CN102120843B - Subnanometer enhanced and toughened transparent master batch and preparation method thereof - Google Patents
Subnanometer enhanced and toughened transparent master batch and preparation method thereof Download PDFInfo
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
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- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a subnanometer enhanced and toughened transparent master batch and a preparation method thereof. The subnanometer enhanced and toughened transparent master batch comprises the following components in percentage by weight: 70-85 percent of subnanometer powder, 1-5 percent of dispersing agent, 0.3-1 percent of lubricating agent, 1-3 percent of coupling agent, 0.3-0.5 percent of thermal stabilizing agent, 0.1-0.5 percent of antioxidant and 10-25 percent of carrier resin. The preparation method comprises the following steps of: putting the subnanometer powder into a high speed mixer, selecting a high gear for stirring and heating, adding the coupling agent and treating for three minutes, then adding other raw materials, discharging and cooling after the raw materials are evenly stirred and mixed by the high speed mixer, then crushing, and extruding and pelleting through an extruding and pelleting device. The invention solves the problem that the mechanical performance of a plastic film is reduced after the common master batch is used in the prior art, in particular the problem that the light transmittance and the transparency are reduced; the mechanical performance of a film product is improved at the same time of reducing the cost; meanwhile, the invention achieves the purposes of enhancing and toughening and can be used in the fields of foods and medicines.
Description
Technical field
The present invention relates to inorganic powder modified high-molecular polymer arts, specifically a kind of inferior nanometer strengthens toughness reinforcing transparent masterbatches and preparation method thereof.
Background technology
The filling-modified masterbatch of plastics is since putting goods on the market the early 1980s; Because it is cheap, excellent product performance can be improved some physical propertys of plastics; Substitute synthetic resins, and production technique is simple, investment is less, have remarkable economic efficiency and social benefit.Thereby the filling-modified masterbatch of plastics is the new industry in the fastest plastics industry of development in recent years, has become one of the integral part of plastic working industry and main interpolation material of plastics.
China has become the great powers in the world that plastics are produced, is only second to the U.S., produces a year amount and surpasses 4,000 ten thousand tons, but also developing continuously and healthily with double-digit growth speed.A large amount of uses of plastics; Human society is convenient, fast, practical and simultaneously efficiently bringing; Also because of arbitrarily being abandoned after the use or can being brought detrimentally affect to ecotope during at back to nature; Particularly no matter disposable use plastics such as mulch film, plastic packaging bag are to remain in the soil, still all can be brought problem to ecotope as a solid refuse part by landfill, burning, are referred to as by society " white pollution ".Along with the enhancing of environmental consciousness, the cry of seeking to solve white pollution is surging gradually, and inorganic powder modified high-molecular polymkeric substance is one of efficient ways; Require wherein the calcium carbonate content must be more than 30% like Japanese convenient bag GB; So not only practice thrift limited petroleum resources, and help environmental protection, burn and do not smolder; Do not melt and drip, do not produce toxic gas.On the other hand, along with back the closing on of petroleum times, crude oil price one tunnel skyrockets, and various resins are also inevitable, and when the river rises the boat goes up thereupon, and under this overall background, numerous plastic working enterprise can't bear the heavy load, and is absorbed in the condition of having difficulty in taking a step.Goods do not appreciate in the face of starting material appreciate, and only reliable inorganic powder modification solves.
