CN109232817B - Preparation method of in-situ reaction compatibilization polypropylene/attapulgite composite material - Google Patents
Preparation method of in-situ reaction compatibilization polypropylene/attapulgite composite material Download PDFInfo
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
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Abstract
The invention belongs to the technical field of organic-inorganic composite materials, and particularly relates to a preparation method of an in-situ reaction compatibilization polypropylene/attapulgite composite material. In the melt blending process, the attapulgite has an initiating function through chemical modification, and the polypropylene graft is formed as a compatibilizer through in-situ initiated grafting reaction, so that the step of preparing the polypropylene graft is omitted, the process flow is simplified, the interface strength of the polypropylene and the attapulgite is further enhanced through the in-situ initiated grafting reaction, and the dispersibility of the attapulgite and the compatibility of the attapulgite and a resin matrix are improved.
Description
Technical Field
The invention belongs to the technical field of organic-inorganic composite materials, and particularly relates to a preparation method of an in-situ reaction compatibilized polypropylene/attapulgite composite material.
Background
Among general thermoplastic plastics, polypropylene has the highest mechanical properties and heat resistance, has the characteristics of small density, low cost, good chemical stability, easy processing and molding and recycling, and has been widely applied in daily life. However, in the engineering fields of automobile industry, building industry and the like, the mechanical property of polypropylene cannot meet the requirement, so that obtaining modified polypropylene with excellent mechanical property by copolymerization, blending, filling and other methods is a hot spot of research and report in recent years.
The surface of the attapulgite has higher polarity and poorer compatibility when being blended with non-polar polymers such as polypropylene, and a compatilizer is usually required to be added. The method generally adopted at present is to take polypropylene melt grafting polar monomer as compatilizer, simultaneously adopt a proper method to carry out surface modification on the attapulgite to reduce agglomeration, introduce organic groups with better interface action with the compatilizer, and finally carry out melt blending. The method has large influence on the design and performance of materials due to different brands of carrier resin and modified resin matrix of the commercially available graft type compatilizer, and often needs to be prepared in advance, so that the process steps are increased, and most polar monomers have large odor and are harmful to human bodies in the preparation process of the compatilizer.
Disclosure of Invention
In view of the problems and defects in the prior art, the invention aims to provide a preparation method of an in-situ reaction compatibilized polypropylene/attapulgite composite material.
The invention relates to a preparation method of polypropylene/attapulgite composite material compatibilized by in-situ reaction, which mainly comprises the following three steps:
the method comprises the following steps: uniformly mixing attapulgite, a dispersion medium, a silane coupling agent and a catalyst by ultrasonic waves, stirring at normal temperature for 30min, heating to reflux for reaction, carrying out solid-liquid separation, washing and drying to obtain the attapulgite modified by the silane coupling agent;
step two: adding the dried attapulgite modified by the silane coupling agent into a dispersion medium again, adding a catalyst and a hydrogen peroxide modifier, reacting for a period of time at normal temperature, washing after solid-liquid separation, drying in vacuum and crushing to obtain the attapulgite modified by peroxy groups;
step three: uniformly mixing polypropylene, crushed peroxy group modified attapulgite, a dispersing lubricant, a grafting monomer and an antioxidant in a mixer, and performing melt extrusion granulation to obtain the in-situ reaction compatibilized polypropylene/attapulgite composite material.
In the first step, the mass ratio of the attapulgite to the silane coupling agent is 1:0.1-1:0.5, the mass ratio of the attapulgite to the dispersion medium is 1:5-1:10, the dispersion medium is a mixture of an organic solvent and water according to the mass ratio of 5:1-9:1, the organic solvent is one of ethanol, xylene, toluene and ethylene glycol, the silane coupling agent is one of chloropropyltrichlorosilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, bromopropyltrichlorosilane, bromopropyltrimethoxysilane or bromopropyltriethoxysilane, the catalyst is one of dibutyltin dilaurate, dimethyltin dilaurate or dioctyltin dilaurate, the dosage of the catalyst is 0.1-0.5% of the mass of the silane coupling agent, and the reaction time is 3-5 hours.
