CN105885228A - Method for preparing silicon dioxide modified polypropylene composite material - Google Patents

Abstract

The invention discloses a method for preparing a silicon dioxide modified polypropylene composite material. The method comprises the following steps: treating silicon dioxide with 3-[bis(2-hydroxyethyl)amino] propyltriethoxysilane; sequentially reacting with 2,2-dimethylol propionic acid and stearic acid under the action of toluenesulfonic acid to obtain modified silicon dioxide; melting and blending in an extruding machine, and adding into polypropylene to prepare the silicon dioxide modified polypropylene composite material. The silicon dioxide modified polypropylene composite material has excellent mechanical performance, can be used for processing and manufacturing plastic profiles, automobile parts and other products with excellent rigidity and other mechanical properties, and can be used for expanding the application range of polypropylene.

Description

A kind of preparation method of silica modified PP composite material

Technical field

The present invention relates to the technology of preparing of a kind of polymer composite, particularly to the system of a kind of PP composite material Preparation Method.

Background technology

Polypropylene is the thermoplastic that a kind of price is less expensive, can be used for making plastic pipe, electronic product casing, vapour Car parts etc..Polypropylene has the series of advantages such as nonpoisonous and tasteless, electrical insulating property good, chemerosiveness resistent is good, but there is also The shortcomings such as big, the product size poor stability of molding shrinkage.In order to overcome this shortcoming, can be by silicon-dioxide powdery, glass The inorganic rigid filler such as fiber, stone powder adds to makes PP composite material in polypropylene.But inorganic silicon dioxide with have During machine polypropene blended composite modified, there is the problem that the interfacial bonding property of composite inner is the highest, thus affect poly-third The mechanical property of alkene/silicon dioxide composite material.The surface of silicon dioxide has silicone hydroxyl, and adding silane coupling agent can be one Determine to improve in degree the interfacial combined function of composite inner.After the silicon dioxide silane treatment with band alkane hydroxyl, then Under catalyst action, it is successively reacted with the organic acid with multiple hydroxyls, the most hydroxyl alkyl acid, with to titanium dioxide Silicon is modified processing, then by modified silicon dioxide, polypropylene melt blending in an extruder, to strengthen inorganic dioxy SiClx is with organic polyacrylic interface cohesion thus improves polyacrylic performance, and such research has not yet to see all reports.

Summary of the invention

It is an object of the invention to provide the preparation method of a kind of composite adding improved silica in polypropylene, The PP composite material utilizing the method to prepare has good mechanical property.

For reaching object above, the present invention adopts the following technical scheme that and is achieved:

The preparation method of a kind of silica modified PP composite material, it is characterised in that comprise the following steps:

The first step, in mass ratio, silicon dioxide: 3-[double (2-ethoxy) amino] propane triethoxysilane=100: (0.5～ 3), after said components being weighed, join grinding in ball grinder mixing, obtain just processing silicon-dioxide powdery；

Second step, in mass ratio, just processes silicon-dioxide powdery: (2,2-dihydromethyl propionic acid): p-methyl benzenesulfonic acid: dimethyl second Amide: stearic acid=100: (10～30): (1～3): (100～200): (5～15), first 4 kinds after weighing by said ratio Component (i.e.: just process silicon-dioxide powdery, 2,2-dihydromethyl propionic acid, p-methyl benzenesulfonic acid, dimethyl acetylamide) join appearance In device, under nitrogen protection in 110～130 DEG C of stirring reactions 5～7 hours, then the 5th kind of component after weighing by said ratio Stearic acid adds in the reaction system in container, under nitrogen protection in 130～150 DEG C of stirring reactions 2～4 hours, obtains Product precipitates in deionized water, is dried, grinds, obtain improved silica powder after the precipitation absolute ethanol washing that will obtain Body；

3rd step, in mass ratio, polypropylene: improved silica powder body=100: (5～30), add after said components is weighed In double screw extruder, under the processing temperature of 180～210 DEG C, melt blending is extruded, and obtains silica modified polypropylene composite materials Material.

