阅读说明：本技术 一种改性蒙脱土增强聚乙烯的复合材料及其在家具中的应用 (Modified montmorillonite reinforced polyethylene composite material and application thereof in furniture ) 是由 张佳燕 王优杰 韩华慧 于 2020-06-09 设计创作，主要内容包括：本发明涉及一种改性蒙脱土增强聚乙烯的复合材料,其制备原料包括聚乙烯、蒙脱土、聚多元醇单醚接枝的丙烯酰胺、丙烯酰胺和引发剂；其中聚多元醇单醚接枝的丙烯酰胺由聚多元醇单醚与丙烯酰胺制备而成。本发明含有聚多元醇单醚接枝的丙烯酰胺支链的复合材料中,各个成分与蒙脱土的相容性大为改善,配合相容剂,可以使得复合材料的均匀性和相容性达到稳定和优异的程度,从而极大地提升了复合材料的力学性能和韧性。本发明还涉及改性蒙脱土增强聚乙烯的复合材料作为家具板材的制备方法和应用。(The invention relates to a composite material of modified montmorillonite reinforced polyethylene, which is prepared from polyethylene, montmorillonite, polyatomic alcohol monoether grafted acrylamide, acrylamide and an initiator; wherein the polyatomic alcohol monoether grafted acrylamide is prepared from polyatomic alcohol monoether and acrylamide. In the composite material containing the polyatomic alcohol monoether grafted acrylamide branched chain, the compatibility of each component and montmorillonite is greatly improved, and the uniformity and the compatibility of the composite material can reach stable and excellent degrees by matching with the compatilizer, so that the mechanical property and the toughness of the composite material are greatly improved. The invention also relates to a preparation method and application of the composite material of modified montmorillonite reinforced polyethylene as furniture board.)

1. The composite material of modified montmorillonite reinforced polyethylene is characterized in that the raw materials for preparing the composite material of modified montmorillonite reinforced polyethylene comprise polyethylene, montmorillonite, polyatomic alcohol monoether grafted acrylamide, acrylamide and an initiator; wherein the polyatomic alcohol monoether grafted acrylamide is prepared from polyatomic alcohol monoether and acrylamide.

2. The modified montmorillonite reinforced polyethylene composite of claim 1, wherein the polymeric polyol monoether is selected from at least one of polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, and polybutylene glycol monomethyl ether.

3. The composite material of modified montmorillonite reinforced polyethylene as claimed in claim 1, wherein the modified montmorillonite reinforced polyethylene is prepared from the following raw materials in parts by mass:

4. the modified montmorillonite reinforced polyethylene composite of claim 1, wherein the number of repeat units in the polymeric polyol monoether is an integer from 5 to 10.

5. The modified montmorillonite-reinforced polyethylene composite of claim 1 wherein the particle size of the montmorillonite is 0.3-0.8 μm.

6. The modified montmorillonite-reinforced polyethylene composite material of claim 1, wherein the polyalcohol monoether grafted acrylamide is obtained by a preparation method comprising the following steps:

mixing the polyether polyol and acrylamide, adding deionized water, stirring, and heating to 70-90 ℃; then reacting for 3-5h under the catalytic system of ammonium persulfate and sodium bisulfite.

7. The modified montmorillonite reinforced polyethylene composite of claim 6, wherein the mass ratio of the polymeric polyol monoether to the acrylamide is 0.1-0.3: 1.

8. The modified montmorillonite reinforced polyethylene composite of claim 1 wherein the polyethylene has a number average molecular weight of 70 to 100 ten thousand.

9. The method of any one of claims 1-8, wherein the modified montmorillonite reinforced polyethylene composite is prepared by the following steps:

s1, adding a foaming agent, a compatilizer and an antioxidant into an extruder, and uniformly mixing;

s2, adding polyethylene, polyatomic alcohol monoether grafted acrylamide, montmorillonite and an initiator from the side edge of a first section of natural exhaust port of an extruder;

and S3, melting, extruding and granulating the materials.

