CN1163906A - Antistatically treated polymers - Google Patents

Antistatically treated polymers Download PDF

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Publication number
CN1163906A
CN1163906A CN97102414A CN97102414A CN1163906A CN 1163906 A CN1163906 A CN 1163906A CN 97102414 A CN97102414 A CN 97102414A CN 97102414 A CN97102414 A CN 97102414A CN 1163906 A CN1163906 A CN 1163906A
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composition
inorganic
acid
adsorptivity
alkyl
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CN1100823C (en
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B·海尔逖
M·布克尔
J·普费夫尔
E·敏德
M·格罗布
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/017—Antistatic agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/91—Antistatic compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/91—Antistatic compositions
    • Y10S524/912—Contains metal, boron, phosphorus, or silicon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/91—Antistatic compositions
    • Y10S524/913—Contains nitrogen nonreactant material

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a composition comprising a thermoplastic, structurally crosslinked elastomeric or thermosetting polymer, which comprises (a) a polar, adsorptive inorganic or organic material in the form of fibres or particles which are in mutual contact, onto which is adsorptively bound (b) a polar antistatic agent comprising a mixture of b1) at least one polar organic compound having at least 5 carbon atoms and at least 3 heteroatoms, and b2) the salt of an inorganic protic acid, which is solvated or complexed in the polar organic compound. The invention also relates to a second composition comprising b) a polar inorganic or organic material, b1) a polar organic compound having at least 5 carbon atoms and at least 3 heteroatoms and b2) an inorganic salt, to the use of this second composition for the antistatic treatment of polymers, and to a process for preparing antistatically treated polymers.

Description

Antistatically treated polymkeric substance
The present invention relates to comprise thermoplastic, the composition of crosslinked, elasticity or thermosetting polymer structurally, said composition comprises: being of (a) being in contact with one another is fibrous or granular, the inorganic or organic materials of polar, adsorptivity, be combined with to adsorptivity (b) polarity static inhibitor thereon, this static inhibitor comprises the mixture of following b1 and b2, (b1) at least a have 5 carbon atoms at least and have 3 heteroatomic polar organic compounds at least and (b2) salt of the inorganic proton acid in polar organic compound by solvation or complexing.The invention still further relates to second composition, said composition comprises b) the inorganic or organic materials of polarity, b1) have 5 carbon atoms and the polar organic compound that has 3 assorted carbon atoms at least at least, and b2) inorganic salt; Relate to the purposes that this second composition is used for polymkeric substance is carried out antistatic treatment; And the preparation method who relates to Antistatically treated polymkeric substance.
Be known that already that polymkeric substance will stand strong electrostatic charging, and, because due to the low electrical conductivity of polymkeric substance, in case be with electric charge, it will dissipate with very slow speed.Yet except that aesthetic factors, safety factors often needs electric charge decline fast.The side effect during use that can mention comprises: make polymer surfaces dirty, make with the contacted people of polymkeric substance and shocked by electricity, owing to sticking together to make to produce, the film sheet width of cloth interrupts, destroy electronic component, make the polymer powder aggegation, and owing to the spark discharge that causes of excessive charge of accumulation when lighting a fire subsequently, this may cause serious blast once in a while in the past.
It is known that limit static is discharged by adding the additive that strengthens surface conductivity.Yet these materials have following shortcoming, and they almost are invalid when low environment humidity.Thereby, the preferred additive that increases the unit volume specific conductivity that uses.Yet the known material that can increase the unit volume specific conductivity for example carbon black and metal-powder will reduce the mechanical property of polymkeric substance, and can not be used for transparent polymkeric substance.Increasing requirement in addition is that these additives must have no side effect to environment.
In addition, can in " plastics additive handbook " (HanserVerlag, the third edition, 1990, the 749-775 pages or leaves) that R.Gachter and H.Muller edit, find the details of relevant anti static additive and electrostatic charging principle.
In order to obtain nonvolatil antistatic treatment, such suggestion has been proposed, in DE 4324062 with the material such as the fiber of colourless semiconductor material such as stannic oxide coating high surface area.This then coating material can be handled with the polymer beads mixing and with them.Yet, because this semi-conductive coating of preparation need be used salt brine solution impregnation of fibers material, then they are carried out drying, and will carry out heat adjustment sedimentary salt; Therefore the preparation of this coating will be very complicated.Because the specific conductivity that reduces is not that semi-conductive specific conductivity is desirable, therefore these chemistry and the thermal treatment to fiber may damage fiber.Another shortcoming is that fiber bends under mechanical load, can destroy crisp coated semiconductor, similarly will damage specific conductivity thus.
Described another selection scheme in DE 4316607, lubricant, binding agent or coating are added in this patent suggestion, so that polymer fiber metallization (existing commercial) is to increase their specific conductivity.Yet metalized fibers is very expensive, is difficult to produce, and will seriously reduces the transparency of mixing polymkeric substance wherein.In addition, can not eliminate fully to conductive coating with even to the physical damage (fracture) of fiber.
Therefore, need a kind of interpolation system that increases the unit volume specific conductivity always, this system has antistatic property, acceptable on ecology, when low environment humidity, be effective, produce simply, can keep the unit volume specific conductivity of giving polymkeric substance for a long time, and can all have the condition of significant limitation to the commercial polymer under, not use.
Have found that, polar organic compound can be mixed thermoplastic, structurally in the crosslinked or curable polymkeric substance (crosslinkable polymkeric substance), thereby give them with outstanding and competent antistatic property; Described organic compound comprises 5 carbon atoms and at least 3 heteroatomss at least, and be combined with as sorbent material and adsorptivity be connected on the surface of inorganic or organic materials or the inorganic salt in the hole.
Because polarity is inorganic or organic materials has hole, therefore, organic compound can insert and be adsorbed on wherein with inorganic salt, forms stable especially antistatic treatment.
Very outstanding advantage is, even the mixture of the relatively low molecular weight of polarity or surface-active compound and inorganic salt (otherwise they often ooze out on the surface of polymeric material) can at first be bonded on the inorganic or organic materials of polarity by absorption.
In addition, the saliniferous polar organic compound also can have functional group, and the functional group of described functional group and solid support material forms ionic linkage or covalent linkage.These functional groups can be polymerisable groups, in this case, and by polymerization or crosslinkedly can produce competent especially coating.
The main prerequisite of good electrical conductivity is, in the time of in mixing polymkeric substance, the particle of the inorganic or organic materials of polarity or fiber are as much as possible staggered or be in contact with one another.This will form the conductive traces that wherein can discharge electric charge.
In addition, in most occasions, the stability of polymkeric substance such as thermostability, light stability and hydrolytic resistance are unaffected substantially.
When the consumption of additive hanged down, optical property also changed widely, and transparent material is still transparent substantially.
The invention provides a kind of thermoplastic, composition of crosslinked, elasticity or thermosetting polymer structurally that comprises, said composition comprises: being of (a) being in contact with one another is fibrous or granular, the inorganic or organic materials of polar, adsorptivity, be combined with to adsorptivity (b) polarity static inhibitor thereon, this static inhibitor comprises the mixture of following b1 and b2, (b1) at least a have 5 carbon atoms at least and have 3 heteroatomic polar organic compounds at least and (b2) salt of the inorganic proton acid in polar organic compound by solvation or complexing.
Thermoplastic, structurally example crosslinked or heat-setting polymkeric substance is as follows.
1. the polymkeric substance of monoolefine and diolefine, polypropylene for example, polyisobutene, poly-1-butylene, poly--4-methyl-1-pentene, polyisoprene or polyhutadiene, and the polymkeric substance of cycloolefin, for example, the polymkeric substance of cyclopentenes or norbornylene, polyethylene (can be crosslinked), for example, high density polyethylene(HDPE) (HDPE), high-density and High molecular weight polyethylene (HDPE-HMW), high-density and ultrahigh molecular weight polyethylene(UHMWPE) (HDPE-UHMW), medium-density polyethylene (MDPE), new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
Polyolefine, the polymkeric substance of the monoolefine that promptly in aforementioned paragraphs, exemplifies, preferably polyethylene and polypropylene, available diverse ways manufacturing, particularly following certain methods:
A) radical polymerization (under high pressure and high temperature, carrying out usually).
B) catalytic polymerization, catalyst for application contain IVb on the periodictable usually, Vb, VIb, or one or more metal of VIII family.These metals have monovalence or multivalence ground and typical oxide compound usually, halogenide, and alcoholate, ester, ether, amine, alkyl, thiazolinyl and/or aryl are with π key or the complexing of σ key.These metal complexs can the free form exist or are fixed on the activatory magnesium chloride, and titanium chloride (III) is on the substrates such as plumbous oxide or silicon oxide.These catalyzer are solvable or be insoluble in the medium of polyreaction.Can be directly used in polyreaction or further use activator, typical activator has metal alkylide, metal hydride, alkyl metal halide, metal alkoxide compound or metal alkyl oxane compounds, above-mentioned metal is Ia on the periodictable, IIa and/or IIIa elements.These activators can further for example be used ester, ether, amine or the modification easily of silyl silicon ethers group.These catalyst systems are commonly referred to Philip (phillipa), Indiana standard oil (Standard Oil Indiana), Ziegler (Natta), TNZ (Du Pont), metallocenes or single site catalysts (SSC).
2.1) mixture of polymers of mentioning down, the mixture of polypropylene and polyisobutene for example, (PP/HDPE for example is PP/LDPE) with dissimilar poly mixtures (for example LDPE/HDPE) for polypropylene and poly mixture.
