CN1616539A - Modified small bulk polypropylene composition and its preparing method - Google Patents
Modified small bulk polypropylene composition and its preparing method Download PDFInfo
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- CN1616539A CN1616539A CN 200410012571 CN200410012571A CN1616539A CN 1616539 A CN1616539 A CN 1616539A CN 200410012571 CN200410012571 CN 200410012571 CN 200410012571 A CN200410012571 A CN 200410012571A CN 1616539 A CN1616539 A CN 1616539A
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Abstract
The present invention belongs to the field of polymer modification technology. The present invention features that the modified small bulk polypropylene composition contains nucleartor capable of inducing beta crystal formation, inorganic nanometer particle, coupling agent, antioxidant, lubricant and chlorine absorbent. The preparation process includes drying and ultrasonic dispersing of nanometer particle, activation with coupling agent, mixing the processed nanometer particle with other components, melting and mixing extrusion in double screw extruder to pelletize small bulk polypropylene composition. The composition has greatly raised shock strength and bending strength.
Description
One, technical field
Modification small-entity polypropylene composition and method of making the same of the present invention belongs to the technical field of polymer modification, in particular to a kind of modification small-entity polypropylene composition and method of making the same.
Two, background technology
Polypropylene (PP) is to belong to one of five big general-purpose plastics by the thermoplastic resin that propylene monomer is polymerized, because its source is enriched cheaply, synthesis technique is simple, and the physical synthesis performance is good in addition, and becomes the fastest kind of increase in the general-purpose plastics.Yet because it also exists many weak points, product fragility is big, and particularly low-temperature impact resistance is bad, and thermostability is little, and weathering resistance is poor, and high temperature rigid deficiency etc. make its application be subjected to certain restriction.Therefore, polypropylene is carried out modification and become important research direction in recent years.
Polypropylene is a kind of crystalline polymer, and the quality of its performance and its crystalline texture have confidential relation.
The crystal habit of isotatic polypropylene has five kinds of α, β, γ, δ and plan six side's attitudes, and is wherein comparatively common with α and beta crystal.Alpha-crystal form is an oblique system the most common and the most stable formed form, mainly contains alpha-crystal form in the commercialization polypropylene.Beta crystal belongs to hexagonal system, compares with alpha-crystal form polypropylene, and Beta-crystalline polyacrylic is easy to stretch, and has lower heat-drawn wire, particularly has high toughness.Add beta crystal-type nucleater and be generally acknowledge at present obtain one of effective way of high-content Beta-crystalline polyacrylic.Because Beta-crystalline polyacrylic has unique toughening effect, thereby investigator day crowd.Patent CN85100465 can make its shock strength improve nearly twice with the crystalline modified polypropylene of β, but makes young modulus by original 10.7 * 10
-3Kg/cm is reduced to 8.6 * 10
-3Kg/cm, tensile strength is by original 358kg/cm
2Be reduced to 276kg/cm
2A.L. (the application number CN98117531.7) of invention such as Bei Sen with the calcium salt of imido acid as β crystallization nucleating agent modified polypropene, resulting composition, charpy impact intensity is by 8.06kJ/m
2Be elevated to 11.7kJ/m
2(23 ℃) and 1.41 are elevated to 7.03 (20 ℃), but modulus in flexure is reduced to 901MPa by 1006MPa.This shows, though the β crystallization can increase polyacrylic toughness, to keeping or to increase its intensity effect not ideal enough.
Inorganic nano-particle is subjected to paying close attention to widely owing to have plurality of advantages in recent years.Adopting the filling-modified polymkeric substance of nanoparticle is the important means that forms the high performance polymer matrix material.It has been generally acknowledged that, the key of optimizing this composite property is to realize that the superfine of nanoparticle in polymkeric substance disperses, therefore present research mainly utilizes special preparation method (as intercalation polymeric and solution blending etc.), improving nanoparticle in the intravital dispersion of polymer-based carbon, but these dispersing method all can not resemble nanoparticle the common widespread use in polymer processing the material of adding.
Utilize conventional melt blending working method directly to add to nanoparticle in the polymkeric substance, be subjected to the control of kinetic factor, have only the nanoparticle of minute quantity may in the resin matrix of viscosity higher, form the dispersion of primary fine particles level, most of nanoparticle will exist with the coacervate form, the structure of these coacervates is comparatively loose, be easy to generate stress concentration and the destruction that takes the lead in when material is stressed, crack growth resistance is little.Therefore, the key of nano modification is to improve dispersion and the compatibility performance of nanoparticle in polymkeric substance.In the prior art, main by to the surface modification of nanoparticle as with means such as coupling agent treatment, surface grafting, interpolation graftomer compatilizers.As described in patent (number of applying for a patent is 00112644.X), nanoparticle is adopted coupling agent such as titanic acid ester or silane treatment; (CN1362441A) is described for patent, and nano silicate or inorganic nano-particle are adopted surface electronic bundle irradiation, carry out graft modification with aminated compounds; Patent (CN1308099A) has been announced employing maleic anhydride, acrylate or acrylic acid-grafted polypropylene as compatilizer, and with coupling agent treatment nanometer CaCO
3
Three, summary of the invention
Modification small-entity polypropylene composition and method of making the same purpose of the present invention is, when adopting the crystal modifier beta nucleater to change the crystalling propylene structure, adopt the method for nano-particles filled to remedy the dissatisfactory deficiency of the crystalline modified reinforced effects of bringing of β, thereby disclose a kind of modification small-entity polypropylene composition and method of making the same.
