CN1296422C - Inorganic whisper reinforced polyolefin composite material in-situ filled polymerization preparing method - Google Patents
Inorganic whisper reinforced polyolefin composite material in-situ filled polymerization preparing method Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 42
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 28
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 title abstract description 17
- -1 polypropylene Polymers 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 15
- 238000011049 filling Methods 0.000 claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract 6
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
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- Reinforced Plastic Materials (AREA)
Abstract
一种无机晶须增强聚烯烃复合材料的原位填充聚合制备方法，包括在经过预先搅拌分散处理的无机晶须表面负载烯烃聚合催化剂，然后在其表面进行烯烃单体聚合，直接得到聚烯烃/晶须复合材料。该复合材料由3-80%的无机矿物晶须和20-97%的聚烯烃聚合物组成。本发明所描述的制备方法简便，用该方法制备复合材料，晶须的填充程度高，晶须的长径比得到保持，而且晶须在基体聚合物中的分布均匀，与基体界面粘结好，充分发挥了晶须的增强特性，得到的聚烯烃/无机晶须复合材料具有易于成型加工、制品表面光洁度好、以及力学性能优异的特点。塑料基体可以制备成从低分子量、中等分子量、高分子量到超高分子量的聚烯烃，如聚丙烯或聚乙烯。所得到的材料既可以直接通过注射成型后作为结构材料使用，也可以用作母料，与商品聚烯烃共混后使用。A preparation method for in-situ filling polymerization of inorganic whisker-reinforced polyolefin composite materials, comprising loading an olefin polymerization catalyst on the surface of inorganic whiskers that have been pre-stirred and dispersed, and then polymerizing olefin monomers on the surface to directly obtain polyolefin/ Whisker composite. The composite material consists of 3-80% inorganic mineral whiskers and 20-97% polyolefin polymer. The preparation method described in the present invention is simple and convenient, and the composite material is prepared by this method, the filling degree of the whiskers is high, the aspect ratio of the whiskers is maintained, and the distribution of the whiskers in the matrix polymer is uniform, and the interface with the matrix is well bonded , giving full play to the reinforcing properties of the whiskers, and the obtained polyolefin/inorganic whisker composite material has the characteristics of easy molding and processing, good surface finish of the product, and excellent mechanical properties. The plastic matrix can be prepared as polyolefins ranging from low molecular weight, medium molecular weight, high molecular weight to ultra-high molecular weight, such as polypropylene or polyethylene. The obtained material can be directly used as a structural material after injection molding, or used as a masterbatch and blended with commercial polyolefins.
Description
Technical field
The present invention relates to a kind of preparation method of composite polyolefine material, relate in particular to the original position filling polymerization process for preparing that a kind of inorganic crystal whisker strengthens composite polyolefine material.
Background technology
Thermoplastic polymer composite material has purposes widely.Traditional preparation method is that the method by melt blending prepares thermoplastic polymer composite material.The shortcoming of this method is that the dispersion of filler in matrix polymer is even inadequately, especially to the filler of fine sizes.In addition, the interfacial bond property on filler and matrix polymer surface is also good inadequately, thereby has influenced the raising of this class material mechanical performance.By improving mixed effect, perhaps filler is carried out surface treatment, as use coupling agent or adopt the surface to coat technology such as (being also referred to as micro encapsulation), can improve the mechanical property of matrix material, but also can bring some such as the problem on equipment, technology, the cost.
In order to solve the scattering problem of filler in polymkeric substance and the interface adhesion problem of filler and matrix polymer effectively, people have proposed original position and have filled the polymeric method, the component that has catalytic activity in filling surface load just with active group, carry out polymer reaction on the surface of this filler then, directly obtain polymer composites.For example Chinese patent CN1252416 discloses a kind of method for preparing composite conductive polyolefine material, be to activate with Ziegler-Natta catalyst through pretreated polymolecularity electroconductive stuffing, carry out the olefinic monomer polymerization on its surface then, prepare the adjustable conductive filler material/polymer composites of conduction scope.Advantages such as the matrix material with this method preparation has filler filling extent height, and filler distribution is even, and physical strength is good, and the conduction scope is adjustable can adapt to the requirement of various electro-conductive materials.Chinese patent CN1150157 has proposed a kind of method for preparing filler/polyolefin composite material, it is the polymerization of on treated polymolecularity metal, metal oxide, metal carbonate, non-metallic material and natural mineral filling surface, carrying out olefinic monomer, prepare filler/polymer composites with various excellent properties, matrix material with this method preparation has filler filling extent height, the all even high deformation-pi of strength of filler distribution, plastic substrate can be prepared as advantages such as high molecular or ultra-high molecular weight.
