CN102827408B - Polyolefin reinforcing and toughening master batch and production method thereof - Google Patents

Polyolefin reinforcing and toughening master batch and production method thereof Download PDF

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Publication number
CN102827408B
CN102827408B CN201210231900.8A CN201210231900A CN102827408B CN 102827408 B CN102827408 B CN 102827408B CN 201210231900 A CN201210231900 A CN 201210231900A CN 102827408 B CN102827408 B CN 102827408B
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powder
master batch
modifier
inorganic
polyolefine
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CN201210231900.8A
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Chinese (zh)
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CN102827408A (en
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李宏武
周玮
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安徽邦尼新材料有限公司
李宏武
周玮
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Abstract

The invention discloses a polyolefin reinforcing and toughening master batch and a production method of the polyolefin reinforcing and toughening master batch. The master batch comprises the following components by weight: 10-42% of polyolefin, 50-80% of composite ultrafine powder, 0.02-1.5% of powder activating activator, 0.8-5% of powder surface modifier, 1.2-5% of powder surface modifying agent, 0.1-0.3% of grafting agent, 0.3-5% of antioxygen, 5-15% of lubricating agent and 0.5-1% of processing agent, wherein the composite ultrafine powder is formed by compounding one-dimensional needle-shaped structural micro-nano powder, two-dimensional needle-shaped structural micro-nano powder and three-dimensional needle-shaped structural micro-nano powder. The nonmetal powders with a needle shaped structure, a lamella structure and a spherical structure are uniformly dispersed in the materials through a three-dimensional grid structure, so that the strength and tenacity of the materials can be improved. According to the production method of the master batch, the composite ultrafine powder is subjected to surface activating and modifying treatment through a multi-layer wrapping composite reaction technology, so that the compatibility of the nonmetal material and the carrier resin can be greatly improved, and the nonmetal material can be uniformly dispersed into the material in form of a three-dimensional grid structural unit to be served as the framework of the material, so that the mechanical property of the material can be improved.

Description

A kind of polyolefine strengthens toughened master batch and production method thereof
Technical field
The present invention relates to a kind of polyolefine functional master batch and production method thereof, particularly a kind of composite superfine powder of the organic/inorganic non-metallic material using the multiple different-shape of modification strengthens toughened master batch and production method thereof as the polyolefine of stopping composition.
Background technology
Method by physics or chemistry is added or blend is inorganic or organic substance in high molecular polymer, object be reduce material cost, improve moulding process, the performance of raising material.By coal and modifying agent, as mixing such as polyethylene, polypropylene, polystyrene, propylene dried meat, natural rubber and butadiene polymers, produce coal-based plastics abroad.Coal-based plastics and composition adopt simple and mechanical blend above, surface chemical modification, and the consistency between coal and matrix is poor, and material mechanical performance is undesirable.The pattern of organic/inorganic materials has determined its contribution to plastics mechanical property, domesticly often adopts simple mechanical blending modification to add in polymkeric substance in calcium carbonate or talcum powder, because the material adding is more single, makes the material property that makes undesirable.
Summary of the invention
One of the technical problem to be solved in the present invention is: provide a kind of composite superfine powder of the organic/inorganic non-metallic material using the multiple different-shape of modification to strengthen toughened master batch as the polyolefine of stopping composition, so that the mechanical property of material is improved.
