CN109232817A - A kind of preparation method of in situ reactive compatibilization polypropylene/attapulgite composite material - Google Patents
A kind of preparation method of in situ reactive compatibilization polypropylene/attapulgite composite material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- 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
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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Abstract
The invention belongs to composite organic-inorganic material technical fields, more particularly to a kind of preparation method of in situ reactive compatibilization polypropylene/attapulgite composite material, this method uses the preparation of surface chemical modification method with the attapulgite modified of peroxy-radical first, attapulgite modified, polypropylene, grafted monomers and antioxidant are uniformly mixed again, and be granulated through melting extrusion, polypropylene/attapulgite composite material is made by In situ Reactive Compatibility.During melt blending, attapulgite is set to be provided with initiation function by chemical modification, initiation grafting in situ reacts to form graft polypropylene as expanding material, eliminate the step of preparing graft polypropylene, simplify process flow, the boundary strength for further enhancing polypropylene and attapulgite by initiation grafting reaction in situ simultaneously, improves the dispersibility of attapulgite and its compatibility with resin matrix.
Description
Technical field
The invention belongs to composite organic-inorganic material technical field more particularly to a kind of in situ reactive compatibilization polypropylene/
The preparation method of attapulgite composite material.
Background technique
In general-purpose thermoplastic plastic, polypropylene has highest mechanical property and heat resistance, and the small, cost with density
It is low, chemical stability is good, easy processing molding and the characteristics of recoverable, extensive use has been obtained in daily life.
But in engineering fields such as auto industry, building trades, polyacrylic mechanical property is unable to satisfy requirement, therefore, by being copolymerized,
The modified polypropene of the methods of blending acquisition excellent mechanical performance is always the hot spot of Recent study report.
Attapulgite's surface polarity is higher, and compatibility is poor when for example polypropene blended with non-polar polymer, usually needs
Compatilizer is added.The method generallyd use at present is used simultaneously using polypropylene fusion graft polar monomer as compatilizer
Method appropriate is surface modified mitigation to attapulgite and reunites, and introduces with compatilizer with preferable interface interaction
Organic group finally carries out melt blending.Vector resin and modified resin of this method due to commercially available graft type compatilizer
The trade mark of matrix is different, has larger impact to the design and performance of material, generally requires to be prepared in advance, so that
Process increases, and in compatilizer preparation process, most of polar monomer smells are larger, are harmful to the human body.
Summary of the invention
In view of the problems existing in the prior art and defect, it is poly- that the purpose of the present invention is to provide a kind of in situ reactive compatibilizations
Propylene/attapulgite composite material preparation method, the present invention use surface chemical modification to introduce in attapulgite's surface first
With the peroxy-radical for causing function, melt blending then is carried out with polypropylene again, a small amount of grafting is added in the blending process
Monomer reacts to form compatilizer in this way, in-situ grafting polymerization occurs during melt blending, and this method is alleviating concave convex rod
While mass of soil is poly-, the compatibility of polypropylene and attapulgite has been taken into account, has eliminated the process for preparing compatilizer, and reduce
The dosage of grafted monomers.
The present invention uses in situ reactive compatibilization polypropylene/attapulgite composite material preparation method, mainly includes following
Three steps:
Step 1: attapulgite, decentralized medium, silane coupling agent, catalyst ultrasonic mixing is uniform, it is stirred under room temperature
It is warming up to reflux after 30min to be reacted, washing and drying obtains silane coupler modified attapulgite after separation of solid and liquid；
Step 2: the silane coupler modified attapulgite after drying is added in decentralized medium again, addition is urged
Agent, hydroperoxide kind modifying agent are reacted under room temperature a period of time, are washed after separation of solid and liquid, are crushed, obtain after vacuum drying
The modified attapulgite of peroxy-radical；
Step 3: by polypropylene, smashed peroxy-radical is attapulgite modified, dispersed lubricant, grafted monomers, resists
Oxygen agent is uniformly mixed in mixing machine, and melting extrusion obtains in situ reactive compatibilization polypropylene/attapulgite clay compounded material after being granulated
Material.
Wherein, in step 1, the mass ratio of attapulgite and silane coupling agent is 1:0.1-1:0.5, attapulgite with point
The mass ratio of dispersion media is 1:5-1:10, and decentralized medium is the mixing that organic solvent and water are obtained according to the mass ratio of 5:1-9:1
Object, the organic solvent be one of ethyl alcohol, dimethylbenzene, toluene, ethylene glycol, silane coupling agent be chloropropyl trichloro-silane,
R-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, bromopropyl trichlorosilane, bromopropyl trimethoxy silane or bromine
One of propyl-triethoxysilicane, catalyst are dibutyl tin dilaurate, dilaurate or tin dilaurate
One of dioctyl tin, catalyst amount are the 0.1-0.5%, reaction time 3-5h of silane coupling agent quality.
