CN110628082B - Multifunctional additive for high polymer material and preparation method thereof - Google Patents

Multifunctional additive for high polymer material and preparation method thereof Download PDF

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Publication number
CN110628082B
CN110628082B CN201910985684.8A CN201910985684A CN110628082B CN 110628082 B CN110628082 B CN 110628082B CN 201910985684 A CN201910985684 A CN 201910985684A CN 110628082 B CN110628082 B CN 110628082B
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coupling agent
silane coupling
polymer
agent modified
multifunctional
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CN110628082A (en
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张哲�
张元硕
潘昊
靳亚娥
孙江波
曹一康
马国超
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Jiangsu Jinhan New Material Co ltd
Northwest Normal University
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Jiangsu Jinhan New Material Co ltd
Northwest Normal University
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

Abstract

The invention discloses a multifunctional auxiliary agent for a high polymer material, which is obtained by reacting silane coupling agent modified attapulgite, silane coupling agent modified montmorillonite and pentaerythritol diphosphonate diphosphoryl chloride; the mass ratio of the silane coupling agent modified attapulgite to the silane coupling agent modified montmorillonite is 1: 10-10: 1, and the amount of the pentaerythritol diphosphonate diphosphoryl chloride is 20-50% of the total mass of the silane coupling agent modified attapulgite and the silane coupling agent modified montmorillonite. Compared with the prior art, the multifunctional additive provided by the invention can obviously improve the oxygen index of the high polymer material, reduce smoke density, improve mechanical properties, improve carbon formation, reduce heat release rate, reduce oxygen consumption during combustion, and has a low addition amount.

Description

Multifunctional additive for high polymer material and preparation method thereof
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a multifunctional auxiliary agent for a high polymer material.
Background
The polymer materials can be classified into natural polymers and synthetic polymer materials. Since the 20 th century, synthetic polymer materials represented by plastics, rubbers and fibers have entered thousands of households. The synthetic polymer materials are widely applied and have important functions in agriculture, energy, information, environment and industrial products. The synthesized high molecular material has the characteristics of large quantity and wide range. Due to the excellent properties of light weight, high strength, temperature resistance, corrosion resistance and the like, the high polymer material is widely applied to the fields of high-end manufacturing, electronic information, transportation, building energy conservation, aerospace, national defense and military industry and the like. Therefore, polymer materials have been developed and developed with great attention from companies across countries, developed countries such as the united states, germany, and japan have been leading global polymer materials, and companies across countries such as basf, dupont, dow, mitsubishi, LG, and SK, which are familiar with the state of the art, have been pilots of polymer materials.
According to incomplete statistics, the consumption of synthetic polymer materials exceeds that of steel, and important contribution is made in the development of global GDP. The synthesized high molecular materials have various types and varieties and different chemical compositions, and the performance of the materials is greatly different due to slight differences of synthesis processes.
The total yield of the synthetic resin is 8558 ten thousand tons in 2018, and the increase is 4.2 percent on the same scale; the import amount is 2995.5 ten thousand tons, which is lower than 3195.9 ten thousand tons in the last year; the apparent consumption is 1.09 million tons, which is consumed over a hundred million tons for 5 consecutive years since 2015. Basic conditions of five general plastics: the production capacity of the polyethylene in China is 1844 ten thousand tons, the yield in the last year is 1583.5 ten thousand tons, and the same ratio is 13.3 percent; an inlet of 1402.5 ten thousand tons with the same ratio of 18.9 percent; the apparent consumption is 2781.6 ten thousand tons, the same ratio is 11.7 percent; the degree of external dependence was 49.6%. The total production capacity of the polypropylene is 2450 million tons, the annual production capacity is 2200 million tons, and the productivity utilization rate is 89.8 percent; the import is 440 ten thousand tons, the apparent consumption is 2640 ten thousand tons, and the same ratio is 8.7 percent. The yield of the polyvinyl chloride is 1986 ten thousand tons, and the yield is 1873.9 ten thousand tons, which is 5.6 percent of the same ratio; the inlet is 93.7 ten thousand tons, the outlet is 77.4 ten thousand tons, the apparent consumption is 1890 ten thousand tons, and the same ratio is 7.1 percent. The yield of the polystyrene is 175.7 ten thousand tons, the import is 115.3 ten thousand tons, the apparent consumption is 258.9 ten thousand tons, and the same ratio is 6.2 percent. The ABS resin yield is 325.8 ten thousand tons, the import is 201 ten thousand tons, and the same ratio is 12.5 percent; the apparent consumption is 522.3 ten thousand tons, and the same ratio is 4.5 percent.