Two of the technical problem to be solved in the present invention is: the production method that provides a kind of said polyolefins to strengthen toughened master batch, and to improve the consistency of organic/inorganic non-metallic material and vector resin.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of polyolefine strengthens toughened master batch, it is characterized in that, masterbatch comprises the component of following weight ratio:
Polyolefine: 10%-42%
Composite superfine powder: 50%-80%
Powder activation exciting agent: 0.02%-1.5%
Powder surface modifier: 0.8%-5%
Powder surface modifier: 1.2%-5%
Grafting agent: 0.1%-0.3%
Oxidation inhibitor: 0.3%-5%
Lubricant: 5%-15%
Processing aid: 0.5%-1%;
Above-mentioned composite superfine powder is to be composited by the micro-nano powder of the organic/inorganic non-metallic material with multiple different-shapes such as one dimension acicular structure, two-dimentional laminated structure and three-dimensional globositys;
Be to comprise in above-mentioned composite superfine powder: A, needle-like powder, there are the non-metallic material of one dimension acicular structure, as: filamentary material (comprising: various glass fibre, wood powder, bamboo powder), crystal whisker materials (comprising: magnesium salt whisker, calcium sulfate crystal whiskers), wollastonite etc.; B, lamella inorganic powder, have the non-metallic material of two-dimentional laminated structure, as: sheet mica, talcum powder etc.; C, inorganic spherical powder, have the non-metallic material of three-dimensional globosity, as calcium carbonate superfine powder more than 800 orders of: order number and nano-calcium carbonate, kaolin, potter's clay, diatomite, glass microballon, ground barium sulfate, pyrophyllite powder etc.;
In above-mentioned composite superfine powder, the weight ratio of each component is:
A, needle-like powder: 1%-20%
B, lamella inorganic powder: 30%-50%
C, inorganic spherical powder: 40%-50%.
In above-mentioned composite superfine powder, the best proportioning of A, B, C tri-components is:
Needle-like powder A: lamella inorganic powder B: inorganic spherical powder C=10:40:50.
Said polyolefins comprises polyethylene and the polypropylene of the various trades mark.
Above-mentioned powder activation exciting agent is vitriol; Above-mentioned powder surface modifier is the carboxylic acid type rare earth of macromolecular structure; Above-mentioned grafting agent is maleic anhydride.
Above-mentioned powder surface modifier is silane coupling agent, titanate coupling agent, aluminate coupling agent, stearic acid, sodium stearate and their mixture.
Above-mentioned oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester (irgasfos 168), 2,6--di-tert-butyl-4-methy phenol (antioxidant 264), Tyox B (anti-oxidant DLTP), thio-2 acid 2 stearyl ester (oxidation inhibitor DSTP) and their mixture.
Above-mentioned lubricant is stearic acid, sodium stearate, Zinic stearas, calcium stearate, oxidized polyethlene wax (OPE), polyethylene wax, paraffin and their mixture.Above-mentioned processing aid is PPA(fluoropolymer process aid).
Said polyolefins strengthens the production method of toughened master batch, it be take polyolefine as vector resin, micro-nano powder is filler, adds the auxiliary agents such as powder activation exciting agent, surface-modifying agent, coating materials, oxidation inhibitor, lubricant; Utilize that high-speed mixing unit mixes, modification, preplasticizing, then by extrude unit carry out melting, plasticizing, mixing, extrude, granulation, last air-cooled pelletizing obtains product; Or, utilize that Banbury mixer mixes, modification, melting, plasticizing, mixing, then extrude by extruding unit, granulation, last air-cooled pelletizing obtains product; It is characterized in that:
The composite superfine powder that described filler is made up of above-mentioned A, B, tri-kinds of micro-nano powders of C;
The production method of described masterbatch comprises the steps:
(1) the high-speed mixing stage: composite superfine powder and vector resin compound before, first adopt multilayer coating structure complex reaction technique to carry out surface active modification to composite superfine powder;
Described multilayer coating structure complex reaction technique, comprises the steps:
1. composite superfine powder drying and dehydrating at 105 ~ 110 ℃;
2. add powder activation exciting agent, carry out the coated complex reaction of one deck, to discharge inorganic powder material surface polarity, reduce powder surface in conjunction with energy;
3. add powder surface modifier, carry out again the coated complex reaction of one deck, powder body material surface is changed to lipophilicity by wetting ability;
4. add powder surface modifier, carry out again the coated complex reaction of one deck, form hinge at powder surface, hinge one end and powder body material bonding, the other end preparation melt extruding bonding in process, strengthens powder and resin compatible with vector resin;
(2) melt extrude the stage: adding under the effect of gentle certain extrusion pressure, material is melting in extrusion equipment, now inject in proportion grafting agent, make powder surface modifier, grafting agent, vector resin certain chemical reaction occur melt extruding in process, make the firmly combination of powder and vector resin.