In recent years, the granular of filler size just attracts much attention, some nano level fillers such as nanoclay, nano silicon, nano-calcium carbonate etc. have been used as the filler or the toughener of polymkeric substance, and the wherein existing original position filling polymeric method that adopts prepares polymer composites.Announced in inert solvent as Chinese patent CN1293692A, with methylaluminoxane (MAO) laminar nano particle montmorillonitic clay (if you would take off stone, saponite, vermiculite etc.) is carried out surface treatment, can promote the catalyzer of alpha-olefin or styrene polymerization to be distributed to again together in the solvent these clay complexes and some other then, carry out polymerization again.Can comprise multiple alkene such as ethene, propylene by the polymeric monomer.The composite polyolefine material that obtains is compared with common polyolefine, and some mechanical propertys such as yielding stress or rupture stress increase significantly.Chinese patent CN1255510 has also proposed the preparation method of the nanocomposite of a kind of polyolefine and clay, fiber rod stone kind clay by the polyethylene and 0.1～60% (weight percent) of 40～99.9% (weight percents) is formed, and used clay mainly is selected from sepiolite or attapulgite.By filler is heat-treated, supported catalyst carries out olefinic polymerization at filling surface then again, mainly is polyethylene.This nanocomposite has excellent mechanical property and thermotolerance.
From the enhanced angle, form of reinforcement and size, particularly toughener length-to-diameter ratio be a very important factor that influences reinforced effects.Comparatively speaking, granular nanometer filler such as CaCO
3, SiO
2Deng through suitable interface processing, may produce toughening effect preferably to polymkeric substance, but the enhanced effect is still not ideal enough, under a lot of situations, these fillers can only play the effects such as dimensional stability that reduce the material use cost or improve material.Even develop more successful exfoliated nano clays filler at present, though can significantly improve the resistance toheat of some polymkeric substance such as nylon 6, but because the intensity of itself and the limitation of length-to-diameter ratio, its reinforced effects is still far away from the fiber reinforced polymer composites of routine.
Conventional fibrous toughener such as carbon fiber, glass fibre etc., diameter is generally at 5～15 mu m ranges.And nano level toughener, as inorganic nano clay, carbon nanotube etc., lamellar spacing or diameter are less than 100nm.The research and development of relevant this two classes toughener are many, but for size between this two classes toughener, the toughener of diameter about 1 μ m obviously paid attention to not enough.It must be emphasized that: on the one hand, this class toughener has the excellent size characteristic, diameter is than the conventional fiber such as a little order of magnitude such as carbon fiber, glass fibre, specific surface area obviously increases like this, very little with the polymkeric substance compound tense to the processing characteristics such as the melt viscosity influence degree of system, and the composite product that obtains has very slick surface, and the processing viscosity of having avoided the conventional fibre matrix material to exist increases, adds wear equipment and shortcoming such as product surface is coarse in man-hour.The dispersion treatment of this class material is more much easier than handling nano level toughener again on the other hand, has avoided the shortcoming of the too tiny buildup effect of bringing of filler size.Should the inorganic mineral whisker be exactly outstanding representative in this class toughener.
Whisker be meant have the fixed shape of cross section, complete profile, perfect internal structure, length-to-diameter ratio be up to 5～1000 fibrous single crystal.Whisker has excellent intensity, Young's modulus, thermotolerance, erosion resistance and wear resistance, is high performance composite toughener of new generation.From the initial stage eighties, China's emphasis is studied whiskers such as silicon carbide, aluminum oxide, silicon nitrides, has obtained some breakthroughs.Though this class whisker excellent performance costs an arm and a leg, and can only be applied to some special dimension at present.
