CN101074306A - Polypropylene modified-nano-SiO2/CaCO3 composite grain - Google Patents

Polypropylene modified-nano-SiO2/CaCO3 composite grain Download PDF

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CN101074306A
CN101074306A CN 200610080875 CN200610080875A CN101074306A CN 101074306 A CN101074306 A CN 101074306A CN 200610080875 CN200610080875 CN 200610080875 CN 200610080875 A CN200610080875 A CN 200610080875A CN 101074306 A CN101074306 A CN 101074306A
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sio
polypropylene
composite particles
nanometer sio
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陈建峰
杨勇
曾晓飞
文利雄
邹海魁
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

A polypropylene modifier--nano-composite particle with SiO2/CaCO3 core-shell structure is preparing nano-composite particle with SiO2/CaCO3 core-shell structure, surface treating by silane coupling agent, filling into PP resin proportionally, milling, granulating by extruder, drying, injection forming to obtain PP sample, surface modification treating for SiO2 nano-particle, and making into obtain final product proportionally. It costs low and has better strength and toughness.

Description

A kind of polypropylene modifier---nanometer SiO 2/ CaCO 3Composite particles
Technical field
The present invention relates to a kind of nano-complex particle polypropylene modifier of special construction, belong to the modifying plastics field.
Background technology
Polypropylene (PP) is as a kind of general-purpose plastics, raw material sources are abundant, cheap, production technique is simple, processing characteristics is good, its tensile strength, yield strength, surface hardness and Young's modulus are all more excellent, and outstanding environmental stress crack resistance and wear resistance are arranged; Its goods are nonpoisonous and tasteless, glossiness good, thereby are widely used in every field such as chemical industry, building materials, household electrical appliances, automobile.
But polypropylene exists that molding shrinkage height, notched Izod impact strength are low, poor toughness, easy shortcoming such as aging, and this has just limited further applying of PP greatly.For this reason, domestic and international tough-increased and reinforced modification to PP has carried out extensive and deep research.The enhancing toughening modifying of PP is in the past more adopts the elastomer blended and fiber of rubber-like, filler filling blend mode.In recent years, the basic theory and the applied research of various polymkeric substance have been begun to fill both at home and abroad, particularly present various synthetic SiO about the nano grade inorganic filler 2Nano composite material has shown good polymer modification over-all properties, shows tempting application prospect.
Document 1: nano redigity particulate and caoutchouc elasticity particulate strengthen the research of tenacity-increased profax simultaneously, Chinese plastics, and 2000, (1): 99-104. Wu Wei, Xu plant moral etc. and have studied and use nanometer SiO 2With caoutchouc elasticity PARTICLE E PDM MODIFIED PP, find that above-mentioned two kinds of particulates can improve toughness, intensity and the modulus of PP simultaneously significantly.
Document 2: silicon-dioxide strengthens the research of tenacity-increased profax, and engineering plastics are used, and 2003,31 (11): 15-17. Wu Run moral etc. has been studied nanometer SiO 2Content found that SiO when loading level is two parts to the influence of material mechanical performance 2Can obviously improve the performance of PP.
Document 3: nanometer SiO 2Strengthen the research of tenacity-increased profax, Chinese plastics, 2002,16 (1): people such as 37-40. Shi Pu have prepared SiO by melt-blending process 2Disperse good PP/ nanometer SiO 2Matrix material, Mechanics Performance Testing show, when using 2 parts of nanometer SiO 2The time, PP/ nanometer SiO 2It is optimum that the mechanical property of matrix material reaches.
Document 4:Jensile yield stress of polypropylene composites filled with ultrafine particles[J], JMater Sci, 1983, the direct dispersion method of employings such as 18:1758-1764.Masao has prepared nanometer SiO 2The filled polypropylene nano composite material has been studied the nanometer SiO of different-grain diameter 2The effect of filled polypropylene.To employed 3 kinds of nanometer SiO 2, in certain loading level scope, the tensile strength of nano composite material all is higher than virgin pp, and tangible reinforced effects is arranged.
Nanometer SiO 2Particle because have that size is little, specific surface area is big, surface energy is high, characteristics such as the serious coordination deficiency in surface, make its easily and the oxygen in the polymer materials play bonding action, improve intermolecular bonding force; Simultaneously be easy to again be distributed in the space of macromolecular chain, intensity, toughness, the ductility of material are all increased substantially, reach polymer-modified purpose.Therefore if can coat one deck SiO at the lower nano grain surface of certain cost by simple production technique 2Film forms a kind of nano-complex particle of nucleocapsid structure, reaches part and replaces SiO 2The effect of kernel, and carry out corresponding surface modification, thus obtain and solid SiO 2The modification ability that nanoparticle is equal even better then can realize more at low cost polymkeric substance being carried out modification, thereby realize more massive application.
Summary of the invention