Be equipped with again and use the screw rod with special construction design to melt extrude granulation, can make powder become 3 D stereo grid according to certain textural association, become the skeleton of material, and improve thus the shared ratio of masterbatch in masterbatch product with 3 D stereo grid structure.
In aforesaid method, described composite superfine powder is made up of (A) needle-like powder 1%-20%, (B) lamella inorganic powder 30%-50%, (C) inorganic spherical powder 40%-50%; Described powder activation exciting agent is vitriol (wherein with sodium sulfate best results), and dosage is 0.02%-1.5%, 3 ~ 5 minutes reaction times; Described powder surface modifier is composite coupler, that is: silane coupling agent, and titanate coupling agent, aluminate coupling agent, stearic acid, sodium stearate and their mixture, dosage is 0.8%-5%, 2 ~ 5 minutes reaction times; Described powder surface modifier is the carboxylic acid type rare earth of macromolecular structure, and dosage is 1.2%-5%, 2 ~ 5 minutes reaction times; Described grafting agent is maleic anhydride, and dosage is 0.1%-0.3%.
Said polyolefins strengthens toughened master batch can be by following two kinds of technical process processings:
Flow process 1: essence is joined (electronic balance) → high-speed mixing activation coated (mixing machine) → reinforced (screw feeding machine) → mixing extrusion (twin screw extruder) → extruding pelletization (single screw extrusion machine) → air-cooled pelletizing and packing (high-pressure blast send, finished product bin, sack closer).
Flow process 2: essence is joined (electronic balance) → banburying admixture activation coated (Banbury mixer) → reinforced (self-lift) → feeding (bi-conical feed unit) → extrude (single screw extrusion machine group) → granulation (air-cooled dicing machine and high-pressure blast send) → packing (finished product bin, sack closer).
Beneficial effect of the present invention:
Superfine powder after polyolefin masterbatch of the present invention is composite modified using the organic/inorganic non-metallic material of multiple different-shape is as stopping composition, in the organic/inorganic non-metallic material of multiple different-shape, fiber, whiskers etc. have the acicular structure of one dimension, mica, talcum powder etc. have two-dimentional laminated structure, calcium carbonate etc. have three-dimensional globosity, according to 3 D stereo blend theory, in conjunction with Special Working Technology, the non-metallic powder of three kinds of structures is dispersed in material with 3 D stereo grid structure, needle-like, lamella, spherical structured material is respectively as the beam of 3 D stereo grid structure, wall, core, intensity and the toughness of material are increased with this.
Modified technique in the present invention adopts inorganic-organic multilayer coating structure complex reaction technique, greatly improve the consistency of organic/inorganic non-metallic material and vector resin, organic/inorganic non-metallic material are dispersed in material with the form of 3 D stereo grid structure unit, as the skeleton of material, material mechanical performance is improved.
Technique of the present invention is simple, with low cost, the production process of polyolefin masterbatch adopts simple technique, a large amount of non-metallic material such as cheap nonmetallic tailings, associated minerals and woodworking industry scrap stock that use, thereby there is lower cost, and excellent property, of many uses, with the national standard contrast of PE corrugated tube and PP pipe, performance all meets or exceeds national standard.
Accompanying drawing explanation
Fig. 1 is the production technological process that in the present invention, polyolefine strengthens toughened master batch;
Fig. 2 is the schematic diagram of 3 D stereo grid structure unit in the present invention;
Wherein, the 1st, the beam of 3 D stereo grid structure unit, the i.e. needle inorganic such as fiber, whisker powder, the 2nd, the wall of 3 D stereo grid structure unit, i.e. lamella inorganic powder, the 3rd, the core of 3 D stereo grid structure unit, i.e. inorganic spherical powder.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
Processing polyolefine strengthens toughened master batch as follows:
One, masterbatch formula:
High-density polyethylene resin 2480:10%
Composite superfine powder:
Magnesium salt whisker 5%
Talcum powder 35%
Calcium carbonate 40%
Powder activation exciting agent: sodium sulfate 1.2%
Powder surface modifier:
The mixture 1.7% of stearic acid: silane coupling agent: sodium stearate=20:60:20
Powder surface modifier: the carboxylic acid type rare earth 1.2% of macromolecular structure
Grafting agent: maleic anhydride 0.1%
Oxidation inhibitor: DSTP 0.3%
Lubricant: polyethylene wax 5%
Processing aid: PPA(fluoropolymer process aid) 0.5%.