Monoolefine and diolefine to each other multipolymer or with the multipolymer of other vinyl monomers, for example, ethylene/propene copolymer, the mixture of linear low density polyethylene (LLDPE) and it and new LDPE (film grade) (LDPE), the propylene/1-butene multipolymer, propylene/isobutylene copolymers, ethene/butene-1 copolymer, the ethylene/hexene multipolymer, ethene/methylpentene multipolymer, ethene/heptene multipolymer, ethylene/octene, propylene/butadienecopolymer, iso-butylene/isoprene copolymer, ethylene/alkyl acrylate copolymer, the ethylene/methacrylic acid alkyl ester copolymer, multipolymer or the ethylene/acrylic acid copolymer and their salt (ionomer) of ethylene/vinyl acetate copolymer and they and carbon monoxide, ethene and propylene and another kind of diene such as hexadiene in addition, the terpolymer of dicyclopentadiene or ethylidene-precipitation sheet alkene; With the mixture of this analog copolymer and with 1) in the mixture of polymers mentioned, for example, polypropylene/ethylene-propylene copolymer, LDPE/ ethylene-vinyl acetate copolymer (EVA), LDPE/ ethylene-acrylic acid copolymer (EAA), LLDPE/EVA, LLDPE/EAA and alternative or unordered polyalkylene/carbon monoxide multipolymer and they and other polymkeric substance are the mixture of polymeric amide for example.
4. hydrocarbon resin (C for example 5-C 9), comprise its hydrogenation modification body (for example tackiness agent) and the mixture of polyalkylene and starch.
5. polystyrene gathers (p-methylstyrene), poly-(alpha-methyl styrene).
6. the multipolymer of vinylbenzene or alpha-methyl styrene and dienes or acrylate derivative, for example, phenylethylene/butadiene, styrene/acrylonitrile, the styrene/methacrylic acid alkyl ester, phenylethylene/butadiene/alkyl acrylate, phenylethylene/butadiene/alkyl methacrylate, phenylethylene/maleic anhydride, the multipolymer of styrene/acrylonitrile/methyl acrylate; Styrol copolymer and another kind of polymkeric substance be polyacrylic ester for example, the mixture of the high impact that diene polymer or ethylene/propylene/diene terpolymers are formed; With cinnamic segmented copolymer, as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.
7. the graft copolymer of vinylbenzene or alpha-methyl styrene, for example, vinylbenzene is connected on the polyhutadiene, vinylbenzene is connected on poly-(butadiene-styrene) or poly-(butadiene-acrylonitrile) multipolymer on; Vinylbenzene and vinyl cyanide (or methacrylonitrile) are connected on the polyhutadiene; Vinylbenzene, vinyl cyanide and methyl methacrylate are connected on the polyhutadiene; Vinylbenzene and maleic anhydride are connected on the polyhutadiene; Vinylbenzene, vinyl cyanide and maleic anhydride or maleimide are connected on the polyhutadiene; Vinylbenzene and maleimide are connected on the polyhutadiene; The alkyl ester of vinylbenzene and acrylic or methacrylic acid is connected on the polyhutadiene; Vinylbenzene and vinyl cyanide are connected on the terpolymer of ethylene/propylene/diene hydrocarbon; Vinylbenzene and vinyl cyanide are connected on polyalkyl acrylate or the polyalkyl methacrylate; Vinylbenzene and vinyl cyanide are connected on the multipolymer of acrylate/divinyl, and they and 6) under the mixture of the multipolymer listed, for example, be called ABS, MBS, these copolymer mixtures of ASA or AES polymkeric substance.
8. halogen-containing polymkeric substance, as neoprene latex, chlorinated rubber, the polyethylene of chlorination or chlorosulphonation, the multipolymer of ethene and ethylene chloride, the homopolymer of Epicholorohydrin and multipolymer, the polymkeric substance of halogen-containing vinyl compound particularly, for example, polyvinyl chloride, polyvinylidene dichloride, fluorinated ethylene propylene, poly(vinylidene fluoride), and their multipolymer, as vinylchlorid/1,1 Ethylene Dichloride, vinylchlorid/vinyl acetate or 1,1-diamino ethylene/vinyl acetate copolymer
9. by α, the polymkeric substance that beta-unsaturated acid and derivative thereof obtain is as polyacrylic ester and polymethacrylate; Polymethylmethacrylate, polyacrylamide and the polyacrylonitrile of impact resistance have been improved with butyl acrylate.
10. 9) under the monomer mentioned to each other or with the multipolymer of other unsaturated monomers, for example, the acrylonitrile/butadiene multipolymer, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or vinyl cyanide/ethylene halide base co-polymer or vinyl cyanide/alkyl methacrylate/butadiene terpolymer.
11. the polymkeric substance that obtains by unsaturated alkohol and amine or their acyl derivative or its acetal; for example; polyvinyl alcohol; polyvinyl acetate (PVA), polyvinyl stearate, polyvinyl benzoate; the polymaleic acid vinyl acetate; polyvinyl butyral acetal, poly-phthalic acid allyl ester or polyene propyl group trimeric cyanamide, and they with 1) multipolymer of the alkene mentioned under the item.
12. the homopolymer of cyclic ethers class and multipolymer, as polyalkylene glycol, polyethylene oxide, the multipolymer of poly(propylene oxide) or they and bisglycidyl ether.
13. polyacetal such as polyoxymethylene and those contain the polyoxymethylene of oxyethane as comonomer; Use thermoplastic resin urethane, the polyacetal of polyacrylic ester or MBS modification.
14. the mixture of polyphenylene oxide and polyphenylene sulfide and polyphenylene oxide and styrene polymer or polymeric amide
15. by the polyethers of end of tape hydroxyl, the polyisocyanates of polyester or polyhutadiene and fat or aromatics, and the urethane that gets of its precursor.
16. with diamines and dicarboxylic acid and/or the polymeric amide and the copolyamide that make by aminocarboxylic acid or corresponding lactam, for example, polymeric amide 4, polyamide 6, polyamide 6/6,6/10,6/9,6/12,4/6,12/12, polymeric amide 11, polymeric amide 12 is the aromatic poly of starting raw material by m-xylene diamine and hexanodioic acid; By hexamethylene-diamine and m-phthalic acid or/and the polymeric amide of terephthalic acid preparation, they can contain or not contain a kind of elastomerics as improving agent, for example gather-2,4,4-tri-methyl hexamethylene terephthalamide or poly-metaphenylene isophthaloyl amine, also have aforementioned polymeric amide and polyolefine, olefin copolymer, ionomer or chemical bonding or the elastomeric segmented copolymer of grafted; Or and polyethers, for example with polyoxyethylene glycol, the segmented copolymer of polypropylene glycol or polytetramethylene glycol, the polymeric amide or the copolyamide of also useful EPDM or ABS modification; With polymeric amide (RIM polymeric amide system) in course of processing polycondensation.
17. polyureas, polyimide, polyamide-imide class and polybenzimidazole class.
18. from dicarboxylic acid and glycol and/or the polyester that gets from hydroxycarboxylic acid or corresponding lactone, for example, polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid 1,4-hydroxymethyl-cyclohexane ester and poly-hydroxy-benzoic acid, and by the polyethers deutero-block copolyether ester of terminal hydroxyl; The polyester of also useful polycarbonate or MBS modification.
19. polycarbonate and polyestercarbonate class.
20. polysulfones, polyether sulfone and polyethers ketone.
21. by aldehyde and phenol, urea or trimeric cyanamide be at the deutero-cross-linking copolymer, as phenol/formaldehyde resin, and urea/formaldehyde resin and melamine/formaldehyde resin
22. the Synolac of dryness and non-dryness
23. by copolyesters class deutero-unsaturated polyester, these copolyesters are to be that linking agent makes by saturated and undersaturated dicarboxylic acid and polyhydroxy-alcohol and with the vinylic chemical compound.The halogen-containing low combustible modification body that also has them.
24. by substituted acrylate, for example, epoxy acrylate, urethane acrylate or the crosslinkable acrylic resin of polyester acrylate deutero-.
25. with melamine resin, urea resin, the Synolac of polyisocyanates or cross linking of epoxy resin, vibrin and acrylate resin.
26. by polyepoxide, as bisglycidyl base ether or cyclic aliphatic di-epoxide deutero-cross-linked epoxy resin class.
27. natural polymer such as Mierocrystalline cellulose, natural rubber, gelatin and, rhodia for example, cellulose propionate and cellulose butyrate, or cellulose ethers such as methylcellulose gum by the close derivatives class of these polymkeric substance through chemical modification; Also have rosin and derivative thereof.
28. the blend of aforementioned polymkeric substance (composition polymer), for example, PP/EPDM, polymeric amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, the PVC/ polyacrylic ester, POM/ thermoplasticity PUR, PC/ thermoplasticity PUR, POM/ polyacrylic ester, POM/MBS, PPO/HIPS, PPO/PA6.6 and multipolymer, PA/HDPE, PA/PP, or PA/PPO.
Thermoplastic, structurally preferred example crosslinked or heat-setting polymkeric substance is selected from: polyolefine, polystyrene, α, the polymkeric substance of beta-unsaturated acid, halogen-containing polymkeric substance, the homopolymer of cyclic ethers and multipolymer, the polymkeric substance of unsaturated alkohol and amine, polyacetal, polyphenylene oxide, urethane, polymeric amide, polyester, polyureas, polycarbonate, polysulfones, the cross-linking products of aldehyde and phenol, urea or melamine, Synolac, crosslinkable acrylic resin, crosslinked Resins, epoxy, Mierocrystalline cellulose or natural rubber.