10. Use of the modified montmorillonite reinforced polyethylene composite of any one of claims 1-8 in furniture.

Technical Field

The invention belongs to the field of composite materials, and particularly relates to a composite material of modified montmorillonite reinforced polyethylene and application thereof in furniture.

Background

The polyethylene has the advantages of low price, wide source, mature preparation method and the like, and is the general plastic with the largest use amount. Polyethylene articles are well known for their wide application in a variety of fields. However, polyethylene has poor toughness, and the toughness needs to be improved so that the polyethylene has more excellent mechanical properties and weather resistance. It is a common method to improve the mechanical properties and weather resistance of polyethylene by physical blending with inorganic filler. Montmorillonite is a common inorganic filler, has a relatively ideal effect after being blended with polyethylene, and is also known (Yuansheng, Master's scientific thesis, research on the influence of the stability of modified montmorillonite and polyethylene, 2008).

Montmorillonite (also known as montmorillonite or microcrystalline kaolinite) is a natural mineral of silicate, and is the main mineral component of bentonite ore. Containing Al₂O₃16.54%; MgO is 4.65%; SiO2 is 50.95%. Structural formula is (Al, Mg)₂(SiO₁₀)(OH)₂·nH₂And O. Monoclinic system, multi-site microcrystals, aggregates in the form of soil, spheres, etc. White, slightly grayish, yellowish, greenish, bluish when containing impurities, earthy luster or dull luster, and slippery feel. After adding water, it can expand several times its volume and become a paste. The volume of the product shrinks after heated dehydration. Has strong adsorption capacity and cation exchange performance, and is mainly produced in the weathering crust of volcanic tuff. Montmorillonite (including calcium-based, sodium-calcium-based, magnesium-based montmorillonite) is peeled, dispersed, purified, modified, ultra-fine graded, and special organically compounded, with average wafer thickness less than 25nm, and can be used as bleaching agent and adsorbent filler, and is called "universal material". Because the polymer can be embedded between the montmorillonites and the polymer can have extraordinary configuration and conformationally regular arrangement, the material performance of the high polymer can be obviously improved. The research of embedding polymer between montmorillonite is receiving extensive attention. For example, some people adopt acrylamide to be embedded into montmorillonite, so that the toughness of the acrylamide is greatly improved (Zhang Guiling, Dabaiqing, Weiyongde, theoretical research on the stability of an interlayer compound hBN-Cu, molecular science, report，2000,16(4):234-238)。

Polyethylene/montmorillonite composites are commonly used in interior furniture composites. For example, polyethylene is blended with high-density polyethylene, maleic anhydride grafted polyethylene, polyethylene wax, paraffin, carbon fiber and the like are added in an auxiliary manner, secondary blending is carried out in a high-speed mixer, then the mixture is added into a double-screw extruder, and melting, mixing and extruding are carried out, so that the furniture composite board can be obtained. The prepared material has locally ideal mechanical properties such as bending strength, impact strength, tensile strength and the like. However, the high polymer is a typical organic matter, the structure of which mainly comprises hydrocarbon, and the montmorillonite is more metal compound and metal element, and the polarity difference between the two is large, so that the poor compatibility caused by the structure difference is a problem which cannot be ignored, which usually causes the finally prepared composite material containing polyethylene and montmorillonite to separate and agglomerate, greatly affects the blending uniformity of each component contained in the granulated and formed furniture composite material, and causes the mechanical property to be remarkably reduced.

Therefore, the problem of how to solve the compatibility between montmorillonite and polyethylene and further optimize the mechanical property of the furniture composite material prepared from montmorillonite and polyethylene is a difficult problem to be solved urgently.

