CN102827408A - Polyolefin reinforcing and toughening master batch and production method thereof - Google Patents
Polyolefin reinforcing and toughening master batch and production method thereof Download PDFInfo
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- CN102827408A CN102827408A CN2012102319008A CN201210231900A CN102827408A CN 102827408 A CN102827408 A CN 102827408A CN 2012102319008 A CN2012102319008 A CN 2012102319008A CN 201210231900 A CN201210231900 A CN 201210231900A CN 102827408 A CN102827408 A CN 102827408A
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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
Technical field
The present invention relates to a kind of polyolefine functional master batch and working method thereof, particularly a kind of composite superfine powder of the organic/inorganic non-metallic material with the multiple different-shape of modification strengthens toughened master batch and working method thereof as the polyolefine of stopping composition.
Background technology
Method through physics or chemistry is added in high molecular polymer or blend is inorganic or organic substance, purpose be reduce material cost, improve moulding process, the performance of raising material.With coal and modifying agent,, produce coal-based plastics abroad like mixing such as Vilaterm, Vestolen PP 7052, PS, propylene dried meat, tree elastomer and butadiene polymers.More than coal-based plastics and compsn adopt simple and mechanical blend, surface chemical modification, the consistency between coal and the matrix is relatively poor, material mechanical performance is undesirable.The pattern of organic has determined its contribution to the plastics mechanical property, domesticly often adopts simple mechanical blending modification to add in the polymkeric substance in lime carbonate or talcum powder, because the material that adds is more single, makes that the material property that makes is undesirable.
Summary of the invention
One of technical problem that the present invention will solve is: the composite superfine powder that a kind of organic/inorganic non-metallic material with the multiple different-shape of modification are provided strengthens toughened master batch as the polyolefine of stopping composition, so that the mechanical property of material is improved.
Two of the technical problem that the present invention will solve is: the working 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, comprises following components in part by weight in the masterbatch:
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 that the micro-nano powder by the organic/inorganic non-metallic material with multiple different-shapes such as one dimension acicular structure, two-dimentional laminated structure and three-dimensional globositys is composited;
Be to comprise in the above-mentioned composite superfine powder: A, needle-like powder; The non-metallic material that promptly have the one dimension acicular structure, as: filamentary material (comprising: various spun glass, wood powder, bamboo powder), crystal whisker materials (comprising: magnesium salt whisker, calcium sulfate crystal whiskers), wollastonite etc.; B, lamella inorganic powder promptly have the non-metallic material of two-dimentional laminated structure, as: sheet mica, talcum powder etc.; C, inorganic spherical powder promptly have the non-metallic material of three-dimensional globosity, like calcium carbonate superfine powder and nano-calcium carbonate more than 800 orders of: order number, kaolin, potter's clay, zeyssatite, glass microballon, ground barium sulfate, pyrophyllite powder etc.;
The weight ratio of each component is in the above-mentioned composite superfine powder:
A, needle-like powder: 1%-20%
B, lamella inorganic powder: 30%-50%
C, inorganic spherical powder: 40%-50%.
The best proportioning of A, B, C three components is in the above-mentioned composite superfine powder:
Needle-like powder A: lamella inorganic powder B: inorganic spherical powder C=10:40:50.
Said polyolefins comprises the Vilaterm and the Vestolen PP 7052 of the various trades mark.
Above-mentioned powder activation exciting agent is a vitriol; Above-mentioned powder surface modifier is the carboxylic acid type rare earth of macromolecular structure; Above-mentioned grafting agent is a maleic anhydride.
Above-mentioned powder surface modifier is a silane coupling agent, titanate coupling agent, aluminate coupling agent, Triple Pressed Stearic Acid, StNa and their mixture.
Above-mentioned oxidation inhibitor is four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) esters (oxidation inhibitor 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 a Triple Pressed Stearic Acid, StNa, Zinic stearas, calcium stearate, OPE (OPE), polyethylene wax, paraffin and their mixture.Above-mentioned processing aid is PPA (fluoropolymer process aid).
