CN102432918B - Plastic processing composite functional aid and preparation method thereof - Google Patents
Plastic processing composite functional aid and preparation method thereof Download PDFInfo
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- CN102432918B CN102432918B CN 201110316192 CN201110316192A CN102432918B CN 102432918 B CN102432918 B CN 102432918B CN 201110316192 CN201110316192 CN 201110316192 CN 201110316192 A CN201110316192 A CN 201110316192A CN 102432918 B CN102432918 B CN 102432918B
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Abstract
The invention discloses a plastic processing composite functional aid and a preparation method thereof. The plastic processing composite functional aid comprises the following raw materials in part by weight: 90 to 100 parts of light calcium carbonate powder, 3 to 5 parts of mica powder, 1 to 2 parts of calcium chloride, 1 to 2 parts of straw ash, 3 to 5 parts of zinc oxide, 3 to 5 parts of fumed silica, 1 to 2 parts of methacrylate polymer, 1 to 2 parts of polyethylene wax, 1 to 2 parts of sodium alkyl benzene sulfonate, and 1 to 2 parts of glycerol. The preparation method comprises the following steps of: drying light calcium carbonate till the moisture content is below 0.3 percent, adding the dried light calcium carbonate into a high-speed kneader, adding other formula materials in part by weight, heating the materials to the temperature of between 100 and 130 DEG C, preserving the heat and stirring for 8 to 10 minutes, discharging, and thus obtaining a finished product. Through the plastic processing composite functional aid prepared by the method, the surface energy among particles is reduced, and the compatibility and the dispersibility of plastics are improved; plasticization of macromolecular materials is promoted, the viscosity of a melt is reduced, and the processing flowability is improved; impact degree, rigidity, heat resistance and dimensional stability of a product are improved; and the plastic processing composite functional aid has the characteristics of energy conservation, emission reduction, environment friendliness, no toxicity and no ''three wastes''.
Description
Technical field
The present invention relates to field of plastics processing, specifically a kind of plastic processing composite functional aid and preparation method thereof.
Background technology
The properties-correcting agent of China's plastic working multifunction still is in developmental stage, and is no matter larger with external gap on kind, Yield and quality and modified function.
The producer that produces in the world plastic processing modifier is a lot, mainly contains U.S. Rohmandhass (ROHM AND HAAS) company and ATOCHEM company, Japanese clock deep pool chemical company etc.Rhom and Hass has developed first acrylic acid or the like impact modifier at middle nineteen sixties, the serial trade mark products such as ParaloidKM323B, KM330, KM334, KM335 have in succession been developed later on, wherein ParaloidKM355 is product of new generation, and superior performance is arranged.At present, Rhom and Hass has become the main provider of plastics additive in the world wide.Japan Wu Yu company is at the Pacific region and in the world other area and Rhom and Hass's joint sales PVC impact modifier and processing aids.The cooperation of above-mentioned two companies is produced ACR class properties-correcting agent in Singapore by Wu Yu chemistry (Singapore) private limited partnership, and its product grade is that the goods of ParalOidKM355P put goods on the market, and annual production is 100,000 tons.More external ACR anti-impacts change the agent trade mark and see Table 1.
The external some ACR impact modifier trades mark of table 1
Core-shell type ACR class impact modifier uses extensively, and multifunctionality is arranged, and application prospect is extensive.At present, high-performance and the most dependence on import of tailored version nuclear-shell ACR class impact modifier that China uses, the minority manufacturer production such as domestic only Qilu Petrochemical, Shanxi chemical institute, Shanghai Shanhu Chemical Factory, Shanghai, and kind is single, far can not satisfy the needs of different model PVC plastics.
Different properties-correcting agent Performance Ratios see Table 2.