Chinese invention patent CN1181128C discloses a kind of polyolefin packing material and working method thereof, and the inorganic powder that adopts is a lime carbonate, does not mention diameter of particle; Chinese invention patent CN10032132C discloses a kind of transparent film masterbatch and preparation method thereof, and the inorganic powder that adopts is 2000% to 2500 order talcum powder, 5% to 8 micron of median size; Chinese invention patent CN100398586C discloses a kind of plastics film with filling master batch and preparation method thereof, and the inorganic powder that adopts is the compound of talcum powder and lime carbonate, 5% to 8 micron of median size; The above masterbatch adds the transparency and the glossiness that can reduce film article in plastics film, cause the decline of film article mechanical property.Chinese invention patent CN101367970A discloses a kind of novel material that is exclusively used in transparent plastics and preparation method thereof, and the inorganic powder that adopts is the fine powder of 1250 purpose silicon-dioxide; Chinese invention patent CN101348586A discloses a kind of transparent enhanced filling mastre batch and preparation method thereof, and the inorganic powder that adopts is 1200% to 1500 order transparent glass powder; Above the used powder Mohs' hardness of said two kinds of masterbatch be about 6, big to processing units wearing and tearing.Chinese invention patent CN100592979C discloses a kind of polyolefin complete transparent master batch and preparation method thereof, and the inorganic powder that adopts is 1250 purpose Sodium sulfate anhydrous.min(99), is a kind of water-soluble inorganic salt, and the heavy corrosion processing units can not be used for food product pack.
Summary of the invention
Technical problem to be solved by this invention is to above-mentioned prior art present situation; And provide a kind of inferior nanometer to strengthen toughness reinforcing transparent masterbatches and preparation method thereof; To solve the problem of mechanical properties decrease, particularly transmittance and the transparency decline after using common masterbatch of plastics film in the prior art; When reducing cost, improve the mechanical property of film article, realize that simultaneously enhancing is toughness reinforcing, and can be used for the food and medicine field.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of inferior nanometer strengthens toughness reinforcing transparent masterbatches, comprise inferior nano-powder, dispersion agent, lubricant, coupling agent, thermo-stabilizer, oxidation inhibitor for and vector resin; By weight percentage, inferior nano-powder is 70% to 85%, and dispersion agent is 1% to 5%, and lubricant is 0.3% to 1%, and coupling agent is 1% to 3%, and thermo-stabilizer is 0.3% to 0.5%, and oxidation inhibitor is 0.1% to 0.5%, and vector resin is 10% to 25%.
For optimizing technique scheme, the measure of taking also comprises:
Above-mentioned inferior nano-powder is the process white of median size less than 500 nanometers.
Above-mentioned dispersion agent is a polyethylene wax, paraffin, and EVA wax, OPE covers dawn acid wax, smart wax, micro mist wax, at least a in AClyc lower molecular weight ionomer and the hyper-dispersant.
Above-mentioned lubricant is the auxiliary agent with inside and outside lubricating function; Coupling agent is the auxiliary agent with coupled action; Thermo-stabilizer is a stearate; Oxidation inhibitor is the auxiliary agent with antioxidant effect; Vector resin is a polyvinyls.
Above-mentioned lubricant is EBS, at least a in modification EBS and the amine hydroxybenzene.
Above-mentioned coupling agent is at least a in Triple Pressed Stearic Acid, lipid acid, silane, aluminic acid ester, titanic acid ester, SULPHOSUCCINIC ACID ESTER and the boric acid ester.
Above-mentioned thermo-stabilizer is at least a in Zinic stearas, calcium stearate and the barium stearate.
Above-mentioned oxidation inhibitor is at least a in 1010 oxidation inhibitor, 1076 oxidation inhibitor, 264 oxidation inhibitor and 300 oxidation inhibitor.
Above-mentioned vector resin is at least a in high density polyethylene(HDPE), new LDPE (film grade), linear polyethylene and the metallocene PE.
A kind of inferior nanometer of the present invention strengthens the preparation method of toughness reinforcing transparent masterbatches; By weight percentage; With inferior nano-powder 70% to 85% put in the high-speed mixer select high gear to stir and be heated to 105 ℃ to 115 ℃ after; Add coupling agent 1% to 3% and handled three minutes, add lubricant 0.3% to 1%, thermo-stabilizer 0.3% to 0.5%, oxidation inhibitor 0.1% to 0.5%, dispersion agent 1% to 5% and vector resin 10% to 25% then, treat that high-speed mixer mixes back blowing cooling; Broken then, and pass through extruding and granulating equipment at 90 ℃ to 170 ℃ following extruding pelletizations; Extruding and granulating equipment is single screw extrusion machine, the reciprocating type machine of extruding, twin screw extruder, three-screw extruder, two rank forcing machine or two rotors forcing machine.