Two, production technique:
Press the processing of technical process shown in Fig. 1 masterbatch by above-mentioned formula, the main production process of product is as follows:
1, by magnesium salt whisker, talcum powder, calcium carbonate in proportion on electronic balance essence prepare, add in high-speed mixer, at 105 ℃, carry out after drying and dehydrating; Add successively again powder activation exciting agent sodium sulfate 1.2%, react 5 minutes, add powder surface modifier 1.7% to react 5 minutes, add the carboxylic acid type rare earth powder surface modifier 1.2% of macromolecular structure to react 2 minutes, thus composite superfine powder is carried out to multilayer coating structure surface active modification;
2, vector resin polyethylene, oxidation inhibitor, lubricant, processing aid are prepared in proportion, add in high-speed mixer and mix together with composite superfine powder, fully mix;
3, material is moved to from high-speed mixer in twin screw extruder and carry out melting, plasticizing, mixing, now inject grafting agent maleic anhydride 0.1% and carry out graft reaction, make the firmly combination of powder and vector resin; Afterwards again by single screw extrusion machine extrude, granulation, finally carry out air-cooled pelletizing, obtain having the polyethylene that three kinds of organic/inorganic powder body materials of one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity distribute wherein with 3 D stereo grid structure form and strengthen toughened master batch product.
Embodiment 2
One, masterbatch formula:
Acrylic resin T30S:20.48%
Composite superfine powder:
Glass fibre 5%
Mica powder 20%
Calcium carbonate 25%
Powder activation exciting agent: calcium sulfate 0.02%
Powder surface modifier:
The mixture 5% of stearic acid: silane coupling agent: aluminate coupling agent=20:40:40
Powder surface modifier: the carboxylic acid type rare earth 3.5% of macromolecular structure
Grafting agent: maleic anhydride 0.3%
Oxidation inhibitor: 264 5%
Lubricant: polyethylene wax 9.5%
Paraffin 5.5%
Processing aid: PPA(fluoropolymer process aid) 0.7%.
Two, production technique:
Press the processing of technical process shown in Fig. 1 masterbatch by above-mentioned formula, the main production process of product is as follows:
1, by glass fibre, mica powder, calcium carbonate in proportion on electronic balance essence prepare, add in Banbury mixer, at 105 ℃, carry out after drying and dehydrating; Add successively again powder activation exciting agent calcium sulfate 0.02% to react 3 minutes, add coating materials (being composite coupler) 5% reaction 2 minutes, add the carboxylic acid type rare earth powder surface modifier 3.5% of macromolecular structure to react 5 minutes, thus composite superfine powder is carried out to multilayer coating structure surface active modification;
2, vector resin polypropylene, oxidation inhibitor, lubricant, processing aid are prepared in proportion, add in Banbury mixer mix together with composite superfine powder, melting, plasticizing, mixing;
3, material in Banbury mixer is added by bi-conical feed unit in single screw extrusion machine, carry out melting, plastify, extrude, granulation, now inject grafting agent maleic anhydride 0.3% and carry out graft reaction, make the firmly combination of powder and vector resin; Carry out again afterwards air-cooled pelletizing, obtain having the polypropylene reinforced plasticized masterbatch product that three kinds of organic/inorganic powder body materials of one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity distribute wherein with 3 D stereo grid structure form.
