CN1334281A - Process for preparing inorganic filler reinforced polymer composite material - Google Patents
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- CN1334281A CN1334281A CN 01114289 CN01114289A CN1334281A CN 1334281 A CN1334281 A CN 1334281A CN 01114289 CN01114289 CN 01114289 CN 01114289 A CN01114289 A CN 01114289A CN 1334281 A CN1334281 A CN 1334281A
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Abstract
A process for preparing the inorganic filler reinforced polymer composite material includes treating inorganic rigid particles as filler with vinyl silane, adding organic monomer, graft copolymerizing reaction, mixing with matrix polymer, and conventional processing. Its advantages are high strength and toughness.
Description
The invention belongs to the preparation method of matrix material, particularly the inorganic rigid particle surface recombination strengthens the method for toughening polymer material.
Inorganic rigid particle strengthens polymer composites (PRPC) and has been widely used in fields such as automobile, building materials, chemical industry, electronic apparatus.Yet, because mineral filler mostly is hydrophilic particles, very high surface energy is arranged usually, hydrophobic polymkeric substance can not soak into filler or with filler generation surface reaction.For improving machinery and other physicals of PRPC, many improve filler and the close-burning researchs of basal body interface have been carried out in recent years.Traditional method is to adopt coupling agent or higher fatty acid processing filler grains such as silane, titanic acid ester, yet because the interaction of long chain alkane base and matrix resin is limited, the amplitude that composite materials property improves is limited; Coat the filler grain surface such as elastomericss such as polyacrylic ester, EVA, rubber, improved the resistance to impact shock of matrix material to a certain extent, but cause the reduction of the strength of materials and modulus simultaneously again; Another method of modifying is that filling surface is carried out the interface structure of Cement Composite Treated by Plasma with the change matrix material, thereby increases the consistency between filler and the polymeric matrix, but this method is subjected to certain restriction aspect industrial application; At present occur some again and improved the novel method of composite material interface, as: sol-gel method, original position insertion polymerization, filling polymerization and in-situ polymerization etc.Sol-gel method is to adopt organic precursor such as silicon, aluminium, titanium, zirconium and polymer monomer to prepare the method for inorganic-organic system molecular composite material, and material preparation cost height is of limited application; The original position insertion polymerization is the good method of a kind of preparation polyalcohol/clay soil matrix material or nano composite material (as nylon 6/ Nano composite material of montmorillonite etc.), but the loading level of this method filler is low; Fill polymerization and be the filler that utilizes filler with catalytic activity or catalyst supported on surface and carry out the polycoordination of alkene on its surface, but this method also has very big distance from industrialization; In-situ polymerization can be used to prepare matrix material, also can be used for handling filling surface, the core of method is that filler grain and the organic monomer of selecting for use are dispersed in the suitable system, make the monomer-polymer of formation evenly be coated on the surface of inorganic particulate, rely on filling surface to improve the state of interface of filler and matrix polymer with the interaction of the polymkeric substance of physical action parcel and matrix polymer, but this method to composite materials property to improve effect also limited." progress that the filled polymer material is handled with inorganic filler surface " literary composition has shown the situation of this respect prior art.
The preparation method who the purpose of this invention is to provide a kind of inorganic filler reinforced polymer composite material, it is applicable to the matrix polymer of broad variety, makes the mechanical property of matrix material all can be greatly improved.
The preparation method of inorganic filler reinforced polymer composite material of the present invention in turn includes the following steps:
1) mineral filler is immersed in the vinyl silanes aqueous solution at normal temperatures, stirs 0.5-5
Hour,
2) leach the mineral filler of handling, be placed on inert gas filled reactor
In, add water soluble starter, emulsifying agent, water medium to this system,
3) aforementioned all materials are stirred, be heated to 30-80 ℃, add organic monomer and advance
Row graft copolymerization 2-10 hour, described organic monomer is according to the polymer phase patibhaga-nimitta
Molten principle is selected and the good organic monomer of matrix polymer consistency to be mixed, does not have
Machine filler/organic monomer weight ratio is 1-100: 1,
4) with 3) in reaction product separate, washing, dry back gained modified inorganic filler grain
Son mixes with matrix polymer proportioning on demand, optionally carries out routine again
Processing.
The preparation method of described inorganic filler reinforced polymer composite material, it is further characterized in that described vinyl silanes concentration of aqueous solution is 0.01%-1.5%, described water soluble starter weight is the 0.1%-5% of organic monomer weight, described emulsifying agent weight is the 0.5%-5% of organic monomer and mineral filler gross weight, and the 10-50 that described water medium weight is mineral filler weight doubly.
