CN102372857A - Processing aid used for plastic and preparation method thereof - Google Patents
Processing aid used for plastic and preparation method thereof Download PDFInfo
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- CN102372857A CN102372857A CN 201110316182 CN201110316182A CN102372857A CN 102372857 A CN102372857 A CN 102372857A CN 201110316182 CN201110316182 CN 201110316182 CN 201110316182 A CN201110316182 A CN 201110316182A CN 102372857 A CN102372857 A CN 102372857A
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Abstract
The invention discloses a processing aid used for plastic and a preparation method thereof. The processing aid comprises the following raw materials in parts by weight: 90-100 parts of light calcium carbonate powder, 3-5 parts of calcium chloride, 2-2 parts of mica powder, 1-2 parts of straw ash, 3-5 parts of activated zinc oxide, 3-5 parts of fumed silica, 1-2 parts of methacrylate polymer, 1-2 parts of polyethylene wax, 1-2 parts of alkyl sodium sulfonate and 1-2 parts of silicone oil. The preparation method comprises the following steps: drying light calcium carbonate until moisture content is below 0.3%; adding into a high-speed kneading machine; adding other formula materials in parts by weight; heating to 100-130DEG C; keeping warm, and stirring for 8-10 minutes; and discharging to obtain a finished product. The processing aid used for plastics, which is prepared by using the preparation method, is characterized in that surface energy among particles are lowered, the compatibility and the dispersibility of the plastics can be enhanced, high polymer materials are accelerated to plastify, fondant viscosity is lowered, and machining mobility is improved; the impact degree, the rigidity, the heat resistance and the size stability of a product can be improved; and the processing aid has the characteristics of energy conservation, consumption reduction, no toxin, no three waste and the like, and is environmentally-friendly.
Description
Technical field
The present invention relates to field of plastics processing, specifically is that a kind of plastics are with processing 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 bigger with external gap on kind, output, quality and modification function.
The producer that produces plastic processing modifier in the world 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; Serial trade mark products such as ParaloidKM323B, KM330, KM334, KM335 have been developed later in succession; Wherein ParaloidKM355 is a 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 other area and Rhom and Hass's joint sales PVC impact modifier and processing aids in the world.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 YO is 100,000 tons.More external ACR anti-impacts change the agent trade mark and see table 1.
The external several A CR impact modifier trade 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; 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 performances are relatively seen 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 several kinds of above-mentioned 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 third glue) grafting vinyl chloride multipolymer, vinylchlorid grafted ethene-Yodo Sol GH 28 and EVACO multipolymer (ethane-acetic acid ethyenyl vinegar-CO terpolymer) etc.In recent years, also obtained remarkable progress, as with CPE/ACR, CPE/MBS composite toughening PVC with the research of two kinds of elastomer composite toughening PVCs.Result of study shows that the impact effect that the synergy of two kinds of toughner produces is superior to single toughner.Except using elastic body toughening PVC, as with 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 the report of elastomerics and non-resilient composite toughening in addition, as with CPE/PS, the ultra-fine CaCO of CPE/
3, composite toughening PVC.And China PVC nanometer CaCO
3The composite study exploitation 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 the branch of double-deck and three layers of " nuclear-shell " structure.Its basic process is first with letex polymerization manufactured seed emulsion particle, and appropriately crosslinked in the presence of linking agent, drips other monomers then, 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 TEB 3K and propenoate; Three layers of " nuclear-shell " structure ACR can be divided into time skin and outermost layer again, and secondly outer is styrene polymer often.According to the needs of using, except that stratum nucleare be certainly lightly crosslinked, other layers can be divided into line style or crosslinked again.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 one type of latex IPN, according to the mensuration of electron microscope observation and dynamic viscoelasticity spectrum appearance, all provable ACR is the heterogeneous structure system.
Its toughening mechanism is comparatively common with crazing-shear zone theoretical explanation usually.The effect of " nuclear-shell " type 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 to consume significant amount of energy, thereby significantly improves the shock resistance of material.Simultaneously; Through bearing part three axial stresses, controlled the development of crazing, and crazing is in time stopped and unlikelyly developed into destructive crackle at crazing and rubber separation surface; The most advanced and sophisticated stress field of crazing can be brought out the generation of shear zone, and shear zone also can stop further developing of crazing.
" nuclear-shell " structure modifier is often carried out crosslinkedly through 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, and separate easily between particle can be dispersed to the PVC base material uniformly; And ability and the interaction of PVC base material; Thereby this type particle also plays the effect of similar ACR processing aid, promotion polyvinyl chloride resin gelation and plasticizing except that 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 bloated 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 better weather.
Lime 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 macromolecule organic generation chemically crosslinkeds such as plastics, rubber, in organic medium, be difficult to homodisperse, the interface is difficult to form good bonding.In addition, the calcium carbonate superfine powder particle diameter is little, has great specific surface area and higher specific surface energy; Particle coalescence, reunion very easily take place in preparation and last handling process; Form offspring, make grain diameter become big, in application process, lose the function that ultrafine particulate possesses; Thereby influence practical application effect, can not play the effect of functional stuffing; On the contrary, can reduce some physicals of goods to a certain extent because of boundary defect.