Compared with prior art, to strengthen the advantage that toughness reinforcing transparent masterbatches has in every respect following for a kind of inferior nanometer of the present invention:
1, the extrusion moulding of product:
1. because narrower size distribution of nano_scale particle and special surface treatment, add can reduce behind the properties-correcting agent and extrude system pressure, improve production efficiency of products thereby can improve screw speed;
2. the adding of properties-correcting agent has reduced the viscosity of compound system, makes melt even, and the thermal expansivity of properties-correcting agent is low can reduce back pressure, is beneficial to compound and extrudes, thereby can increase the extrusion capacity in the unit time;
3. because the high thermal conductivity of properties-correcting agent so product cooling forming rapid speed makes product anisotropic occur, helps the raising of product mechanical property;
4. add this properties-correcting agent and can improve the stability of technology in the production, optimization production technology;
5. add the stiffness that improves product behind the properties-correcting agent, the polyolefine that properties-correcting agent can substitute in original prescription uses, and for reducing product thickness possibility is provided;
6. add the consumption that properties-correcting agent can reduce Masterbatch, and can keep cleaning in the forcing machine;
2, the physical strength of product:
1. in production formula, add the properties-correcting agent of suitable proportion, the physicals of product is made moderate progress;
2. improve hammer falling impact strength;
3. improve tear strength;
4. improve secant modulus;
5. improve film seal intensity;
3, density of product and size:
1. owing to added the particulate through special processing in the properties-correcting agent, particulate is distributed in the mixed system uniformly, combines closely with molecular resin, so the proportion of product can increase to some extent behind the adding properties-correcting agent;
2. do not have automatic size control system like production line, need to recalibrate product size after adding properties-correcting agent;
4, the transparency of product:
1. along with the increase of properties-correcting agent content in product, transparency of products can reduce.Add the light transmission that 15% properties-correcting agent does not influence film basically in the low pressure transparent film product; Add the light transmission that 10% properties-correcting agent does not influence film basically in the high pressure transparent film product; Tubing and sheet material can require corresponding adjustment adding proportion according to the transparency; If in the white film goods, alternative part white master material uses, and masterbatch adds 30% to still can keep goods good tensile and luminance brightness;
2. the oxygen transmission rate of product and permeability rate;
3. adding product behind the properties-correcting agent is improved to the barrier of oxygen and water vapour;
5, the decorating printing of product:
1. can make product produce persistent surface tension after adding this properties-correcting agent, reduce the processing intensity of corona in producing, make printing-ink be difficult for fading, help the printing of product;
2. after adding this properties-correcting agent, product appearance is beautiful, and feel is fine and smooth; Fold, twine and process more convenient.
Embodiment
Below embodiments of the invention are described in further detail.
A kind of inferior nanometer of the present invention strengthens toughness reinforcing transparent masterbatches, comprise inferior nano-powder, dispersion agent, lubricant, coupling agent, thermo-stabilizer, oxidation inhibitor for and vector resin; By weight percentage, inferior nano-powder is 70% to 85%, and dispersion agent is 1% to 5%, and lubricant is 0.3% to 1%, and coupling agent is 1% to 3%, and thermo-stabilizer is 0.3% to 0.5%, and oxidation inhibitor is 0.1% to 0.5%, and vector resin is 10% to 25%.
Above-mentioned inferior nano-powder is the process white of median size less than 500 nanometers.
Above-mentioned dispersion agent is a polyethylene wax, paraffin, and EVA wax, OPE covers dawn acid wax, smart wax, micro mist wax, at least a in AClyc lower molecular weight ionomer and the hyper-dispersant.
Above-mentioned lubricant is EBS, at least a in modification EBS and the amine hydroxybenzene.
Above-mentioned coupling agent is at least a in Triple Pressed Stearic Acid, lipid acid, silane, aluminic acid ester, titanic acid ester, SULPHOSUCCINIC ACID ESTER and the boric acid ester.
Above-mentioned thermo-stabilizer is at least a in Zinic stearas, calcium stearate and the barium stearate.