A kind of said polyolefins strengthens the working method of toughened master batch, and it is to be that vector resin, micro-nano powder are filler with the polyolefine, adds auxiliary agents such as powder activation exciting agent, surface-modifying agent, coating materials, oxidation inhibitor, lubricant; Utilize that the mixed at high speed unit mixes, modification, preplasticizing, again through extrude unit carry out fusion, plasticizing, mixing, extrude, granulation, last air-cooled pelletizing obtains product; Perhaps, utilize that Banbury mixer mixes, modification, fusion, plasticizing, mixing, extrude through extruding unit, granulation again, last air-cooled pelletizing obtains product; It is characterized in that:
The composite superfine powder that said filler is made up of above-mentioned A, B, three kinds of micro-nano powders of C;
The working method of said masterbatch comprises the steps:
(1) the mixed at high speed stage: before composite superfine powder and vector resin are compound, adopt multilayer to coat complex reaction technology earlier and composite superfine powder is carried out the surface active modification handle;
Said multilayer coats complex reaction technology, comprises the steps:
1. composite superfine powder is at 105 ~ 110 ℃ of following drying and dehydratings;
2. add powder activation exciting agent, carry out one deck and coat complex reaction,, reduce the powder surface bound energy to discharge the inorganic powder material surface polarity;
3. add the powder surface modifier, carry out again one deck and coat complex reaction, powder body material surface is changed to oleophilicity by wetting ability;
4. the adding powder surface modifier carries out one deck again and coats complex reaction, forms hinge at powder surface, hinge one end and powder body material bonding, and the other end is prepared and vector resin bonding in melt extruding process, and powder and resin compatible are strengthened;
(2) melt extrude the stage: under the effect that adds gentle certain extrusion pressure; Material is fusion in extrusion equipment; Inject grafting agent this moment in proportion; Make powder surface modifier, grafting agent, vector resin that certain chemical reaction take place in melt extruding process, powder and vector resin are firmly combined.
Be equipped with again and use screw rod to melt extrude granulation with special construction design; Can make powder according to the synthetic 3 D stereo grid of certain structural group; Become the skeleton of material, and improve the shared ratio of masterbatch that has the 3 D stereo grid structure in the masterbatch product thus.
In the aforesaid method, said 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%; Said powder activation exciting agent is vitriol (wherein with the sodium sulfate best results), and dosage is 0.02%-1.5%, 3 ~ 5 minutes reaction times; Said powder surface modifier is a composite coupler, that is: silane coupling agent, and titanate coupling agent, aluminate coupling agent, Triple Pressed Stearic Acid, StNa and their mixture, dosage are 0.8%-5%, 2 ~ 5 minutes reaction times; Said powder surface modifier is the carboxylic acid type rare earth of macromolecular structure, and dosage is 1.2%-5%, 2 ~ 5 minutes reaction times; Said grafting agent is a 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 the activation of (electronic balance) → mixed at high speed and is coated (mixing machine) → reinforced (spiral feeder) → mixing extruding (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 and is 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:
Polyolefin masterbatch of the present invention with the organic/inorganic non-metallic material of multiple different-shape the superfine powder after composite modified as stopping composition; In the organic/inorganic non-metallic material of multiple different-shape, fiber, whisker etc. has the unidimensional acicular structure, and mica, talcum powder etc. has the laminated structure of two dimension; Lime carbonate etc. have three-dimensional globosity; Theoretical according to the 3 D stereo blend, in conjunction with Special Working Technology, make the non-metallic powder of three kinds of structures be dispersed in the material with the 3 D stereo grid structure; Needle-like, lamella, spheric structured material as beam, wall, the nuclear of 3 D stereo grid structure, have increased the intensity and the toughness of material with this respectively.
Modified technique among the present invention adopts inorganic-organic multilayer to coat complex reaction technology; Improved the consistency of organic/inorganic non-metallic material and vector resin greatly; The organic/inorganic non-metallic material are dispersed in the material with the unitary form of 3 D stereo grid structure; As the skeleton of material, material mechanical performance is improved.
Technology of the present invention is simple, with low cost; The production process of polyolefin masterbatch adopts simple technology; A large amount of non-metallic material such as nonmetal mine tailing, associated minerals and woodworking industry scrap stock of using cheapness, thereby have 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.
Description of drawings
Fig. 1 is the technological process of production figure that polyolefine strengthens toughened master batch among the present invention;
Fig. 2 is the unitary synoptic diagram of 3 D stereo grid structure among the present invention;
Wherein, the 1st, the unitary beam of 3 D stereo grid structure, i.e. needle inorganic such as fiber, whisker powder, the 2nd, the unitary wall of 3 D stereo grid structure, i.e. lamella inorganic powder, the 3rd, the unitary nuclear of 3 D stereo grid structure, i.e. inorganic spherical powder.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described further.