The purpose of this invention is to provide the lower nano-complex particle polypropylene modifier of a kind of cost, with realization polymkeric substance is carried out modification more at low cost, thereby realize more massive application.
Polypropylene modifier provided by the invention is a kind of at nanometer CaCO 3The surface coats one deck SiO 2The composite structure inorganic nano-particle SiO of film 2/ CaCO 3, it is a nucleocapsid structure, and carries out surface modification treatment through silane coupling agent.This composite particles SiO 2/ CaCO 3Particle diameter in the 40-100nm scope, the thick about 1-10nm of shell wall, CaCO 3Account for the 60-95% of whole composite particles volume, can be used as polypropylene modifier.
Be used for modification composite particles SiO 2/ CaCO 3Silane coupling agent be: KH570, KH560 or KH858.
The loading level of this polypropylene modifier in polypropylene is: add 1-5 part nanometer SiO in per 100 parts of polypropylene 2/ CaCO 3Composite particles.
This polypropylene modifier modified polypropene preferably loading level be: add 1-3 part nanometer SiO in per 100 parts of polypropylene 2/ CaCO 3Composite particles.
The preparation process of polypropylene modifier is as follows:
A. accurately preparation contains the sodium silicate solution that silica concentration is 0.3-0.5mol/L, with concentration is that calcium carbonate suspension about 0.7-0.9mol/L adds in the reactor, be warming up to 50-75 ℃, mass ratio by silicon/carbon dioxide acid calcium is the amount that 5-20% calculates required sodium silicate solution, in 2 hours, join in the suspension evenly above-mentioned sodium silicate solution, regulating and keep pH of suspension with hydrochloric acid simultaneously is 8-10, reinforced back ageing 2-3 hour that finishes, with its filtration, in temperature is 100～110 ℃ of dryings down, with the screening of 250 mesh sieves, promptly obtain nanometer SiO 2/ CaCO 3Composite particles;
Being warmed up to 80 ℃ in mulser after, the suspension liquid that B. will be made into 8% concentration adds silane coupling agent KH570, KH560 or KH858, the add-on of silane coupling agent is the 1-10% of nanoparticle total mass in the suspension liquid, and constant temperature stirred 30 minutes, filters, drying obtains the nanometer SiO that surface modification is crossed 2/ CaCO 3Composite particles.
The preferable range of reaction temperature of steps A is at 65-75 ℃, and the pH of control reaction system is 8-9.
The SiO that the present invention makes 2Coat CaCO 3The TEM photo of the nano-complex particle of nucleocapsid structure as shown in Figure 1.Fig. 2 be for the explanation particle nucleocapsid structure with SiO 2/ CaCO 3CaCO is removed in middle dissolving 3The TEM photo, can clearly see by Fig. 2 and to remove CaCO 3Formed hollow structure after the template.
Fig. 3 is the nanometer SiO that uses after surface modification 2/ CaCO 3The TEM photo of the matrix material that composite particles makes when loading level is 2 parts.Find out nanometer SiO by Fig. 3 2/ CaCO 3The dispersion of composite particles in the PP matrix is more uniform.With respect to unmodified nanometer SiO 2/ CaCO 3Particle, the nanometer SiO after surface modification 2/ CaCO 3Dispersion of particles is then more or less freely, also can combine well with matrix, thereby can improve the mechanical property of material.
Respectively with 1,2,3,4,5 part of surface treated SiO 2/ CaCO 3Composite particles (embodiment 1 obtains) mixes with 100 parts of polypropylene (model is 4220), and uses the forcing machine mixing granulator, oven dry back injection moulding.Simultaneously with homemade SiO 2Nanoparticle has also been made corresponding PP sample and SiO by identical proportioning through after the same surface modification treatment 2/ CaCO 3Nano-complex particle is done contrast.Carry out various performance tests then, the results are shown in Figure 4,5,6 and table 1.
Comparing result is nanometer SiO 2/ CaCO 3Composite particles and SiO 2The modified effect of nanoparticle is suitable, and analyzing reason is for the suitable nanometer SiO of granular size 2/ CaCO 3Composite particles and SiO 2Nanoparticle, upper layer all are again SiO 2, modified effect nature difference is little.Take all factors into consideration the cost of these two kinds of properties-correcting agent again, then nanometer SiO 2/ CaCO 3Composite particles has more market outlook, is a kind of better PP properties-correcting agent.
Beneficial effect of the present invention:
1. nanometer SiO 2/ CaCO 3Composite particles shock strength to PP when loading level is 1-5 part has raising.Its effect and SiO 2Solid particle is suitable, and compares SiO 2Solid particle cost is lower.
2. nanometer SiO 2/ CaCO 3Composite particles stretching and flexural strength to PP when loading level is 1-5 part also has raising.
3, the preparation technology of this nano-complex particle is simple, and raw material is cheap, thereby can substitute nanometer SiO effectively 2Solid particle carries out filling-modified to polymer materials, have vast market prospect.
Description of drawings
Fig. 1: nucleocapsid structure SiO 2/ CaCO 3The TEM photo of nano-complex particle.
Fig. 2: acid dissolves away composite particles nucleus CaCO 3The resulting hollow SiO in back 2Particulate TEM photo.
Fig. 3: nanometer SiO 2/ CaCO 3The composite particles loading level makes the TEM photo of matrix material when being two parts.
Fig. 4: nanometer SiO 2Solid particle and nanometer SiO 2/ CaCO 3Composite particles is when different loading level, to the influence of PP infill system shock strength.