Embodiment 3
One, masterbatch formula:
Linear low density polyethylene resin 7042:15%
Composite superfine powder:
Calcium sulfate crystal whiskers: 14.5%
Talcum powder 30%
Calcium carbonate 30%
Powder activation exciting agent: zinc sulfate 1.5%
Powder surface modifier:
The mixture 0.8% of stearic acid: silane coupling agent: titanate coupling agent=20:30:50
Powder surface modifier: carboxylic acid type rare earth 1.2%
Oxidation inhibitor: 1,010 0.8%
Grafting agent: maleic anhydride 0.2%
Lubricant: calcium stearate 1%
Polyethylene wax 2%
Paraffin 2%
Processing aid: PPA(fluoropolymer process aid) 1%.
Two, production technique:
Press the processing of technical process shown in Fig. 1 masterbatch by above-mentioned formula, the main production process of product is as follows:
1, by calcium sulfate crystal whiskers, talcum powder, calcium carbonate in proportion on electronic balance essence prepare, add in high-speed mixer, at 110 ℃, carry out after drying and dehydrating; Add successively again powder activation exciting agent zinc sulfate 1.5% to react 4 minutes, add coating materials (being composite coupler) 0.8% reaction 4 minutes, add the carboxylic acid type rare earth powder surface modifier 1.2% of macromolecular structure to react 3 minutes, thus composite superfine powder is carried out to multilayer coating structure surface active modification;
2, vector resin polyethylene, oxidation inhibitor, lubricant, processing aid are prepared in proportion, add in high-speed mixer and mix together with composite superfine powder, fully mix;
3, material is moved to from high-speed mixer in the twin screw extruder with special screw-rod structure flute profile dish and carry out melting, plasticizing, mixing, now inject grafting agent maleic anhydride 0.2% and carry out graft reaction, make the firmly combination of powder and vector resin; Afterwards again by single screw extrusion machine extrude, granulation, finally carry out air-cooled pelletizing, obtain having the polyethylene that three kinds of organic/inorganic powder body materials of one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity distribute wherein with 3 D stereo grid structure form and strengthen toughened master batch product.
Embodiment 4
One, masterbatch formula:
Acrylic resin PA14D:42%
Composite superfine powder:
Wollastonite: 10%
Talcum powder 15%
Calcium carbonate 25%
Powder activation exciting agent: sodium sulfate 0.1%
Powder surface modifier:
The mixture 0.8% of stearic acid: silane coupling agent: sodium stearate=20:60:20
Powder surface modifier: carboxylic acid type rare earth 1.2%
Oxidation inhibitor: DLTP 0.3%
Grafting agent: maleic anhydride 0.1%
Lubricant: sodium stearate 5%
Processing aid: PPA(fluoropolymer process aid) 0.5%.
Two, production technique:
Press the processing of technical process shown in Fig. 1 masterbatch by above-mentioned formula, the main production process of product is as follows:
1, by wollastonite, talcum powder, calcium carbonate in proportion on electronic balance essence prepare, add in Banbury mixer, at 108 ℃, carry out after drying and dehydrating; Add successively again powder activation exciting agent sodium sulfate 0.1% to react 4 minutes, add coating materials (being composite coupler) 0.8% reaction 3 minutes, add the carboxylic acid type rare earth powder surface modifier 1.2% of macromolecular structure to react 3 minutes, thus composite superfine powder is carried out to multilayer coating structure surface active modification;
2, vector resin polypropylene, oxidation inhibitor, lubricant, processing aid are prepared in proportion, add in high-speed mixer and mix together with composite superfine powder, fully mix;
3, material is moved to from high-speed mixer in twin screw extruder and carry out melting, plasticizing, mixing, now inject grafting agent maleic anhydride 0.1% and carry out graft reaction, make the firmly combination of powder and vector resin; Afterwards again by single screw extrusion machine extrude, granulation, finally carry out air-cooled pelletizing, obtain having the polyethylene that three kinds of organic/inorganic powder body materials of one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity distribute wherein with 3 D stereo grid structure form and strengthen toughened master batch product.