In the second step, the dispersion medium is one of tetrahydrofuran, trichloromethane, dioxane, dimethyl sulfoxide or N, N-dimethylformamide, the mass ratio of the attapulgite to the dispersion medium is 1:5-1:10, the catalyst is one of ferric chloride or metallic sodium, the dosage of the catalyst is 1-5% of the mass of the hydrogen peroxide compound, the dosage of the hydrogen peroxide compound is 1.2-1.5 times of the mass of the silane coupling agent in the first step, and the hydrogen peroxide compound is one of tert-butyl hydroperoxide, tert-butyl peroxide or cumene hydroperoxide; the reaction time is 3-8h at normal temperature.
In the third step, the amount of the peroxy group modified attapulgite is 0.5-2% of the mass of the polypropylene, the grafting monomer is one or more of maleic anhydride, methyl methacrylate, styrene, acrylic acid or glycidyl methacrylate, and the amount of the grafting monomer is 0.3-1% of the total mass of the polypropylene and the attapulgite;
the dispersing lubricant is liquid paraffin, silicone oil or PE wax, and the dosage of the dispersing lubricant is 0.1-0.3 percent of the mass of the polypropylene; the antioxidant is formed by mixing an antioxidant 1010 and an antioxidant 168 according to the mass ratio of 1:1-1:2, and the using amount of the antioxidant is 0.1-0.2% of the mass of the polypropylene;
the extrusion temperature was 190 ℃ and 210 ℃.
The invention firstly modifies the attapulgite by a silane coupling agent, then carries out chemical modification on the surface of the attapulgite to immobilize peroxy groups, then uses the immobilized peroxy groups as an initiator, adds a grafting monomer in the process of melt blending, and leads the monomer to graft polypropylene to form a compatilizer while the grafting monomer carries out graft polymerization on the surface of the attapulgite.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
on one hand, after the modification of the oxygen group, the agglomeration of the attapulgite is obviously improved; on the other hand, in the process of melt blending of the surface peroxide modified attapulgite and polypropylene, the peroxide groups on the surfaces can simultaneously initiate the graft polymerization of the polypropylene and the attapulgite surfaces, and the same molecules can be grafted on the polypropylene molecular chains and the attapulgite surfaces by adding a small amount of grafting monomers, so that the interface bonding strength of the polypropylene and the attapulgite is remarkably improved. In addition, the chemical modification of the surface of the attapulgite can realize continuous production (namely, the solution of the modifier can be recycled), the equipment is simple, and the technology is convenient to master. Importantly, the method omits the procedure of preparing the compatilizer, and the mechanical property of the prepared composite material is improved to a certain extent.
Drawings
FIG. 1 is an SEM image of the in-situ reaction-compatibilized polypropylene/attapulgite composite material obtained in example 2.
Detailed Description
The invention is described in more detail below with reference to the following examples:
example 1
The method comprises the following steps: fully mixing 50g of attapulgite with 250g of an absolute ethyl alcohol/water mixed solvent with the mass ratio of 9:1 to prepare a suspension, then adding 10g of chloropropyl triethoxysilane and 0.05g of dibutyl tin dilaurate, uniformly stirring at normal temperature, heating to reflux reaction for 3 hours, carrying out centrifugal separation, washing and drying to obtain chloropropyl modified attapulgite;
step two: adding 50g of chloropropyl modified attapulgite into 250g of dioxane again for uniform dispersion, adding 4.5g of tert-butyl peroxide and 0.08g of ferric chloride, reacting at normal temperature for 5h, washing after solid-liquid separation, drying in vacuum, and crushing to obtain peroxy group modified attapulgite;
step three: 2500g of polypropylene, 50g of peroxy group modified attapulgite, 2.5g of liquid paraffin, 8g of maleic anhydride and 2.5g of antioxidant (antioxidant 1010 and antioxidant 168 in a ratio of 1:1) are uniformly mixed in a mixer, and the mixture is melted and extruded at 200 ℃ for granulation to obtain the in-situ reaction compatibilized polypropylene/attapulgite composite material.
Example 2
The method comprises the following steps: fully mixing 50g of attapulgite with 500g of ethylene glycol/water mixed solvent with the mass ratio of 8:1 to prepare suspension, then adding 20g of chloropropyl triethoxysilane and 0.1g of dibutyltin dilaurate, uniformly stirring at normal temperature, heating to reflux reaction for 3 hours, centrifugally separating, washing and drying to obtain chloropropyl modified attapulgite;
step two: adding 50g of chloropropyl modified attapulgite into 500g of dioxane again for uniform dispersion, simultaneously adding 9g of tert-butyl hydroperoxide and 0.2g of ferric chloride, reacting at normal temperature for 8h, washing after solid-liquid separation, drying in vacuum and crushing to obtain peroxy group modified attapulgite;
step three: 5000g of polypropylene, 50g of peroxy group modified attapulgite, 5g of silicone oil, 15g of glycidyl methacrylate and 5g of antioxidant (antioxidant 1010 and antioxidant 168 in a ratio of 1:1) are uniformly mixed in a mixer, and the mixture is melted, extruded and granulated at 210 ℃ to obtain the in-situ reaction compatibilized polypropylene/attapulgite composite material.