The preparation method of described inorganic filler reinforced polymer composite material,
(1) described mineral filler can be selected from a kind of of following inorganic rigid particle:
Talcum powder, lime carbonate, quartz sand, silica, glass microballon, hydroxyapatite, whisker, mica, kaolin,
(2) described vinyl silanes can be selected from the one of the following kind:
Vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (beta-methoxy-Ethoxysilane),
(3) described matrix polymer can be selected from the one of the following kind:
Polyethylene, polypropylene, polyvinyl chloride, polyphenylene oxide, polyester, polymeric amide,
(4) described organic monomer is selected and the good organic monomer of matrix polymer intermiscibility, can
Should be the one of the following kind mutually:
Methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, acrylamide, methyl acrylate, ethyl propenoate, butyl acrylate, vinylbenzene.The preparation method of described inorganic filler reinforced polymer composite material, described water soluble starter can be selected from the one of the following kind: ammonium persulphate, Potassium Persulphate, water soluble oxidized reductive agent, described emulsifying agent can be selected from the one of the following kind: sodium laurylsulfonate, sodium stearate, potassium rosinate.
This preparation method of the present invention is owing to adopt vinyl silanes to handle earlier to inorganic rigid particle, have vinyl with the chemical bond combination on the surface of filler, close reaction with polymer monomer generation in-situ copolymerization, form graft copolymer on the inorganic rigid particle surface.Because this graft copolymer and matrix polymer have good consistency, reduced the surface energy of inorganic rigid particle, inorganic rigid particle is uniformly dispersed in matrix polymer, the bonding interface situation of inorganic rigid particle and matrix polymer is improved greatly, and the mechanical property of matrix material (tensile strength, modulus, toughness etc.) is greatly enhanced.
Table 1 is the preparation method and the performance comparison of the glass microballon of the different-grain diameter polyphenylene oxide based composites of filling.
Table 1
| Comparative group | ????1 | ????2 | ????3 | ????4 | ????5 | |
| The preparation method | Injection molding behind 3000 order glass microballons (15Wt%) and the polyphenylene oxide melt blending | 3000 order glass microballon/vinylbenzene are handled with 4: 1 in-situ polymerizations, with injection molding behind the polyphenylene oxide melt blending (loading level 15wt%) | 3000 order glass microballoons process rear with VTES and styrene closes processing with 4: 1 in-situ copolymerizations, with injection moulding behind the polyphenylene oxide melt blending (loading 15Wt%) | Injection molding behind 6000 order glass microballons (15wt%) and the polyphenylene oxide melt blending | 6000 order glass microballoons process rear with VTES and styrene closes processing with 4: 1 in-situ copolymerizations, with injection moulding behind the polyphenylene oxide melt blending (loading 15wt%) | |
| Mechanical property | Shock strength KJ/m 2 | ????5.8 | ????7.2 | ????8.6 | ????6.5 | ????12.3 |
| Tensile strength MPa | ????46.0 | ????48.5 | ????50.0 | ????48.0 | ????52.0 | |
| Tensile modulus Gpa | ????2.10 | ????2.13 | ????2.20 | ????2.11 | ????2.24 | |
| The form of surface of fracture | State of interface is poor | Bonding interface is better | Bonding interface is excellent | State of interface is poor | Bonding interface is excellent | |
Annotate: the polyphenylene oxide trade mark is N22X, and the form of surface of fracture is observed by scanning electron microscope and obtained.
As can be seen from Table 1, the glass microballon in the comparative group 1,4 does not carry out surface treatment, and the glass microballon in the comparative group 2 carries out in-situ polymerization with vinylbenzene with 4: 1 mass ratio to be handled, and comparative group 3,5 has adopted preparation method of the present invention.Now compare with comparative group 1,2,3, silane and vinylbenzene are handled in 3000 order glass microballon surface in situ copolymerizations, and the modulus of polyphenylene oxide/glass bead composite is slightly improved, but the tensile strength of matrix material improves 4MPa, and shock strength improves 48.3%; Compare with comparative group 4,5, silane and vinylbenzene are handled in 6000 order glass microballon surface in situ copolymerizations, and the modulus of polyphenylene oxide/glass bead composite is obviously improved, and tensile strength improves 4MPa, and shock strength improves 89.2%.
Table 2 is enhancing polymer composites preparation method and property comparison for the inorganic rigid particle talcum powder.