However, a single polymer material does not have comprehensive use ability due to its single property, such as poor heat resistance, easy combustion, release of a large amount of smoke during combustion, mismatch in rigidity and toughness, poor electrical conductivity, poor thermal conductivity, and easy variability. In order to make the use of the high polymer materials more extensive and the performance more comprehensive, at present, researchers and manufacturers mainly compound different high polymer materials and add various additives.
Among various additives for polymer materials, non-metallic minerals have been widely used, and the amount of use has increased year by year. At present, the non-metallic minerals added in the high molecular material mainly comprise calcium carbonate, heavy calcium carbonate, light calcium carbonate, talc, kaolin, mica, wollastonite, graphite, brucite, barite (including precipitated barium sulfate), dolomite, montmorillonite, attapulgite, feldspar, silicon dioxide, aluminum hydroxide, magnesium hydroxide, titanium dioxide, aluminosilicate and the like. The materials are added into the polymer, which is of great help to reduce material cost, improve strength, aging resistance, cracking resistance, flame retardance, smoke suppression, thermal stability, reduction of thermal deformation and the like.
For example, chinese patent document CN101280086A discloses a flame retardant modified polypropylene special material, which is composed of the following raw materials by mass: 35-68% of polypropylene resin, 20-35% of compound flame retardant, 2-10% of inorganic material, 5-10% of nylon resin and 5-10% of compatibilizer. The compound flame retardant is preferably a compound of ammonium polyphosphate and pentaerythritol or a compound of pentaerythritol diphosphonate diphosphoryl chloride melamine and magnesium hydroxide in a mass ratio of 3: 1. The inorganic material is any one of montmorillonite, hydrotalcite, zeolite, talcum powder and attapulgite with the grain diameter not more than 10 microns. The special material for the flame-retardant modified polypropylene has good flame-retardant and mechanical properties, but the addition amount of the auxiliary agent is large, and the functions of all the auxiliary agents are single.
Disclosure of Invention
Aiming at the defect of single function of the high polymer material auxiliary agent, the invention aims to provide the multifunctional auxiliary agent for the high polymer material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a multifunctional auxiliary agent for high molecular materials is obtained by the reaction of silane coupling agent modified attapulgite, silane coupling agent modified montmorillonite and pentaerythritol diphosphonate diphosphoryl chloride; the mass ratio of the silane coupling agent modified attapulgite to the silane coupling agent modified montmorillonite is 1: 10-10: 1, and the amount of the pentaerythritol diphosphonate diphosphoryl chloride is 20-50% of the total mass of the silane coupling agent modified attapulgite and the silane coupling agent modified montmorillonite.
Preferably, the silane coupling agent is an aminosilane coupling agent, and more preferably, the silane coupling agent is a KH-550 coupling agent.
Preferably, the mesh number of the multifunctional additive for the high polymer material is more than or equal to 1500 meshes.
The preparation method of the multifunctional assistant for the high polymer material comprises the following steps:
heating and refluxing the silane coupling agent modified attapulgite, the silane coupling agent modified montmorillonite and pentaerythritol diphosphonate diphosphoryl chloride in an organic solvent to react to obtain the multifunctional assistant for the high polymer material.
Preferably, triethylamine is added into the reaction system as an acid-binding agent.
Preferably, the dosage of the triethylamine is 1-10% of the total mass of the silane coupling agent modified attapulgite and the silane coupling agent modified montmorillonite.
Preferably, the organic solvent is dichloromethane, and the reaction time is 3-12 hours.
A halogen-free low-smoke flame-retardant high polymer material comprises a high polymer material used as a matrix and the multifunctional additive added in the matrix and used for the high polymer material.