The present invention compared with prior art has the advantage that

When the present invention prepares improved silica, first by silicon dioxide 3-[double (2-ethoxy) amino] propane triethoxysilicane The silane of alkane this band alkane hydroxyl (ethoxy) processes, and makes silica surface by coupling with a certain amount of alkane hydroxyl Base, then by its priority and organic acid (2, the 2-dihydroxymethyls third with multiple hydroxyls under the effect of catalyst (p-methyl benzenesulfonic acid) Acid), the most hydroxyl alkyl acid (stearic acid, i.e. octadecanoid acid) react, make the silicon hydroxyl that silica surface itself has Base and coupling with alkane hydroxyl react with the carboxyl on the organic acid with multiple hydroxyls, the multiple hydroxyls on organic acid are again Can continue to continue hyperbranched polyreaction to occur, then with the most hydroxyl alkane with the carboxyl on the organic acid with multiple hydroxyls Base acid generation end capping reaction, silica surface to be carried out organic modification process, then by modified silicon dioxide, poly-third Alkene melt blending in an extruder, to strengthen inorganic silicon dioxide and organic polyacrylic interface cohesion, so that preparing Add improved silica PP composite material there is good mechanical property.

The PP composite material adding improved silica that the present invention prepares, can be used for being processed into the power such as stiffness Learn the goods such as plastic material of good performance, auto parts and components, polyacrylic range of application can be expanded.

Detailed description of the invention

Below by specific embodiment, technical scheme is described in further detail.

Embodiment 1

The preparation method of a kind of silica modified PP composite material, comprises the following steps:

The first step, joins grinding in ball grinder mixing by quality 1. in table 1 after component being weighed than formula, obtain just processing Silicon-dioxide powdery；

Front 4 kinds of components, after component being weighed than formula by quality 2. in table 1, are joined in container by second step, protect at nitrogen Protect down in 120 DEG C of stirring reactions 6 hours, then the 5th kind of component stearic acid after weighing than formula by quality 2. in table 1 adds In reaction system in container, under nitrogen protection in 140 DEG C of stirring reactions 3 hours, the product obtained sinks in deionized water Form sediment, be dried after the precipitation absolute ethanol washing that will obtain, grind, obtain improved silica powder body；

3rd step, adds after component being weighed than formula by quality 3. in table 1 in double screw extruder, from charging aperture to going out The temperature of material mouth sets gradually melt blending extrusion under conditions of being 180 DEG C-190 DEG C-200 DEG C-210 DEG C, obtains silicon dioxide Modified polypropylene composite material.

Embodiment 2

The preparation method of a kind of silica modified PP composite material, comprises the following steps:

The first step, joins grinding in ball grinder mixing by quality 1. in table 1 after component being weighed than formula, obtain just processing Silicon-dioxide powdery；

Front 4 kinds of components, after component being weighed than formula by quality 2. in table 1, are joined in container by second step, protect at nitrogen Protect down in 110 DEG C of stirring reactions 7 hours, then the 5th kind of component stearic acid after weighing than formula by quality 2. in table 1 adds In reaction system in container, under nitrogen protection in 130 DEG C of stirring reactions 4 hours, the product obtained sinks in deionized water Form sediment, be dried after the precipitation absolute ethanol washing that will obtain, grind, obtain improved silica powder body；

3rd step, adds after component being weighed than formula by quality 3. in table 1 in double screw extruder, from charging aperture to going out The temperature of material mouth sets gradually melt blending extrusion under conditions of being 180 DEG C-190 DEG C-205 DEG C-210 DEG C, obtains silicon dioxide Modified polypropylene composite material.

Embodiment 3

The preparation method of a kind of silica modified PP composite material, comprises the following steps:

The first step, joins grinding in ball grinder mixing by quality 1. in table 1 after component being weighed than formula, obtain just processing Silicon-dioxide powdery；

Front 4 kinds of components, after component being weighed than formula by quality 2. in table 1, are joined in container by second step, protect at nitrogen Protect down in 125 DEG C of stirring reactions 5 hours, then the 5th kind of component stearic acid after weighing than formula by quality 2. in table 1 adds In reaction system in container, under nitrogen protection in 138 DEG C of stirring reactions 4 hours, the product obtained sinks in deionized water Form sediment, be dried after the precipitation absolute ethanol washing that will obtain, grind, obtain improved silica powder body；

3rd step, adds after component being weighed than formula by quality 3. in table 1 in double screw extruder, from charging aperture to going out The temperature of material mouth sets gradually melt blending extrusion under conditions of being 180 DEG C-195 DEG C-200 DEG C-210 DEG C, obtains silicon dioxide Modified polypropylene composite material.