Handle on the talcum powder surface of comparative group 6,8 in the table 2, and comparative group 7,9,10 has adopted preparation method of the present invention.Can find out that from table 1 and table 2 inorganic rigid particle provided by the invention surface vinyl silanes-polymer monomer in-situ copolymerization closes tensile strength and the modulus that processing can significantly improve the inorganic rigid particle filled polymer composite, especially can increase substantially the toughness of matrix material, make inorganic rigid particle and strengthen toughened composite polymer material simultaneously.
Table 2
| Comparative group | ????6 | ????7 | ????8 | ????9 | ????10 |
| The preparation method | Compression molding behind 2500 order talcum powder (20Wt%) and the polyvinyl chloride melt blending | 2500 order talcum powder are processed with combined polymerization in 4: 1 with methyl methacrylate after using vinyl three (beta-methoxy-ethyoxyl) silane treatment, with compression molding behind the polyvinyl chloride melt blending (loading 20wt%) | Injection molding after 2500 order talcum powder (30wt%) and the polypropylene fusion blend | 2500 order talcum powder process rear with VTES and methyl methacrylate is processed with combined polymerization in 6: 1, with injection moulding after the polypropylene fusion blend (loading 30wt%) | 2500 order talcum powder process rear with VTES and butyl acrylate is processed with combined polymerization in 30: 1, with injection moulding after the polypropylene fusion blend (loading 30wt%) |
| Shock strength KJ/m 2 | ????4.1 | ????6.3 | ????3.6 | ????4.2 | ????6.2 |
| Tensile strength MPa | ????45.0 | ????51.2 | ????30.2 | ????38.4 | ????33.8 |
| Tensile modulus Gpa | ????1.35 | ????1.53 | ????- | ????- | ????- |
| The form of surface of fracture | State of interface is poor | Bonding interface is better | State of interface is poor | Bonding interface is excellent | Bonding interface is excellent |
The comparative group 3,5 of table 1 is as embodiments of the invention 1:
Embodiment 1: glass microballon was handled 1 hour with the 0.05% vinyltriethoxysilane aqueous solution; In the reactor of nitrogen protection, under 70 ℃, carry out in-situ copolymerization and close processing with vinylbenzene (granulated glass sphere and cinnamic weight ratio are 4: 1), the Potassium Persulphate that adopts monomer weight 2% is that the sodium laurylsulfonate of initiator, monomer and glass microballon gross weight 2% is made emulsifying agent, the water medium that adds in the reaction system is 15 times of glass microballon weight, and polymerization reaction time is 4 hours; Separate the glass microballon that drying treatment is crossed, then with polyphenylene oxide (glass microballon/polyphenylene oxide is 15: 85) blend after injection moulding.
The comparative group 7,9,10 of table 2 is respectively as embodiments of the invention 2,3,4:
Embodiment 2: talcum powder was handled 2 hours with 0.5% vinyl three (beta-methoxy-oxyethyl group) silane-water solution; In the reactor of nitrogen protection, under 80 ℃, carry out in-situ copolymerization and close processing with methyl methacrylate (weight ratio of talcum powder and methyl methacrylate is 4: 1), the ammonium persulphate that adopts monomer weight 1% is that the sodium laurylsulfonate of initiator, monomer and talcum powder gross weight 2% is made emulsifying agent, the water medium that adds in the reaction system is talcous 20 times, and polymerization reaction time is 2 hours; Separate the talcum powder that drying treatment is crossed, then with polyvinyl chloride (weight ratio of talcum powder and polyvinyl chloride is 20: 80) blend after compression molding.
Embodiment 3: talcum powder was handled 1 hour with the 0.1% vinyltriethoxysilane aqueous solution; In the reactor of nitrogen protection, under 70 ℃, carry out in-situ copolymerization and close processing with methyl methacrylate (weight ratio of talcum powder and methyl methacrylate is 6: 1), the Potassium Persulphate that adopts monomer weight 2% is that the sodium laurylsulfonate of initiator, monomer and talcum powder gross weight 3% is made emulsifying agent, the water medium that adds in the reaction system is 15 times of talcum powder weight, and polymerization reaction time is 5 hours; Separate the talcum powder that drying treatment is crossed, then with polypropylene (talcum powder and polyacrylic weight ratio are 30: 70) blend after injection moulding.
Embodiment 4: talcum powder was handled 2 hours with the 0.2% vinyltriethoxysilane aqueous solution; In the reactor of nitrogen protection, under 70 ℃, carry out in-situ copolymerization and close processing with butyl acrylate (weight ratio of talcum powder and butyl acrylate is 30: 1), the Potassium Persulphate that adopts monomer weight 2% is that the sodium laurylsulfonate of initiator, monomer and talcum powder gross weight 3% is made emulsifying agent, the water medium that adds in the reaction system is 15 times of talcum powder weight, and polymerization reaction time is 5 hours; Separate the talcum powder that drying treatment is crossed, then with polypropylene (talcum powder and polyacrylic weight ratio are 30: 70) blend after injection moulding.