Preferably, the multifunctional assistant for polymer materials accounts for 1-3% of the halogen-free low-smoke flame-retardant polymer materials by mass.
Compared with the existing polymer material auxiliary agent, the multifunctional auxiliary agent disclosed by the invention can obviously improve the oxygen index of a corresponding product, reduce smoke density, improve mechanical properties, improve carbon formation, reduce heat release rate and reduce oxygen consumption during combustion by only adding 1-3 wt% of the multifunctional auxiliary agent into a polymer material.
Drawings
FIG. 1 is an infrared spectrum of the multifunctional assistant of the present invention.
FIG. 2 is a scanning electron micrograph of the multifunctional additive of the present invention.
FIG. 3 is a transmission electron microscope photograph of the multifunctional additive of the present invention.
FIG. 4 is an EDS analysis of the multifunctional additive of the present invention.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to preferred embodiments.
The attapulgite (soil) modified by the silane coupling agent and the montmorillonite (stone) modified by the silane coupling agent can be prepared by referring to the prior conventional method. Such as:
juyaqing, et al, preparation of modified attapulgite and its effect on the properties of polylactic acid materials [ J ] Plastic additives, 3 rd stage in 2015, pages 19-23.
Zhu Wei Ju, et al preparation of modified attapulgite by aminosilane coupling agent and its adsorption property [ J ] applied chemistry, vol 29, 2 nd in 2012, page 180-185.
Yaoqiao, et al, modified study of silane coupling agent on surface of nano attapulgite [ J ]. nonmetallic mine, No. 30, Vol.6, pages 1-3, 2007.
Application study of amino silane coupling agent modified attapulgite in UF adhesive [ J ] China adhesive, volume 22, stage 12 in 2013, pages 21-26.
Modification of montmorillonite with aminosilane coupling agent [ J ] chemical journal, volume 62, page 83-87, 2004.
Yaoneng, and the like, influence of silane coupling agent grafted modified montmorillonite on PBT performance [ J ] plastics industry, volume 41, No. 3, page 98-100 in 2013.
Li jin Mei, et al. Gamma-aminopropyl dimethyl ethoxy silane modified montmorillonite and silanized montmorillonite Performance [ J ] chemical engineering progress, No. 33, No. 1, page 178-182 in 2014.
The surface modification of superfine montmorillonite by silane coupling agent [ J ] plastics, volume 44, No. 6, page 35-40, 2015.
The silane coupling agent has a hydrolyzable group and an organic functional group which can generate coupling reaction, the silane coupling agent is grafted to the surfaces of attapulgite (A) and montmorillonite (B) through the hydrolyzable group, then the silane coupling agent and an acyl chloride group on pentaerythritol diphosphonate diphosphoryl chloride (C) generate coupling reaction through the organic functional group, because two ends of the pentaerythritol diphosphoryl chloride respectively have an acyl chloride, A-C-B, A-C-A and B-C-B type polymer material multifunctional auxiliary agent which are combined by chemical bonds can be obtained, the prepared material is subjected to a large amount of water washing, ethanol washing, methylene dichloride and chloroform Soxhlet extraction, organic matters which are not grafted are removed, infrared characterization is carried out (see figure 1), we can find that an organic matter group diffraction peak appears, and the peak is a stretching vibration peak of a C-H bond through analysis, it is derived from pentaerythritol diphosphate diphosphoryl chloride, indicating successful grafting of C onto the surface of both clays. The analysis of the graphs in fig. 2-4 shows that the attapulgite is adhered to the surface of the montmorillonite, the attapulgite and the montmorillonite do not exist independently, and two kinds of independently dispersed clay are not seen in the characterization process of a transmission electron microscope after the attapulgite and the montmorillonite are dispersed by ultrasonic treatment, which indicates that the two kinds of clay are combined together, and the binding force is realized by the chemical reaction of the two kinds of clay and pentaerythritol diphosphonate diphosphoryl chloride. EDS analysis shows that all elements are uniformly distributed, which indicates that the reaction is successful, and the invention prepares the product at the beginning of design.