Fig. 5: nanometer SiO 2Solid particle and nanometer SiO 2/ CaCO 3Composite particles is when different loading level, to the influence of PP infill system tensile strength.
Fig. 6: nanometer SiO 2Solid particle and nanometer SiO 2/ CaCO 3Composite particles is when different loading level, to the influence of PP infill system flexural strength.
Embodiment
Embodiment 1
A. preparation contains the sodium silicate solution that silica concentration is 0.5mol/L, by the mass ratio of silicon/carbon dioxide acid calcium is to calculate the amount of required sodium silicate solution at 1: 5, the calcium carbonate suspension of measuring concentration and be about 0.8mol/L adds in the reactor, after being warming up to 75 ℃, in 2 hours, join in the calcium carbonate suspension evenly sodium silicate solution while stirring, regulating and keep pH of suspension with hydrochloric acid simultaneously is 9, the reinforced back ageing 2 hours that finishes, with its filtration, in temperature is 100 ℃ of dryings down, with the screening of 250 mesh sieves, promptly obtain SiO 2/ CaCO 3Inorganic nano combined particle.
The nanoparticle suspension liquid that B. will be made into 8% concentration is warmed up to 80 ℃ in mulser, add KH570 silane coupling agent 1.5%, constant temperature stir process 30 minutes, and filtration, drying with the screening of 250 mesh sieves, promptly obtain nanometer SiO 2/ CaCO 3Composite particles properties-correcting agent.Composite particles SiO 2/ CaCO 3Particle diameter is 60nm, the thick 5nm that is about of shell wall, CaCO 3Account for 77% of whole composite particles volume.
Application examples 1
Respectively with 1,2,3,4,5 part of SiO 2/ CaCO 3Properties-correcting agent joins in the polypropylene (model is 4220) and mixes, and uses the forcing machine mixing granulator, and oven dry back injection moulding is made the standard test specimen that various performance tests are used, i.e. the PP sample.For contrasting, with homemade solid nanometer SiO 2Particle is also made corresponding PP sample by identical proportioning through after the same processing.Test contains every performance of polypropylene composite material of different loading levels then, relatively contains the size of every performance of the polypropylene composite material of different loading levels, and the results are shown in Table 1.
Table 1
Shock strength is tested by the GB/T1043-93 regulation, and tensile strength is tested by the GB/T1040-92 regulation, and flexural strength is tested by the GB/T9341-88 regulation.
As seen the result when add-on is 1-5 part, has added surface-treated SiO 2/ CaCO 3The over-all properties of the polypropylene behind the composite particles (model is 4220) is greatly improved, the shock strength of material presents and increases the trend that afterwards subtracts earlier, and the shock strength increase rate of material is between 2% to 16%, when loading level is 2 parts, the shock strength of material is the highest, reaches 14.15kJ/m 2, with respect to the 12.2kJ/m of blank sample 2, improved nearly 16%.And simultaneously when loading level is 1-5 part, the tensile strength of material also presents and increases the trend that afterwards subtracts earlier, and amplification is between 1-3%, flexural strength presents the trend that increases progressively, and amplification is between 0.6-3%, so comprehensive, when loading level is 2 parts, the various aspects of performance optimum of material.Simultaneously with homemade SiO 2Nanoparticle has also been made corresponding PP sample and SiO by identical proportioning through after the same surface modification treatment 2/ CaCO 3Nano-complex particle is done contrast.
Embodiment 2
A. preparation contains the sodium silicate solution that silica concentration is 0.5mol/L, by the mass ratio of silicon/carbon dioxide acid calcium is to calculate the amount of required sodium silicate solution at 1: 20, the calcium carbonate suspension of measuring concentration and be about 0.8mol/L adds in the reactor, after being warming up to 65 ℃, in 2 hours, join in the calcium carbonate suspension evenly sodium silicate solution while stirring, regulating and keep pH of suspension with hydrochloric acid simultaneously is 9, the reinforced back ageing 2 hours that finishes, with its filtration, in temperature is 100 ℃ of dryings down, screening (250 order) promptly obtains SiO 2/ CaCO 3Inorganic nano combined particle.
The nanoparticle suspension liquid that B. will be made into 8% concentration is warmed up to 80 ℃ in mulser, add KH570 silane coupling agent 1.5%, constant temperature stir process 30 minutes, and filtration, drying with the screening of 250 mesh sieves, promptly obtain nanometer SiO 2/ CaCO 3Composite particles properties-correcting agent.Composite particles SiO 2/ CaCO 3Particle diameter is about 55nm, the thick 1nm that is about of shell wall, CaCO 3Account for 95% of whole composite particles volume.
Application examples 2
Respectively with 1,2,3,4,5 part of SiO 2/ CaCO 3Properties-correcting agent joins in the polypropylene (model is 4220) and mixes, and uses the forcing machine mixing granulator, and oven dry back injection moulding is made the standard test specimen that various performance tests are used, i.e. the PP sample.For contrasting, with homemade solid nanometer SiO 2Particle is also made corresponding PP sample by identical proportioning through after the same processing.Test contains every performance of polypropylene composite material of different loading levels then, relatively contains the size of every performance of the polypropylene composite material of different loading levels, and the results are shown in Table 2.
Table 2
Figure A20061008087500071