Particularly preferably be, polyolefine, polystyrene, α, the polymkeric substance of beta-unsaturated acid, halogen-containing polymkeric substance, especially PVC, cyclic ethers especially with the homopolymer and the multipolymer of bisphenol A diglycidyl ether.
Particularly preferably be again, polyolefine, as various modified polyethylene, with polypropylene, or halogen-containing polymkeric substance, polyvinyl chloride (PVC) for example is especially with the form of suspension polymer or mass polymer.
Inorganic or the organic materials of polarity, adsorptivity can be fiber or discontinuous particulate state.Absorption can be carried out in fiber or particulate surface and/or porous cavity.
In the context of the present invention, the characteristic hole represents that inorganic or organic materials has internal surface area and is at least 1m 2The inner chamber of/g and in these holes, holding and stored substance and ion.
Internal surface area for example can be measured according to the BET method.If inorganic or organic materials is a porous, so, preferred internal surface area is 5-500m 2/ g.
The example of the inorganic materials of spendable, porous, adsorptivity is naturally occurring inorganic powder, as calcite, and talcum, kaolin, diatomite, montmorillonite or attapulgite.Also can use phyllosilicate in addition, as sepiolite or wilkinite, the silicic acid of polymolecularity, the silicic acid of synthetic, high absorbability, silica gel, molecular sieve zeolites, float stone, the brick of pulverizing or sintered glass.
In the aqueous solution, the inorganic materials of porous, adsorptivity can be carried out acidity, neutrality or alkali reaction.
The molecular sieves zeolite is synthetic or naturally occurring crystalline, hydrated aluminium silicate, and skeleton structure includes interchangeable basic metal or alkaline earth metal cation (according to " zeolite molecular sieve " of D.W.Breck, J.Wiley, New York, 1974 definition.
The example of suitable molecular sieve zeolites is to be Na, the zeolite A of K or Ca form, zeolite ZSM-5, mordenite, zeolite L, X zeolite, zeolite Y.
Suitable in addition is that wherein Siliciumatom is by the phyllosilicate of Sauerstoffatom completely encircle.Connect by Sauerstoffatom by one deck octahedral coordinate metal such as aluminium or magnesium between these tetrahedron silicon layers two-layer.This will produce tetrahedron, octahedra and tetrahedral layered arrangement, and they are separated by two-dimentional spacing, till next repeated structural unit.The counter ion that can contain balancing charge in this spacing.Possible counter ion are metal ions, oligomeric-and poly oxo-hydroxy metal ion, or organic cation.
Specially suitable phyllosilicate is those materials with fibrous component.Particularly, the sepiolite group has the performance of the chain fibrous texture that forms tape channel shape cavity, and is specially suitable.
Particularly preferred being to use as attapulgite or sepiolite as fibrous phyllosilicate.
Equally also be specially suitablely to be, the mixture of different fibrous phyllosilicate, or the mixture of its () and molecular sieve zeolites.
Observing the sepiolite group and distribute can be at " Ullmann industrial chemistry encyclopaedia " lnd.Chem., in find (1986 the 5th edition, VCH Verlag Weinheim, A7 volume, the 118th page).
Natural inorganic materials with synthetic porous, adsorptivity can obtain widely from the market.
The organic materials of spendable porous, adsorptivity for example is the synthetic porous polymer, as melocol polycondensate (Pergopak), goes back the porous crude substance of naturally occurring adsorptivity in addition.
As the organic fibre of adsorptivity, can use many particulate state or fibrous, naturally occurring organic materials, as timber or the plant stubble of pulverizing, or the natural fiber of handling.
The example of preferred naturally occurring fiber is a cellulosic fibre, as cotton, and phloem fiber, kapok, jute, piemarker, flax and hemp.Yet, also can use wool or cocoon fiber.
This naturally occurring Mierocrystalline cellulose can further be derived, and for example becomes viscose yarn, cellulose ester or ether of cellulose.Described ether or ester can have different average substitution degrees, and this is worth usually between 1 and 3.
Organic fibrous material can long spinning fibre or is used with the form of chopped strand.Also can the netted form in plane use described fiber, as woven cloth, non-woven fabrics or felt.
In addition, also can use synthetic polymeric fibers, precondition is that they must have sufficiently high surface polarity, and energy adsorptivity ground is in conjunction with the polarity static inhibitor.The example of suitable fibers is polymeric amide, polyester and polyacrylonitrile fibre.Also can carry out modification by subsequently chemistry and/or physical treatment in addition, also can be used for the present invention to cause these fibers to the surface of nonpolar fiber own such as polyolein fiber.The exemplary of described modification is for example to the plasma body or the corona treatment of polypropylene fibre.
If use the polar polymer fiber, tynex for example, so, absorption polar organic compound thereon preferably has can carry out polymerization or crosslinked functional group.Since this polymerization or crosslinked due to, therefore obtained competent especially antistatic property.
In order to obtain desirable favourable effect, fiber in polymeric matrix or particle must be in contact with one another, because the unit volume specific conductivity can produce by the conduction of ion or electronics in this way.
Inorganic or organic granular can needle-like, and sheet is cylindric, fork sheet (must shape), and regular or irregular spherical existence maybe can have any other irregular shape.
These particulate median sizes preferably from 10-1000, particularly preferably are the micron from 50-500 from 1-5000.
Preferably, these particles are aspheric, and mainly extend in one direction.Its example has needle-like, cylindric and sheet.
Inorganic or the organic fibre of preferred use polar is because keeping obtaining the compactedness lower than spheroidal particle under the good electrical conductivity in this way.The length of described inorganic or organic fibre is usually from 0.01-200mm, preferably from 0.1-20mm.
Static inhibitor contains some to be had 5 carbon atoms at least and has 3 heteroatomic polar organic compounds at least.Heteroatomic example has the oxygen that is various oxidation state, nitrogen, sulphur and phosphorus.
According to static inhibitor used in the present invention is many known substances, and as be described in Kunststoffe 67 (1977) 3, in the 154-159 page or leaf.
Can solvation or the salt of complexing inorganic proton acid, have 5 carbon atoms at least and have at least the example of 3 heteroatomic polar organic compounds to have: polyethers, crown ether, polyvalent alcohol, poly-imines, polyamine is by the pyridine derived polymkeric substance that obtains, big ring nitric heterocyclic compound, polysulfide and poly-phosphine.
Polar organic compound preferably has 3-20 heteroatoms and 5-100 carbon atom.Preferred heteroatoms is oxygen and nitrogen.
The molecular weight of this polar organic compound is preferably from 200-5000, especially preferably from 300-3000 dalton.
At this polar organic compound liquid or be dissolved in organic solvent preferably 60 ℃ time the at the most.
The example of polymerizable functional group has, the undersaturated carbon bond of olefinic, and they for example are by α, beta-unsaturated carboxylic acid or their derivative are derived and are obtained, glycidyl, for example glycidyl ether, or isocyanate group.
The example that can be used for inorganic salt of the present invention has, mineral acid, zinc salt, an alkali metal salt, alkaline earth salt or the ammonium salt of oxygen acid or low alkyl group sulfonic acid.
Inorganic salt are preferably selected from: LiClO 4, LiCF 3SO 3, NaClO 4, LiBF 4, NaBF 4, KBF 4, NaCF 3SO 3, KClO 4, KPF 6, KCF 3SO 3, KC 4F 9SO 3, Ca (ClO 4) 2, Ca (PF 6) 2, Ca (CF 3SO 3) 2, Mg (ClO 4) 2, Mg (CF 3SO 3) 2, Zn (ClO 4) 2, Zn (PF 6) 2And Ca (CF 3SO 3) 2
Preferably comprise thermoplastic, structurally crosslinked elasticity or the composition of thermosetting polymer, said composition comprises: being of (a) being in contact with one another is fibrous or granular, the inorganic or organic materials of polar, adsorptivity, be combined with to adsorptivity (b) polarity static inhibitor thereon, this static inhibitor comprises the mixture of following b1 and b2, (b1) polyoxyalkylene of formula (I): R 1-O-[CH (R 3)-CH 2-O-] n-[CH 2-[CH (OH)] p-CH 2-O] q-[C (O)] r-R 2(I), R in the formula 1Be H, C 1-C 24Alkyl, C 2-C 24Thiazolinyl, C 1-C 24Alkyl-C (O)-, C 2-C 24Thiazolinyl-C (O)-, CH 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-, R 2Be C 1-C 24Alkyl, C 2-C 24Thiazolinyl, CH 2-COOH or N (C 1-C 8Alkyl) 3Halogen, if perhaps r is 0, R 2Be CH in addition 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-, R 3Be H or CH 3, halogen is Cl, and Br or I, n are the numbers more than or equal to 2, and p is the number of 1-6, and q and r are 0 or 1 independently of one another; (b2) formula { M wherein Z+ aA (aZ/b)- bInorganic salt be complexing or solvation, M is a Z-valency basic metal in the formula, the positively charged ion of alkaline-earth metal or zinc, a and b are the number between 1 and 6 independently of one another, A is the negatively charged ion of the organic oxacid of the negatively charged ion of inorganic proton acid or sulphur.