Embodiment 5
One, masterbatch formula:
Linear low density polyethylene resin 7042:10%
Composite superfine powder:
Glass fibre 5%
Talcum powder 40%
Diatomite 25%
Powder activation exciting agent: magnesium sulfate 1%
Powder surface modifier:
The mixture 5% of stearic acid: silane coupling agent: titanate coupling agent=20:30:50
Powder surface modifier: the carboxylic acid type rare earth 3% of macromolecular structure
Oxidation inhibitor: 168 0.8%
Grafting agent: maleic anhydride 0.2%
Lubricant: oxidized polyethlene wax 5.5%
Stearic acid 2.5%
Paraffin 1.5%
Processing aid: PPA(fluoropolymer process aid) 0.5%.
Two, production technique:
Press the processing of technical process shown in Fig. 1 masterbatch by above-mentioned formula, the main production process of product is as follows:
1, by glass fibre, talcum powder, diatomite in proportion on electronic balance essence prepare, add in Banbury mixer, at 105 ℃, carry out after drying and dehydrating; Add successively again powder activation exciting agent magnesium sulfate 1% to react 4 minutes, add coating materials (being composite coupler) 5% reaction 3 minutes, add the carboxylic acid type rare earth powder surface modifier 3% of macromolecular structure to react 3 minutes, thus composite superfine powder is carried out to multilayer coating structure surface active modification;
2, vector resin polyethylene, oxidation inhibitor, lubricant, processing aid are prepared in proportion, add in Banbury mixer mix together with composite superfine powder, melting, plasticizing, mixing;
3, by material in Banbury mixer by bore extra quality unit add in single screw extrusion machine, carry out melting, plasticizing, mixing, extrude, granulation, now inject grafting agent maleic anhydride 0.2% and carry out graft reaction, make the firmly combination of powder and vector resin; Afterwards again by carrying out air-cooled pelletizing, obtain having the polyethylene that three kinds of organic/inorganic powder body materials of one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity distribute wherein with 3 D stereo grid structure form and strengthen toughened master batch product.
Embodiment 6
One, masterbatch formula:
Acrylic resin PA14D:35%
Composite superfine powder:
Wood powder 10%
Sheet mica 25%
Kaolin 20%
Powder activation exciting agent: sodium sulfate 0.8%
Powder surface modifier:
The mixture 1.5% of stearic acid: silane coupling agent: sodium stearate=20:60:20
Powder surface modifier: carboxylic acid type rare earth 1.2%
Grafting agent: maleic anhydride 0.2%
Oxidation inhibitor: DLTP 0.3%
Lubricant: Zinic stearas 5.2%
Paraffin 0.3%
Processing aid: PPA(fluoropolymer process aid) 0.5%.
Two, production technique:
Press the processing of technical process shown in Fig. 1 masterbatch by above-mentioned formula, the main production process of product is as follows:
1, by wood powder, sheet mica, kaolin in proportion on electronic balance essence prepare, add in high-speed mixer, at 110 ℃, carry out after drying and dehydrating; Add successively again powder activation exciting agent sodium sulfate 0.8% to react 4 minutes, add coating materials (being composite coupler) 1.5% reaction 4 minutes, add the carboxylic acid type rare earth powder surface modifier 1.2% of macromolecular structure to react 3 minutes, thus composite superfine powder is carried out to multilayer coating structure surface active modification;
2, vector resin polypropylene, oxidation inhibitor, lubricant, processing aid are prepared in proportion, add in high-speed mixer and mix together with composite superfine powder, fully mix;
3, material is moved to from high-speed mixer in the twin screw extruder with special screw-rod structure flute profile dish and carry out melting, plasticizing, mixing, now inject grafting agent maleic anhydride 0.2% and carry out graft reaction, make the firmly combination of powder and vector resin; Afterwards again by single screw extrusion machine extrude, granulation, finally carry out air-cooled pelletizing, obtain having the polypropylene reinforced plasticized masterbatch product that three kinds of organic/inorganic powder body materials of one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity distribute wherein with 3 D stereo grid structure form.