In step 2, decentralized medium is tetrahydrofuran, chloroform, dioxane, dimethyl sulfoxide or N, N- dimethyl
The mass ratio of one of formamide, attapulgite and decentralized medium is 1:5-1:10, and catalyst is in iron chloride or metallic sodium
One kind, catalyst amount be hydroperoxide kind compound quality 1-5%, hydroperoxide kind compound amount be step 1
1.2-1.5 times of middle silane coupling agent amount of substance, hydroperoxide kind compound are tert-butyl hydroperoxide, tertbutanol peroxide
Or one of cumyl hydroperoxide；The room temperature lower reaction time is 3-8h.
In step 3, the modified attapulgite dosage of peroxy-radical is the 0.5-2% of polypropylene quality, and grafted monomers are
One of maleic anhydride, methyl methacrylate, styrene, acrylic or methacrylic acid ethylene oxidic ester are a variety of, connect
The dosage of branch monomer is the 0.3-1% of polypropylene and attapulgite gross mass；
Dispersed lubricant is atoleine, silicone oil or PE wax, and dosage is the 0.1-0.3% of polypropylene quality；It is described anti-
Oxygen agent is that antioxidant 1010 and irgasfos 168 are mixed according to the mass ratio of 1:1-1:2, and dosage is polypropylene quality
0.1%-0.2%；
Extrusion temperature is 190-210 DEG C.
The present invention passes through silane coupling agent first and is modified to attapulgite, is then chemically modified on its surface
Immobilized peroxy-radical, then using immobilized peroxy-radical as initiator, grafted monomers are added during melt blending, it is concave-convex
While the peroxy-radical on stick soil surface causes monomer graft polypropylene formation compatilizer, grafted monomers are in attapulgite's surface
Also it will do it graft polymerization, when polymerization reaction terminates in a manner of being coupled, attapulgite will pass through altogether with polypropylene matrix
Valence link combines, and this combination acts on the interface cohesion between organic matrix (polypropylene) and inorganic particulate (attapulgite)
Stronger, intensity is much larger than the interface interaction of Hydrogenbond.
Due to the adoption of the above technical scheme, the invention has the following advantages:
On the one hand, modified through peroxy-radical, the reunion of attapulgite is obviously improved；On the other hand, surface mistake
For the attapulgite and polypropylene of oxidation modification during melt blending, the peroxy-radical on surface can cause polypropylene simultaneously
It is graft-polymerized with attapulgite's surface, a small amount of grafted monomers, which are added, to be grafted in polypropylene molecular chain and attapulgite's surface
Same molecules, and then significantly improve the interface bond strength of polypropylene and attapulgite.In addition, attapulgite table of the invention
Face chemical modification can realize continuous production (i.e. the solution of modifying agent is reusable), and equipment is simple, and technology is convenient for grasp.Weight
What is wanted is the process that this method eliminates compatilizer preparation, and the composite materials property tool prepared has a certain upgrade.
Detailed description of the invention
Fig. 1 is in situ reactive compatibilization polypropylene/attapulgite composite material SEM figure that embodiment 2 obtains.
Specific embodiment
The present invention is described in further detail below with reference to embodiment:
Embodiment 1
Step 1: dehydrated alcohol/water mixed solvent 250g that 50g attapulgite and mass ratio are 9:1 is sufficiently mixed system
At suspension, 10g chloropropyl triethoxysilane and 0.05g dibutyl tin dilaurate is then added, is stirred evenly under room temperature
After be warming up to back flow reaction 3h, washing and drying obtains the modified attapulgite of chloropropyl after centrifuge separation；
Step 2: the modified attapulgite of 50g chloropropyl is added to again in 250g dioxane and is uniformly dispersed, together
When tertbutanol peroxide 4.5g and iron chloride 0.08g, normal-temperature reaction 5h is added, wash after separation of solid and liquid, powder after vacuum drying
It is broken, obtain the modified attapulgite of peroxy-radical；
Step 3: by 2500g polypropylene, 50g peroxy-radical is attapulgite modified, 2.5g atoleine, 8g maleic acid
Acid anhydride, 2.5g antioxidant (antioxidant 1010 and irgasfos 168, ratio 1:1) are uniformly mixed in mixing machine, are melted and are squeezed at 200 DEG C
In situ reactive compatibilization polypropylene/attapulgite composite material is obtained after being granulated out.