Above-mentioned oxidation inhibitor is at least a in 1010 oxidation inhibitor, 1076 oxidation inhibitor, 264 oxidation inhibitor and 300 oxidation inhibitor.
Above-mentioned vector resin is at least a in high density polyethylene(HDPE), new LDPE (film grade), linear polyethylene and the metallocene PE.
A kind of inferior nanometer of the present invention strengthens the preparation method of toughness reinforcing transparent masterbatches; By weight percentage; With inferior nano-powder 70% to 85% put in the high-speed mixer select high gear to stir and be heated to 105 ℃ to 115 ℃ after; Add coupling agent 1% to 3% and handled three minutes, add lubricant 0.3% to 1%, thermo-stabilizer 0.3% to 0.5%, oxidation inhibitor 0.1% to 0.5%, dispersion agent 1% to 5% and vector resin 10% to 25% then, treat that high-speed mixer mixes back blowing cooling; Broken then, and pass through extruding and granulating equipment at 90 ℃ to 170 ℃ following extruding pelletizations; Extruding and granulating equipment is single screw extrusion machine, the reciprocating type machine of extruding, twin screw extruder, three-screw extruder, two rank forcing machine or two rotors forcing machine.
Embodiment 1:
Take by weighing raw material by weight: 70 kilograms of median size 100 nanometer Ya Nami process whites, 2.3 kilograms of polyethylene waxs, 2 kilograms of Triple Pressed Stearic Acid, EBS0.3 kilogram, 0.3 kilogram of Zinic stearas, 0.1 kilogram in 1010 oxidation inhibitor, linear polyethylene LLDPE25 kilogram.
After the Ya Nami process white put into the high-speed mixer high speed and stir and be heated to 110 ℃; Add the Triple Pressed Stearic Acid coupling agent treatment three minutes, and added EBS, Zinic stearas, 1010 oxidation inhibitor then, add polyethylene wax and linear polyethylene LLDPE at last; Treat that the high-speed mixer electric current increases back blowing cooling suddenly; Broken then, add single screw extrusion machine and under 170 ℃, extrude at 140 ℃, the pelletizing of water tie rod obtains the masterbatch finished product.
Embodiment 2:
Take by weighing raw material by weight: 75 kilograms of median size 200 nanometer Ya Nami process whites, 2 kilograms of OPEs, 1.5 kilograms of aluminic acid esters; Modification EBS0.5 kilogram; 0.5 kilogram of calcium stearate, 0.2 kilogram in 1076 oxidation inhibitor, 20.3 kilograms of low density polyethylenes.
After the Ya Nami process white put into the high-speed mixer high speed and stir and be heated to 110 ℃; Add aluminate coupling agent and handled three minutes, add modification EBS, calcium stearate, 1076 oxidation inhibitor then, add OPE and low density polyethylene at last; Treat that the high-speed mixer electric current increases back blowing cooling suddenly; Broken then, add the reciprocating type machine of extruding and under 170 ℃, extrude at 140 ℃, the pelletizing of water tie rod obtains the masterbatch finished product.
Embodiment 3:
Take by weighing raw material by weight: 80 kilograms of median size 300 nanometer Ya Nami process whites, 2 kilograms in EVA wax, 2 kilograms of titanic acid ester, 0.5 kilogram of amine hydroxybenzene, 0.5 kilogram of barium stearate, 0.3 kilogram in 264 oxidation inhibitor, 14.7 kilograms of high density polyethylenes.
After the Ya Nami process white put into the high-speed mixer high speed and stir and be heated to 110 ℃; Add titanate coupling agent and handled three minutes, add amine hydroxybenzene, barium stearate, 264 oxidation inhibitor then, add EVA wax and high density polyethylene at last; Treat that the high-speed mixer electric current increases back blowing cooling suddenly; Broken then, add twin screw extruder and under 150 ℃, extrude the air-cooled masterbatch finished product that earnestly obtains at 110 ℃.