Embodiment 5, example example 6 below are provided again:
Embodiment 5: hydroxyapatite was handled 0.5 hour with the 0.02% vinyltrimethoxy silane aqueous solution; In the reactor of nitrogen protection, under 80 ℃, carry out in-situ copolymerization and close processing with acrylic acid amides (weight ratio of hydroxyapatite and acrylic acid amides is 100: 1), the Potassium Persulphate that adopts monomer weight 4% is that the sodium laurylsulfonate of initiator, monomer and hydroxyapatite gross weight 5% is made emulsifying agent, the water medium that adds in the reaction system is 10 times of hydroxyapatite weight, and polymerization reaction time is 6 hours; Separate the hydroxyapatite that drying treatment is crossed, then with nylon 6 (polymeric amide) (weight ratio of hydroxyapatite and nylon 6 is 10: 90) blend after injection moulding.
Embodiment 6: kaolin was handled 6 hours with the 1% vinyltriethoxysilane aqueous solution; In the reactor of helium protection, under 30 ℃, carry out in-situ copolymerization and close processing with methyl acrylate (weight ratio of kaolin and methyl acrylate is 1: 1), the water soluble oxidized reductive agent that adopts monomer weight 2% is that the sodium stearate of initiator, monomer and kaolin gross weight 5% is made emulsifying agent, the water medium that adds in the reaction system is 50 times of kaolin weight, and polymerization reaction time is 10 hours; Separate the kaolin that drying treatment is crossed, then with polyester (weight ratio of kaolin and polyester is 20: 80) blend after injection moulding.
Claims (5)
1. the preparation method of an inorganic filler reinforced polymer composite material in turn includes the following steps:
1) mineral filler is immersed in the vinyl silanes aqueous solution at normal temperatures, stirs
0.5-5 hour,
2) leach the mineral filler of handling, be placed on inert gas filled reaction
In the device, add water soluble starter, emulsifying agent, water medium to this system,
3) aforementioned all materials are stirred, be heated to 30-80 ℃, add organic monomer
Carried out graft copolymerization 2-10 hour, described organic monomer is according to polymkeric substance
The similar principle that mixes is selected and good the having of matrix polymer consistency to be mixed
The machine monomer, mineral filler/organic monomer weight ratio is 1-100: 1,
4) with 3) in reaction product separate, washing, dry back gained modified inorganic fill out
Material particle and matrix polymer proportioning on demand mix, more optionally
Carry out routine processing.
2. the preparation method of inorganic filler reinforced polymer composite material as claimed in claim 1, it is characterized in that described vinyl silanes concentration of aqueous solution is 0.01%-1.5%, described water soluble starter weight is the 0.1%-5% of organic monomer weight, described emulsifying agent weight is the 0.5%-5% of organic monomer and mineral filler gross weight, and the 10-50 that described water medium weight is mineral filler weight doubly.
3. the preparation method of inorganic filler reinforced polymer composite material as claimed in claim 1 or 2 is characterized in that:
(1) described mineral filler is selected from a kind of of following inorganic rigid particle:
Talcum powder, lime carbonate, quartz sand, silica, glass microballon, hydroxyapatite,
Whisker, mica, kaolin,
(2) described vinyl silanes is selected from the one of the following kind:
Vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (β
-methoxy (ethoxy) base silane),
(3) described matrix polymer is selected from the one of the following kind:
Polyethylene, polypropylene, polyvinyl chloride, polyphenylene oxide, polyester, polymeric amide,
(4) described organic monomer is selected and the good organic list of matrix polymer intermiscibility
Body should be the one of the following kind mutually:
Methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, third
Alkene acid amides, methyl acrylate, ethyl propenoate, butyl acrylate, vinylbenzene.
4. the preparation method of inorganic filler reinforced polymer composite material as claimed in claim 1 or 2, it is characterized in that: described water soluble starter is selected from the one of the following kind: ammonium persulphate, Potassium Persulphate, water soluble oxidized reductive agent, described emulsifying agent is selected from the one of the following kind: sodium laurylsulfonate, sodium stearate, potassium rosinate.
5. the preparation method of inorganic filler reinforced polymer composite material as claimed in claim 3, it is characterized in that: described water soluble starter is selected from the one of the following kind: ammonium persulphate, Potassium Persulphate, water soluble oxidized reductive agent, described emulsifying agent is selected from the one of the following kind: sodium laurylsulfonate, sodium stearate, potassium rosinate.
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