FIG. 1 is a scanning electron micrograph of the in-situ reaction-compatibilized polypropylene/attapulgite composite material of the present embodiment, from which it can be seen that: the attapulgite modified by the oxygen groups has good dispersibility in a polypropylene matrix, is uniformly dispersed and is almost in a nanometer level, so that the surface energy of the attapulgite can be reduced by modifying the peroxide groups on the surface of the attapulgite, the agglomeration is improved, the peroxide groups initiate grafting in situ to form a compatilizer, and the compatibility of the attapulgite and the resin matrix is improved.
Example 3
The method comprises the following steps: fully mixing 50g of attapulgite with 250g of toluene/water mixed solvent with the mass ratio of 8:1 to prepare suspension, then adding 15g of chloropropyltrimethoxysilane and 0.03g of dioctyltin dilaurate, stirring uniformly at normal temperature, heating to reflux reaction for 5 hours, centrifugally separating, washing and drying to obtain chloropropyl modified attapulgite;
step two: adding 50g of chloropropyl modified attapulgite into 250g of chloroform again for uniform dispersion, adding 6.5g of tert-butyl peroxide and 0.15g of ferric chloride, reacting at normal temperature for 8h, washing after solid-liquid separation, drying in vacuum and crushing to obtain peroxy group modified attapulgite;
step three: 2500g of polypropylene, 50g of peroxy group modified attapulgite, 6g of PE wax, 8g of styrene and 2.5g of antioxidant (antioxidant 1010 and antioxidant 168 in a ratio of 1:1.5) are uniformly mixed in a mixer, and the mixture is melted and extruded at 190 ℃ for granulation to obtain the in-situ reaction compatibilized polypropylene/attapulgite composite material.
Example 4
The method comprises the following steps: fully mixing 50g of attapulgite with 400g of toluene/water mixed solvent with the mass ratio of 6:1 to prepare suspension, then adding 15g of bromopropyltrichlorosilane and 0.03g of dioctyltin dilaurate, uniformly stirring at normal temperature, heating to reflux reaction for 8 hours, carrying out centrifugal separation, washing and drying to obtain chloropropyl modified attapulgite;
step two: adding 50g of chloropropyl modified attapulgite into 400g of N, N-dimethylformamide again to be uniformly dispersed, adding 6.5g of tert-butyl peroxide and 0.15g of metallic sodium at the same time, reacting at normal temperature for 8h, washing after solid-liquid separation, drying in vacuum and crushing to obtain peroxy group modified attapulgite;
step three: 2500g of polypropylene, 50g of peroxy group modified attapulgite, 5g of PE wax, 8g of styrene and 2.5g of antioxidant (antioxidant 1010 and antioxidant 168 in a ratio of 1:2) are uniformly mixed in a mixer, and the mixture is melted and extruded at 190 ℃ for granulation to obtain the in-situ reaction compatibilized polypropylene/attapulgite composite material.
Comparative example 1
5000g of polypropylene, 50g of attapulgite, 5g of silicone oil, 15g of glycidyl methacrylate and 5g of antioxidant (antioxidant 1010 and antioxidant 168 in a ratio of 1:1) are uniformly mixed in a mixer, and are subjected to melt extrusion granulation at 210 ℃ to obtain the polypropylene/attapulgite composite material.
Comparative example 2
4900g of polypropylene, 50g of attapulgite, 100g of polypropylene grafted maleic anhydride, 5g of silicone oil and 5g of antioxidant (antioxidant 1010 and antioxidant 168 in a ratio of 1:1) are uniformly mixed in a mixer, and the mixture is subjected to melt extrusion granulation at 210 ℃ to obtain the in-situ reaction compatibilized polypropylene/attapulgite composite material.
The performance test standards and test results of the examples and comparative examples are shown in table 1.