Three kinds of properties-correcting agent of table 2 relatively
Annotate: from 1 to 5, performance is from bad to excellent
In addition, except above-mentioned several impact modifying agents, also have many plastic processing functional properties-correcting agent that can be used for.For example, CPE grafting vinyl chloride multipolymer, EVA grafting vinyl chloride multipolymer, ACR grafting vinyl chloride multipolymer, EPR (second the third glue) grafting vinyl chloride multipolymer, vinylchlorid grafted ethene-acrylate copolymer and EVACO multipolymer (ethane-acetic acid ethyenyl vinegar-CO terpolymer) etc.In recent years, also obtained remarkable progress with the research of two kinds of elastomer composite toughening PVCs, as with CPE/ACR, CPE/MBS composite toughening PVC.Result of study shows, the impact effect that the synergy of two kinds of toughner produces is better than single toughner.Except using elastic body toughening PVC, as using organic rigid-particle (PMMA, AS etc.), inorganic rigid particle (ultra-fine CaCO
3) report of toughening PVC, these inelastic body co-mixing systems also can be used as plastic processing modifier.Use in addition the report of elastomerics and non-resilient composite toughening, as using the ultra-fine CaCO of CPE/PS, CPE/
3, composite toughening PVC.And China PVC nanometer CaCO
3The research and development of matrix material had obtained remarkable break-throughs over the past two years.
" nuclear " of ACR generally is the esters of acrylic acid rubber polymer of low cross-linking, and " shell " layer can be one deck or bilayer, so anti-impact type ACR has dividing of double-deck and three layers of " nuclear-shell " structure.Its basic process is to make the seed emulsion particle with emulsion polymerization first, and appropriately crosslinked in the presence of linking agent, then drips other monomers, makes it carry out graft copolymerization on seed emulsion particle top layer.The skin of double-deck " nuclear-shell " structure ACR mainly is the multipolymer of methyl methacrylate polymer or methyl methacrylate and acrylate; Three layers of " nuclear-shell " structure ACR can be divided into again time skin and outermost layer, and secondly outer is styrene polymer often.According to the needs of using, except stratum nucleare certainly be lightly crosslinked, other layers can be divided into again line style or crosslinked.No matter double-deck or three layers of " nuclear-shell " structure ACR, the IPN that polymer chain is arranged between its stratum nucleare and the shell, so ACR is in fact again a class latex IPN, according to the mensuration of electron microscope observation and Dynamic Viscoelastic spectrometer, all provable ACR is the heterogeneous structure system.
Its toughening mechanism is usually comparatively common with crazing-shear zone theoretical explanation.The effect of " nuclear-shell " class rubber particles on the one hand as the stress concentration center, is brought out matrix and is produced a large amount of crazings and shear zone, and the generation of its crazing or shear zone and development need lot of energy, thereby significantly improves the shock resistance of material.Simultaneously, by bearing part three axial stresses at crazing and rubber separation surface, controlled the development of crazing, and crazing is in time stopped and unlikelyly developed into destructive crackle, the stress field at crazing tip can be brought out the generation of shear zone, and shear zone also can stop further developing of crazing.
" nuclear-shell " structure modifier, often undertaken crosslinked by the covalent linkage that adds typical cross-linking monomer, its nuclear core has good elasticity, shell is the superpolymer that has than high glass transition temperature, easily separates between particle, can be dispersed to uniformly the PVC base material, and energy and the interaction of PVC base material, thereby this class particle also plays the effect of similar ACR processing aid, promotion polyvinyl chloride resin gelation and plasticizing except can improving the PVC erosion-resisting characteristics.The major advantage of ACR class impact modifier has: good impact modification effect, wider processing temperature scope, the swollen property of low mould, product size are stablized, are had concurrently the processing aid characteristics, can shorten the fusion plastification time of compound, improve the co-mixing system moulding processability, have preferably weathering resistance.