Modification small-entity polypropylene composition of the present invention, it is characterized in that in the small-entity polypropylene composition, contain the modification small-entity polypropylene composition of inducing the nucleator that forms beta crystal, inorganic nano-particle, coupling agent, oxidation inhibitor, lubricant, its each component concentration (by ratio of quality and the number of copies) is: 100 parts in small-entity polypropylene (PP) powder; 1～10 part of inorganic nano-particle; Coupling agent be nanoparticle weight 0.5～2%, 0.1～1 part of beta nucleater; 0.1～0.5 part of primary antioxidant; 0.1～0.5 part of auxiliary anti-oxidant; 0.1～1 part of lubricant.
Above-mentioned a kind of modification small-entity polypropylene preparation of compositions method, it is characterized in that the inorganic nano-particle drying, after the ultrasonic dispersing, carry out activation treatment with coupling agent, nanoparticle after the processing and small-entity polypropylene, beta crystal-type nucleater, inorganic nano-particle, coupling agent, oxidation inhibitor, the chlorine absorption agent, lubricant carries out just mixing, in twin screw extruder, carry out the melt blending extruding pelletization then, make modification small-entity polypropylene composition, employed beta crystal-type nucleater can be that the single component beta crystal-type nucleater also can be the two-pack beta crystal-type nucleater that contains component A and B component, and employed inorganic nano-particle is the CaCO less than 100nm
3Or SiO
2One or both mixture, employed coupling agent is titanate ester, aluminic acid ester or silane coupling agent or aluminium titanium composite coupler, employed oxidation inhibitor is B215 and 168, chlorine absorption agent and lubricant are calcium stearate, and used each component and proportioning thereof (by the massfraction ratio) are: 100 parts in small-entity polypropylene (PP) powder; 1～10 part of inorganic nano-particle; Coupling agent be inorganic nano-particle weight 0.5～2%, 0.1～1 part of beta nucleater; 0.1～0.5 part of primary antioxidant; 0.1～0.5 part of auxiliary anti-oxidant; 0.1～1 part of lubricant.
Above-mentioned a kind of modification small-entity polypropylene preparation of compositions method is characterized in that described single component beta nucleater is aryl amide such as TMB-5; In the two-pack beta nucleater, component A is organic dibasic acid or its salt, and wherein organic dibasic acid is a pimelic acid, or other aliphatic dibasic acid; B component is an alkaline earth metal compound: calcium hydroxide or calcium oxide.
Above-mentioned a kind of modification small-entity polypropylene preparation of compositions method is characterized in that inorganic nano-particle at first at 100～140 ℃ of down dry 1～4hr, disperses 5～20min then under the ultrasonic wave effect.
Above-mentioned a kind of modification small-entity polypropylene preparation of compositions method, the inorganic nano-particle that it is characterized in that using ultrasonic dispersing activates with coupling agent in kneader under 60～120 ℃.
Above-mentioned a kind of modification small-entity polypropylene preparation of compositions method, it is characterized in that carrying out just mixing through inorganic nano-particle and small-entity polypropylene, β crystallization nucleating agent, oxidation inhibitor, the lubricant of coupling agent activation treatment, it just is mixed in high-speed mixer or carries out in kneader, and the temperature of twin screw blended melting extruding pelletization is carried out under 170～240 ℃.
Four, embodiment
Embodiment one
The 40g nano-calcium carbonate behind 100 ℃ of dry 2hr, is used ultrasonic dispersing 15min; In kneader, mediate 15min down at 60 ℃ with the 4g coupling agent; With 1.0kg small-entity polypropylene, 3g oxidation inhibitor B215,2g oxidation inhibitor 168 and 5g calcium stearate mix 10min in high-speed mixer, melt extrude granulation in parallel dual-screw extruding machine, and temperature is 170～240 ℃, get modification small-entity polypropylene composition.
Embodiment two
The 20g nano-calcium carbonate behind 120 ℃ of dry 2hr, is used ultrasonic dispersing 15min; In kneader, mediate 15min down at 80 ℃ with the 4g coupling agent; With 1.0kg small-entity polypropylene, 3g beta nucleater, 3g oxidation inhibitor B215,2g oxidation inhibitor 168 and 5g calcium stearate mix 10hr in high-speed mixer, in parallel dual-screw extruding machine, react extrude, granulation, temperature is 170～240 ℃.Get modification small-entity polypropylene composition.
