CN101792617B - Calcium carbonate/montmorillonite nano composite particle for PP filling and preparation method thereof - Google Patents
Calcium carbonate/montmorillonite nano composite particle for PP filling and preparation method thereof Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 57
- 239000002245 particle Substances 0.000 title claims abstract description 55
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 30
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 30
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000011049 filling Methods 0.000 title claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229920002545 silicone oil Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 230000008676 import Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 5
- 230000006835 compression Effects 0.000 abstract description 5
- 238000007906 compression Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 230000035939 shock Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 description 22
- 239000011246 composite particle Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 polynite Chemical compound 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a calcium carbonate/montmorillonite nano composite particle for PP filling and a preparation method thereof. The preparation method comprises the following steps: ball-milling and mixing calcium-based montmorillonite, CTAB and industrial alcohol in proportion, then adding calcium hydroxide suspended slurry for continuous ball milling, introducing the obtained mixture into an overweight reactor, adding a crystal-form control agent, introducing CO2 for reaction, obtaining nano composite particle slurry, finally adding a modifier for modifying, and centrifugally drying. The method is simple, the principle is different from the original physical synthesis, but chemical synthesis, nano calcium carbonate particles are formed in the montmorillonite layer to lead the prepared nano composite particles to have reasonable form and distribution, good dispersion, less agglomerated particles and large specific surface area, as well as high activation index, good hydrophobicity and high surface activity. The adopted PP filled by the nano composite particles improves the shock resistance, elastic modulus and compression strength by larger degree and the compatibility between the nano composite particle and the PP polymer is good.
Description
Background technology
The present invention relates to PP filling technique field, particularly a kind of calcium carbonate/montmorillonite nano composite particle of filling for PP and preparation method thereof.
Technical field
The nano inoganic particles such as calcium carbonate, talcum, wollastonite, polynite, silicon-dioxide all can be used as the PP weighting material, replace the PP resin to play the effect of increment on the one hand, reduce production cost, can improve on the other hand mechanics, electricity, the thermal property of PP polymkeric substance.But the single particle filled composite of different shape, can produce Different Effects to the PP plastics performance, for example have good stable on heating organic montmorillonoid with the process of the processing blend of PP in oxidative degradation less, and can in the PP matrix, disperse with nanometer laminated structure, under less content, can improve the shock strength of PP, rigidity, thermotolerance, barrier and processing characteristics, spherical calcium carbonate particles can improve the compressive strength of PP, Young's modulus, improve dimensional stability, reduce compound cost, and composite filled because synergistic effect often can play beyond thought effect.The inorganic nanoparticles sub-surface has wetting ability, before being applied to the PP filling, need adding first properties-correcting agent and carry out surface modification, and different nano inoganic particles has the selection absorptivity to properties-correcting agent, and the modification of composite particles is these those skilled in the art's of puzzlement difficult point always.
In sum, how the advantage with each particle filled composite mutually combines, preparation can farthest improve the composite particles of PP material over-all properties, how to improve effectively and rationally the composite particles surface property, improving the consistency between particle and the PP polymkeric substance, is the key technical problem of the required solution of those skilled in the art.
Summary of the invention
Purpose of the present invention aims to provide calcium carbonate/montmorillonite nano composite particle of filling for PP and preparation method thereof.
The inventive method is a kind of chemical synthesis process of complete technology different from the past, the nano-complex particle good dispersion for preparing with the method, form distributes rationally, good surface activity and have strong-hydrophobicity, PP material impact intensity, the ultimate compression strength that adopts this nano-complex particle to fill all has largely raising, consistency is good between nano-complex particle and the PP polymkeric substance, has reduced production cost.
The purpose of this invention is achieved through the following technical solutions.
(1) according to mass ratio 4-6: 1: 8-12, calcium-base montmorillonite, CTAB and industrial spirit are added ball mill, ball milling 20-40min is made into slurries A;
(2) postdigestive calcium oxide and decon water are added high-speed mixer in mass ratio at 1: 40, utilize its high shear to be pulverized and mixed, separate except degranulation and impurity through multistage spinning liquid, obtain the refining calcium hydroxide suspension slurry B of 8-12wt%;
(3) with the slurries A in the slurries B adding (1) that makes in (2), the mass ratio of calcium-base montmorillonite and calcium hydroxide is 2～5: 1, is preferably 3: 1.Ball milling 40-70min obtains mixture C;
(4) mixture C in (3) is put into supergravity reactor, add chemical additives water glass or yellow soda ash, addition is 0.1～0.3% of calcium hydroxide quality, logical CO
2Reaction 50-70min obtains the calcium carbonate/montmorillonite nano composite particle slurries, and adds decon water, and adjusting slurries solid masses concentration is 45-55%.