The demonstration of SEM scanning electron microscope result, the polyethylene that embodiment 1-6 obtains strengthens in toughened master batch product, and three kinds of organic/inorganic powder body materials with one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity distribute wherein with 3 D stereo grid structure form.As shown in Figure 2, the present invention adopts 3 D stereo grid frame theory of ship structures in formulating of recipe, take into full account the contribution of different-shape non-metallic material to polyolefine mechanical property, employing possesses the filamentary material of one dimension acicular structure and possesses the crystal whisker materials of certain length-to-diameter ratio as the beam 1 of 3 D stereo grid structure unit, employing possesses the material of two-dimentional laminated structure as the wall 2 of 3 D stereo grid structure unit, employing possesses the material of solid sphere structure as the core 3 of 3 D stereo grid structure unit, and gap is polyolefin substrate.According to 3 D stereo blend theory, in conjunction with Special Working Technology, the organic/inorganic non-metallic powder of three kinds of structures is evenly distributed in material with 3 D stereo grid structure form, needle-like, sheet, spherical structured material be respectively as beam, wall, the core of 3 D stereo grid structure, increases intensity and the toughness of material with this.
Performance test example:
Produce by the formula of embodiment 1-6 and production technique the polyolefine obtaining and strengthen toughened master batch product, the ratio machining that is 2:1 according to matrix resin (being vector resin) and masterbatch proportioning obtains finished product, carry out performance test according to GB/T1843, GB/T1040, GB/T1042, performance data is after tested in table 1:
Table 1: performance test data
Product performance test data by embodiment 1-6 also can be found out, strengthen toughened master batch by the polyolefine of formula of the present invention and production method processing thereof, there is good shock resistance and bending property, this masterbatch adds in polyolefin plastic products, can make rigidity, toughness and the tensile strength of goods be significantly increased.

Claims (10)

1. polyolefine strengthens a toughened master batch, it is characterized in that, masterbatch comprises the component of following weight ratio:
Described composite superfine powder is to be composited by the micro-nano powder of organic/inorganic non-metallic material of three kinds of different-shapes with one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity;
In above-mentioned composite superfine powder, comprise: A, needle-like powder, there are the non-metallic material of one dimension acicular structure, described in there is one dimension acicular structure non-metallic material comprise: filamentary material, crystal whisker materials, wollastonite; Described filamentary material comprises various glass fibre, wood powder, bamboo powder; Described crystal whisker materials comprises magnesium salt whisker, calcium sulfate crystal whiskers; B, lamella inorganic powder, have the non-metallic material of two-dimentional laminated structure, described in there is two-dimentional laminated structure non-metallic material comprise: sheet mica, talcum powder; C, inorganic spherical powder, there are the non-metallic material of three-dimensional globosity, described in there is three-dimensional globosity non-metallic material comprise: the calcium carbonate superfine powder of order number more than 800 orders and nano-calcium carbonate, kaolin, potter's clay, diatomite, glass microballon, ground barium sulfate, pyrophyllite powder;
In above-mentioned composite superfine powder, the weight ratio of each component is:
A, needle-like powder: 1%-20%
B, lamella inorganic powder: 30%-50%
C, inorganic spherical powder: 40%-50%;
Described powder activation exciting agent is vitriol; Described powder surface modifier is the carboxylic acid type rare earth of macromolecular structure; Described powder surface modifier is silane coupling agent, titanate coupling agent, aluminate coupling agent, stearic acid, sodium stearate and their mixture;
Composite superfine powder and vector resin compound before, first adopt multilayer coating structure complex reaction technique to carry out surface active modification to composite superfine powder, comprise: powder is drying and dehydrating at 105~110 ℃ first, then order adds powder activation exciting agent, powder surface modifier, powder surface modifier to carry out multilayer coating structure complex reaction successively.
2. polyolefine as claimed in claim 1 strengthens toughened master batch, it is characterized in that, in described composite superfine powder, the best proportioning of A, B, C tri-components is:
Needle-like powder A: lamella inorganic powder B: inorganic spherical powder C=10:40:50.