According to the present invention, it is normally known and can obtain from the market or by known simple chemical prepared in reaction: R to be used as the following polyoxyalkylene of formula (I) component (b1) 1-O-[CH (R 3)-CH 2-O-] n-[CH 2-[CH (OH)] p-CH 2-O] q-[C (O)] r-R 2(I), R in the formula 1Be H, C 1-C 24Alkyl, C 2-C 24Thiazolinyl, C 1-C 24Alkyl-C (O)-, C 2-C 24Thiazolinyl-C (O)-, CH 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-, R 2Be C 1-C 24Alkyl, C 2-C 24Thiazolinyl, CH 2-COOH or N (C 1-C 8Alkyl) 3Halogen, if perhaps r is 0, R 2Be CH in addition 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-, R 3Be H or CH 3, halogen is Cl, and Br or I, n are the numbers more than or equal to 2, and p is the number of 1-6, and q and r are 0 or 1 independently of one another.
When the substituting group in formula (I) compound was the alkyl of 1-24 carbon atom, suitable group was a methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl and tetracosyl, and the isomer that also has corresponding side chain position.
When the substituting group in formula (I) compound was the thiazolinyl of 1-24 carbon atom, these groups were derived by abovementioned alkyl and are obtained, and contain one or more pairs of keys.When having only one pair of key, this pair key is preferably placed at the central authorities of hydrocarbon chain.When two or more pairs of keys were arranged in hydrocarbon chain, described group was preferably derived by unsaturated fatty acids and is obtained.Particularly preferred thiazolinyl is the vaccenic acid base.
In the compound of formula (I), R 1H preferably, C 1-C 4Alkyl, CH 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-.
In the compound of formula (I), R 1C preferably 6-C 20Alkyl, C 6-C 20Thiazolinyl or N (C 1-C 8Alkyl) 3Cl, CH 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-.
In the compound of formula (I), n is the number between 2 and 20 preferably, and p is the number of 2-6 preferably.
Particularly preferred, each compound of formula I is: the polypropylene glycol laurate, polypropylene glycol oil ether, polypropylene glycol methyl diethyl ammonium chloride, the polyoxyethylene glycol monomethyl ether, the polyoxyethylene glycol dimethyl ether, polyethylene glycol laurate, polyethylene glycol (PEG) oleate, polyoxyethylene glycol oil ether, polyoxyethylene glycol Arlacel-20, polyethylene glycol stearate, polyoxyethylene glycol polypropylene glycol bay ether ether, polyoxyethylene glycol bay ether-carboxylic acid, the diacrylate of polyoxyethylene glycol, mono acrylic ester and triacrylate, or the dimethacrylate of polyoxyethylene glycol, monomethacrylates and trimethacrylate.
If the use alefinically unsaturated compounds, so, can be with its polymerization or crosslinked on fiber.This will produce wherein inorganic salt by coating complexing or solvation, on fiber.
If use polyethyleneglycol diacrylate or polyethylene glycol dimethacrylate and polymerization or crosslinked on polarity organic or inorganic material, can obtain particularly advantageous configuration.Therefore, obtained specially suitable antistatic treatment, wherein, basically eliminate oozing out of inorganic salt or organic constituent.Crosslinked can on fiber or particulate surface, carrying out, or also can in inner chamber (hole), carry out.
The example of spendable in addition suitable linked has Viscoat 295, trimethylolpropane trimethacrylate, or the compound of other trifunctional.These compounds are commercially available.
Crosslinked or polyreaction is known and can carries out under heat or photochemistry condition.The example of catalyzer is a superoxide, as H 2O 2Or light trigger, as benzyl dimethyl ketal.These catalyzer are known and can obtain from market equally.
Polarity consumption inorganic or organic materials is preferably, and per 100 parts by weight polymer are from the 0.01-70 weight part, especially preferably from the 0.1-30 weight part.
Have 5 carbon atoms at least and have at least the consumption of 3 heteroatomic polar organic compounds to be preferably, per 100 parts by weight polymer are from the 0.01-20 weight part.
Be as the criterion with 100 parts by weight polymer, the consumption of used inorganic salt is from the 0.01-5 weight part.
Have 5 carbon atoms at least and have at least 3 heteroatomic polar organic compounds to the ratio of inorganic salt preferably from 200: 1-1: 1.
Usually, at first with inorganic salt with have 5 carbon atoms and have at least 3 heteroatomic polar organic compounds to mix at least, use the inorganic or organic materials of this impregnation mixture polar then.
This novelty thermoplastic, structurally crosslinked or heat cured polymkeric substance also can comprise other additive.These additives particularly belong to heat and/or light stabilizers such.In this article, thermally-stabilised when referring to processing and using (permanent stability).In addition, these additives are known to those skilled in the art, and mainly obtain from market.
As mentioned above, when described polymkeric substance was anlistatig polymer containing halogen, they can be easily and additionally comprise at least a zinc, barium, cadmium, aluminium, calcium, the mineral compound of magnesium or rare earths, for example, zinc oxide, zinc hydroxide, zinc chloride or zinc sulphide, or the oxide/hydroxide addition compound of the zinc of hyperalkaline, or the zinc of following material, barium, cadmium, aluminium, calcium, the organic compound of magnesium or rare earths, described organic section material comprises, at least by the aliphatic saturated C of a hydroxyl replacement 2-C 22Carboxylicesters, the C that aliphatic series is saturated 3-C 22Carboxylicesters, or the C of aliphatic series 2-C 22Carboxylicesters, or their chain cut off by at least one Sauerstoffatom (oxygen acid), the ring-type of 5-22 carbon atom and two cyclic carboxylic esters, unsubstituted or by at least one hydroxyl and/or C 1-C 16The phenyl carboxylicesters that alkyl replaces, unsubstituted or by at least one hydroxyl and/or C 1-C 16The naphthyl carboxylicesters that alkyl replaces, phenyl-C 1-C 16The alkyl carboxylic acid ester, naphthyl-C 1-C 16Alkyl carboxylic acid ester, or unsubstituted or C 1-C 12The phenates that alkyl replaces.Above-mentioned metallic compound can different compounds mixture exist.In this occasion, preferred so-called collaborative metallic soap mixture, for example, metal Ca and Zn or Ba and Zn.In addition, also can be with zinc, barium, cadmium, aluminium, calcium, the organic compound of magnesium or rare earths is applied to hydrotalcite, on zeolite or the dawsonite; About this point, see also DE-A-4031818.
The example of suitable oxidation inhibitor has:
1. alkylation monobasic phenols, for example 2,6 di tert butyl 4 methyl phenol, 2-butyl-4,6-xylenol, 2,6-two-tertiary butyl-4-ethylphenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2,6-two-tertiary butyl-4-isobutyl-phenol, 2,6-two cyclopentyl-4-methylphenol, 2-(Alpha-Methyl cyclohexyl)-4,6-xylenol, 2,6-two-octadecyl-4-methylphenol, 2,4,6-thricyclohexyl phenol, 2,6-two-tertiary butyl-4-methoxymethyl phenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(phenol of 1 '-methyl-ten-alkane-1 '-yl), 2,4-dimethyl-6-(phenol of 1 '-methyl-heptadecane-1 '-yl), 2,4-dimethyl-6-(1 '-methyl-tridecane-1 '-yl) phenol and their mixture
2. alkylthio methyl phenols, for example, 2,4-two hot sulfenyl methyl-6-tert butyl phenol, 2,4-two hot sulfenyl methyl-6-methylphenols, 2,4-two hot sulfenyl methyl-6-ethylphenols, 2,6-two-dodecane sulfenyl methyl-4-nonylphenol.
3. hydroquinones and alkylation hydroquinones, for example, 2,6-di-t-butyl-4-methoxyphenol, 2,5 di tert butylhydroquinone, 2,5-two-amyl hydroquinone, 2,6-phenylbenzene-4-octadecane oxygen base phenol, 2,6-di-tert-butyl hydroquinone, 2,5 ,-di-t-butyl-4-hydroxyanisol, 3,5-di-t-butyl-4-hydroxyanisol, 3,5-di-tert-butyl-hydroxy phenyl stearate, two (3, the 5-di-tert-butyl-hydroxy phenyl) esters of hexanodioic acid.
4. hydroxylation phenyl ether sulphur class, for example, 2,2 '-sulphur connects two (the 6-tertiary butyl-4-methylphenol), and 2,2 '-sulphur connects two (4-octyl phenol), 4,4 '-sulphur connects two (the 6-tertiary butyls-3-methylphenol), 4,4 '-sulphur connects two (the 6-tertiary butyl-2-methylphenol), and 4,4 '-sulphur connects two (3,6-di-sec-amyl phenol), 4,4 '-two (2,6-dimethyl-4-hydroxy phenyl) disulphide.