(5) adopt two or three in titanate coupling agent, silane coupling agent and the silicone oil to mix as combination properties-correcting agent with arbitrary proportion, add the calcium carbonate/montmorillonite nano composite particle slurries according to 1%-4wt%, change the high speed modifying machine over to, the control temperature is at 55-75 ℃, and to adjust pH value with ammoniacal liquor and acetic acid be 7-10, reacts 40-60min;
(6) mixture separation that (5) is made, drying namely obtains calcium carbonate/montmorillonite nano composite particle, centrifugal rotational speed is made as 1000-1400r/min, then vacuum-drying, drying temperature 65-75 ℃, be 40-60min time of drying, vacuum tightness＜-0.050Mpa.
The polynite that the present invention adopts is calcium-base montmorillonite, described calcium-base montmorillonite median size＜300nm, smectite content＞90%, whiteness＞80.
The present invention prepares the complete technology different from the past of method of calcium carbonate/montmorillonite nano composite particle, it has utilized the principle of chemosynthesis, and method in the past only is that polynite and the simple physics of calcium carbonate granule is synthetic, calcium carbonate granule is difficult to enter the interlayer of polynite structure, the product that obtains often disperses inhomogeneous, easily reunite again between calcium carbonate particles, the scale operation quality is unstable, and the hardness of montmorillonite and calcium carbonate there are differences, can cause the particle diameter of heterogeneity particle inconsistent, can not give full play to synergy.And the inventive method has been utilized the cationic exchange effect of polynite, at first with polynite and aqua calcis reaction, introduces Ca between cheating engaging layer
2+, again with CO
2Reaction generates nano-calcium carbonate between cheating engaging layer, support the montmorillonite sheet interlayer spacing large, is conducive to and the PP formation type composite structure of delaminating, thereby can improves largely the PP material property.Simultaneously the method preparation, a compound step finish, and have save the preparation process in early stage of nano-calcium carbonate, and be energy-efficient in the industrial production, is suitable for scale operation, and solved that the dispersion that causes because material character is inconsistent is inhomogeneous, the inhomogenous problem of particle diameter.
Calcium carbonate/montmorillonite nano composite particle of the present invention, its advantage is:
(1) this nano-complex particle form distributes rationally, good dispersion, and agglomerating particles is few, and specific surface area is large;
(2) this nano-complex particle activation index is high, and hydrophobicity is good, and surfactivity is high;
(3) PP that adopts this nano-complex particle to fill, shock strength, Young's modulus, ultimate compression strength all have largely to be carried
Height, consistency is good between nano-complex particle and the PP polymkeric substance.
Description of drawings
Fig. 1 is the XRD spectrum of Comparative Examples 1 composite particles sample A and embodiment 1 composite particles sample B;
Fig. 2 is the TEM figure of embodiment 2 physical mixed particle-PP sample A1;
Fig. 3 is the TEM figure of embodiment 2 chemically composited particles-PP sub-sample B1;
Fig. 4 is the XRD spectrum of embodiment 2 chemically composited particle-PP sample B1 and pure PP;
Fig. 5 is that ((tensile strength of chemically composited particle-PP) is with the changing trend diagram of composite particles addition for physical mixed particle-PP) and sample B1 for embodiment 2 sample A1;
Fig. 6 is that ((ultimate compression strength of chemically composited particle-PP) is with the changing trend diagram of composite particles addition for physical mixed particle-PP) and sample B1 for embodiment 2 sample A1;
Fig. 7 is the schema that embodiment 1 hypergravity reaction method is produced calcium carbonate/montmorillonite nano composite particle.