Embodiment 2
Step 1: 50g attapulgite is sufficiently mixed with mass ratio for the glycol/water mixed solvent 500g of 8:1 and is made
Suspension, is then added 20g chloropropyl triethoxysilane and 0.1g dibutyl tin dilaurate, under room temperature after mixing evenly
It is warming up to back flow reaction 3h, washing and drying obtains the modified attapulgite of chloropropyl after centrifuge separation；
Step 2: the modified attapulgite of 50g chloropropyl is added to again in 500g dioxane and is uniformly dispersed, together
When tert-butyl hydroperoxide 9g and iron chloride 0.2g, normal-temperature reaction 8h is added, wash after separation of solid and liquid, crushed after vacuum drying,
Obtain the modified attapulgite of peroxy-radical；
Step 3: by 5000g polypropylene, 50g peroxy-radical is attapulgite modified, 5g silicone oil, 15g methacrylic acid contract
Water glyceride, 5g antioxidant (antioxidant 1010 and irgasfos 168, ratio 1:1) are uniformly mixed in mixing machine, are melted at 210 DEG C
In situ reactive compatibilization polypropylene/attapulgite composite material is obtained after melting extruding pelletization.
Fig. 1 is the present embodiment in situ reactive compatibilization polypropylene/attapulgite composite material stereoscan photograph, from figure
It is upper it can be seen that there is dispersibility well in polypropylene matrix through the modified attapulgite of peroxy-radical, and disperse compared with
It is almost in nanoscale to be uniform, this just illustrates that the table of attapulgite can be reduced by carrying out peroxy-radical modification to attapulgite's surface
Face energy, so that reuniting is improved, and peroxy-radical original position initiation grafting forms compatilizer, improves attapulgite and resin
The compatibility of matrix.
Embodiment 3
Step 1: the toluene/water mixed solvent 250g that 50g attapulgite and mass ratio are 8:1 is sufficiently mixed be made it is outstanding
Then supernatant liquid is added 15g r-chloropropyl trimethoxyl silane and 0.03g tin dilaurate dioctyl tin, rises after mixing evenly under room temperature
Temperature is to back flow reaction 5h, and washing and drying obtains the modified attapulgite of chloropropyl after centrifuge separation；
Step 2: the modified attapulgite of 50g chloropropyl is added to again in 250g chloroform and is uniformly dispersed, together
When tertbutanol peroxide 6.5g and iron chloride 0.15g, normal-temperature reaction 8h is added, wash after separation of solid and liquid, powder after vacuum drying
It is broken, obtain the modified attapulgite of peroxy-radical；
Step 3: by 2500g polypropylene, 50g peroxy-radical is attapulgite modified, 6g PE wax, 8g styrene, 2.5g resist
Oxygen agent (antioxidant 1010 and irgasfos 168, ratio 1:1.5) is uniformly mixed in mixing machine, and melting extrusion is granulated at 190 DEG C
After obtain in situ reactive compatibilization polypropylene/attapulgite composite material.
Embodiment 4
Step 1: the toluene/water mixed solvent 400g that 50g attapulgite and mass ratio are 6:1 is sufficiently mixed be made it is outstanding
Then supernatant liquid is added 15g bromopropyl trichlorosilane and 0.03g tin dilaurate dioctyl tin, is warming up to after mixing evenly under room temperature
Back flow reaction 8h, washing and drying obtains the modified attapulgite of chloropropyl after centrifuge separation；
Step 2: the modified attapulgite of 50g chloropropyl is added to 400gN again, is dispersed in dinethylformamide
Uniformly, tertbutanol peroxide 6.5g and metallic sodium 0.15g being added while, normal-temperature reaction 8h is washed after separation of solid and liquid, and vacuum is dry
It is crushed after dry, obtains the modified attapulgite of peroxy-radical；
Step 3: by 2500g polypropylene, 50g peroxy-radical is attapulgite modified, 5g PE wax, 8g styrene, 2.5g resist
Oxygen agent (antioxidant 1010 and irgasfos 168, ratio 1:2) is uniformly mixed in mixing machine, after melting extrusion is granulated at 190 DEG C
Obtain in situ reactive compatibilization polypropylene/attapulgite composite material.
Comparative example 1
5000g polypropylene, 50g attapulgite, 5g silicone oil, 15g glycidyl methacrylate, 5g antioxidant is (anti-
Oxygen agent 1010 and irgasfos 168, ratio 1:1) it is uniformly mixed in mixing machine, melting extrusion obtains poly- third after being granulated at 210 DEG C
Alkene/attapulgite composite material.
Comparative example 2
4900g polypropylene, 50g attapulgite, 100g polypropylene grafted maleic anhydride, 5g silicone oil, 5g antioxidant is (anti-
Oxygen agent 1010 and irgasfos 168, ratio 1:1) it is uniformly mixed in mixing machine, melting extrusion obtains original position after being granulated at 210 DEG C
Increasing reaction polypropylene/attapulgite composite material.