Embodiment 4:
Take by weighing raw material by weight: 85 kilograms of median size 400 nanometer Ya Nami process whites, 1.1 kilograms of AClyc lower molecular weight ionomers, 2.5 kilograms of boric acid esters; 0.5 kilogram of amine hydroxybenzene; 0.5 kilogram of Zinic stearas, 0.4 kilogram in 300 oxidation inhibitor, 10 kilograms of metallocene PEs.
The Ya Nami process white is put into the weight-loss metering feed hopper; Ionomer, boric acid ester, Zinic stearas, oxidation inhibitor and amine hydroxybenzene are mixed another weight-loss metering feed hopper of adding at high-speed mixer; Metallocene PE drops into another weight-loss metering feed hopper; Extrude the air-cooled master batch sample that earnestly obtains with two rank machine at 90 ℃ to 130 ℃.
Embodiment 5
The dispersion agent of arbitrary embodiment in the foregoing description 1 to 4 is replaced with illiteracy dawn acid wax, can realize technique effect of the present invention equally.
Embodiment 6
The dispersion agent of arbitrary embodiment in the foregoing description 1 to 4 is replaced with smart wax, can realize technique effect of the present invention equally.
Embodiment 7
The dispersion agent of arbitrary embodiment in the foregoing description 1 to 4 is replaced with micro mist wax, can realize technique effect of the present invention equally.
Embodiment 8
The dispersion agent of arbitrary embodiment in the foregoing description 1 to 4 is replaced with hyper-dispersant, can realize technique effect of the present invention equally.
Embodiment 9
The coupling agent of arbitrary embodiment in the foregoing description 1 to 8 is replaced with lipid acid, can realize technique effect of the present invention equally.
Embodiment 10
The coupling agent of arbitrary embodiment in the foregoing description 1 to 8 is replaced with silane, can realize technique effect of the present invention equally.
Embodiment 11
The coupling agent of arbitrary embodiment in the foregoing description 1 to 8 is replaced with SULPHOSUCCINIC ACID ESTER, can realize technique effect of the present invention equally.
Most preferred embodiment of the present invention is illustrated, and various variations or the remodeling made by those of ordinary skills can not depart from the scope of the present invention.
Claims (8)
1. an inferior nanometer strengthens toughness reinforcing transparent masterbatches, it is characterized in that: comprise inferior nano-powder, dispersion agent, lubricant, coupling agent, thermo-stabilizer, oxidation inhibitor and vector resin; By weight percentage; Described inferior nano-powder is 70% to 85%, and described dispersion agent is 1% to 5%, and described lubricant is 0.3% to 1%; Described coupling agent is 1% to 3%; Described thermo-stabilizer is 0.3% to 0.5%, and described oxidation inhibitor is 0.1% to 0.5%, and described vector resin is 10% to 25%; Described inferior nano-powder is the process white of median size less than 500 nanometers; Described vector resin is at least a in high density polyethylene(HDPE), new LDPE (film grade), linear polyethylene and the metallocene PE.
2. a kind of inferior nanometer according to claim 1 strengthens toughness reinforcing transparent masterbatches, it is characterized in that: described dispersion agent is a polyethylene wax, paraffin, and EVA wax, OPE covers dawn acid wax, smart wax, at least a in micro mist wax and the hyper-dispersant.
3. a kind of inferior nanometer according to claim 1 strengthens toughness reinforcing transparent masterbatches, it is characterized in that: described lubricant is the auxiliary agent with inside and outside lubricating function; Described coupling agent is the auxiliary agent with coupled action; Described thermo-stabilizer is a stearate; Described oxidation inhibitor is the auxiliary agent with antioxidant effect.
4. a kind of inferior nanometer according to claim 3 strengthens toughness reinforcing transparent masterbatches, it is characterized in that: described lubricant is EBS, at least a in modification EBS and the amine hydroxybenzene.
5. a kind of inferior nanometer according to claim 3 strengthens toughness reinforcing transparent masterbatches, it is characterized in that: described coupling agent is at least a in lipid acid, silane, aluminic acid ester, titanic acid ester, SULPHOSUCCINIC ACID ESTER and the boric acid ester.