TABLE 1
The data in table 1 results show that: by adopting the method of the invention, the attapulgite and the polypropylene matrix are combined through covalent bonds, so that the obtained in-situ reaction compatibilized polypropylene/attapulgite composite material has better mechanical property.
Claims (8)
1. A preparation method of an in-situ reaction compatibilized polypropylene/attapulgite composite material is characterized by comprising the following steps:
(1): uniformly mixing attapulgite, a dispersion medium, a silane coupling agent and a catalyst by ultrasonic waves, stirring at normal temperature for 30min, heating to reflux for reaction, performing solid-liquid separation, and drying to obtain the attapulgite modified by the silane coupling agent;
the silane coupling agent is one of chloropropyl trichlorosilane, chloropropyl trimethoxy silane, chloropropyl triethoxy silane, bromopropyl trichlorosilane, bromopropyl trimethoxy silane or bromopropyl triethoxy silane;
(2): adding the dried attapulgite modified by the silane coupling agent into a dispersion medium again, adding a catalyst and an organic hydrogen peroxide compound, reacting at normal temperature, carrying out solid-liquid separation, vacuum drying and crushing to obtain the attapulgite modified by peroxy groups;
the organic hydrogen peroxide compound is tert-butyl hydroperoxide, 3, 5-diisopropylbenzene hydroperoxide or cumene hydroperoxide;
(3): uniformly mixing polypropylene, crushed peroxy group modified attapulgite, a dispersing lubricant, a grafting monomer and an antioxidant in a mixer, and performing melt extrusion granulation to obtain the in-situ reaction compatibilized polypropylene/attapulgite composite material.
2. The method for preparing the in-situ reaction compatibilized polypropylene/attapulgite composite material according to claim 1, wherein in the step (1), the dispersion medium is a mixture of an organic solvent and water, wherein the mass ratio of the organic solvent to the water is 5:1-9:1, and the organic solvent is one of ethanol, xylene, toluene and ethylene glycol; the catalyst is one of dibutyltin dilaurate, dimethyltin dilaurate or dioctyltin dilaurate.
3. The method for preparing an in-situ reaction compatibilized polypropylene/attapulgite composite material according to claim 1, wherein in the step (1), the mass ratio of the attapulgite to the dispersion medium is 1:5-1: 10; the mass ratio of the attapulgite to the silane coupling agent is 1:0.1-1: 0.5; the dosage of the catalyst is 0.1-0.5% of the mass of the silane coupling agent; the reaction time is 3-5 h.
4. The method for preparing an in-situ reaction compatibilized polypropylene/attapulgite composite material according to claim 1, wherein in the step (2), the dispersion medium is one of tetrahydrofuran, chloroform, dioxane, dimethyl sulfoxide or N, N-dimethylformamide; the catalyst is one of ferric chloride or metallic sodium.
5. The method for preparing an in-situ reaction compatibilized polypropylene/attapulgite composite material according to claim 1, wherein in the step (2), the mass ratio of the attapulgite to the dispersion medium is 1:5-1: 10; the dosage of the catalyst is 1-5% of the mass of the organic hydrogen peroxide compound; the dosage of the organic hydrogen peroxide compound is 1.2 to 1.5 times of the mass of the silane coupling agent in the step (1); the reaction time at normal temperature is as follows: 3-8 h.
6. The method for preparing the in-situ reaction compatibilized polypropylene/attapulgite composite material according to claim 1, wherein in the step (3), the using amount of the peroxy group modified attapulgite is 0.5-2% of the mass of the polypropylene; the grafting monomer is one or more of maleic anhydride, methyl methacrylate, styrene, acrylic acid or glycidyl methacrylate; the dosage of the polypropylene/attapulgite composite material is 0.3-1% of the total mass of the polypropylene and the attapulgite.
7. The method for preparing the in-situ reaction compatibilized polypropylene/attapulgite composite material according to claim 1, wherein in the step (3), the dispersing lubricant is liquid paraffin, silicone oil or PE wax, the dosage of the dispersing lubricant is 0.1-0.3% of the mass of the polypropylene, and the antioxidant is prepared by mixing the antioxidant 1010 and the antioxidant 168 according to the mass ratio of 1:1-1:2, and the dosage of the antioxidant is 0.1-0.2% of the mass of the polypropylene.
8. The method for preparing an in-situ reaction-compatibilized polypropylene/attapulgite composite material as claimed in claim 1, wherein the extrusion temperature in the step (3) is 190-210 ℃.
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