Disclosure of Invention

The invention aims to provide a modified montmorillonite reinforced polyethylene composite material which is applied to furniture. Wherein the montmorillonite contains polyatomic alcohol monoether grafted acrylamide, and then the polyacrylamide containing polyethylene glycol monomethyl ether graft can be grafted to polyethylene again under the conditions of high temperature of an extruder and an initiator. Surprisingly, it has been found that in the furniture composite material containing the polyatomic alcohol monoether grafted acrylamide branched chain, the compatibility of each component with montmorillonite is greatly improved, and the uniformity and compatibility of the furniture composite material can reach stable and excellent degree by matching with the effect of the compatilizer, so that the mechanical properties of the granulated and molded composite material, especially the mechanical properties at higher temperature, such as notch impact strength, are greatly improved.

The invention aims to provide a composite material of modified montmorillonite reinforced polyethylene, which is realized by the following technical means.

The composite material of modified montmorillonite reinforced polyethylene comprises raw materials for preparing the composite material of modified montmorillonite reinforced polyethylene, montmorillonite, polyatomic alcohol monoether grafted acrylamide, acrylamide and an initiator; the polyatomic alcohol monoether grafted acrylamide is prepared from polyatomic alcohol monoether and acrylamide.

Further, the polymeric polyol monoether is selected from polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether or polytetramethylene glycol monomethyl ether.

Further, the modified montmorillonite reinforced polyethylene is prepared from the following raw materials in parts by mass:

further, the number of repeating units in the polymeric polyol monoether is an integer of 5 to 10.

Furthermore, the particle size of the montmorillonite is 0.3-0.8 μm.

Further, the preparation method of the polyatomic alcohol monoether grafted acrylamide is as follows:

mixing the polyether polyol and acrylamide, adding deionized water, stirring, and heating to 70-90 ℃; then reacting for 3-5h under the catalytic system of ammonium persulfate and sodium bisulfite.

Further, the mass ratio of the polymeric polyol monoether to the acrylamide is 0.1-0.3: 1.

Further, the adding amount of the ammonium persulfate is 0.1-0.3 wt% of the polyethylene glycol monomethyl ether; the addition amount of the sodium bisulfite is 0.1 to 0.3 weight percent of the polyethylene glycol monomethyl ether.

Further, the number average molecular weight of the polyethylene is 70 to 100 ten thousand.

The compatibilizing agent, the antioxidant and the initiator in the present invention are not particularly limited, and may be those commonly used in the art. Examples of the compatibilizing agent include, but are not limited to, GMG9801, GPM200 or NG2002, examples of the antioxidant include, but are not limited to, tert-butylhydroquinone, tea polyphenol or hydroquinone, the initiator is a radical initiator, and examples of the antioxidant include, but are not limited to, dibenzoyl peroxide, azobisisobutyronitrile or cyclohexanone peroxide.

Another object of the present invention is to provide a method for preparing a composite material of modified montmorillonite reinforced polyethylene, wherein the method for preparing the composite material of dealcoholized reinforced polyethylene comprises the following steps:

s1, adding a foaming agent, a compatilizer and an antioxidant into an extruder, and uniformly mixing;

s2, adding polyethylene, polyatomic alcohol monoether grafted acrylamide, montmorillonite and an initiator from the side edge of a first section of natural exhaust port of an extruder;

and S3, melting, extruding and granulating the materials.

The invention also aims to provide the application of the modified montmorillonite reinforced polyethylene composite material in furniture.

The invention has the following technical effects:

1. in the invention, part of the polyatomic alcohol monoether grafted acrylamide is mixed into the acrylamide, so that the mechanical property of the modified montmorillonite reinforced polyethylene composite material can be effectively improved. This is because acrylamide and the polyether-polyol-monoether-grafted acrylamide have a good synergistic effect. Specifically, first, by introducing a polyol monoether-grafted acrylamide branch chain into a part of a polyethylene backbone, the linear structure of polyethylene is changed into a network structure extending in the direction of the branch chain, and the polyol branch chain, as a high polymer, can be inserted into montmorillonite from different directions, and the montmorillonite can be further uniformly dispersed as compared with the case where polyethylene is inserted into montmorillonite only from two dimensions; in addition, the acrylamide and the polyatomic alcohol monoether grafted acrylamide both contain acrylamide structures, so that the compatibility of the acrylamide and the polyatomic alcohol monoether grafted acrylamide is good, the acrylamide and the polyatomic alcohol monoether grafted acrylamide are respectively well compatible with products formed after polyethylene is physically mixed, the uniformity is excellent, and a muddy integral structure is formed, so that the dispersibility and the uniformity of the whole composite material are fully improved in a macroscopic view