In recent years, people's developing low-cost inorganic mineral Preparation of Whiskers technology competitively.The inorganic crystal whisker material of some relative low price and excellent performance is developed in succession.These whiskers comprise: potassium titanate crystal whisker, [as Chinese patent ZL1035443, CN1259593, ZL1077611, described in the CN1271786 etc.], aluminium borate whisker [seeing described in the Chinese patent CN1093065], ZnOw [see Chinese patent ZL1031838, ZL1031895 described in], magnesium salt whisker [seeing described in the Chinese patent CN1288860] etc.Inorganic crystal whisker is early had report as the research of polymkeric substance toughener, as Chinese patent CN1281009 disclosure of the Invention a kind of polybutylene terephthalate matrix material that contains whisker and TLCP.The production technique of composite material with stereospecific whisker strengthened polymer has been described in Chinese patent ZL1068352, be that polymkeric substance and whisker are mixed with whisker dispersion spinning solution highly uniformly, adopt the solvent spinning technology to form the fiber blank then, the fiber blank is arranged in hot pressing or pressureless sintering after the required shape by the element strained condition again, produces the polymer matrix composite of the controlled orientation of whisker.Whisker is uniformly dispersed in the material of gained, be without damage, and directional effect is good.The intensity of matrix material, Young's modulus and tension set are greatly improved than the material of whisker chaotic distribution.But obviously, the described method of this patent seems too loaded down with trivial details, lacks the feasibility of actual production.A kind of preparation method with potassium titanate crystal whisker reinforced polyimide composite material has also been described in Chinese patent ZL1085707.
Yet up to the present, whisker is not used widely in polymer composites.Trace it to its cause, except some early stage whiskers such as silicon carbide nitrogen or change silicon wafer must cost than higher, also, need handle the whisker surface because the whisker surface is poor with the interface bonding of matrix polymer.But the treatment process of some glass fibre or carbon fiber is mainly still continued to use in the measure of taking at present, as using the method for silane coupling agent.So far also do not find the effective surface treatment method of inorganic crystal whisker material, the mechanical property of resulting polymkeric substance/metal whisker composite can not be satisfactory, becomes the major reason of restriction whisker widespread use in polymer composites.The toughener that whisker is used for general-purpose plastics is to enlarge the better approach that whisker is used at thermoplastic resin.But the prerequisite that whisker has been used in a large scale in general-purpose plastics is: the adding of whisker can obviously improve the over-all properties of matrix material, otherwise, to compare with other more cheap filler such as lime carbonate, talcum powder, mica etc., inorganic crystal whisker has no competitive edge and can say.
Though people have taked the whole bag of tricks that whisker is carried out surface treatment, or change different processing molding methods, also do not adopt at present the method for in-situ polymerization to prepare the patent and the bibliographical information of polyolefine/inorganic crystal whisker matrix material.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of polyolefine/inorganic mineral metal whisker composite, the polyolefine that the present invention obtains/inorganic mineral metal whisker composite has following characteristics:
1. the dispersion of whisker in matrix polymer is more even.
2. injection molding polyolefine/inorganic mineral metal whisker composite smooth surface, even.
3. the mechanical property of matrix material material is compared with common polyolefine and is increased significantly, and the increase rate that also is better than generally polyolefine/inorganic mineral metal whisker composite, particularly tensile property of being obtained by melt blending is remarkable.
4. the loading level of whisker can be regulated arbitrarily, filling the low matrix material of the resulting whisker content of polymerization can directly use as structured material separately, and the high material of whisker content can be used as masterbatch and other polyolefin blend, make well behaved matrix material again, thereby can adapt to the needs of different field.
Technical scheme of the present invention be earlier with catalyst cupport on the whisker surface, carry out the original position olefinic polymerization on the whisker surface then, thereby obtain that whisker is uniformly dispersed, the whisker surface has better agglutinating polyolefine/metal whisker composite with the matrix polymer interface.
Specifically, the preparation method of matrix material of the present invention is as follows:
The inorganic mineral whisker that A. will contain crystal water carries out vacuum drying treatment, to remove free moisture.
B. use rare gas element that reactor is replaced.The product of steps A is placed dried inert solvent, and powerful the stirring guarantees that whisker fully disperses.
C. carrying transition metal compound catalyst at first on step B basis, adding organo-aluminium compound again is promotor, makes the whisker that the surface has catalytic activity.
D. on the basis of step C, carry out the olefinic monomer polymerization.
E. stop polyreaction with ethanol on the basis of step D, the washing drying obtains polyolefine/metal whisker composite.
The used whisker of described (A) step is the inorganic mineral whisker, comprise potassium titanate crystal whisker, magnesium salts (or alkali magnesium sulfate) whisker, ZnOw, silicon carbide whisker, aluminium borate whisker, calcium sulfate crystal whiskers and calcium carbonate crystal whisker etc., these whisker morphology are viewed as needle-like crystal like white powder under the Electronic Speculum.Preferred whisker is that (chemical structural formula is MgSO to magnesium salt whisker
45Mg (OH)
23H
2O or MgSO
45MgO8H
2O).The diameter of whisker is at the 0.5-5 mu m range, and length is at the 5-1000 mu m range.