The performance test standard and test result of each embodiment and comparative example are shown in Table 1.
Table 1
Data result in table 1 shows: due to passing through covalent bond using the method for the present invention attapulgite and polypropylene matrix
In conjunction with so that obtained in situ reactive compatibilization polypropylene/attapulgite composite material mechanical property is preferable.
Claims (8)
1. a kind of preparation method of in situ reactive compatibilization polypropylene/attapulgite composite material, which is characterized in that the preparation method
Steps are as follows:
(1): attapulgite, decentralized medium, silane coupling agent, catalyst ultrasonic mixing is uniform, it is risen after stirring 30min under room temperature
Temperature to reflux is reacted, and drying obtains silane coupler modified attapulgite after separation of solid and liquid；
(2): the silane coupler modified attapulgite after drying being added in decentralized medium again, catalyst, mistake is added
Hydrogen species modifying agent is aoxidized, is reacted under room temperature, is crushed after being separated by solid-liquid separation vacuum drying, the modified attapulgite of peroxy-radical is obtained；
(3): by polypropylene, smashed peroxy-radical is attapulgite modified, dispersed lubricant, grafted monomers, antioxidant are mixed
It is uniformly mixed in conjunction machine, melting extrusion obtains in situ reactive compatibilization polypropylene/attapulgite composite material after being granulated.
2. the preparation method of in situ reactive compatibilization polypropylene/attapulgite composite material according to claim 1, feature
It is, in step (1), the decentralized medium is the mixture of organic solvent and water, wherein the mass ratio of organic solvent and water is
5:1-9:1, organic solvent are one of ethyl alcohol, dimethylbenzene, toluene, ethylene glycol；The silane coupling agent is chloropropyl trichlorine
Silane, r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, bromopropyl trichlorosilane, bromopropyl trimethoxy silane
Or one of bromopropyl triethoxysilane；The catalyst be dibutyl tin dilaurate, dilaurate or
One of tin dilaurate dioctyl tin.
3. the preparation method of in situ reactive compatibilization polypropylene/attapulgite composite material according to claim 1, feature
It is, in step (1), the mass ratio of the attapulgite and decentralized medium is 1:5-1:10；The attapulgite and silane are even
The mass ratio for joining agent is 1:0.1-1:0.5；The catalyst amount is the 0.1-0.5% of silane coupling agent quality；The reaction
Time is 3-5h.
4. the preparation method of in situ reactive compatibilization polypropylene/attapulgite composite material according to claim 1, feature
It is, in step (2), the decentralized medium is tetrahydrofuran, chloroform, dioxane, dimethyl sulfoxide or N, N- diformazan
One of base formamide；The catalyst is one of iron chloride or metallic sodium；The hydroperoxide kind compound is uncle
One of butylhydroperoxide, tertbutanol peroxide or cumyl hydroperoxide.
5. the preparation method of in situ reactive compatibilization polypropylene/attapulgite composite material according to claim 1, feature
It is, in step (2), the mass ratio of the attapulgite and decentralized medium is 1:5-1:10；The catalyst amount is peroxide
Change the 1-5% of hydrogen species compound quality；The hydroperoxide kind compound amount is silane coupling agent amount of substance in step (1)
1.2-1.5 again；The room temperature lower reaction time are as follows: 3-8h.
6. the preparation method of in situ reactive compatibilization polypropylene/attapulgite composite material according to claim 1, feature
It is, in step (3), the attapulgite modified dosage of peroxy-radical is the 0.5-2% of polypropylene quality；The grafted monomers
For one of maleic anhydride, methyl methacrylate, styrene, acrylic or methacrylic acid ethylene oxidic ester or a variety of；
Its dosage is the 0.3-1% of polypropylene and attapulgite gross mass.
7. the preparation method of in situ reactive compatibilization polypropylene/attapulgite composite material according to claim 1, feature
It is, in step (3), the dispersed lubricant is atoleine, silicone oil or PE wax, and dosage is the 0.1- of polypropylene quality
0.3%, the antioxidant is that antioxidant 1010 and irgasfos 168 are mixed according to the mass ratio of 1:1-1:2, and dosage is
The 0.1-0.2% of polypropylene quality.
8. the preparation method of in situ reactive compatibilization polypropylene/attapulgite composite material according to claim 1, feature
It is, in step (3), the extrusion temperature is 190-210 DEG C.
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| CN111040368A (en) * | 2019-12-20 | 2020-04-21 | 广州市聚赛龙工程塑料股份有限公司 | ABS alloy material with low linear expansion coefficient, and preparation method and application thereof |
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