2. The polyethylene glycol chain segment has good dispersibility, which is beneficial to the dispersion of montmorillonite particles; the polylol chain segment has polarity, so that the polylol chain segment has certain affinity with a metal compound with strong polarity, such as montmorillonite, and the compatibility of a polyethylene structure containing a polylol monoether grafted acrylamide branched chain and the montmorillonite is favorably improved; the main chain is polyethylene, and the polyethylene has excellent affinity with the acrylamide modified polyethylene which is not grafted by the polyalcohol monoether in the composite material, so that the polyethylene composite material has an amphiphilic effect on the components with strong polarity, such as montmorillonite, and the components with weak polarity, such as polyethylene, and the compatibility of the polyethylene and the montmorillonite in the formula is improved.

3. The double bond of acrylamide generates grafting reaction with polyethylene main chain under the initiation action, the nature of the acrylamide is exothermic reaction, the montmorillonite sheet layer can be propped open by the released heat, and the grafted chain segment has certain probability to be wrapped around the montmorillonite sheet layer, so that the montmorillonite is further dispersed by the polymer chain segment, and the stable and uniform intercalation composite material is favorably formed.

4. Due to the three reasons, the compatibility of the modified montmorillonite reinforced polyethylene composite material is obviously improved, so that the strength of the material serving as a furniture composite material is obviously improved. The montmorillonite layer and the polyethylene matrix are not easy to slip when the composite material is stretched and stressed, and the montmorillonite layer and the polyethylene matrix play a role in sharing external load to a greater extent, so that the composite material has better mechanical property; in addition, the montmorillonite is added from the side edge of the extruder, so that the lamellar structure can be kept from being damaged to a greater extent while the montmorillonite is stripped, and the thermal stability and the wear resistance of the material are improved. The properties enable the modified montmorillonite reinforced polyethylene composite material to have good application prospect in furniture.

Detailed Description

The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. The starting materials described in the examples of the present invention are commercially available and, unless otherwise specified, the starting materials and methods employed are those conventional in the art.

In the embodiments of the present invention disclosed herein,

the montmorillonite is purchased from Guangzhou Xijia chemical industry Co., Ltd, and has a particle size of 0.3-1 μm;

polyethylene is purchased from Yihong chemical Co., Ltd, of Jinan, and has a model number of 2200J and a number average molecular weight of 90 ten thousand;

polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether are purchased from the Haian petrochemical plant of Jiangsu province.

Preparation example 1

The preparation method of the polyethylene glycol monomethyl ether grafted acrylamide 1 is as follows: in a reaction kettle, 0.1mol of polyethylene glycol monomethyl ether (wherein the number of repeating units of the polyethylene glycol monomethyl ether is 5) is mixed with 1mol of acrylamide, and then deionized water with the mass of 20 wt% of the polyethylene glycol monomethyl ether is added and stirred uniformly; and then heating to 70 ℃, respectively adding 0.1 wt% of ammonium persulfate and 0.1 wt% of sodium bisulfite of polyethylene glycol monomethyl ether as catalysts, and reacting for 3h to obtain the polyethylene glycol monomethyl ether grafted acrylamide 1.

Preparation example 2

The preparation method of the polyethylene glycol monomethyl ether grafted acrylamide 2 is as follows: in a reaction kettle, 0.3mol of polyethylene glycol monomethyl ether (wherein the number of repeating units of the polyethylene glycol monomethyl ether is 10) is mixed with 1mol of acrylamide, and then deionized water with the mass of 40 wt% of the polyethylene glycol monomethyl ether is added and stirred uniformly; and then heating to 90 ℃, respectively adding 0.3 wt% of ammonium persulfate and 0.3 wt% of sodium bisulfite of polyethylene glycol monomethyl ether as catalysts, and reacting for 5 hours to obtain the polyethylene glycol monomethyl ether grafted acrylamide 2.