1.NH
3Steel cylinder; 2.CO
2Steel cylinder; 3,4. air volume regulating valve; 5,6. tolerance under meter; 7. gas mixer; 8. rotating bed gas is crossed the threshold; 9. supergravity reactor; 10. impeller pump; 11. liquid measure variable valve; 12. liquid meter; 13. sampling spot; 14. reaction solution import; 15. product liquid outlet; 16. feed valve; 17. stock liquid storage tank; 18. product liquid storage tank; 19. discharge valve; The T-temperature measuring point; The P-pressure measurement point; PH-pH value measurement point.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Comparative Examples 1
Add the 30Kg calcium-base montmorillonite in the QMJ200 vertical ball mill, then 6KgCTAB and 60Kg industrial spirit add light calcium carbonate serosity (light calcium carbonate granularity D97＜2um, whiteness 〉=90%, CaCO3 〉=97% of 100Kg10%.), ball milling 75min, drum's speed of rotation 65r/min, the gained slurries change modifying machine over to, and adding decon water adjustment concentration of slurry is 50%, adds titanate coupling agent and silicone oil (titanic acid ester: silicone oil=5: 1) according to 1.5% of slurries quality, regulating temperature is 60 ℃, and to adjust the pH value with ammoniacal liquor and acetic acid be 8.0, starts stirring rake, modification 50min.
Slurries after the modification carry out solid-liquid separation in LGZ1000-N is centrifugal, centrifugal rotational speed is made as 1200r/min, and then vacuum-drying obtains physical mixed particle A, 70 ℃ of drying temperatures, and be 50min time of drying, vacuum tightness＜-0.050Mpa.
Sample A censorship XRD analysis, and measure its activation index, contact angle, oil-absorption(number) and specific surface area, the results are shown in Table 1.
Embodiment 1
In the QMJ200 vertical ball mill, add the 30Kg calcium-base montmorillonite, 6KgCTAB and 60Kg industrial spirit, ball milling 30min, drum's speed of rotation 65r/min, the refining calcium hydroxide that then adds 100Kg10% hangs turbid slurries, ball milling 45min, drum's speed of rotation 65r/min.The gained slurries change supergravity reactor over to, then add water glass as chemical additives, start CO
2Valve, control CO
2Flow is 1.2m
3/ s, change modifying machine over to behind the reaction 60min, adding decon water adjustment concentration of slurry is 50%, add titanate coupling agent and silicone oil (titanic acid ester: silicone oil=5: 1) according to 1.5% of slurries quality, regulating temperature is 60 ℃, and to adjust the pH value with ammoniacal liquor and acetic acid be 8.0, starts stirring rake, modification 50min.
Slurries after the modification carry out solid-liquid separation in LGZ1000-N is centrifugal, centrifugal rotational speed is made as 1200r/min, and then vacuum-drying gets chemically composited particle B, 70 ℃ of drying temperatures, and be 50min time of drying, vacuum tightness＜-0.050Mpa.
Sample B censorship XRD analysis, and measure its activation index, contact angle, oil-absorption(number) and specific surface area.
The result is referring to table 1, and embodiment 1 is the calcium carbonate/montmorillonite nano composite particle that adopts the inventive method to make, and the performance perameters such as its activation index, contact angle, oil-absorption(number) and specific surface area all are better than the physical mixed particle that Comparative Examples 1 makes.
Referring to Fig. 1, in the calcium carbonate/montmorillonite nano composite particle that employing the inventive method makes, polynite 001 characteristic diffraction peak moves to the low angle direction, and showing has the part calcium carbonate particle to enter between cheating engaging layer, supportted interlamellar spacing large, polynite and nano-calcium carbonate success are compound.
The particle (physical mixed particle A and chemically composited particle B), grafts and the PP that make among Comparative Examples 1 and the embodiment 1 (according to weight ratio 1: 5: 15) mixed 5min in pony mixer, use again on the SK160B two roller mixing rolls melting compound after the mixing, mixing even pulling-on piece takes off, then (180 ℃ of molding temperatures hot-forming on vulcanizing press, press gauge pressure 5MPa), pressurize cooling (press gauge pressure 5MPa in chilling press, temperature is down to 60 ℃), take out sample preparation, particle A makes sample and is designated as A1, and particle B makes sample and is designated as B1.
With above-mentioned sample A1, B1 censorship mechanical property and XRD, the tem analysis of making.
Referring to Fig. 2 and Fig. 3, in the TEM image, chemically composited calcium carbonate/montmorillonite nano composite particle B is compatible with PP good, is uniformly dispersed between particle, and without obvious agglomeration, montmorillonite layer reaches the state of peeling off, and the composite particles particle size is nano level.Adopt simple composite particles A and the PP consistency of mixing of physical method relatively poor, and it is comparatively serious to reunite.