The used rare gas element of described (B) step is nitrogen, argon gas or helium, preferred nitrogen.
The used inert solvent of described (B) step is C
5～C
10Alkane, gasoline, sherwood oil or toluene, preferred hexane or toluene.
Described (C) step is carried out in reactor.At first be metered into transition metal compound catalyst, stirred 0.5 hour～3 hours, adding organo-aluminium compound again is promotor, stirs 10～20 minutes, after stablizing to the inert solvent absorption, carries out the olefinic polymerization of (D) step again.
Described (C) step also can be carried out in the following manner: at first be metered into excessive transistion metal compound on (B) step basis, stirred 0.5 hour-6 hours, filter, collect solid product, be promotor again with the organo-aluminium compound, stirred 10-20 minute, and after stablizing to the inert solvent absorption, carried out the olefinic polymerization of (D) step again.
The transistion metal compound that described (C) step is used can be selected from halogenide, oxyhalogenation thing, the C of one of Ti, Zr, Hf, V, Sc, Nb and Ta
1-C
10Alcoxyl halogenide or hydrohalogen or the mixture between them, as TiCl
4, TiBr
4, Ti (OCH
3)
4, Ti (OCH
3) Cl
3, Ti (OCH
3)
2Cl
2, Ti (OCH
3)
3Cl, VCl
4, VOCl
3Deng, TiCl preferably
4, Ti (OCH
3)
4, Ti (OCH
3) Cl
3, Ti (OCH
3)
2Cl
2, Ti (OCH
3)
3Cl etc., more preferably TiCl
4
The promotor that adds in described (C) step is an organo-aluminium compound, can be selected from aluminum alkyls, and alkyl aluminum halide or aluminum alkoxide are as Al (C
2H
5)
3, Al (C
2H
5)
2Cl, Al
2(C
2H
5)
3Cl
3, Al (i-C
4H
9)
3, Al (C
6H
13)
3, Al
2(C
2H
5)
3Cl
3, Al
2(C
2H
5)
2(OC
2H
5) etc., preferably triethyl aluminum, triisobutyl aluminium and aluminum alkoxide.
Transistion metal compound is the amount adding by every gram whisker 0.5-100 mmole in described (C) step, preferred add-on is 0.5-50 mmole/gram, the consumption mol ratio of the Al in the organo-aluminium compound and the transition metal of transistion metal compound is 5-200, preferably 10-100.
Olefinic monomer used in described (D) step can be C
2-C
8Alkene, preferably ethene and propylene.
Polymerization temperature in described (D) step can be controlled at 0-100 ℃ of scope, and preferred temperature range is 50-90 ℃.
Polymerization pressure 0.1-2MPa in described (D) step.
Polymerization time in described (D) step is 0.2-5 hour.Preferably 0.5-3 hour.
Description of drawings
In order to describe technical characterstic of the present invention better, provide some embodiment below and also be described further in conjunction with the accompanying drawings, but be not to have a mind to limit scope involved in the present invention.
Fig. 1 is the electromicroscopic photograph of magnesium salt whisker in the inorganic mineral whisker of the present invention's employing;
Fig. 2 and Fig. 3 are the electromicroscopic photograph of embodiment 2;
Fig. 4 is the electromicroscopic photograph of Comparative Examples 2.
Embodiment
Embodiment 1
To restrain through the magnesium salt whisker 0.6 that super-dry, dehydration deoxygenation are handled, at N
2Protection joins in the polymerization bottle of drying, dehydration deoxygenation down, after the vinyl monomer displacement several times, adds 100mL toluene, stirs 30 minutes, to guarantee the abundant dispersion of whisker, adds catalyzer TiCl with syringe fast
41mL, be stirred to toluene absorb stable after, press the triethyl aluminum that Al/Ti (mol ratio) 30/1 adds metering, be warming up to 80 ℃, ethylene pressure keeps 0.1MPa to begin polymerization, react after 30 minutes, add the ethanol stopped reaction, left standstill 12 hours, filter, vacuum-drying obtains fluffy Powdered white polyethylene/metal whisker composite 12.8 grams.After the injection molding, measure the mechanical property of matrix material, tensile strength 39MPa, tensile modulus 960MPa, elongation at break 58%.
