen, the generated water dilutes the oxygen in the combustion zone and takes away the heat of reaction, thereby exerting an excellent synergistic flame retardant effect.

Tetrapropylene titanate has high activity and can provide rapid cross-linking reaction. Due to the existence of four unsaturated double bonds in its structure, itself or multiple molecules can be connected to form a π-π conjugated system, and due to its conjugation Both ends of the system have the same double bond, the atoms at both ends of the conjugate have the same electronegativity, and the electron delocalization has no directionality, which can promote the SG-3 resin to interact with dioctyl phthalate and tris(2-chloroethyl phosphate) base) ester cross-linking reaction, improve the van der Waals force between SG-3 resin, dioctyl phthalate and tris (2-chloroethyl) phosphate, make its bond energy increase, and at the same time it can interact with The chlorine atom in the SG-3 resin forms a p-π conjugation, which delocalizes the conjugated electron away from the end of the chlorine element with large electronegativity, and the alternating electron-donating conjugation effect of δ ^- and δ ⁺ appears on the conjugated chain , Improve the monomer activity of SG-3 resin, improve the degree of cross-linking, and further improve the strength and wear resistance.

In the process of fire and flame retardant, tetrapropylene titanate will decompose and absorb a lot of heat under the action of crystal water released by zinc water borate, and release titanium hydroxide and propylene ester. When the temperature exceeds 325 ℃, titanium hydroxide will Under the catalysis of zinc, ·OH and ·H are captured in the gas phase, and form a composite structure with the hydroxyl groups rich in the modified carbon nanotubes to form a non-flammable, heat-insulating, oxygen-blocking carbon nanotube-titanium dioxide porous protective layer. Under the catalysis of titanium dioxide, the hydrogen chloride released by propylene ester and SG-3 resin and chlorinated paraffin-52 is replaced by heat and heat absorption, which reduces the concentration of hydrogen chloride and the concentration of pyrolysis products of SG-3 resin, and reduces the amount of smoke and smoke. Generation of open flames.

Carbon nanotubes have good thermal stability due to their stable carbon six-membered ring structure. In the present invention, it is modified. Through π-π stacking, the flame retardant material is coated on the surface of carbon nanotubes to form a core-shell structure. The modified carbon nanotubes are added into nanometer polymer materials, which can be combined with traditional flame retardants. It forms a good synergy, and captures a large number of fluoride ions released by the modified polyether at high temperature to capture the active radicals H ⁺ and OH ^- to generate stable HF, which can effectively reduce the concentration of flammable gas and inhibit the generation of open flames.

Detailed ways

Various exemplary embodiments of the present invention will now be described in detail, which detailed description should not be construed as a limitation of the invention, but rather as a more detailed description of certain aspects, features, and embodiments of the invention.

It should be understood that the terms described in the present invention are only used to describe particular embodiments, and are not used to limit the present invention. Additionally, for numerical ranges in the present disclosure, it should be understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated value or intervening value in that stated range is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention relates. Although only the preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials in connection with which the documents are referred. In the event of conflict with any incorporated document, the content of this specification controls.

It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present invention without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the present invention. The description and examples of the present application are only exemplary.

As used herein, "comprising," "including," "having," "containing," and the like, are open-ended terms, meaning including but not limited to.

The "parts" described in the present invention are all in parts by mass unless otherwise specified.

Example 1

Preparation of modified polyether:

In a closed reaction vessel, an arc generator and a microwave generator are provided in the reaction vessel. After evacuating, fill with helium, argon, carbon dioxide and carbon monoxide in a mass ratio of 5:1:1:0.1, so that the pressure in the container is 75MPa.

The catalyst includes the following components in parts by weight: 0.7 part of sodium hydrogen silicate, 0.4 part of methanol, and 0.2 part of silicone oil.