3. polyolefine as claimed in claim 1 or 2 strengthens toughened master batch, it is characterized in that, described grafting agent is maleic anhydride.
4. polyolefine as claimed in claim 3 strengthens toughened master batch, it is characterized in that, described polyolefine comprises polyethylene and the polypropylene of the various trades mark; Described lubricant is stearic acid, sodium stearate, Zinic stearas, calcium stearate, oxidized polyethlene wax (OPE), polyethylene wax, paraffin and their mixture.
5. polyolefine as claimed in claim 4 strengthens toughened master batch, it is characterized in that, described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester (irgasfos 168), 2,6-di-tert-butyl-4-methy phenol (antioxidant 264), Tyox B (anti-oxidant DLTP), thio-2 acid 2 stearyl ester (oxidation inhibitor DSTP) and their mixture; Described processing aid is PPA fluoropolymer process aid.
6. polyolefine as claimed in claim 5 strengthens toughened master batch, it is characterized in that, described powder activation exciting agent is sodium sulfate.
7. polyolefine as claimed in claim 5 strengthens toughened master batch, it is characterized in that, three kinds of organic/inorganic powder body materials in described masterbatch product with one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity distribute wherein with 3 D stereo grid structure form.
8. the polyolefine as described in as arbitrary in claim 1-7 strengthens a production method for toughened master batch, it is characterized in that:
The production method of masterbatch comprises the steps:
(1) the high-speed mixing stage: composite superfine powder and vector resin compound before, first adopt multilayer coating structure complex reaction technique to carry out surface active modification to composite superfine powder;
Described multilayer coating structure complex reaction technique, comprises the steps:
1. composite superfine powder drying and dehydrating at 105~110 ℃;
2. add powder activation exciting agent, carry out the coated complex reaction of one deck, make powder surface in conjunction with reducing;
3. add powder surface modifier, carry out again the coated complex reaction of one deck, powder surface is changed to lipophilicity by wetting ability;
4. add powder surface modifier, carry out again the coated complex reaction of one deck, form hinge at powder surface, powder and resin compatible are strengthened;
(2) melt extrude the stage: adding under the effect of gentle certain extrusion pressure, material is melting in extrusion equipment, now inject grafting agent, make powder surface modifier, grafting agent, vector resin certain chemical reaction occur melt extruding in process, make the firmly combination of powder and vector resin.
9. polyolefine as claimed in claim 8 strengthens the production method of toughened master batch, it is characterized in that: described composite superfine powder is made up of (A) needle-like powder 1%-20%, (B) lamella inorganic powder 30%-50%, (C) inorganic spherical powder 40%-50%; Described powder activation exciting agent is vitriol, and dosage is 0.02%-1.5%, 3~5 minutes reaction times; Described powder surface modifier is silane coupling agent, titanate coupling agent, and aluminate coupling agent, stearic acid, sodium stearate and their mixture, dosage is 0.8%-5%, 2~5 minutes reaction times; Described powder surface modifier is the carboxylic acid type rare earth of macromolecular structure, and dosage is 1.2%-5%, 2~5 minutes reaction times; Described grafting agent is maleic anhydride, and dosage is 0.1%-0.3%.
10. polyolefine strengthens the production method of toughened master batch as claimed in claim 8 or 9, it is characterized in that: it be utilize that high-speed mixing unit mixes, modification, preplasticizing, again by extrude unit carry out melting, plasticizing, mixing, extrude, granulation, last air-cooled pelletizing, obtains having the masterbatch product that three kinds of organic/inorganic powder body materials of one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity distribute wherein with 3 D stereo grid structure form; Or, utilize that Banbury mixer mixes, modification, melting, plasticizing, mixing, extrude by extruding unit again, granulation, last air-cooled pelletizing, obtains having the masterbatch product that three kinds of organic/inorganic powder body materials of one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity distribute wherein with 3 D stereo grid structure form.
CN201210231900.8A 2012-07-05 2012-07-05 Polyolefin reinforcing and toughening master batch and production method thereof CN102827408B (en)

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