The processing polyolefine strengthens toughened master batch as follows:
One, masterbatch prescription:
High-density polyethylene resin 2480:10%
Composite superfine powder:
Magnesium salt whisker 5%
Talcum powder 35%
Lime carbonate 40%
Powder activation exciting agent: sodium sulfate 1.2%
The powder surface modifier:
The mixture 1.7% of Triple Pressed Stearic Acid: silane coupling agent: StNa=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:
By technical process processing masterbatch shown in Figure 1, the main production process of product is following by above-mentioned prescription:
1, with magnesium salt whisker, talcum powder, lime carbonate in proportion on electronic balance essence prepare, add in the high-speed mixer, after carrying out drying and dehydrating under 105 ℃; Add powder activation exciting agent sodium sulfate 1.2% more successively; Reacted 5 minutes; Add powder surface modifier 1.7% reaction 5 minutes, the carboxylic acid type rare earth powder surface modifier 1.2% that adds macromolecular structure reacted 2 minutes, thus composite superfine powder was carried out multilayer clad surface activation modification and handled;
2, vector resin Vilaterm, oxidation inhibitor, lubricant, processing aid are prepared in proportion, add in the high-speed mixer and mix with composite superfine powder, thorough mixing is even;
3, material is moved to from high-speed mixer carry out fusion, plasticizing, mixing in the twin screw extruder, inject grafting agent maleic anhydride 0.1% and carry out graft reaction this moment, and powder and vector resin are firmly combined; Afterwards again through single screw extrusion machine extrude, granulation; Carry out air-cooled pelletizing at last, three kinds of organic/inorganic powder body materials that promptly obtain having one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity are with 3 D stereo grid structure form distribution Vilaterm enhancing toughened master batch product wherein.
One, masterbatch prescription:
Acrylic resin T30S:20.48%
Composite superfine powder:
Spun glass 5%
Mica powder 20%
Lime carbonate 25%
Powder activation exciting agent: calcium sulfate 0.02%
The powder surface modifier:
The mixture 5% of Triple Pressed 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:
By technical process processing masterbatch shown in Figure 1, the main production process of product is following by above-mentioned prescription:
1, with spun glass, mica powder, lime carbonate in proportion on electronic balance essence prepare, add in the Banbury mixer, after carrying out drying and dehydrating under 105 ℃; Add powder activation exciting agent calcium sulfate 0.02% reaction 3 minutes more successively; Add coating materials (being composite coupler) 5% reaction 2 minutes; The carboxylic acid type rare earth powder surface modifier 3.5% that adds macromolecular structure reacted 5 minutes, thus composite superfine powder was carried out multilayer clad surface activation modification and handled;
2, vector resin Vestolen PP 7052, oxidation inhibitor, lubricant, processing aid are prepared in proportion, add in the Banbury mixer with composite superfine powder mix, fusion, plasticizing, mixing;
3, material in the Banbury mixer is added in the single screw extrusion machine through the bi-conical feed unit carry out fusion, plastify, extrude, granulation, inject grafting agent maleic anhydride 0.3% and carry out graft reaction this moment, and powder and vector resin are firmly combined; Carry out air-cooled pelletizing afterwards again, three kinds of organic/inorganic powder body materials that promptly obtain having one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity are with 3 D stereo grid structure form distribution polypropylene reinforced plasticized masterbatch product wherein.
One, masterbatch prescription:
Linear low density polyethylene resin 7042:15%
Composite superfine powder:
Calcium sulfate crystal whiskers: 14.5%
Talcum powder 30%
Lime carbonate 30%
Powder activation exciting agent: zinc sulfate 1.5%
The powder surface modifier:
The mixture 0.8% of Triple Pressed 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%
Processing aid: PPA (fluoropolymer process aid) 1%.
Two, production technique:
By technical process processing masterbatch shown in Figure 1, the main production process of product is following by above-mentioned prescription:
1, with calcium sulfate crystal whiskers, talcum powder, lime carbonate in proportion on electronic balance essence prepare, add in the high-speed mixer, after carrying out drying and dehydrating under 110 ℃; Add powder activation exciting agent zinc sulfate 1.5% reaction 4 minutes more successively; Add coating materials (being composite coupler) 0.8% reaction 4 minutes; The carboxylic acid type rare earth powder surface modifier 1.2% that adds macromolecular structure reacted 3 minutes, thus composite superfine powder was carried out multilayer clad surface activation modification and handled;
2, vector resin Vilaterm, oxidation inhibitor, lubricant, processing aid are prepared in proportion, add in the high-speed mixer and mix with composite superfine powder, thorough mixing is even;
3, material is moved to from high-speed mixer carry out fusion, plasticizing, mixing in the twin screw extruder with special screw-rod structure flute profile dish, inject grafting agent maleic anhydride 0.2% and carry out graft reaction this moment, and powder and vector resin are firmly combined; Afterwards again through single screw extrusion machine extrude, granulation; Carry out air-cooled pelletizing at last, three kinds of organic/inorganic powder body materials that promptly obtain having one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity are with 3 D stereo grid structure form distribution Vilaterm enhancing toughened master batch product wherein.