Example 1
Preparation of KH-550 coupling agent modified attapulgite: 150mL of ethanol (80%) and 3g of attapulgite are added into a 250mL three-neck flask, 1.5g of KH-550 is added dropwise, the mixture is refluxed and stirred at 80 ℃ for 3h, the product is repeatedly washed by ethanol and water after the reaction is finished, and finally the product is dried at 110 ℃ for 12h to obtain the modified attapulgite.
Preparing KH-550 coupling agent modified montmorillonite: 150mL of ethanol (80%) and 3g of montmorillonite are added into a 250mL three-neck flask, 1.5g of KH-550 is added dropwise, the mixture is refluxed and stirred for 3h at 80 ℃, the product is repeatedly washed by ethanol and water after the reaction is finished, and finally the product is dried for 12h at 110 ℃ to obtain the modified attapulgite.
Preparing a multifunctional auxiliary agent: mixing the attapulgite modified by the KH-550 coupling agent and the montmorillonite modified by the KH-550 coupling agent according to the mass ratio of 1:1 to obtain the mixed clay. 10g of mixed clay, 3g of pentaerythritol diphosphate diphosphoryl chloride, 0.1g of triethylamine and 150mL of dichloromethane were added to a three-necked flask, and the mixture was heated to reflux. The reaction solution is cooled in 6 hours of reflux reaction, filtered, washed by a large amount of water and ethanol, and then subjected to Soxhlet extraction by using dichloromethane and chloroform respectively for 12 hours to remove pentaerythritol diphosphonate diphosphoryl chloride which does not participate in grafting to the clay surface, and then washed by distilled water until no chloride ions exist. The product is dried in vacuum to constant weight and ball milled to 1500 meshes for later use.
FIG. 1 is an infrared spectrum of the multifunctional assistant of the present invention.
FIG. 2 is a scanning electron micrograph of the multifunctional additive of the present invention.
FIG. 3 is a transmission electron microscope photograph of the multifunctional additive of the present invention.
FIG. 4 is an EDS analysis of the multifunctional additive of the present invention.
Comparative example 1
Auxiliary agent: mixing the attapulgite modified by the KH-550 coupling agent and the montmorillonite modified by the KH-550 coupling agent according to the mass ratio of 1: 1.
Comparative example 2
Auxiliary agent: KH-550 coupling agent modified attapulgite.
Comparative example 3
Auxiliary agent: KH-550 coupling agent modified montmorillonite.
Comparative example 4
Auxiliary agent: the reaction product of the KH-550 coupling agent modified attapulgite and pentaerythritol diphosphonate diphosphoryl chloride, i.e., the mixed clay of example 1, was replaced with the same amount of KH-550 coupling agent modified attapulgite.
Comparative example 5
Auxiliary agent: the reaction product of KH-550 coupling agent modified montmorillonite and pentaerythritol bisphosphate diphosphoryl chloride, i.e., the mixed clay of example 1, was replaced with the same amount of KH-550 coupling agent modified montmorillonite.
Comparative examples 1-5 the preparation of each adjuvant was carried out according to example 1.
The additives are added into the commercial halogen-free flame-retardant wire and cable material granules according to the content of 1 wt%, and the performances of the materials are tested according to the national standard GB/T32129-2015. The results (see table 1) show that the multifunctional additive of the invention can obviously improve the oxygen index of the corresponding product, reduce the smoke density, improve the mechanical property, improve the carbon formation, reduce the heat release rate and reduce the oxygen consumption during combustion. The blank sample is a commercial halogen-free flame-retardant wire and cable material granule.
Table 1 results of performance tests of halogen-free low smoke resistant fuels with different additives.