Embodiment 2
To restrain through the calcium sulfate crystal whiskers 1.2 that super-dry, dehydration deoxygenation are handled, at N
2Protection joins in the polymerization bottle of drying, dehydration deoxygenation down, after the vinyl monomer displacement several times, adds the 100mL hexanaphthene, stirs 30 minutes, to guarantee the abundant dispersion of whisker, adds catalyzer TiCl with syringe fast
41ml, be stirred to toluene absorb stable after, press the triethyl aluminum that Al/Ti (mol ratio) 30/1 adds metering, be warming up to 80 ℃, ethylene pressure keeps 0.1MPa to begin polymerization, react after 30 minutes, add the ethanol stopped reaction, left standstill 12 hours, filter, vacuum-drying obtains fluffy Powdered white polyethylene/metal whisker composite 17.3 grams.After the injection molding, measure the mechanical property of matrix material, tensile strength 41MPa, tensile modulus 1.2GPa, elongation at break 22%.
Embodiment 3
To restrain through the magnesium salt whisker 1.2 that super-dry, dehydration deoxygenation are handled, at N
2Protection joins in the polymerization bottle of drying, dehydration deoxygenation down, after the vinyl monomer displacement several times, adds 100mL toluene, stirs 30 minutes, to guarantee the abundant dispersion of whisker, adds catalyzer TiCl with syringe fast
41ml, be stirred to toluene absorb stable after, press the triisobutyl aluminium that Al/Ti (mol ratio) 30/1 adds metering, be warming up to 80 ℃, ethylene pressure keeps 0.1MPa to begin polymerization, react after 30 minutes, add the ethanol stopped reaction, left standstill 12 hours, filter, vacuum-drying obtains fluffy Powdered white polyethylene/metal whisker composite 8.2 grams.After the injection molding, measure the mechanical property of matrix material, tensile strength 36MPa, tensile modulus 990MPa, elongation at break 62%.
Embodiment 4
To restrain through the magnesium salt whisker 4.5 that super-dry, dehydration deoxygenation are handled, at N
2Protection joins in the polymerization bottle of drying, dehydration deoxygenation down, after the vinyl monomer displacement several times, adds 100mL toluene, stirs 30 minutes, to guarantee the abundant dispersion of whisker, adds catalyzer TiCl with syringe fast
42.0ml, be stirred to toluene absorb stable after, press the aluminum alkoxide (MAO) that Al/Ti (mol ratio) 30/1 adds metering, be warming up to 80 ℃, ethylene pressure keeps 0.1MPa to begin polymerization, react after 30 minutes, add the ethanol stopped reaction, left standstill 12 hours, filter, vacuum-drying obtains Powdered white polyethylene/metal whisker composite 19.8 grams.After the injection molding, measure the mechanical property of matrix material, tensile strength 56MPa, tensile modulus 1.3GPa, elongation at break 18%.Whisker is evenly distributed in the matrix material, and length-to-diameter ratio is higher, (see figure 2).From matrix material profile scanning electromicroscopic photograph (see figure 3), do not see the existence of tangible whisker, show that whisker combines better with matrix resin.
Embodiment 5
To restrain through the magnesium salt whisker 3.0 that super-dry, dehydration deoxygenation are handled, at N
2Protection joins in the polymerization bottle of drying, dehydration deoxygenation down, after the vinyl monomer displacement several times, adds 100mL toluene, stirs 30 minutes, to guarantee the abundant dispersion of whisker, adds catalyzer TiCl with syringe fast
41.0ml, be stirred to toluene absorb stable after, press the aluminum alkoxide (MAO) that Al/Ti (mol ratio) 30/1 adds metering, be warming up to 80 ℃, ethylene pressure keeps 0.1MPa to begin polymerization, reacts after 30 minutes, add the ethanol stopped reaction, leave standstill filtration in 12 hours, vacuum-drying obtains fluffy Powdered white polyethylene/metal whisker composite 21.3 grams.After the injection molding, measure the mechanical property of matrix material, tensile strength 44MPa, tensile modulus 1.1GPa, elongation at break 38%.