Embodiment 4
One, masterbatch prescription:
Acrylic resin PA14D:42%
Composite superfine powder:
Wollastonite: 10%
Talcum powder 15%
Lime carbonate 25%
Powder activation exciting agent: sodium sulfate 0.1%
The powder surface modifier:
The mixture 0.8% of Triple Pressed Stearic Acid: silane coupling agent: StNa=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: StNa 5%
Processing aid: PPA (fluoropolymer process aid) 0.5%.
Two, production technique:
By technical process processing masterbatch shown in Figure 1, the main production process of product is following by above-mentioned prescription:
1, with wollastonite, talcum powder, lime carbonate in proportion on electronic balance essence prepare, add in the Banbury mixer, after carrying out drying and dehydrating under 108 ℃; Add powder activation exciting agent sodium sulfate 0.1% reaction 4 minutes more successively; Add coating materials (being composite coupler) 0.8% reaction 3 minutes; The carboxylic acid type rare earth powder surface modifier 1.2% that adds macromolecular structure reacted 3 minutes, thus composite superfine powder was carried out multilayer clad surface activation modification and handled;
2, vector resin Vestolen PP 7052, oxidation inhibitor, lubricant, processing aid are prepared in proportion, add in the high-speed mixer and mix with composite superfine powder, thorough mixing is even;
3, material is moved to from high-speed mixer carry out fusion, plasticizing, mixing in the twin screw extruder, inject grafting agent maleic anhydride 0.1% and carry out graft reaction this moment, and powder and vector resin are firmly combined; Afterwards again through single screw extrusion machine extrude, granulation; Carry out air-cooled pelletizing at last, three kinds of organic/inorganic powder body materials that promptly obtain having one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity are with 3 D stereo grid structure form distribution Vilaterm enhancing toughened master batch product wherein.
Embodiment 5
One, masterbatch prescription:
Linear low density polyethylene resin 7042:10%
Composite superfine powder:
Spun glass 5%
Talcum powder 40%
Zeyssatite 25%
Powder activation exciting agent: sal epsom 1%
The powder surface modifier:
The mixture 5% of Triple Pressed 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: OPE 5.5%
Triple Pressed Stearic Acid 2.5%
Paraffin 1.5%
Processing aid: PPA (fluoropolymer process aid) 0.5%.
Two, production technique:
By technical process processing masterbatch shown in Figure 1, the main production process of product is following by above-mentioned prescription:
1, with spun glass, talcum powder, zeyssatite in proportion on electronic balance essence prepare, add in the Banbury mixer, after carrying out drying and dehydrating under 105 ℃; Add powder activation exciting agent sal epsom 1% reaction 4 minutes more successively; Add coating materials (being composite coupler) 5% reaction 3 minutes; The carboxylic acid type rare earth powder surface modifier 3% that adds macromolecular structure reacted 3 minutes, thus composite superfine powder was carried out multilayer clad surface activation modification and handled;
2, vector resin Vilaterm, oxidation inhibitor, lubricant, processing aid are prepared in proportion, add in the Banbury mixer with composite superfine powder mix, fusion, plasticizing, mixing;
3, with material in the Banbury mixer through bore extra quality unit add carry out in the single screw extrusion machine fusion, plasticizing, mixing, extrude, granulation, inject grafting agent maleic anhydride 0.2% and carry out graft reaction this moment, and powder and vector resin are firmly combined; Again through carrying out air-cooled pelletizing, three kinds of organic/inorganic powder body materials that promptly obtain having one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity are with 3 D stereo grid structure form distribution Vilaterm enhancing toughened master batch product wherein afterwards.