Calcium carbonate belongs to the inorganic non-metallic mineral, the surface has many hydroxyls, easy adsorption moisture, the hydrophilic oleophobic of not surface treated calcium carbonate powder particle surface, be strong polarity, thereby can not with the polymer organism generation chemically crosslinkeds such as plastics, rubber, in organic medium, be difficult to Uniform Dispersion, the interface is difficult to form good bonding.In addition, the calcium carbonate superfine powder particle diameter is little, have great specific surface area and higher specific surface energy, particle coagulation, reunion very easily occur in preparation and last handling process, form offspring, make grain diameter become large, in application process, lose the function that ultrafine particulate possesses, thereby affect practical application effect, can not play the effect of functional stuffing; On the contrary, can reduce to a certain extent some physicals of goods because of boundary defect.
Summary of the invention
The invention provides a kind of plastic processing composite functional aid and preparation method thereof, prepared plastic processing composite functional aid has reduced intergranular surface energy, has strengthened consistency and the dispersiveness of plastics; Promote high polymer material plasticizing, reduced melt viscosity, improved processing fluidity; Improve goods shock extent, rigidity, thermotolerance and dimensional stability, have energy-saving and cost-reducing, environmental protection, nontoxic, without the characteristics of " three wastes ".
Technical scheme of the present invention is:
A kind of plastic processing composite functional aid is characterized in that: each feed composition is by weight than being: light calcium carbonate powder 90-100, mica powder 3-5, calcium chloride 1-2, stalk ashes 1-2, zinc oxide 3-5, aerosil 3-5, polymkeric substance 1-2, the polyethylene wax 1-2 of methacrylic ester, sodium alkyl benzene sulfonate 1-2, glycerine 1-2.
The preparation method of described plastic processing composite functional aid, it is characterized in that: light calcium carbonate is dried to contain weight to moisture content be below 0.3%, add in the high-speed kneading machine, then by weight than adding mica powder, calcium chloride, stalk ashes, zinc oxide, aerosil, the polymkeric substance of methacrylic ester, polyethylene wax, sodium alkyl benzene sulfonate, glycerine, after having added, be warming up to 100-130 ℃, behind the insulated and stirred 8-10min, discharging gets finished product.
Polynary composite theory refers to: can not rely on single method in modifying plastics, according to different resins, different plastics and different use occasion and different sorts, the mineral filler (powder) of different loading levels, after using properties-correcting agent, also to use one or more methods to carry out modifying plastics to reach better modification actual effect.Main method with tri compound (polymkeric substance/elastomerics/inorganic powder) the replacement inorganic powder of inorganic powder, rubber (elastomerics), plastics and the binary compound (polymer/inorganic powder) of plastics wherein.
Beneficial effect of the present invention: the present invention selects the tensio-active agent of several functions to mix, the surface energy of decrease particle and interfacial tension, effectively prevent the autohemagglutination of miniaturization particle, increase its consistency and dispersiveness in rubber, plastics, can promote high polymer material plasticizing, reduce melt viscosity, improve processing fluidity, improve goods shock extent, rigidity, thermotolerance and dimensional stability, thereby can realize the increment filling, reduce the goods cost.
Embodiment
A kind of plastic processing composite functional aid, each feed composition are by weight than being: the polymkeric substance 2 of light calcium carbonate powder 100, mica powder 4, calcium chloride 2, stalk ashes 2, zinc oxide 4, aerosil 4, methacrylic ester, polyethylene wax 1, sodium alkyl benzene sulfonate 1, glycerine 2.
The preparation method of plastic processing composite functional aid, light calcium carbonate dried to contain weight to moisture content be below 0.3%, add in the high-speed kneading machine, then by weight than adding mica powder, calcium chloride, stalk ashes, zinc oxide, aerosil, the polymkeric substance of methacrylic ester, polyethylene wax, sodium alkyl benzene sulfonate, glycerine, after having added, be warming up to 100-130 ℃, behind the insulated and stirred 8-10min, discharging gets finished product.
Calcium carbonate modified front and back microscopic pattern compares:
Ordinary calcium carbonate particle distribution scope is wide, form mainly with state of aggregation exists, although and the amounts of particles under Electronic Speculum of the calcium carbonate particles after plastic processing composite functional aid-modification of the present invention is more, but can obviously find out after surface modification treatment, surface energy is low, agglomeration does not occur, reach Uniform Dispersion, exist mainly with the primary partical state, wherein part is to have (particle diameter is less than 100nm) with the nanoparticle state, thereby it can reach better dispersion in the PVC plastics, plays toughened and reinforced effect.