Embodiment three
The 40g nano-calcium carbonate behind 140 ℃ of dry 2hr, is used ultrasonic dispersing 15min; In kneader, mediate 15min down at 120 ℃ with the 4g coupling agent; With 1.0kg small-entity polypropylene, 3g beta nucleater, 3g oxidation inhibitor B215,2g oxidation inhibitor 168,5g calcium stearate mix 10hr in high-speed mixer, in parallel dual-screw extruding machine, react extrude, granulation, temperature is 170～240 ℃.Get modification small-entity polypropylene composition.
Table 1 modification small-entity polypropylene composition mechanical property
Claims (6)
1. modification small-entity polypropylene composition, it is characterized in that a kind of in the small-entity polypropylene composition, contain the modification small-entity polypropylene composition of inducing the nucleator, inorganic nano-particle, coupling agent, oxidation inhibitor and the lubricant that form beta crystal, its each component concentration (by ratio of quality and the number of copies) is: 100 parts in small-entity polypropylene (PP) powder; 1～10 part of inorganic nano-particle; Coupling agent be nanoparticle weight 0.5～2%, 0.1～1 part of beta nucleater; 0.1～0.5 part of primary antioxidant; 0.1～0.5 part of auxiliary anti-oxidant; 0.1～1 part of lubricant.
2. the described a kind of modification small-entity polypropylene preparation of compositions method of claim 1, it is characterized in that the inorganic nano-particle drying, after the ultrasonic dispersing, carry out activation treatment with coupling agent, nanoparticle after the processing and small-entity polypropylene, beta crystal-type nucleater, inorganic nano-particle, coupling agent, oxidation inhibitor, the chlorine absorption agent, lubricant carries out just mixing, in twin screw extruder, carry out the melt blending extruding pelletization then, make modification small-entity polypropylene composition, employed beta crystal-type nucleater can be that the single component beta crystal-type nucleater also can be the two-pack beta crystal-type nucleater that contains component A and B component, and employed inorganic nano-particle is the CaCO less than 100nm
3Or SiO
2One or both mixture, employed coupling agent is titanate ester, aluminic acid ester or silane coupling agent or aluminium titanium composite coupler, employed oxidation inhibitor is B215 and 168, chlorine absorption agent and lubricant are calcium stearate, and used each component and proportioning thereof (by the massfraction ratio) are: 100 parts in small-entity polypropylene (PP) powder; 1～10 part of inorganic nano-particle; Coupling agent be inorganic nano-particle weight 0.5～2%, 0.1～1 part of beta nucleater; 0.1～0.5 part of primary antioxidant; 0.1～0.5 part of auxiliary anti-oxidant; 0.1～1 part of lubricant.
3. according to the described a kind of modification small-entity polypropylene preparation of compositions method of claim 2, it is characterized in that described single component beta nucleater is aryl amide such as TMB-5; In the two-pack beta nucleater, component A is organic dibasic acid or its salt, and wherein organic dibasic acid is a pimelic acid, or other aliphatic dibasic acid; B component is an alkaline earth metal compound: calcium hydroxide or calcium oxide.
4. according to the described a kind of modification small-entity polypropylene preparation of compositions method of claim 2, it is characterized in that inorganic nano-particle at first at 100～140 ℃ of down dry 1～4hr, disperses 5～20min then under the ultrasonic wave effect.
5. according to the described a kind of modification small-entity polypropylene preparation of compositions method of claim 2, the inorganic nano-particle that it is characterized in that using ultrasonic dispersing activates with coupling agent in kneader under 60～120 ℃.
6. according to the described a kind of modification small-entity polypropylene preparation of compositions method of claim 2, it is characterized in that carrying out just mixing through inorganic nano-particle and small-entity polypropylene, β crystallization nucleating agent, oxidation inhibitor, the lubricant of coupling agent activation treatment, it just is mixed in high-speed mixer or carries out in kneader, and the temperature of twin screw blended melting extruding pelletization is carried out under 170～240 ℃.
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| CN 200410012571 CN1254503C (en) | 2004-09-29 | 2004-09-29 | Modified small bulk polypropylene composition and its preparing method |
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| CN 200410012571 CN1254503C (en) | 2004-09-29 | 2004-09-29 | Modified small bulk polypropylene composition and its preparing method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168609B (en) * | 2007-09-30 | 2010-05-19 | 广州市合诚化学有限公司 | Special-purpose material for beta nucleater modified random copolymerization polypropylene pipe and preparation method thereof |
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2004
- 2004-09-29 CN CN 200410012571 patent/CN1254503C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168609B (en) * | 2007-09-30 | 2010-05-19 | 广州市合诚化学有限公司 | Special-purpose material for beta nucleater modified random copolymerization polypropylene pipe and preparation method thereof |
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