5. alkylidene bisphenols class, for example, 2,2 '-methylene-bis (the 6-tertiary butyl-4-cresylol), 2,2 '-methylene-bis (the 6-tertiary butyl-4-ethylphenol), 2,2 '-methylene-bis [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol], 2,2 '-methylene-bis(4-methyl-6-cyclohexyl phenol), 2,2 '-methylene-bis (6-nonyl-4-methylphenol), 2,2 '-methylene-bis (4,6-two-tert.-butyl phenol), 2,2 '-ethylenebis (4,6-two-tert.-butyl phenol), 2,2 '-ethylenebis (the 6-tertiary butyl-4-isobutyl-phenol), 2,2 '-methylene-bis [6-(α-Jia Jibianji)-4-nonylphenol], 2,2 '-methylene-bis [6-(α, α-Er Jiajibianji)-4-nonylphenol], 4,4 '-methylene-bis (2,6-di-tert-butyl phenol), 4,4 '-methylene-bis (the 6-tertiary butyl-2-methylphenol), 1, two (5-tertiary butyl-4-hydroxy-2-tolyl) butane of 1-, 2, two (the 3-tertiary butyl-5-methyl-2-hydroxybenzyl)-4-methylphenols of 6-, 1,1,3-three (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 1, two (5-tertiary butyl-4-hydroxy-2-methyl-phenyl) the 3-n-dodecane sulfenyl butane of 1-, two [3, two (3 '-tertiary butyl-4 '-hydroxy phenyl) the butyric acid glycol esters of 3-, two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) Dicyclopentadiene (DCPD), two [2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-the methyl-benzyl)-6-tertiary butyl-4-aminomethyl phenyl] esters of terephthalic acid, 1,1-two (3,5-dimethyl-2-hydroxy phenyl) butane, 2,2-two (3, the 5-di-tert-butyl-hydroxy phenyl) propane, 2, two (5-tertiary butyl-4-hydroxy-2-the aminomethyl phenyl)-4-n-dodecane sulfenyl butane of 2-, 1,1,5,5-four (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) pentane.
6.O-, N-and S-benzyl compounds class, for example 3,5,3 ', 5 '-tetra-tert-4,4 '-dihydroxyl dibenzyl ether, 4-hydroxyl-3,5-dimethyl benzyl ethyl thioglycollic acid stearyl, 4-hydroxyl-3,5-di-t-butyl dibenzylsulfide guanidine-acetic acid tridecyl ester, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) amine, two (4-tertiary butyls-3-hydroxyl-2, the 6-dimethyl benzyl) dithio terephthalate, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether, 3, the different monooctyl ester of 5-di-tert-butyl-4-hydroxyl benzyl ethyl thioglycollic acid.
7. hydroxybenzyl malonic ester class, for example, 2, two (3, the 5-di-t-butyl-2-hydroxybenzyl) propanedioic acid two-stearyl of 2-, 2-(3-tertiary butyl-4-hydroxy-5-methyl-benzyl) propanedioic acid two-stearyl, 2, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) propanedioic acid two-dodecane sulfenyl ethyl esters of 2-, 2, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) propanedioic acid of 2-are two, and [4-(1,1,3, the 3-tetramethyl butyl) phenyl] ester.
8. aromatic hydroxy group benzyl compounds class, for example, 1,3,5-three (3,5-two-tertiary butyl 4-hydroxyl-benzyl)-2,4,6-Three methyl Benzene, 1, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,3 of 4-, 5,6-tetramethyl-benzene, 2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) phenol.
9. triaizine compounds class, for example, 2, two (hot the sulfenyl)-6-(3 of 4-; 5-di-t-butyl-4-hydroxybenzene amido)-and 1,3,5-triazines, the hot sulfenyl-4 of 2-; two (3,5-di-t-butyl-4-hydroxybenzene the amido)-1,3,5-triazines of 6-; the hot sulfenyl-4 of 2-, two (3,5-di-t-butyl-4-hydroxyphenoxy)-1,3 of 6-; the 5-triazine, 2,4,6-three (3; 5-di-t-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1; 3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1; 3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester, 2; 4,6-three (3,5-di-t-butyl-4-leptodactyline)-1,3; the 5-triazine, 1,3,5-three (3; 5-di-t-butyl-4-hydroxybenzene propionyl)-and hexahydro--1,3,5-triazines, 1; 3,5-three (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanuric acid ester.
10. phosphonic acid ester, phosphorous acid ester and phosphinate, for example, 2,5-di-tert-butyl-4-hydroxyl benzyl-phosphonic acids dimethyl esters, 3,5-di-tert-butyl-4-hydroxyl benzyl-phosphonic acids diethyl ester, 3,5-di-tert-butyl-4-hydroxyl benzyl-phosphonic acids two-stearyl, 5-tertiary butyl-4-hydroxy-3-methyl-benzyl-phosphonic acids two-stearyl, 3, the calcium salt of 5-di-tert-butyl-4-hydroxyl benzyl phosphonic mono ethyl ester, triphenyl phosphite, phosphorous acid diphenyl alkyl ester, phosphorous acid phenyl dialkyl ester, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite Lauryl Ester, tricresyl phosphite-stearyl, diphosphorous acid distearyl pentaerythritol ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, diphosphorous acid diiso decyl pentaerythritol ester, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol esters of diphosphorous acid, diphosphorous acid two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol ester, the two isodecyl oxygen base pentaerythritol esters of diphosphorous acid, two (2, the 4-di-t-butyl-6-aminomethyl phenyl) pentaerythritol esters of diphosphorous acid, diphosphorous acid two (2,4,6-tri-tert phenyl) pentaerythritol ester, three tricresyl phosphite stearyl sorbitol esters, 4,4 '-biphenyl, two phosphonous acid four (2, the 4-di-tert-butyl-phenyl), 6-different octyloxy-2,4,8,10-tetra-tert-12H-dibenzo [d, g]-1,3, the hot English of 2-two oxa-phosphorus, 6-fluoro-2,4,8,10-tetra-tert-12-methyldiphenyl is [d, g]-1,3 also, the hot English of 2-two oxa-phosphorus, two (2, the 4-di-t-butyl-6-aminomethyl phenyl) methyl ester of phosphorous acid, phosphorous acid two (2,4-di-t-butyl-6-aminomethyl phenyl) ethyl ester, (C 9H 19-C 6H 4) 1.5-P-(O-C 12-13H 25-27) 1.5
11. amido phenol, for example, N-(4-hydroxy phenyl) laurylamide, N-(4-hydroxy phenyl) stearylamide, N-(3, the 5-di-tert-butyl-hydroxy phenyl) carboxylamine monooctyl ester.
12. the ester of β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid and unit alcohol or polyvalent alcohol, for example, same methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1,6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, thiodiglycol, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-thia undecyl alcohol, 3-thia pentadecanol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane.
13. the ester of β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and monohydroxy-alcohol or polyvalent alcohol, for example, same methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, stearyl alcohol, 1,6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl) oxamide, 3-thia ten alcohol, 3-thia pentadecanol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane.
14. the ester of β-(3,5-dicyclohexyl-4-hydroxy phenyl) propionic acid and monobasic or polyvalent alcohol, for example, same methyl alcohol, ethanol, octanol, stearyl alcohol, 1,6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl)-oxamide, 3-thia undecyl alcohol, 3-thia pentadecanol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane
15.3, the ester of 5-di-tert-butyl-hydroxy phenyl acetate and monobasic or polyvalent alcohol, for example, same methyl alcohol, ethanol, octanol, stearyl alcohol, 1,6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, sulfo-glycol ether, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) isocyanuric acid ester, N, N '-two (hydroxyethyl)-oxamide, 3-thia undecyl alcohol, 3-thia pentadecanol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), the 4-methylol is at-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane.
16. β-(3; 5-two-tert-butyl-hydroxy phenyl) acid amides of propionic acid; N for example, N '-two (3,5-di-t-butyl-4-hydroxybenzene propionyl) hexamethylene-diamine; N; two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamoyl) the trimethylene diamines of N-, N; N '-two (3,5-di-t-butyl-4-hydroxybenzene propionyl) hydrazine.
17, sulphur connects the ester that oxalic acid and sulphur connect dipropionic acid
Preferably derive from 5,10 and 14 groups oxidation inhibitor, especially 2, two (4-hydroxyphenyl) propane of 2-, 3, the ester of 5-di-t-butyl-4-hydroxyphenylpropionic acid and stearyl alcohol or tetramethylolmethane, or three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
If desired, also can use the mixture of different structure oxidation inhibitor.Be as the criterion with 100 parts by weight polymer, the consumption of oxidation inhibitor for example can be from the 0.01-10 weight part, preferably from the 0.1-10 weight part, particularly from the 0.1-5 weight part.
(1.2-2 '-hydroxy phenyl) benzotriazole category, for example, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-benzotriazole, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl) benzotriazole, 2-(5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-(1,1,3, the 3-tetramethyl butyl) benzotriazole phenyl), 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-aminomethyl phenyl)-5-chloro-benzotriazole, 2-(3 '-sec-butyl-the 5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole, 2-(3 ', 5 '-two tert-pentyls-2 '-hydroxy phenyl) benzotriazole, 2-(3 ', 5 '-two (α, α-Er Jiajibianji)-2 '-hydroxy phenyl) benzotriazole; And 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-carbonyl octyloxy ethyl) phenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethyl hexyl oxy) carbonyl ethyl]-2 '-hydroxy phenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl) phenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the hot oxygen carbonyl of 2-ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-5 '-[and 2-(2-ethyl hexyl oxy) carbonyl ethyl)-2 '-hydroxy phenyl) benzotriazole, 2-(3 '-dodecyl-2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, and 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the different carbonyl octyloxy ethyl of 2-) phenyl) benzotriazole, 2, [4-(1 for 2 '-methylene-bis, 1,3, the 3-tetramethyl butyl)-6-benzotriazole-2-base phenol]; Mixture; The 2-[3 '-tertiary butyl-5 '-(2-methoxycarbonyl ethyl)-2 '-hydroxy phenyl]-transesterification products of 2H-benzotriazole and Liquid Macrogol; (the R-CH of R=3 '-tertiary butyl-4 '-hydroxyl-5 '-2H-benzotriazole-2-base phenyl wherein 2CH 2-COO (CH 2) 3) 2
2. 2-hydroxy benzophenone class, for example, its 4-hydroxyl, 4-methoxyl group, 4-octyloxy, 4-oxygen in last of the ten Heavenly stems base, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4 '-trihydroxy-and 2 '-hydroxyl-4,4 '-dimethoxy derivatives class.