Calcium carbonate powder particle after plastic processing composite functional aid-modification of the present invention exists mainly with similar circle or fusiform, and such powder adds in the plastics, and is more liquid, can play toughened and reinforced effect.But the ordinary calcium carbonate powder, then surperficial corner angle are more, easily cause rheological poor, the problems such as easy fracture.
Respectively by the prescription batch mixing, room temperature is carried out rheological experiment at PLE331 type torque rheometer after placing 8h with the calcium carbonate after ordinary calcium carbonate and the plastic processing composite functional aid-modification of the present invention, and the result is as shown in table 3:
Table 3 rheological experiment result
| Title | Peak torque/N.m | Balancing torque/N.m | Fusion time/S | Melt temperature/℃ |
| Common CaCO 3 | 37.4 | 25.0 | 150 | 187 |
| Modification CaCO 3 | 34.2 | 24.05 | 112 | 182 |
Prescription: 100 parts of PVC, 5 parts of one package stabilizers, 6 parts of KM355P, common CaCO
3Or modification CaCO
315 parts
As can be seen from Table 3, add modified calcium carbonate and compare with ordinary calcium carbonate, moment of torsion reduces, and fusion time obviously shortens, melt temperature descends, and plasticizing rate accelerates, and illustrates that modified calcium carbonate and PVC plastics Miscibility are good, be conducive to processing, can improve extruded velocity, make the smooth exquisiteness of products appearance.This is because properties-correcting agent and the PVC plastics of modified calcium carbonate surface chemistry bonding have excellent compatibility, shows strong interior lubrication, thereby has weakened the intermolecular reactive force of PVC, so that system rheological performance changes.Also illustrate under equal conditions simultaneously, modified calcium carbonate can increase loading level, also can reach good processing characteristics.
Calcium carbonate-filled PVC Mechanics Performance Testing before and after the modification:
PVC test piece test result compares:
With raw materials such as polyvinyl chloride resin, one package stabilizer, DOP, ordinary calcium carbonate or modified calcium carbonates, by the prescription batching, in high-speed mixer, fully mix the 10min discharging for subsequent use.Compound is plasticated at double roller plastic-making device, and film is at 165 ℃ of lower fully plasticizing 6min, and hard sheet is made the thick thin slice of 0.5mm at 190 ℃ of abundant plasticizing 8min, and room temperature cuts into the standby test of dumbbell specimen after transferring 24h.
Ordinary calcium carbonate and modified calcium carbonate are produced respectively hard, soft test piece, test at INSTRON 4466 type universal testing machines, the results are shown in Table 4, table 5.