Summary of the invention
The invention provides a kind of plastics with processing aid and preparation method thereof, prepared plastics have reduced intergranular surface energy with processing aid, have strengthened the 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, the characteristics of not having " three wastes ".
Technical scheme of the present invention is:
A kind of plastics are used processing aid, it is characterized in that: each feed composition is by weight than being: light calcium carbonate powder 90-100, calcium chloride 3-5, mica powder 2-2, stalk ashes 1-2, active zinc flower 3-5, aerosil 3-5, the polymkeric substance 1-2 of methacrylic ester, polyethylene wax 1-2, alkyl sodium sulfonate 1-2, silicone oil 1-2.
Described plastics are with the preparation method of processing 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 kneader, then by weight than adding calcium chloride, mica powder, stalk ashes, active zinc flower, aerosil, the polymkeric substance of methacrylic ester, polyethylene wax, alkyl sodium sulfonate, silicone oil; After having added; Be warming up to 100-130 ℃, behind the insulated and stirred 8-10min, discharging gets finished product.
Polynary composite theory is meant: in modifying plastics, can not rely on single method; According to different resins, different plastics goods 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.Wherein replacing the binary compound (polymer/inorganic powder) of inorganic powder and plastics with the ternary of inorganic powder, rubber (elastomerics), plastics compound (polymkeric substance/elastomerics/inorganic powder) is main method.
Beneficial effect of the present invention: the present invention selects the tensio-active agent of multiple function to mix, and reduces the surface energy and the IT of particle significantly, prevents the autohemagglutination of miniaturization particle effectively; 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
Plastics are used processing aid, and each feed composition is by weight than being: the polymkeric substance 2 of light calcium carbonate powder 100, calcium chloride 4, mica powder 2, stalk ashes 2, active zinc flower 4, aerosil 4, methacrylic ester, polyethylene wax 1, alkyl sodium sulfonate 1, silicone oil 2.
Plastics are with the preparation method of processing aid; Light calcium carbonate dried to contain weight to moisture content be below 0.3%, add in the high speed kneader, then by weight than adding calcium chloride, mica powder, stalk ashes, active zinc flower, aerosil, the polymkeric substance of methacrylic ester, polyethylene wax, alkyl sodium sulfonate, silicone oil; 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, and how the forms with state of aggregation exist, though and calcium carbonate particles under Electronic Speculum the amounts of particles of plastics of the present invention after with processing aid-modification is more; But can find out obviously that after surface modification treatment, surface energy is low, and agglomeration does not take place; Reach homodisperse, how to exist 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.
The calcium carbonate powder particle of plastics of the present invention after with processing aid-modification is many to be existed 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, cause rheological poor easily, 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 ordinary calcium carbonate and plastics of the present invention lime carbonate after with processing aid-modification, 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 | 32.88 | 22.95 | 114.68 | 182 |
Prescription: 100 parts of PVC, 5 parts of one package stabilizers, 6 parts of KM355P, common CaCO
3Or modification CaCO
315 parts
Can find out that from table 3 add plastics and compare with ordinary calcium carbonate with processing aid, moment of torsion reduces; Fusion time obviously shortens, and melt temperature descends, and plasticizing rate accelerates; Explain that plastics are good with processing aid and PVC plastics system consistency; Help processing, can improve extruded velocity, make the smooth exquisiteness of products appearance.This is because plastics have excellent compatibility with the properties-correcting agent and the PVC plastics of processing aid surface chemistry bonding, shows strong interior lubrication, thereby has weakened the intermolecular reactive force of PVC, makes the system rheological performance change.Explain under equal conditions also that simultaneously plastics can increase loading level with processing aid, also can reach good processing properties.
Calcium carbonate-filled PVC Mechanics Performance Testing before and after the modification:
PVC test piece test result compares:
With raw materials such as processing aids, by the prescription batching, thorough mixing 10min discharging is subsequent use in high-speed mixer with polyvinyl chloride resin, one package stabilizer, DOP, ordinary calcium carbonate or plastics.Compound is plasticated at double roller plastic-making device, and film is at 165 ℃ of abundant down plasticizing 6min, and hard sheet is processed the thick thin slice of 0.5mm at 190 ℃ of abundant plasticizing 8min, and room temperature cuts into dumbbell specimen test fully after transferring 24h.
Ordinary calcium carbonate and plastics are produced hard, soft test piece respectively with processing aid, on INSTRON 4466 type universal testing machines, test, the result sees table 4, table 5.