3. replace and unsubstituted benzoates, for example, Whitfield's ointment 4-tert-butyl-phenyl ester, the Whitfield's ointment phenylester, Whitfield's ointment octyl phenyl ester, Resorcinol dibenzoate, Resorcinol two (4-p t butylbenzoic acid ester), the Resorcinol benzoic ether, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2,4-di-tert-butyl-phenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid cetyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid stearyl, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di-tert-butyl-phenyl ester.
4. acrylate, for example, alpha-cyano-β, β-diphenyl-ethyl acrylate, alpha-cyano-β, β-diphenyl 2-Propenoic acid-2-ethylhexyl ester, α-methoxycarbonyl methyl cinnamate, alpha-cyano-Beta-methyl-p-methoxycinnamic acid methyl esters, alpha-cyano-Beta-methyl-p-methoxycinnamic acid butyl ester, α-methoxycarbonyl-p-methoxycinnamic acid methyl esters and N-(beta-carbomethoxy-3-β-acrylonitrile base)-2-methyl indoline.
5. nickel compound class, for example, 2,2 '-sulphur connects the nickel complex of two [4-(1,1,3, the 3-tetramethyl butyl) phenol], as 1: 1 or 1: 2 title complex, has or do not have additional ligand (as n-Butyl Amine 99, trolamine or N-cyclohexyl diethanolamine); Nickel dibutyl dithiocarbamate, the nickel salt of-alkyl esters, for example, 4-hydroxyl-3, the methyl or the ethyl ester of 5-di-t-butyl benzylphosphonic acid; The nickel complex of ketoxime, for example, the nickel complex of 2-hydroxy-4-methyl phenyl ten-alkyl ketoxime; Has or do not have the nickel complex of the 1-phenyl-4-lauroyl-5-hydroxypyrazoles of additional ligand.
6. sterically hindered amine, for example, sebacic acid two (2; 2,6,6-tetramethyl--4-piperidyl) ester; Succinic Acid two (2,2,6; 6-tetramethyl--4-piperidyl) ester, sebacic acid two (1,2; 2,6,6-pentamethyl--4-piperidyl) ester; sebacic acid two (1-octyloxy-2,2,6; 6-tetramethyl--4-piperidyl) ester, n-butyl-3,5-di-tert-butyl-4-hydroxyl benzyl propanedioic acid two (1; 2,2,6; 6-pentamethyl--4-piperidyl) ester, 1-(2-hydroxyethyl) 2,2; 6, the condenses of 6-tetramethyl--4-hydroxy piperidine and Succinic Acid, N; N '-two (2,2,6; 6-tetramethyl--4-piperidyl) the hot amino-2 of hexamethylene-diamine and uncle 4-, 6-two chloro-1,3; the condenses of 5-triazine, nitrilotriacetic acid(NTA) three (2,2; 6,6-tetramethyl--4-piperidyl) ester, 1; 2,3,4 fourth tetracids four (2; 2,6,6-tetramethyl--4-piperidyl) ester; 1,1 '-(ethylene) two (3; 3,5, the 5-tetramethylpiperidone); 4-benzoyl-2,2,6; the 6-tetramethyl piperidine, 4-stearoyl-oxy-2,2; 6,6-four-methyl piperidine, 2-normal-butyl-2-(2-hydroxyl-3; 5-di-t-butyl benzyl) propanedioic acid two (1,2,2; 6,6-five-methyl piperidine base) ester, 3-n-octyl-7; 7,9,9-tetramethyl--1; 3,8-three nitrogen spiral shell [4.5] last of the ten Heavenly stems-2,4-diketone; sebacic acid two (1-octyloxy-2,2,6; the 6-tetramethyl-piperidyl) ester, two (the 1-octyloxies-2,2 of Succinic Acid; 6, the 6-tetramethyl-piperidyl) succinate, N; N '-two (2,2,6; 6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-morpholino-2,6-two chloro-1,3; the condenses of 5 triazines, 2-chloro-4, two (the 4-n-butyl amine bases-2 of 6-; 2,6, the 6-tetramethyl piperidine)-1; 3,5-triazine and 1, the condenses of two (the 3-aminopropyl amino) ethane of 2-; 2-chloro-4,6-two (4-n-butyl amine base-1,2; 2,6,6-pentamethyl-piperidyl)-1; 3,5-triazine and 1, the condenses of two (the 3-aminopropyl amino) ethane of 2-; 8-ethanoyl-3-dodecyl-7; 7,9,9-tetramethyl--1; 3; 8-thriazaspiro [4.5] last of the ten Heavenly stems-2,4-diketone, 3-dodecyl-1-(2; 2; 6,6-tetramethyl--4-piperidyl) tetramethyleneimine-2, the 5-diketone; 3-dodecyl-1-(1; 2,2,6; 6-pentamethyl--4-piperidyl) tetramethyleneimine-2,5-diketone and Chimassorb 966.
7. oxamide, for example, 4,4 '-two octyloxies-N, N '-oxalyl pentanoic, 2,2 '-two octyloxies-5,5 '-di-t-butyl-N, N '-oxalyl pentanoic, 2,2 '-two-dodecyloxy-5,5 '-di-t-butyl-N, N '-oxalyl pentanoic, 2-oxyethyl group-2 '-ethyl-N, N '-oxalyl pentanoic, N, N '-two (3-dimethylamino-propyl) oxamide, 2-oxyethyl group-5-the tertiary butyl-2 '-ethyl-N, N '-oxalyl pentanoic and it is with 2-oxyethyl group-2 '-ethyl-5,4 '-di-t-butyl-N, the mixture of N '-oxalyl pentanoic, with adjacent and to methoxyl group disubstituted-N, the mixture of N '-oxalyl pentanoic.
8. 2-(2-hydroxy phenyl)-1,3,5-triazines, for example, 2,4,6-three (2-hydroxyl-4-octyloxyphenyl)-1,3, the 5-triazine, 2 (2-hydroxyls-4-octyloxyphenyl) 4, two (2, the 4-3,5-dimethylphenyl)-1 of 6-, 3,5-triazine, 2-(2, the 4-dihydroxy phenyl)-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-, 2, two (2-hydroxyl-4-propoxy-the phenyl)-6-(2, the 4-3,5-dimethylphenyl)-1,3 of 4-, the 5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4, two (the 4-aminomethyl phenyls)-1,3 of 6-, the 5-triazine, 2-(2-hydroxyl-4-dodecyloxy phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-tridecane oxygen base phenyl)-4, two (2, the 4-3,5-dimethylphenyl)-1 of 6-, 3,5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-butoxy propoxy-) phenyl]-4, two (2, the 4-3,5-dimethylphenyl)-1,3 of 6-, the 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-octyloxy-propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines.
The example of suitable peroxide scavenger has: β-sulphur connects the ester of propionic acid, for example, lauryl, stearyl ester, tetradecane ester or tridecane ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, two-octadecyl disulphide, tetramethylolmethane four (β-dodecyl sulfydryl) propionic ester or ethylene glycol bisthioglycolate sulphur connect acetic ester.
In addition, the present invention also provides Antistatically treated thermoplastic, structurally crosslinked elasticity or the preparation method of thermosetting polymer, this method comprises, use as rolling press, mixing tank, compounding machine, the device of forcing machine etc. be with following composition or with the form of their independent components, and (and containing or do not contain other additive) mixes with thermoplastic, structurally crosslinked elasticity or thermosetting polymer; Described composition comprises: being of (a) being in contact with one another is fibrous or granular, the inorganic or organic materials of polar, adsorptivity, be combined with to adsorptivity (b) polarity static inhibitor thereon, this static inhibitor comprises the mixture of following b1 and b2, (b1) at least a have at least 5 carbon atoms and have at least 3 heteroatomic polar organic compounds and (b2) in polar organic compound by the salt of the inorganic proton acid of solvation or complexing.
With known mode itself, by using known devices own, as rolling press, mixing tank, the compounding machine, forcing machines etc. are prepared above-mentioned additive and other if desired additive and mixed with polymers.In the method, additive can add separately or add with the form of mixture.Also can use so-called master batch.
By known technology, the Antistatically treated thermoplastic polymer that the present invention can be obtained becomes desirable shape.The example of these technology has, and grinds calendering, extrusion molding, injection moulding, sintering, compression sintering or reel off raw silk from cocoons, and extrusion blow molded, or the processing by the plastisol method.Antistatically treated thermoplastic polymer also can be processed into foam material.
The present invention also provides a kind of composition, said composition comprises: the inorganic or organic materials that (a) is fibrous or granular, polar, adsorptivity, be combined with to adsorptivity (b) polarity static inhibitor thereon, this static inhibitor comprises the mixture of following b1 and b2, (b1) at least a have 5 carbon atoms at least and have 3 heteroatomic polar organic compounds at least and (b2) salt of the inorganic proton acid in polar organic compound by solvation or complexing.