Embodiment 6
One, masterbatch prescription:
Acrylic resin PA14D:35%
Composite superfine powder:
Wood powder 10%
Sheet mica 25%
Kaolin 20%
Powder activation exciting agent: sodium sulfate 0.8%
The powder surface modifier:
The mixture 1.5% of Triple Pressed Stearic Acid: silane coupling agent: StNa=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:
By technical process processing masterbatch shown in Figure 1, the main production process of product is following by above-mentioned prescription:
1, with wood powder, sheet mica, kaolin in proportion on electronic balance essence prepare, add in the high-speed mixer, after carrying out drying and dehydrating under 110 ℃; Add powder activation exciting agent sodium sulfate 0.8% reaction 4 minutes more successively; Add coating materials (being composite coupler) 1.5% reaction 4 minutes; The carboxylic acid type rare earth powder surface modifier 1.2% that adds macromolecular structure reacted 3 minutes, thus composite superfine powder was carried out multilayer clad surface activation modification and handled;
2, vector resin Vestolen PP 7052, oxidation inhibitor, lubricant, processing aid are prepared in proportion, add in the high-speed mixer and mix with composite superfine powder, thorough mixing is even;
3, material is moved to from high-speed mixer carry out fusion, plasticizing, mixing in the twin screw extruder with special screw-rod structure flute profile dish, inject grafting agent maleic anhydride 0.2% and carry out graft reaction this moment, and powder and vector resin are firmly combined; Afterwards again through single screw extrusion machine extrude, granulation; Carry out air-cooled pelletizing at last, three kinds of organic/inorganic powder body materials that promptly obtain having one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity are with 3 D stereo grid structure form distribution polypropylene reinforced plasticized masterbatch product wherein.
SEM ESEM result shows that the Vilaterm that embodiment 1-6 obtains strengthens in the 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 of the contribution of different-shape non-metallic material to the polyolefine mechanical property; The crystal whisker materials that employing possesses the filamentary material of one dimension acicular structure and possesses certain length-to-diameter ratio is as the unitary beam 1 of 3 D stereo grid structure; Employing possesses the material of two-dimentional laminated structure as the unitary wall 2 of 3 D stereo grid structure, adopts the material that possesses the solid sphere structure as the unitary nuclear 3 of 3 D stereo grid structure, and the gap is a polyolefin substrate.Theoretical according to the 3 D stereo blend; In conjunction with Special Working Technology; Make the organic/inorganic non-metallic powder of three kinds of structures be distributed in the material with 3 D stereo grid structure uniform form; Needle-like, sheet, spheric structured material as beam, wall, the nuclear of 3 D stereo grid structure, increase the intensity and the toughness of material with this respectively.
The PT example:
The polyolefine that obtains by prescription and the production technique production of embodiment 1-6 strengthens the toughened master batch product; According to matrix resin (being vector resin) and masterbatch proportioning is the ratio processing gained finished product of 2:1; Carry out performance test according to GB/T1843, GB/T1040, GB/T1042, see table 1 through the performance data of test:
Table 1: performance test data
Product performance test data by embodiment 1-6 also can be found out; Polyolefine by prescription of the present invention and working method processing thereof strengthens toughened master batch; Have good shock resistance and bending property; This masterbatch adds in the polyolefin plastic products, and rigidity, toughness and the tensile strength of goods are significantly increased.
Claims (10)
1. a polyolefine strengthens toughened master batch, it is characterized in that, comprises following components in part by weight in the masterbatch:
Said composite superfine powder is that the micro-nano powder by the organic/inorganic non-metallic material of three kinds of different-shapes with one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity is composited;
Comprise in the above-mentioned composite superfine powder: A, needle-like powder, promptly have the non-metallic material of one dimension acicular structure, comprising: filamentary material (various spun glass, wood powder, bamboo powder), crystal whisker materials (magnesium salt whisker, calcium sulfate crystal whiskers), wollastonite; B, lamella inorganic powder promptly have the non-metallic material of two-dimentional laminated structure, comprising: sheet mica, talcum powder; C, inorganic spherical powder promptly have the non-metallic material of three-dimensional globosity, comprising: calcium carbonate superfine powder and nano-calcium carbonate, kaolin, potter's clay, zeyssatite, glass microballon, ground barium sulfate, the pyrophyllite powder of order number more than 800 orders; The weight ratio of each component is in the above-mentioned composite superfine powder:
A, needle-like powder: 1%-20%
B, lamella inorganic powder: 30%-50%
C, inorganic spherical powder: 40%-50%.
2. polyolefine as claimed in claim 1 strengthens toughened master batch, it is characterized in that the best proportioning of A, B, C three components is in the said composite superfine powder:
Needle-like powder A: lamella inorganic powder B: inorganic spherical powder C=10:40:50.