6. a kind of inferior nanometer according to claim 3 strengthens toughness reinforcing transparent masterbatches, it is characterized in that: described thermo-stabilizer is at least a in Zinic stearas, calcium stearate and the barium stearate.
7. a kind of inferior nanometer according to claim 3 strengthens toughness reinforcing transparent masterbatches, it is characterized in that: described oxidation inhibitor is at least a in 1010 oxidation inhibitor, 1076 oxidation inhibitor, 264 oxidation inhibitor and 300 oxidation inhibitor.
8. a kind of inferior nanometer as claimed in claim 1 strengthens the preparation method of toughness reinforcing transparent masterbatches, it is characterized in that: by weight percentage, inferior nano-powder 70% put in the high-speed mixer to 85% select high gear to stir and be heated to 105
oC to 115
oBehind the C; Adding coupling agent 1% to 3% handled three minutes; Add lubricant 0.3% to 1%, thermo-stabilizer 0.3% to 0.5%, oxidation inhibitor 0.1% to 0.5%, dispersion agent 1% to 5% and vector resin 10% to 25% then; Treat that high-speed mixer mixes back blowing cooling, broken then, and pass through extruding and granulating equipment 90
oC to 170
oExtruding pelletization under the C; Described extruding and granulating equipment is single screw extrusion machine, the reciprocating type machine of extruding, twin screw extruder, three-screw extruder, two rank forcing machine or two rotors forcing machine.
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| CN102807684B (en) * | 2012-08-31 | 2014-05-21 | 南京工程学院 | High concentration sericite master batch and preparation method and application thereof |
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| CN103333397B (en) * | 2013-07-23 | 2016-02-24 | 河南惠强新能源材料科技有限公司 | A kind ofly increase filling master batch of plastics intensity and toughness and preparation method thereof |
| CN103881418B (en) * | 2014-03-05 | 2016-04-06 | 苏州克莱明新材料有限公司 | The preparation of modified nano-barium sulfate and application thereof |
| CN104710673A (en) * | 2014-07-07 | 2015-06-17 | 苍琳琳 | Environment-friendly stone plastic film material |
| CN104497406B (en) * | 2014-12-05 | 2017-05-10 | 成都菲斯特化工有限公司 | Filling master batch for transparent film and preparation method of filling master batch |
| CN104530546B (en) * | 2014-12-22 | 2017-01-25 | 山东农业大学 | Special anti-reflection reinforced master batch for agricultural greenhouse film and preparation method of anti-reflection reinforced master batch |
| CN104844898A (en) * | 2015-04-28 | 2015-08-19 | 芜湖众力部件有限公司 | Heat-resistant antioxidant modified plastic and manufacturing method thereof |
| CN106543761A (en) * | 2015-09-20 | 2017-03-29 | 营口亿丰环保材料有限公司 | A kind of blanc fixe high transparency modified master |
| CN106497123A (en) * | 2016-10-26 | 2017-03-15 | 山东友谊机械有限公司 | A kind of plasticizing mother particle and its processing method |
| CN108892846A (en) * | 2018-06-28 | 2018-11-27 | 庆云诺鑫塑胶新材料有限公司 | Degradable masterbatch of nano biological and preparation method thereof |
| CN109021354A (en) * | 2018-06-28 | 2018-12-18 | 庆云诺鑫塑胶新材料有限公司 | Blown film degradable masterbatch and preparation method thereof |
| CN110724333B (en) * | 2018-07-16 | 2022-04-08 | 中国石油化工股份有限公司 | Linear low-density polyethylene additive master batch, preparation method and application thereof |
| CN110498938B (en) * | 2019-08-27 | 2020-12-04 | 广州百沙塑胶新材料有限公司 | Plastic transparent master batch containing self-assembly composite transparent powder and preparation method thereof |
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| CN101348586A (en) * | 2008-09-12 | 2009-01-21 | 赵建伟 | Transparent reinforced filling master batch |
| CN101942126B (en) * | 2009-07-08 | 2012-08-08 | 中国石油天然气股份有限公司 | Transparent antistatic polyethylene film master batch |
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