Claims (5)

1. a polypropylene modifier is at nanometer CaCO 3The surface coats one deck SiO 2The nanometer SiO that film constitutes 2/ CaCO 3Composite particles, it is a nucleocapsid structure; And carry out surface modification treatment through silane coupling agent; SiO 2/ CaCO 3Particle diameter in the 40-100nm scope, the thick about 1-10nm of shell wall, CaCO 3Account for the 60-95% of whole composite particles volume;
Be used for modification composite particles SiO 2/ CaCO 3Silane coupling agent be: KH570, KH560 or KH858.
2. the application of a polypropylene modifier as claimed in claim 1, its loading level in polypropylene is: add 1-5 part nanometer SiO in per 100 parts of polypropylene 2/ CaCO 3Composite particles.
3. the application of a polypropylene modifier as claimed in claim 2 is characterized in that the loading level of this properties-correcting agent in polypropylene is: add 1-3 part nanometer SiO in per 100 parts of polypropylene 2/ CaCO 3Composite particles.
4. the preparation method of a polypropylene modifier as claimed in claim 1, concrete steps are as follows:
A. accurately preparation contains the sodium silicate solution that silica concentration is 0.3-0.5mol/L, with concentration is that calcium carbonate suspension about 0.7-0.9mol/L adds in the reactor, be warming up to 50-75 ℃, mass ratio by silicon/carbon dioxide acid calcium is the amount that 5-20% calculates required sodium silicate solution, in 2 hours, join in the suspension evenly above-mentioned sodium silicate solution, regulating and keep pH of suspension with hydrochloric acid simultaneously is 8-10, reinforced back ageing 2-3 hour that finishes, with its filtration, in temperature is 100～110 ℃ of dryings down, with the screening of 250 mesh sieves, promptly obtain nanometer SiO 2/ CaCO 3Composite particles;
Being warmed up to 80 ℃ in mulser after, the suspension liquid that B. will be made into 8% concentration adds silane coupling agent KH570, KH560 or KH858, the add-on of silane coupling agent is the 1-10% of nanoparticle total mass in the suspension liquid, and constant temperature stirred 30 minutes, filters, drying obtains the nanometer SiO that surface modification is crossed 2/ CaCO 3Composite particles.
5. the preparation method of a polypropylene modifier as claimed in claim 4, the range of reaction temperature that it is characterized in that steps A is at 65-75 ℃, and the pH of reaction system is controlled at 8-9.
CN 200610080875 2006-05-19 2006-05-19 Polypropylene modified-nano-SiO2/CaCO3 composite grain Pending CN101074306A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009106348A2 (en) * 2008-02-27 2009-09-03 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Optical trapping particle and optical trapping method
CN102399391A (en) * 2010-09-15 2012-04-04 哈尔滨鑫达高分子材料工程中心有限责任公司 Method for preparing nano SiO2/CaCO3 composite particles modified polypropylene
CN102585557A (en) * 2012-01-05 2012-07-18 池州凯尔特纳米科技有限公司 Method for industrially preparing transparent filler nano calcium carbonate for agricultural polyethylene (PE) film
CN101760049B (en) * 2009-12-09 2013-01-23 衢州卫凯化工有限公司 Method for preparing core-shell silicon dioxide-coated ammonium polyphosphate (APP)
CN103087352A (en) * 2013-01-23 2013-05-08 浙江理工大学 Method for preparing filling modified material taking CaCO3 as matrix
CN104479226A (en) * 2012-04-16 2015-04-01 上海韬鸿化工科技有限公司 Polypropylene plastic filled with coupling agent modified calcium carbonate
WO2015153637A3 (en) * 2014-04-01 2015-11-26 Uwm Research Foundation, Inc. Hollow silicon structures for use as anode active materials in lithium-ion batteries