Preferred said composition comprises: the inorganic or organic materials that (a) is fibrous or granular, polar, adsorptivity, be combined with to adsorptivity (b) polarity static inhibitor thereon, this static inhibitor comprises the mixture of following b1 and b2, (b1) polyoxyalkylene of formula (I): R 1-O-[CH (R 3)-CH 2-O-] n-[CH 2-[CH (OH)] p-CH 2-O] q-[C (O)] r-R 2(I), R in the formula 1Be H, C 1-C 24Alkyl, C 2-C 24Thiazolinyl, C 1-C 24Alkyl-C (O)-, C 2-C 24Thiazolinyl-C (O)-, CH 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-, R 2Be C 1-C 24Alkyl, C 2-C 24Thiazolinyl, CH 2-COOH or N (C 1-C 8Alkyl) 3Halogen, if perhaps r is 0, R 2Be CH in addition 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-, R 3Be H or CH 3, halogen is Cl, and Br or I, n are the numbers more than or equal to 2, and p is the number of 1-6, and q and r are 0 or 1 independently of one another; (b2) formula { M wherein Z+ aA (az/b)- bInorganic salt be complexing therein or solvation, M is a Z-valency basic metal in the formula, the positively charged ion of alkaline-earth metal or zinc, a and b be the number between 1 and 6 independently of one another, A is the negatively charged ion of the organic oxacid of the negatively charged ion of inorganic proton acid or sulphur.
Each component of this mixture is arranged by above-mentioned preferably combination; Similarly, said composition also can comprise aforesaid other component.
That the present invention also is provided for improving is thermoplastic, the purposes of the novel composition of the antistatic property of crosslinked elasticity or thermosetting polymer structurally.This novel polymeric component is particularly suitable for the purposes of metal wire foreskin and cable insulation.Yet, also can produce decorating film, foam, agricultural film, sebific duct, seal profile and office diaphragm.
This novel polymerizable compositions also can be used as moulding compound, is used for producing hollow piece (bottle), packaging film (thermoforming film), blown film, crash pad film (automobile), pipe, foam, heavy section (window frame), translucent wall section bar, structural shapes, wallboard, joint, office diaphragm and device outer cover (computer, domestic appliances).
Therefore, the present invention also provides the purposes of the novel composition that is used for metal wire foreskin and cable insulation.
To the present invention be described with embodiment below.Embodiment 1
With fiberboard (leaf wood, bleaching the) (about 6 * 1cm that cuts into inch strips 2), with wherein 7.28 the gram place in the solution of the polyethylene glycol laurate (Irgastat 51, Sheba company) that contains 10% methylsulphonic acid lithium.In the tea china of described converted top in the jar of can finding time.The degassing is 30 minutes under 0.5 millibar pressure.Shelve impregnated then to drip-dry.Now, the weight of impregnation of fibers element is 11.39 grams.Will be in this way impregnated be cut into about 1 * 1cm 2Sheet, and in the ultra centrifugal mill (Retsch, ZM 1000 types) of band 0.5mm annular sieve, grind to form fiber.Embodiment 2
The impregnated Mierocrystalline cellulose of described in the example 1 4.0 gram is added among the polypropylene Moplen FLF20 of 50 grams, and carefully these two kinds of components are mixed.This mixture was processed 5 minutes in two roller mills (rolling press) at 180 ℃, to form roll-in film (roll gap 0.5mm).Then, utilize metal form (15 * 15 * 0.05cm 3), under pressure, in the hydraulic press of heating, prepare fiberboard (190 ℃ of processing 5 minutes).The plate that makes in this way demonstrates 4 * 10 11The unit volume resistance R in Europe v(with voltage and the 20cm of 500V 3Ring electrode, the gap of 0.5cm records (DIN 53482) at 22 ℃).After about 70% relative temperature and 22 ℃ store a week, R vReduce to 6 * 10 7Europe (ring electrode), surface resistance R sBe 4.2 * 10 8Europe (according to the tongue electrode of DIN 53482).Embodiment 3
(Fischer CH-Dottikon) grinds in the ultra centrifugal mill (Retsch, ZM 1000 types) of band 0.12mm annular sieve for length 6mm, 290 types with the piemarker fiber.3 gram fibers are placed glass beaker, with poly(oxyethylene glycol) 400 diacrylate Sartomer SR 344 and 4%NaClO 4H 2O covers, and stirs in 0.5 millibar vacuum tank and outgases about 30 minutes.Then, this solution is filtered, and between the filter paper of hydraulic press, from excessive solution, take out residuum (impregnated fiber), residuum=4.9 grams.Embodiment 4
The impregnated fiber of described in the example 32 gram is added among the polypropylene Moplen FLF 20 of 60 grams, and mix.This mixture was processed 7 minutes in two roller mills (rolling press) at 180 ℃, to form roll-in diaphragm (roll gap 0.5mm).Then, utilize metal form (15 * 5 * 0.05cm 3), under pressure, in the hydraulic press of heating, prepare fiberboard (190 ℃ of processing 5 minutes).After just having prepared, the plate that makes in this way demonstrates 9.9 * 10 10The unit volume resistance R in Europe v(with voltage and the 20cm of 500V 3Ring electrode, the gap of 0.5cm records (DIN 53482) at 22 ℃).In about 30-40% relative temperature and room temperature storage after two months, R vReduce to 2.5 * 10 9Europe, surface resistance R sBe 6.0 * 10 10Europe.Embodiment 5
With 446 gram fiberboards (leaf wood, bleaching the) (about 2.5 * 14.8cm that cut into inch strips 2), and divide 3 parts to place and contain poly(oxyethylene glycol) 400 diacrylate Sartomer SR 344 and 4%NaClO 4H 2In the solution that O forms.In the container of described converted top in the jar of can finding time.The degassing is 30 minutes under 0.3 millibar pressure.Shelve impregnated then to doing.Now, the weight of impregnation of fibers element is 681 grams.Will be in this way impregnated be cut into about 1 * 1cm 2Sheet, and earlier in the ultra centrifugal mill (Retsch, ZM 1000 types) of band 1mm annular sieve, grind to form fiber then at band 2mm annular sieve.Embodiment 6
All the impregnated fiber described in the example 5 (consumption and measuring result see Table 1) is added in all cases among the polypropylene Profax 6501 of 45 grams, and these components are carefully mixed.This mixture was processed 9 minutes in two roller mills (rolling press) at 180 ℃, to form roll-in diaphragm (roll gap 0.4mm).Then, utilize metal form (15 * 15 * 0.05cm 3), under pressure, in the hydraulic press of heating, prepare fiberboard (200 ℃ of processing 5 minutes).Week when the dry plate that makes in this way is on blue gel.Surface measurements resistance value R then s(according to the tongue electrode of DIN 53482, voltage is 500V, in the dry atmosphere of 22 ℃ of peace treaties less than 15% relative humidity).The results are shown in Table 1.Table 1
Polypropylene Profax 6501 Impregnated fiber embodiment 5 Surface resistance R s[Europe]
45.0 gram 3.0 gram ????2×10 11
45.0 gram 2.0 gram ????3×10 11
45.0 gram 1.5 gram ????2×10 12
45.0 gram 0 gram=reference ???＞2×10 14

Claims (28)

1, a kind ofly comprise thermoplastic, structurally crosslinked elasticity or the composition of thermosetting polymer, said composition comprises: being of (a) being in contact with one another is fibrous or granular, the inorganic or organic materials of polar, adsorptivity, be combined with to adsorptivity (b) polarity static inhibitor thereon, this static inhibitor comprises the mixture of following b1 and b2, (b1) at least a have 5 carbon atoms at least and have 3 heteroatomic polar organic compounds at least and (b2) salt of the inorganic proton acid in polar organic compound by solvation or complexing.
2, according to the composition of claim 1, wherein, thermoplastic, structurally crosslinked elasticity or heat cured polymkeric substance are selected from: polyolefine, polystyrene, α, the polymkeric substance of beta-unsaturated acid, halogen-containing polymkeric substance, the homopolymer of cyclic ethers and multipolymer, the polymkeric substance of unsaturated alkohol and amine, polyacetal, polyphenylene oxide, urethane, polymeric amide, polyester, polyureas, polycarbonate, polysulfones, the cross-linking products of aldehyde and phenol, urea or melamine, Synolac, crosslinkable acrylic resin, crosslinked Resins, epoxy, Mierocrystalline cellulose or natural rubber.
3, composition as claimed in claim 2, wherein, thermoplastic, structurally crosslinked elasticity or heat cured polymkeric substance are selected from: polyolefine, polystyrene, α, the polymkeric substance of beta-unsaturated acid, halogen-containing polymkeric substance, the homopolymer of cyclic ethers and multipolymer.
4, according to the composition of claim 1, wherein, if the organic or inorganic material is the porous words, its internal surface area is 5-500m 2/ g.
5, according to the composition of claim 1, wherein, the inorganic materials of used porous, adsorptivity is naturally occurring inorganic powder, as calcite, and talcum, kaolin, diatomite, polynite or attapulgite, phyllosilicate, as sepiolite or wilkinite, the silicic acid of polymolecularity, the silicic acid of synthetic, high absorbability, silica gel, molecular sieve zeolites, float stone, the brick of pulverizing or sintered glass.
6, according to the composition of claim 1, wherein, used porous adsorptivity organic materials is the synthetic porous polymer, especially the melocol polycondensate.