Table 4 rheological experiment result
| Title | Yield strength/Mpa | Breaking tenacity/Mpa | Elongation at break/% | Young's modulus/Mpa |
| Common CaCO 3 | 50.835 | 21.364 | 46.569 | 2666.59 |
| Modification CaCO 3 | 53.952 | 45.456 | 106.360 | 2755.27 |
Prescription: 5 parts of common CaCO of 5 parts of DOP of 100 parts of one package stabilizers of PVC
3Or modification CaCO
320 parts
Table 5 soft pvc plastic test piece test result relatively
| Title | Yield strength/Mpa | Breaking tenacity/Mpa | Elongation at break/% | Young's modulus/Mpa |
| Common CaCO 3 | 7.09 | 6.91 | 48.7 | 75.7 |
| Modification CaCO 3 | 5.08 | 7.34 | 106.6 | 60.5 |
Prescription: 50 parts of common CaCO of 5 parts of DOP of 100 parts of one package stabilizers of PVC
3Or modification CaCO
3120 parts
Can find out from table 4, table 5, in the situation that same addition, hard, the flexible article of PVC no matter, use modified calcium carbonate, the elongation at break that the mechanical property of test piece all obviously is better than ordinary calcium carbonate, particularly test piece doubles many, and material easily plastifies, roll banding not, surface brightness is high, and processing characteristics is good.This is because the ordinary calcium carbonate surface polarity is strong, and surface energy is high, is easy to reunite in polyvinyl chloride resin, is difficult for disperseing, thereby affects the goods processibility, and destroy the mechanical property of goods.And modified calcium carbonate surface organic modification, surface energy significantly reduces, be difficult for reuniting, basically be to be distributed in the polyvinyl chloride resin with the primary partical state, and the molecule crane span structure effect by organic modifiers, produce strong adhesive effect at the interface, and wherein part is penetrated in the polyvinyl chloride resin three-dimensional net structure with the rigid particles that the nanometer state disperses.According to Toughening By Non-elastomers modification viewpoint, rigidity nanometer grade calcium carbonate particle surface defective is few, the non-matching atom is many, be combined firmly with polyvinyl chloride resin, when being subject to External Force Acting, cause matrix resin crazing absorption energy, crisp-tough transformation occurs, thereby avoid cracking of stress raisers, make matrix material reach toughened and reinforced effect, have preferably mechanical property.
Calcium carbonate after plastic processing composite functional aid-modification of the present invention is at wave number 2979cm
-1, 2917cm
-1, 2512cm
-1, 1797cm
-1, 875cm
-1, etc. locate stretching vibration absorption band width and obviously widen, and displacement has occured, show between the calcium carbonate after the modification to have formed firmly chemical bond.
Claims (2)
1. plastic processing composite functional aid, it is characterized in that: each feed composition is by weight than being: light calcium carbonate powder 90-100, mica powder 3-5, calcium chloride 1-2, stalk ashes 1-2, zinc oxide 3-5, aerosil 3-5, polymkeric substance 1-2, the polyethylene wax 1-2 of methacrylic ester, sodium alkyl benzene sulfonate 1-2, glycerine 1-2.
2. the preparation method of plastic processing composite functional aid claimed in claim 1, it is characterized in that: light calcium carbonate is dried to water content by weight below 0.3%, add in the high-speed kneading machine, then by weight than adding mica powder, calcium chloride, stalk ashes, zinc oxide, aerosil, the polymkeric substance of methacrylic ester, polyethylene wax, sodium alkyl benzene sulfonate, glycerine, after having added, be warming up to 100-130 ℃, behind the insulated and stirred 8-10min, discharging gets finished product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005126561A (en) * | 2003-10-23 | 2005-05-19 | Dainichi Giken Kogyo Kk | Composition for multi-functional coating |
| CN101012324A (en) * | 2007-01-25 | 2007-08-08 | 宝鸡市云鹏塑料科技有限公司 | Nano modified plastic composite material, preparing method thereof and special-purpose apparatus |
| CN101704961A (en) * | 2009-11-04 | 2010-05-12 | 池州市金艺超细粉有限公司 | Plastic processing functional auxiliary agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005126561A (en) * | 2003-10-23 | 2005-05-19 | Dainichi Giken Kogyo Kk | Composition for multi-functional coating |
| CN101012324A (en) * | 2007-01-25 | 2007-08-08 | 宝鸡市云鹏塑料科技有限公司 | Nano modified plastic composite material, preparing method thereof and special-purpose apparatus |
| CN101704961A (en) * | 2009-11-04 | 2010-05-12 | 池州市金艺超细粉有限公司 | Plastic processing functional auxiliary agent and preparation method thereof |
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Effective date of registration: 20170316 Address after: 242800 Anhui city of Chizhou province Qingyang County Ding Qiao Zhen Ma Tang Industrial Zone Patentee after: ANHUI HUAYU PIPELINE MANUFACTURING CO., LTD. Address before: 242800 Anhui city of Chizhou province Qingyang County Ding Qiao Zhen Ma Tang Industrial Zone Patentee before: Sanbao Plastic Co., Ltd. |