3. according to claim 1 or claim 2 polyolefine strengthens toughened master batch, it is characterized in that said powder activation exciting agent is a vitriol; Said powder surface modifier is the carboxylic acid type rare earth of macromolecular structure; Said grafting agent is a maleic anhydride; Said powder surface modifier is a silane coupling agent, titanate coupling agent, aluminate coupling agent, Triple Pressed Stearic Acid, StNa and their mixture.
4. polyolefine as claimed in claim 3 strengthens toughened master batch, it is characterized in that said polyolefine comprises the Vilaterm and the Vestolen PP 7052 of the various trades mark; Said lubricant is a Triple Pressed Stearic Acid, StNa, Zinic stearas, calcium stearate, OPE (OPE), polyethylene wax, paraffin and their mixture.
5. polyolefine as claimed in claim 4 strengthens toughened master batch, it is characterized in that said oxidation inhibitor is four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) esters (oxidation inhibitor 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; Said processing aid is PPA (fluoropolymer process aid).
6. polyolefine as claimed in claim 5 strengthens toughened master batch, it is characterized in that said powder activation exciting agent is a 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 that have one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity in the said masterbatch product distribute wherein with 3 D stereo grid structure form.
8. one kind strengthens the working method of toughened master batch like the described polyolefine of claim 1-7, it is characterized in that:
The working method of masterbatch comprises the steps:
(1) the mixed at high speed stage: before composite superfine powder and vector resin are compound, adopt multilayer to coat complex reaction technology earlier and composite superfine powder is carried out the surface active modification handle;
Said multilayer coats complex reaction technology, comprises the steps:
1. composite superfine powder is at 105 ~ 110 ℃ of following drying and dehydratings;
2. add powder activation exciting agent, carry out one deck and coat complex reaction, the powder surface bound energy is reduced;
3. add the powder surface modifier, carry out again one deck and coat complex reaction, powder surface is changed to oleophilicity by wetting ability;
4. the adding powder surface modifier carries out one deck again and coats complex reaction, forms hinge at powder surface, and powder and resin compatible are strengthened;
(2) melt extrude the stage: under the effect that adds gentle certain extrusion pressure; Material is fusion in extrusion equipment; Inject grafting agent this moment, makes powder surface modifier, grafting agent, vector resin that certain chemical reaction take place in melt extruding process, and powder and vector resin are firmly combined.
9. polyolefine as claimed in claim 8 strengthens the working method of toughened master batch, and it is characterized in that: said 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%; Said powder activation exciting agent is a vitriol, and dosage is 0.02%-1.5%, 3 ~ 5 minutes reaction times; Said powder surface modifier is a silane coupling agent, titanate coupling agent, and aluminate coupling agent, Triple Pressed Stearic Acid, StNa and their mixture, dosage are 0.8%-5%, 2 ~ 5 minutes reaction times; Said powder surface modifier is the carboxylic acid type rare earth of macromolecular structure, and dosage is 1.2%-5%, 2 ~ 5 minutes reaction times; Said grafting agent is a maleic anhydride, and dosage is 0.1%-0.3%.
10. strengthen the working method of toughened master batchs like claim 8 or 9 described polyolefine; It is characterized in that: it be utilize that the mixed at high speed unit mixes, modification, preplasticizing; Again through extrude unit carry out fusion, plasticizing, mixing, extrude, granulation; Last air-cooled pelletizing, three kinds of organic/inorganic powder body materials that obtain having one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity are with 3 D stereo grid structure form distribution masterbatch product wherein; Or; Utilize that Banbury mixer mixes, modification, fusion, plasticizing, mixing; Extrude through extruding unit again, granulation; Last air-cooled pelletizing, three kinds of organic/inorganic powder body materials that obtain having one dimension acicular structure, two-dimentional laminated structure and three-dimensional globosity are with 3 D stereo grid structure form distribution masterbatch product wherein.
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Effective date of registration: 20180419 Address after: 230000 Yulan Avenue, peach blossom Industrial Park, Hefei economic and Technological Development Zone, Anhui, China Patentee after: Anhui national state Yongsheng Polymer Technology Co., Ltd. Address before: 230022 Anhui province Hefei city Hefei open area peach blossom Industrial Park Wen Shan Road and Tang Kou intersection. Co-patentee before: Li Hongwu Patentee before: Anhui Banni New Materials Co.,Ltd. Co-patentee before: Zhou Wei |