Referring to Fig. 5 and Fig. 6, sample B1 (tensile strength, ultimate compression strength and the basic correlation of composite particles addition of chemically composited particle-PP), (physical mixed particle-PP) then is parabola rule to sample A1, the PP mechanical property reached peak value when chemically composited particle addition was 4%, reduced production cost largely, sample A1 and B1 and the correlation data of pure PP on mechanical property also can see Table 2.
Table 1 composite particles performance perameter
Table 2 composite particles-PP mechanical property parameters
Claims (9)
1. the preparation method who is used for the calcium carbonate/montmorillonite nano composite particle of PP filling, it is characterized in that, with the in proportion ball milling mixing of calcium-base montmorillonite, CTAB and industrial spirit, then add the calcium hydroxide suspension slurry and continue ball milling, import supergravity reactor and add chemical additives, pass into CO
2Reaction 50-70mins, CO
2With the calcium hydroxide mol ratio be 1～1.6:1; Obtain the nano-complex particle slurries, and add decon water, adjusting slurries solid masses concentration is 45-55%, adds properties-correcting agent again, and centrifugal drying gets final product.
2. preparation method according to claim 1 is characterized in that, the mass ratio of described calcium-base montmorillonite, CTAB and industrial spirit is 4～6:1:8～12.
3. preparation method according to claim 1 is characterized in that, the mass ratio of described calcium-base montmorillonite and calcium hydroxide is 2～5:1, and calcium hydroxide suspension slurry mass concentration is 8～12%.
4. according to claim 1 or 3 described preparation methods, it is characterized in that, described calcium hydroxide suspension slurry be with postdigestive calcium oxide and decon water in mass ratio 1:40 add high-speed mixer and mix, separate through multistage spinning liquid and remove degranulation and impurity obtains.
5. preparation method according to claim 1 is characterized in that, the time that adds calcium hydroxide suspension slurry continuation ball milling is 40-70mins.
6. preparation method according to claim 1 is characterized in that, described chemical additives is water glass or yellow soda ash, and addition is 0.1～0.3% of calcium hydroxide quality.
7. preparation method according to claim 1 is characterized in that, described properties-correcting agent is that two or three in titanate coupling agent, silane coupling agent and the silicone oil mixes with arbitrary proportion, accounts for altogether 1～4% of nano-complex particle slurries total mass.
8. according to claim 1 or 7 described preparation methods, it is characterized in that, temperature is 55～75 ℃ during modification, and modification time is 40-60min, and to adjust the pH value with ammoniacal liquor and acetic acid be 7-10.
9. one kind is used for the calcium carbonate/montmorillonite nano composite particle that PP fills, and it is characterized in that, described nano-complex particle is prepared by method claimed in claim 1.
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| CN102286170B (en) * | 2010-06-18 | 2013-05-01 | 中国石油化工股份有限公司 | Inorganic composite powder reinforced polypropylene composition and preparation method thereof |
| CN102875899A (en) * | 2012-10-12 | 2013-01-16 | 南京金杉汽车工程塑料有限责任公司 | Wollastonite toughened and strengthened modified polypropylene and preparation method thereof |
| CN112812587A (en) * | 2021-01-08 | 2021-05-18 | 深圳市锦昊辉实业发展有限公司 | Active nano calcium, preparation method thereof and application thereof in preparation of silicone sealant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5126300A (en) * | 1990-07-16 | 1992-06-30 | Board Of Trustees Operating Michigan State University | Clay composites for the removal of SOx from flue gas streams |
| CN101020775A (en) * | 2007-03-15 | 2007-08-22 | 复旦大学 | High strength and high toughness modified poly-propylene material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5126300A (en) * | 1990-07-16 | 1992-06-30 | Board Of Trustees Operating Michigan State University | Clay composites for the removal of SOx from flue gas streams |
| CN101020775A (en) * | 2007-03-15 | 2007-08-22 | 复旦大学 | High strength and high toughness modified poly-propylene material |
Non-Patent Citations (1)
| Title |
|---|
| 周正发等.微乳液法制备MMT-CaCO3复合粒子及其增强聚丙烯的研究.《高分子材料科学与工程》.2007,第23卷(第6期),第32－35页. * |
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