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009106348A2 (en) * 2008-02-27 2009-09-03 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Optical trapping particle and optical trapping method
WO2009106348A3 (en) * 2008-02-27 2009-11-12 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Optical trapping particle and optical trapping method
CN101760049B (en) * 2009-12-09 2013-01-23 衢州卫凯化工有限公司 Method for preparing core-shell silicon dioxide-coated ammonium polyphosphate (APP)
CN102399391A (en) * 2010-09-15 2012-04-04 哈尔滨鑫达高分子材料工程中心有限责任公司 Method for preparing nano SiO2/CaCO3 composite particles modified polypropylene
CN102585557A (en) * 2012-01-05 2012-07-18 池州凯尔特纳米科技有限公司 Method for industrially preparing transparent filler nano calcium carbonate for agricultural polyethylene (PE) film
CN104479226A (en) * 2012-04-16 2015-04-01 上海韬鸿化工科技有限公司 Polypropylene plastic filled with coupling agent modified calcium carbonate
CN103087352A (en) * 2013-01-23 2013-05-08 浙江理工大学 Method for preparing filling modified material taking CaCO3 as matrix
CN103087352B (en) * 2013-01-23 2014-07-16 浙江理工大学 Method for preparing filling modified material taking CaCO3 as matrix
WO2015153637A3 (en) * 2014-04-01 2015-11-26 Uwm Research Foundation, Inc. Hollow silicon structures for use as anode active materials in lithium-ion batteries
US10381641B2 (en) 2014-04-01 2019-08-13 Uwm Research Foundation, Inc. Hollow silicon structures for use as anode active materials in lithium-ion batteries

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