Preparation example 3

The preparation method of the polyethylene glycol monomethyl ether grafted acrylamide 3 is as follows: in a reaction kettle, 0.05mol of polyethylene glycol monomethyl ether (wherein the number of repeating units of the polyethylene glycol monomethyl ether is 7) is mixed with 1mol of acrylamide, and then deionized water with the mass of 30 wt% of the polyethylene glycol monomethyl ether is added and stirred uniformly; and then heating to 80 ℃, respectively adding 0.2 wt% of ammonium persulfate and 0.2 wt% of sodium bisulfite of the polyethylene glycol monomethyl ether as catalysts, and reacting for 5 hours to obtain the acrylamide 3 grafted with the polyethylene glycol monomethyl ether.

Preparation example 4

The preparation method of the polyethylene glycol monomethyl ether grafted acrylamide 4 in the reaction kettle is as follows: mixing 0.5mol of polyethylene glycol monomethyl ether (wherein the number of the repeating units of the polyethylene glycol monomethyl ether is 7) with 1mol of acrylamide, and then adding deionized water accounting for 30 wt% of the polyethylene glycol monomethyl ether by mass and uniformly stirring; and then heating to 80 ℃, respectively adding 0.2 wt% of ammonium persulfate and 0.2 wt% of sodium bisulfite of the polyethylene glycol monomethyl ether as catalysts, and reacting for 5 hours to obtain the acrylamide 4 grafted with the polyethylene glycol monomethyl ether.

Preparation example 5

The preparation method of the polyethylene glycol monomethyl ether grafted acrylamide 5 in the reaction kettle is as follows: mixing 0.3mol of polyethylene glycol monomethyl ether (wherein the number of repeating units of the polyethylene glycol monomethyl ether is 3) with 1mol of acrylamide, and then adding deionized water accounting for 30 wt% of the polyethylene glycol monomethyl ether by mass and uniformly stirring; and then heating to 80 ℃, respectively adding 0.2 wt% of ammonium persulfate and 0.2 wt% of sodium bisulfite of the polyethylene glycol monomethyl ether as catalysts, and reacting for 5 hours to obtain the acrylamide 5 grafted with the polyethylene glycol monomethyl ether.

Preparation example 6

The preparation method of the polyethylene glycol monomethyl ether grafted acrylamide 6 in the reaction kettle is as follows: mixing 0.3mol of polyethylene glycol monomethyl ether (wherein the number of the repeating units of the polyethylene glycol monomethyl ether is 15) with 1mol of acrylamide, and then adding deionized water accounting for 30 wt% of the polyethylene glycol monomethyl ether by mass and uniformly stirring; and then heating to 80 ℃, respectively adding 0.2 wt% of ammonium persulfate and 0.2 wt% of sodium bisulfite of the polyethylene glycol monomethyl ether as catalysts, and reacting for 5 hours to obtain the acrylamide 6 grafted with the polyethylene glycol monomethyl ether.

Preparation example 7

The preparation method of the acrylamide grafted by polypropylene glycol monomethyl ether in the reaction kettle comprises the following steps: mixing 0.3mol of polypropylene glycol monomethyl ether (wherein the number of repeating units of the polypropylene glycol monomethyl ether is 7) with 1mol of acrylamide, and then adding deionized water accounting for 30 wt% of the polypropylene glycol monomethyl ether to stir uniformly; and then heating to 80 ℃, respectively adding 0.2 wt% of ammonium persulfate and 0.2 wt% of sodium bisulfite of polypropylene glycol monomethyl ether as catalysts, and reacting for 5 hours to obtain the polypropylene glycol monomethyl ether grafted acrylamide.