Aluminum fluoride, propylene oxide, catalyst, and polytetrafluoroethylene with mass fractions of 1:0.9:1.3:1.3, respectively, under the reaction conditions of temperature 560°C, pressure 75MP, voltage 15,000 volts, and microwave frequency 100GHz, passed The reaction was obtained in 3 hours.

Example 2

Preparation of modified carbon nanotubes:

Add carbon nanotubes, ammonium carbonate and ethanol in a mass fraction of 1:1.2:250 into a three-necked flask, and under the action of ultrasound with a power of 380W and a frequency of 45kHz, disperse for 1.5h; adjust the temperature to 1°C, and slowly add phenylphosphonyl Dichloro, 4,4'-diaminodiphenylmethane, the mass ratio of the carbon nanotubes, phenylphosphonyl dichloride and 4,4'-diaminodiphenylmethane is 1:1:1.22, and the temperature is raised to 110°C , react for 12h; filter the reaction mixture with suction, then wash it with ethanol for 3 times, then with deionized water for 3 times, and dry the obtained solid product under vacuum at 90°C to constant weight.

Example 3

Preparation of nano-polymer materials:

Formulation: in parts by mass, as shown in the table below.

Preparation:

(1) Under the condition of 70-85 ℃, mix the nano aluminum hydroxide, micron magnesium hydroxide, antimony trioxide and zinc borate evenly;

(2) Add coupling agent and acrylic hydroxyl resin, stir, add polyvinyl chloride resin, tetrapropylene titanate, tris(2-chloroethyl) phosphate, heat up to 105°C, add modified polyether, mix for 10min ;

(3) adding chlorinated paraffin, dioctyl phthalate, modified carbon nanotubes, stirring for 2min, cooling to 50-60°C, and stirring for 10min;

(4) Putting the material obtained in step (3) into a twin-screw extruder for extrusion to form a strip-shaped nano-polymer material.

Comparative Example 1

The difference from Example 3 is that the equivalent amount of tetrapropylene titanate is replaced by tetrabutyl titanate.

Comparative Example 2

The difference from Example 3 is that the same amount of micro-magnesium hydroxide is replaced by nano-magnesium hydroxide.

Comparative Example 3

At present, the commonly used flame retardant formulations of polymer materials on the market (in parts by mass) are 100 parts of polyvinyl chloride resin, 50 parts of aluminum hydroxide, 6 parts of lead stearate, 10 parts of antimony trioxide, and 6 parts of tribasic lead sulfate. , 2 parts of dibasic lead phosphite, 13 parts of cobalt silicate, 3 parts of nano-hydrotalcite, 0.5 parts of liquid paraffin, 20 parts of calcium carbonate additive flame retardant.

The nano-polymer materials described in the above Examples 3-5 and Comparative Examples 1-3 were pressed into sheets, and their performance was tested. The number of tests was 5 times, and the average value was taken. The results are shown in the following table.

Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Shore Wear (mm³) 83 78 75 76 77 56 Tensile strength (MPa) 20.1 19.7 19.2 19.9 19.2 17.6 Elongation at break (%) 662 572 597 635 618 459 Hardness (SH) 62 63 66 62 62 52 Smoke Density Rating (SDR) 33.52 36.28 35.69 45.35 52.82 70.89 Oxygen Index,% 54.7 52.3 53.7 43.6 42.59 41.26

Through the above tests, the nano-polymer material of the present invention fully complies with the current A-level standards of the People's Republic of China GB 8624-2006 "Classification of Combustion Performance of Building Materials and Products" and the People's Republic of China GB5022--95 "Code for Fire Protection of Interior Decoration Design of Buildings" of the People's Republic of China. A-level requirements.

The above-mentioned embodiments are only to describe the preferred modes of the present invention, but not to limit the scope of the present invention. Without departing from the design spirit of the present invention, those of ordinary skill in the art can make various modifications to the technical solutions of the present invention. Variations and improvements should fall within the protection scope determined by the claims of the present invention.