Embodiment 4

The preparation method of a kind of silica modified PP composite material, comprises the following steps:

The first step, joins grinding in ball grinder mixing by quality 1. in table 1 after component being weighed than formula, obtain just processing Silicon-dioxide powdery；

Front 4 kinds of components, after component being weighed than formula by quality 2. in table 1, are joined in container by second step, protect at nitrogen Protect down in 130 DEG C of stirring reactions 5 hours, then the 5th kind of component stearic acid after weighing than formula by quality 2. in table 1 adds In reaction system in container, under nitrogen protection in 150 DEG C of stirring reactions 2 hours, the product obtained sinks in deionized water Form sediment, be dried after the precipitation absolute ethanol washing that will obtain, grind, obtain improved silica powder body；

3rd step, adds after component being weighed than formula by quality 3. in table 1 in double screw extruder, from charging aperture to going out The temperature of material mouth sets gradually melt blending extrusion under conditions of being 180 DEG C-190 DEG C-200 DEG C-210 DEG C, obtains silicon dioxide Modified polypropylene composite material.

Comparative example 1

In mass ratio, polypropylene: silicon dioxide powder: APTES=100: 10: 0.2, said components is claimed Amount mixing, obtains compound, adds mixture in double screw extruder, set gradually in the temperature from charging aperture to discharging opening Under conditions of being 180 DEG C-190 DEG C-200 DEG C-210 DEG C, melt blending extrusion, obtains using common coupling agent (3-aminopropyl three Ethoxysilane, i.e. KH550) polypropylene/silicon dioxide composite material of processing.

Table 1 embodiment 1～4 and the quality of comparative example 1 compare compositing formula.

Performance evaluation mode and the standard of implementation: sample will be made by the quality of table 1 than material prepared by compositing formula, point Do not press ASTM D790 standard testing bending strength, by ASTM D638 standard testing hot strength, by ASTM D256 standard testing Impact strength.Above-mentioned test the results are shown in Table 2.

From the mechanical performance data of table 2 it will be seen that in the case of the proportioning of polypropylene, silicon dioxide is identical, and adopt Polypropylene/the silicon dioxide composite material processed with common coupling agent (APTES, i.e. KH550) is (right Ratio 1) compare, modified silicon dioxide is added to the composite (embodiment 1) made in polypropylene bending strength, Impact strength, hot strength are more preferable；Embodiment 2～4 is respectively provided with good mechanical property.This explanation: silicon dioxide is carried out Again with 2 after just processing, the method that 2-dihydromethyl propionic acid and stearic acid etc. are modified process to it, be conducive to improving poly-third The mechanical property of alkene/silicon dioxide composite material, makes the mechanics of the PP composite material adding improved silica prepared Functional.

Table 2 embodiment 1～4 and the performance test results of comparative example 1

	Bending strength (Mpa)	Impact strength (kJ/m2)	Hot strength (Mpa)
				Embodiment 1	28.3	4.7	33.5
Embodiment 2	28.1	4.6	32.8
				Embodiment 3	29.5	4.5	32.9
Embodiment 4	30.1	4.3	32.6
				Comparative example 1	28.0	4.2	32.4

Claims (1)

1. the preparation method of a silica modified PP composite material, it is characterised in that comprise the following steps:

The first step, in mass ratio, silicon dioxide: 3-[double (2-ethoxy) amino] propane triethoxysilane=100: (0.5～ 3), after said components being weighed, join grinding in ball grinder mixing, obtain just processing silicon-dioxide powdery；

Second step, in mass ratio, just processes silicon-dioxide powdery: (2,2-dihydromethyl propionic acid): p-methyl benzenesulfonic acid: dimethyl second Amide: stearic acid=100: (10～30): (1～3): (100～200): (5～15), first 4 kinds after weighing by said ratio Component (i.e.: just process silicon-dioxide powdery, 2,2-dihydromethyl propionic acid, p-methyl benzenesulfonic acid, dimethyl acetylamide) join appearance In device, under nitrogen protection in 110～130 DEG C of stirring reactions 5～7 hours, then the 5th kind of component after weighing by said ratio Stearic acid adds in the reaction system in container, under nitrogen protection in 130～150 DEG C of stirring reactions 2～4 hours, obtains Product precipitates in deionized water, is dried, grinds, obtain improved silica powder after the precipitation absolute ethanol washing that will obtain Body；

3rd step, in mass ratio, polypropylene: improved silica powder body=100: (5～30), add after said components is weighed In double screw extruder, under the processing temperature of 180～210 DEG C, melt blending is extruded, and obtains silica modified polypropylene composite materials Material.