Blank sample The invention Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example5
Tensile strength (MPa) 10.1 14.2 13.8 8.9 10.3 11.6 11.0
Elongation at Break (%) 160 179 161 142 150 141 139
Oxygen index 34 40 34 31 30 35 37
Smoke density (flameless) 389 289 346 379 362 345 312
Heat release Rate (kW/m)2) 156.50 121.69 180.09 155.45 157.59 138.45 134.22
Total Heat Release amount (MJ/m)2) 225.96 140.29 228.56 218.49 231.48 176.22 187.15
Total smoke emission (m)2/m2) 4077.82 2978.19 3542.99 3977.23 3796.11 3790.28 3109.79
Total oxygen consumption (g) 59.62 35.26 49.3 58.14 50.23 45.69 47.11
Residual carbon amount (%) 28 48 37 26 32 40 41
Example 2
Mixing the attapulgite modified by the KH-550 coupling agent and the montmorillonite modified by the KH-550 coupling agent according to the mass ratio of 10:1 to obtain the mixed clay. 10g of mixed clay, 2g of pentaerythritol diphosphate diphosphoryl chloride, 0.15 g of triethylamine and 100mL of dichloromethane were added to a three-necked flask and heated to reflux. Cooling the mixture after reflux reaction for 6 hours, filtering the mixture, performing Soxhlet extraction on the mixture by using trichloromethane for 12 hours to remove pentaerythritol diphosphonate diphosphoryl chloride which is not grafted on the clay surface, and washing the mixture by using distilled water until no chloride ions exist. The product is dried in vacuum to constant weight and ball milled to 1500 meshes for later use.
Example 3
Mixing the attapulgite modified by the KH-550 coupling agent and the montmorillonite modified by the KH-550 coupling agent according to the mass ratio of 1:10 to obtain the mixed clay. 10g of mixed clay, 5g of pentaerythritol diphosphate diphosphoryl chloride, 0.5 g of triethylamine and 200mL of dichloromethane were added to a three-necked flask, and the mixture was heated to reflux. Cooling the mixture after reflux reaction for 6 hours, filtering the mixture, performing Soxhlet extraction on the mixture by using trichloromethane for 12 hours to remove pentaerythritol diphosphonate diphosphoryl chloride which is not grafted on the clay surface, and washing the mixture by using distilled water until no chloride ions exist. The product is dried in vacuum to constant weight and ball milled to 1500 meshes for later use.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A multifunctional auxiliary agent for high polymer materials is characterized in that: the multifunctional additive for the high polymer material is obtained by reacting silane coupling agent modified attapulgite, silane coupling agent modified montmorillonite and pentaerythritol diphosphonate diphosphoryl chloride; the mass ratio of the silane coupling agent modified attapulgite to the silane coupling agent modified montmorillonite is 1: 10-10: 1, and the using amount of the pentaerythritol diphosphonate diphosphoryl chloride is 20-50% of the total mass of the silane coupling agent modified attapulgite and the silane coupling agent modified montmorillonite;
the silane coupling agent is an aminosilane coupling agent.
2. The multifunctional assistant for high molecular materials according to claim 1, wherein: the silane coupling agent is KH-550 coupling agent.
3. The multifunctional assistant for high molecular materials according to claim 1, wherein: the mesh number of the multifunctional additive for the high polymer material is more than or equal to 1500 meshes.
4. A method for preparing a multifunctional assistant for polymer materials according to any one of claims 1 to 3, comprising the steps of:
heating and refluxing the silane coupling agent modified attapulgite, the silane coupling agent modified montmorillonite and pentaerythritol diphosphonate diphosphoryl chloride in an organic solvent to react to obtain the multifunctional assistant for the high polymer material.
5. The method of claim 4, wherein: triethylamine as an acid-binding agent is added into the reaction system.
6. The method of claim 5, wherein: the dosage of the triethylamine is 1% -10% of the total mass of the silane coupling agent modified attapulgite and the silane coupling agent modified montmorillonite.
7. The method of claim 4, wherein: the organic solvent is dichloromethane, and the reaction time is 3-12 hours.
8. A halogen-free low-smoke flame-retardant polymer material, which comprises a polymer material used as a matrix and the multifunctional additive which is added into the matrix and is used for the polymer material according to any one of claims 1 to 3.
9. The halogen-free low-smoke flame-retardant polymer material according to claim 8, characterized in that: the multifunctional auxiliary agent for the high polymer material accounts for 1-3% of the halogen-free low-smoke flame-retardant high polymer material by mass.
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