Embodiment 6
To restrain through the magnesium salt whisker 3.0 that super-dry, dehydration deoxygenation are handled, at N
2Protection joins in the polymerization bottle of drying, dehydration deoxygenation down, after the propylene monomer displacement several times, adds 100mL toluene, stirs 30 minutes, to guarantee the abundant dispersion of whisker, adds catalyzer TiCl with syringe fast
41.0ml, be stirred to toluene absorb stable after, press the aluminum alkoxide (MAO) that Al/Ti (mol ratio) 30/1 adds metering, be warming up to 80 ℃, propylene pressure keeps 0.1MPa to begin polymerization, reacts after 30 minutes, add the ethanol stopped reaction, leave standstill filtration in 12 hours, vacuum-drying obtains fluffy Powdered white polypropylene/metal whisker composite 19.5 grams.After the injection molding, measure the mechanical property of matrix material, tensile strength 43MPa, tensile modulus 1.4GPa, elongation at break 47%.
Comparative Examples 1
To after vinyl monomer displacement several times, add 100mL exsiccant toluene through the polymerization bottle of super-dry, dehydration deoxygenation processing, add catalyzer TiCl with syringe fast
41.0ml, be stirred to toluene absorb stable after, press the aluminum alkoxide (MAO) that Al/Ti (mol ratio) 30/1 adds metering, be warming up to 80 ℃, pressure keeps 0.1MPa (gauge pressure) beginning polymerization, reacts after 30 minutes, add the ethanol stopped reaction, leave standstill filtration in 12 hours, vacuum-drying, the polyethylene 22.5 that obtains Powdered white restrains.After the injection molding, measure poly mechanical property, tensile strength 22MPa, tensile modulus 664MPa, elongation at break 260%.
Comparative Examples 2
Will be through magnesium salt whisker 10 grams of drying treatment, handle with silane coupling agent, after the drying, in Haake Rheomixer, carry out melt blending, 5 minutes time, 200 ℃ of blending temperatures with exsiccant high density polyethylene(HDPE) 45 grams, with the matrix material injection molding that obtains is the mechanical test batten, the mechanical property of the matrix material that obtains is: tensile strength 28Mpa, tensile modulus 990MPa, elongation at break 27%.(see figure 4) can find out obviously that whisker extracts the cavity that stays behind the matrix from matrix material section microphotograph, although this shows the processing through silane coupling agent, the interface bonding between whisker and the matrix is still good inadequately.
Claims (8)
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| CN101423639B (en) * | 2008-12-09 | 2011-02-02 | 中山大学 | A kind of PPR/SiO2 nanocomposite material and preparation method thereof |
| CN102127262B (en) * | 2011-01-25 | 2012-10-24 | 太原科技大学 | Polypropylene antistatic composite material and preparation method thereof |
| CN102234390B (en) * | 2011-04-18 | 2012-07-11 | 刘立文 | A kind of calcium sulfate whisker modified low-density polyethylene composite material and preparation method thereof |
| CN102504409A (en) * | 2011-11-04 | 2012-06-20 | 上海大学 | Method for enhancing polypropylene using calcium sulfate whisker |
| CN102408631B (en) * | 2011-11-09 | 2014-02-19 | 东莞上海大学纳米技术研究院 | A kind of high-strength flame-retardant polypropylene modified material and preparation method thereof |
| CN103509242B (en) * | 2012-06-29 | 2017-06-27 | 上海杰事杰新材料(集团)股份有限公司 | One kind enhancing polypropylene flame redardant/inorganic crystal whisker composite and preparation method thereof |
| CN103497391A (en) * | 2013-10-22 | 2014-01-08 | 四川万润非金属矿物材料有限公司 | Calcium sulfate crystal whisker master batch and method for preparing same |
| WO2015085133A1 (en) | 2013-12-06 | 2015-06-11 | Georgia-Pacific Gypsum Llc | Calcium sulfate crystals and methods for making the same |
| WO2015085236A1 (en) * | 2013-12-06 | 2015-06-11 | Flint Hills Resources, Lp | Gypsum composite modifiers |
| CN113683431A (en) * | 2021-06-23 | 2021-11-23 | 重庆科技学院 | Aluminum borate whisker reinforced and toughened nonmetal-based composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5187021A (en) * | 1989-02-08 | 1993-02-16 | Diamond Fiber Composites, Inc. | Coated and whiskered fibers for use in composite materials |
| CN1293692A (en) * | 1998-03-16 | 2001-05-02 | 陶氏化学公司 | Polyolefin nanocomposites |
-
2003
- 2003-10-29 CN CNB2003101044649A patent/CN1296422C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5187021A (en) * | 1989-02-08 | 1993-02-16 | Diamond Fiber Composites, Inc. | Coated and whiskered fibers for use in composite materials |
| CN1293692A (en) * | 1998-03-16 | 2001-05-02 | 陶氏化学公司 | Polyolefin nanocomposites |
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