Claims (9)

1. The nanometer high polymer material is characterized by comprising the following raw materials in parts by weight:

40-55 parts of polyvinyl chloride resin, 10-20 parts of acrylic hydroxyl resin, 5-8 parts of nano aluminum hydroxide, 1-2 parts of micro magnesium hydroxide, 7-12 parts of modified carbon nano tube, 3-5 parts of chlorinated paraffin, 2-4 parts of tetrapropylene titanate, 5-6 parts of dioctyl phthalate, 9-11 parts of tris (2-chloroethyl) phosphate, 1-2 parts of antimony trioxide, 3-5 parts of zinc borate hydrate, 8-13 parts of modified polyether and 1-3 parts of coupling agent.

2. The nano polymer material as claimed in claim 1, wherein the average particle size of the nano aluminum hydroxide is less than or equal to 100nm, the initial weight loss temperature is 340-370 ℃, and the weight loss rate is 48-52%.

3. The nano polymer material according to claim 1, wherein the micro magnesium hydroxide has an average particle size of 1 to 8 μm.

4. The nano polymer material according to claim 1, wherein the modified carbon nanotube is prepared by the following method: the mass portions are respectively 1: 0.6-1.2: ultrasonic treatment is carried out on a carbon nano tube of 200-300, an acid-binding agent and an organic solvent with the power of 350-400W, the frequency of 40-50kHz and the time of 1-2h, phenylphosphonyl dichloride and 4,4 '-diaminodiphenylmethane are slowly added under the condition of-20-10 ℃, the mass ratio of the carbon nano tube to the phenylphosphonyl dichloride to the 4,4' -diaminodiphenylmethane is 1:1:1.2-2.3, the temperature is raised to 110 ℃, and the reaction is carried out for 12h, so as to obtain the product.

5. The nano polymer material of claim 4, wherein the acid-binding agent is triethylamine or ammonium carbonate; the organic solvent is tetrahydrofuran, toluene, acetone, methanol, ethanol or acetonitrile.

6. The nano polymer material according to claim 1, wherein the modified polyether is prepared by the following method: the mass portions are respectively 1: 0.9: 1.3: 1.3, reacting aluminum fluoride, propylene oxide, a catalyst and polytetrafluoroethylene for 2-4h under the reaction conditions of the temperature of 520 ℃ and 600 ℃, the pressure of 60-75MPa and the voltage of 1.2-1.5 ten thousand volts; preferably, the reaction is carried out at 560 ℃ and 75MP under 1.5 ten thousand volts for 3 hours.

7. The nano polymer material of claim 6, wherein the reaction for preparing the modified polyether is carried out in a closed reaction container, and the reaction container is filled with a non-oxidizing gas, wherein the non-oxidizing gas is helium, argon, carbon dioxide and carbon monoxide in a mass ratio of 5:1:1: 0.1.

8. The nanometer polymer material as claimed in claim 6, wherein the catalyst comprises the following components in parts by weight: 0.6-0.8 part of sodium hydrogen silicate, 0.3-0.5 part of methanol and 0.1-0.2 part of silicone oil.

9. The method for preparing a nano polymer material according to any one of claims 1 to 8, comprising the steps of:

(1) mixing nanometer aluminum hydroxide, micrometer magnesium hydroxide, antimony trioxide and zinc borate at 70-85 deg.C;

(2) adding coupling agent and acrylic hydroxy resin, stirring, adding polyvinyl chloride resin, tetrapropylene titanate and tris (2-chloroethyl) phosphate, heating to 105 ℃, adding modified polyether, and mixing for 10 min;

(3) adding chlorinated paraffin, dioctyl phthalate and modified carbon nanotube, stirring for 2min, cooling to 50-60 deg.C, and stirring for reaction for 10 min;

(4) and (4) putting the substance obtained in the step (3) into a double-screw extruder for extrusion to form the strip-shaped nanometer high polymer material.