7, according to the composition of claim 1, wherein, used porous adsorptivity organic fibre is a particulate state or fibrous, naturally occurring organic materials, especially timber of Yan Moing or plant stubble.
8, according to the composition of claim 1, wherein, used naturally occurring fiber is cotton, phloem fiber, kapok, jute, piemarker, flax, hemp, wool or cocoon fiber.
9, according to the composition of claim 1, wherein, the particulate median size is from 1-5000 μ m.
10, according to the composition of claim 1, wherein, the length of organic or inorganic fiber is from 0.01-200mm.
11, according to the composition of claim 1, wherein, have 5 carbon atoms at least and have at least 3 heteroatomic polar organic compounds to be selected from: polyethers, crown ether, polyvalent alcohol, poly-imines, polyamine, by the pyridine derived polymkeric substance that obtains, encircle nitric heterocyclic compound greatly, polysulfide and poly-phosphine.
12, according to the composition of claim 11, wherein, polar organic compound is that the olefinic unsaturated carbon bond is arranged, by α, and the functional group that the beta-unsaturated carboxylic acid or derivatives thereof obtains, isocyanate groups or glycidyl group.
13, according to the composition of claim 1, wherein, used inorganic salt are the zinc salt of mineral acid or oxygen acid, an alkali metal salt, alkaline earth salt or ammonium salt.
14, according to the composition of claim 13, wherein, inorganic salt are preferably selected from: LiClO 4, LiCF 3SO 3, NaClO 4, LiBF 4, NaBF 4, KBF 4, NaCF 3SO 3, KClO 4, KPF 6, KCF 3SO 3, KC 4F 9SO 3, Ca (ClO 4) 2, Ca (PF 6) 2, Ca (CF 3SO 3) 2, Mg (ClO 4) 2, Mg (CF 3SO 3) 2, Zn (ClO 4) 2, Zn (PF 6) 2And Ca (CF 3SO 3) 2
15, composition according to claim 1, comprise thermoplastic, crosslinked elasticity or thermosetting polymer structurally, said composition comprises: being of (a) being in contact with one another is fibrous or granular, the inorganic or organic materials of polar, adsorptivity, be combined with to adsorptivity (b) polarity static inhibitor thereon, this static inhibitor comprises the mixture of following b1 and b2, (b1) polyoxyalkylene of formula (I): R 1-O-[CH (R 3)-CH 2-O-] n-[CH 2-[CH (OH)] p-CH 2-O] q-[C (O)] r-R 2(I), R in the formula 1Be H, C 1-C 24Alkyl, C 2-C 24Thiazolinyl, C 1-C 24Alkyl-C (O)-, C 2-C 24Thiazolinyl-C (O)-, CH 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-, R 2Be C 1-C 24Alkyl, C 2-C 24Thiazolinyl, CH 2-COOH or N (C 1-C 8Alkyl) 3Halogen, if perhaps r is 0, R 2Be CH in addition 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-, R 3Be H or CH 3, halogen is Cl, and Br or I, n are the numbers more than or equal to 2, and p is the number of 1-6, and q and r are 0 or 1 independently of one another; (b2) formula { M wherein Z+ aA (aZ/b)- bInorganic salt be complexing or solvation, M is a Z-valency basic metal in the formula, the positively charged ion of alkaline-earth metal or zinc, a and b are the number between 1 and 6 independently of one another, A is the negatively charged ion of the organic oxacid of the negatively charged ion of inorganic proton acid or sulphur.
16, according to the composition of claim 15, wherein, R 1Be H, C 1-C 4Alkyl, CH 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-.
17, according to the composition of claim 15, wherein, R 2Be C 6-C 20Alkyl, C 6-C 20Thiazolinyl or N (C 1-C 8Alkyl) 3Cl, CH 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-.
18, according to the composition of claim 15, wherein, n is the number between 2 and 20, and p is the number of 2-6.
19, composition according to claim 15, wherein, the compound of formula I is: the polypropylene glycol laurate, polypropylene glycol oil ether, polypropylene glycol methyl diethyl ammonium chloride, polyoxyethylene glycol monomethyl ether, the polyoxyethylene glycol dimethyl ether, polyethylene glycol laurate, polyethylene glycol (PEG) oleate, polyoxyethylene glycol oleyl ether, the polyoxyethylene glycol Arlacel-20, polyethylene glycol stearate, polyoxyethylene glycol polypropylene glycol lauryl ether, polyoxyethylene glycol bay ether-carboxylic acid, the diacrylate of polyoxyethylene glycol, mono acrylic ester and triacrylate, or the dimethacrylate of polyoxyethylene glycol, monomethacrylates and trimethacrylate.
20, according to the composition of claim 1, wherein, the consumption of the inorganic or organic materials of polarity is counted the 0.01-70 weight part with 100 parts by weight polymer.
21, according to the composition of claim 1, wherein, have 5 carbon atoms at least and have at least 3 heteroatomic polar organic compounds to count the 0.01-20 weight part with 100 parts by weight polymer.
22, according to the composition of claim 1, wherein, used inorganic salt are counted the 0.01-5 weight part with 100 parts by weight polymer.
23, according to the composition of claim 1, wherein, have 5 carbon atoms at least and have at least 3 heteroatomic polar organic compounds to the weight ratio of inorganic salt from 200: 1 to 1: 1.
24, a kind of Antistatically treated thermoplastic, structurally crosslinked elasticity or the preparation method of thermosetting polymer, this method comprises, use as rolling press, mixing tank, compounding machine, the device of forcing machine etc. be with following composition or with the form of their independent components, and add or do not add other additive and mix with thermoplastic, structurally crosslinked elasticity or thermosetting polymer; Described composition comprises: being of (a) being in contact with one another is fibrous or granular, the inorganic or organic materials of polar, adsorptivity, be combined with to adsorptivity (b) polarity static inhibitor thereon, this static inhibitor comprises the mixture of following b1 and b2, (b1) at least a have at least 5 carbon atoms and have at least 3 heteroatomic polar organic compounds and (b2) in polar organic compound by the salt of the inorganic proton acid of solvation or complexing.
25, a kind of composition, comprise: the inorganic or organic materials that (a) is fibrous or granular, polar, adsorptivity, be combined with to adsorptivity (b) polarity static inhibitor thereon, this static inhibitor comprises the mixture of following b1 and b2, (b1) at least a have 5 carbon atoms at least and have 3 heteroatomic polar organic compounds at least and (b2) salt of the inorganic proton acid in polar organic compound by solvation or complexing.
26, composition according to claim 25, comprise: the inorganic or organic materials that (a) is fibrous or granular, polar, adsorptivity, be combined with to adsorptivity (b) polarity static inhibitor thereon, this static inhibitor comprises the mixture of following b1 and b2, (b1) polyoxyalkylene of formula (I): R 1-O-[CH (R 3)-CH 2-O-] n-[CH 2-[CH (OH)] p-CH 2-O] q-[C (O)] r-R 2(I), R in the formula 1Be H, C 1-C 24Alkyl, C 2-C 24Thiazolinyl, C 1-C 24Alkyl-C (O)-, C 2-C 24Thiazolinyl-C (O)-, CH 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-, R 2Be C 1-C 24Alkyl, C 2-C 24Thiazolinyl, CH 2-COOH or N (C 1-C 8Alkyl) 3Halogen, if perhaps r is 0, R 2Be CH 2=CH-C (O)-or CH 2=C (CH 3)-C (O)-, R 3Be H or CH 3, halogen is Cl, and Br or I, n are the numbers more than or equal to 2, and p is the number of 1-6, and q and r are 0 or 1 independently of one another; (b2) formula { M wherein Z+ aA (az/b)- bInorganic salt be complexing or solvation, M is a Z-valency basic metal in the formula, the positively charged ion of alkaline-earth metal or zinc, a and b are the number between 1 and 6 independently of one another, A is the negatively charged ion of the organic oxacid of the negatively charged ion of inorganic proton acid or sulphur.
27, be used to improve thermoplastic, the purposes of the antistatic property of crosslinked elasticity or thermosetting polymer structurally according to the composition of claim 25.
28, be used for the purposes of metal wire foreskin and cable insulation according to the composition of claim 25.
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CN102051156B (en) * 2010-05-21 2012-12-19 东阳市聚科新材料有限公司 High-temperature resistant poly(ester-ether) polymer antistatic agent and preparation method and application of poly(ester-ether) polymer antistatic agent
CN102225647A (en) * 2011-04-15 2011-10-26 江阴升辉包装材料有限公司 Permanently antistatic multilayer coextruded film and processing method thereof
CN105542417A (en) * 2016-01-23 2016-05-04 中山聚昌自动化设备科技有限公司 Fully-automatic rotating bead stringing machine
CN107459727A (en) * 2016-06-03 2017-12-12 中国石油化工股份有限公司 A kind of antistatic PVC board composition
CN113402741A (en) * 2021-07-05 2021-09-17 湖南工业大学 Rare earth modified fiber reinforced polylactic acid and preparation method thereof
CN113402741B (en) * 2021-07-05 2022-05-06 湖南工业大学 Rare earth modified fiber reinforced polylactic acid and preparation method thereof
CN114907756A (en) * 2022-04-24 2022-08-16 陈秋月 Antistatic polyurethane water-based paint and preparation method thereof

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BR9700904A (en) 1999-01-12
ID15893A (en) 1997-08-14
RU2161635C2 (en) 2001-01-10
CN1100823C (en) 2003-02-05

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