Table 4 rheological experiment result
| Title | Ys/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 | 53.876 | 44.879 | 106.002 | 2744.35 |
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 | Ys/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 | 6.25 | 6.98 | 107.6 | 63.8 |
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, under the situation of same addition, hard, the flexible article of PVC no matter; Use plastics to use processing aid, the elongation at break that the mechanical property of test piece all obviously is superior to ordinary calcium carbonate, particularly test piece doubles many; And material is prone to plasticizing; Roll banding not, surface brightness is high, and processing characteristics is good.This is that surface energy is high because the ordinary calcium carbonate surface polarity is strong, in polyvinyl chloride resin, is easy to reunite, and is difficult for disperseing, thereby influences the goods processibility, and destroy the mechanical property of goods.And plastics are with processing aid surface organic modification; Surface energy significantly reduces; Being difficult for reuniting, is to be distributed in the polyvinyl chloride resin with the primary partical state basically, and passes through the molecule crane span structure effect of organic modifiers; On the interface, produce strong adhesive effect, and wherein part is penetrated in the polyvinyl chloride resin three-dimensional net structure with nanometer state dispersive rigid particles.According to inelastic body toughening modifying viewpoint, rigidity nanometer grade calcium carbonate particle surface defective is few, and the non-matching atom is many; Combine firmly with polyvinyl chloride resin, do the time spent receiving external force, cause matrix resin crazing absorption energy; Crisp-tough transformation takes place; Thereby avoid cracking of stress raisers, make matrix material reach toughened and reinforced effect, have mechanical property preferably.
The lime carbonate of plastics of the present invention after with processing aid-modification 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 taken place, show between the lime carbonate after the modification to have formed firm chemical bond.
Claims (2)
1. plastics are used processing aid, it is characterized in that: each feed composition is by weight than being: light calcium carbonate powder 90-100, calcium chloride 3-5, mica powder 2-2, stalk ashes 1-2, active zinc flower 3-5, aerosil 3-5, the polymkeric substance 1-2 of methacrylic ester, polyethylene wax 1-2, alkyl sodium sulfonate 1-2, silicone oil 1-2.
2. the described plastics of claim 1 are with the preparation method of processing 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 kneader, then by weight than adding calcium chloride, mica powder, stalk ashes, active zinc flower, aerosil, the polymkeric substance of methacrylic ester, polyethylene wax, alkyl sodium sulfonate, silicone oil; After having added; Be warming up to 100-130 ℃, behind the insulated and stirred 8-10min, discharging gets finished product.
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| CN 201110316182 CN102372857B (en) | 2011-10-18 | 2011-10-18 | Processing aid used for plastic and preparation method thereof |
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|---|---|---|---|
| CN 201110316182 CN102372857B (en) | 2011-10-18 | 2011-10-18 | Processing aid used for plastic and preparation method thereof |
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| Publication Number | Publication Date |
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| CN102372857B CN102372857B (en) | 2012-12-12 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482486A (en) * | 2015-12-29 | 2016-04-13 | 王丽萍 | Novel high-performance plastic additive |
| CN105504849A (en) * | 2015-12-29 | 2016-04-20 | 王璐 | Novel green and environmental protection type plastic additive |
| CN105949810A (en) * | 2016-05-20 | 2016-09-21 | 福建天蕊光电有限公司 | Nanoscale plastic additive |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10139966A (en) * | 1996-11-13 | 1998-05-26 | Taiyo Enbi Kk | Vinyl chloride-based polymer composition and its production |
| CN1431246A (en) * | 2003-01-15 | 2003-07-23 | 四川大学 | Functional agglomerate of expandability plastic and agglomerate of maintains film for farm crops as well as its preparing method |
| CN101235162A (en) * | 2008-03-04 | 2008-08-06 | 四川大学 | Method for preparing granulating auxiliary agent for processing plastic |
| CN101805460A (en) * | 2010-04-06 | 2010-08-18 | 湖北众联塑业有限公司 | Assistant packet used for polyvinyl chloride high-calcium compound pipe |
-
2011
- 2011-10-18 CN CN 201110316182 patent/CN102372857B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10139966A (en) * | 1996-11-13 | 1998-05-26 | Taiyo Enbi Kk | Vinyl chloride-based polymer composition and its production |
| CN1431246A (en) * | 2003-01-15 | 2003-07-23 | 四川大学 | Functional agglomerate of expandability plastic and agglomerate of maintains film for farm crops as well as its preparing method |
| CN101235162A (en) * | 2008-03-04 | 2008-08-06 | 四川大学 | Method for preparing granulating auxiliary agent for processing plastic |
| CN101805460A (en) * | 2010-04-06 | 2010-08-18 | 湖北众联塑业有限公司 | Assistant packet used for polyvinyl chloride high-calcium compound pipe |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482486A (en) * | 2015-12-29 | 2016-04-13 | 王丽萍 | Novel high-performance plastic additive |
| CN105504849A (en) * | 2015-12-29 | 2016-04-20 | 王璐 | Novel green and environmental protection type plastic additive |
| CN105949810A (en) * | 2016-05-20 | 2016-09-21 | 福建天蕊光电有限公司 | Nanoscale plastic additive |
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|---|---|
| CN102372857B (en) | 2012-12-12 |
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