CN101910264B - Inorganic foaming accelerator, process for producing the inorganic foaming accelerator, and polymer composition - Google Patents
Inorganic foaming accelerator, process for producing the inorganic foaming accelerator, and polymer composition Download PDFInfo
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- CN101910264B CN101910264B CN2008801228728A CN200880122872A CN101910264B CN 101910264 B CN101910264 B CN 101910264B CN 2008801228728 A CN2008801228728 A CN 2008801228728A CN 200880122872 A CN200880122872 A CN 200880122872A CN 101910264 B CN101910264 B CN 101910264B
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- Prior art keywords
- mineral
- zinc
- auxiliary agent
- foaming
- zinc oxide
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- 238000000034 method Methods 0.000 title claims abstract description 23
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- 239000000203 mixture Substances 0.000 title claims abstract description 6
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- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
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- 239000003795 chemical substances by application Substances 0.000 claims description 49
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 claims description 45
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- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/101—Agents modifying the decomposition temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/038—Use of an inorganic compound to impregnate, bind or coat a foam, e.g. waterglass
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- Engineering & Computer Science (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
This invention provides an inorganic foaming accelerator, which can accelerate the decomposition of a foaming agent by using a small amount of zinc and can realize a fine and even size of foamed cells and foaming at a high expansion ratio, a process for producing the inorganic foaming accelerator, and a polymer composition using the inorganic foaming accelerator. The inorganic foaming accelerator is an inorganic foaming accelerator that accelerates the decomposition of a heat decomposable foaming agent and is characterized by comprising a particle of a silicate, preferably a particle of an anhydrous aluminum silicate mineral, and a fine particle of zinc oxide or a fine particle of basic zinc carbonate supported on the surface of the particle of the silicate.
Description
Technical field
The mineral-type foaming that the present invention relates to promote thermal decomposition of blowing agent to decompose promotes auxiliary agent and method of manufacture thereof and uses this mineral-type foaming to promote the polymer compsn of auxiliary agent.
Background technology
In the foaming of plastics or rubber, known have through cooperating thermolysis type whipping agent and making its foaming be shaped to the method for foam.Known in such thermolysis type whipping agent, through making the zinc oxide coexistence, can reduce the decomposition temperature of thermolysis type whipping agent, and can promote the decomposition of whipping agent.
Foaming as above-mentioned such thermolysis type whipping agent promotes auxiliary agent, and various zn cpdss have been carried out studying (for example, patent documentation 1 and 2).
As MOX, known activity zinc white etc. promote auxiliary agent as foaming.But, because active zinc white is extremely fine Zinc oxide particles, easily aggegation takes place and constitute relatively large offspring, it is insufficient that the dispersion in resin or rubber becomes easily, and the foaming facilitation effect becomes inhomogeneous easily.
In addition, known composite particles (patent documentation 3) with zinc oxide coated caco3 surface.But such composite particles may not be that the excellent foaming of specific activity zinc white promotes auxiliary agent.
Patent documentation 1: japanese kokai publication sho 53-145876 communique
Patent documentation 2: japanese kokai publication sho 58-201825 communique
Patent documentation 3: japanese kokai publication sho 60-264324 communique
Summary of the invention
The polymer compsn that the object of the present invention is to provide a kind of mineral-type foaming to promote auxiliary agent and method of manufacture thereof and use this mineral-type foaming promotion auxiliary agent to obtain; The foaming of this mineral-type promote auxiliary agent can with a spot of zinc amount promote whipping agent decomposition, can make the big or small fine even of foaming bubble, and make its foaming with higher expansion ratio.
Mineral-type foaming of the present invention promotes auxiliary agent, is that the mineral-type foaming that promotes thermolysis type whipping agent to decompose promotes auxiliary agent, it is characterized in that, is carried with zinc oxide fine particles or alkaline carbonic acid zinc particulate on the surface of silicate granules.
According to the present invention, can promote the decomposition of whipping agent with a spot of zinc amount, can make the big or small fine of foaming bubble evenly and with higher expansion ratio make its foaming.
Among the present invention, be carried with zinc oxide fine particles or alkaline carbonic acid zinc particulate on the surface of silicate granules.The surface of silicate granules has affinity to zinc oxide fine particles and alkaline carbonic acid zinc particulate, therefore can carry equably and hold zinc oxide fine particles or alkaline carbonic acid zinc particulate.Therefore, promote to be carried with fine zinc oxide fine particles or fine alkaline carbonic acid zinc particulate on the surface in the auxiliary agent, utilize these surface activity of particles, can promote the decomposition of thermal decomposition of blowing agent effectively in mineral-type foaming of the present invention.
In addition, mineral-type foaming of the present invention promotes the excellent dispersion of auxiliary agent in polymkeric substance such as plastics or rubber.Therefore, can in polymkeric substance, bring into play the effect that promotes foaming equably, can promote the decomposition of whipping agent equably with a spot of zinc amount.Therefore, can make the big or small fine of foaming bubble evenly and with higher foam expansion make the polymer materials foaming.
Among the present invention, the loading amount of preferred zinc oxide fine particles or alkaline carbonic acid zinc particulate converts with metallic zinc and is in the scope of 6～75 weight %.Here, the loading amount that so-called metallic zinc converts can be calculated as follows, that is, calculate and change contained zinc oxide fine particles of holding or alkaline carbonic acid zinc particulate into obtain for metallic zinc Zn converted weight, uses to be worth, and is calculated by following formula.
Loading amount (weight %)=(the Zn converted weight) that metallic zinc converts/(the mineral-type foaming promotes the weight of auxiliary agent)
If, then there is the situation that can not make the big or small fine even of foaming bubble and foam with higher expansion ratio less than above-mentioned scope in loading amount.In addition, if loading amount excessively more than above-mentioned scope, there is disadvantageous economically situation in the effect that then can not be accompanied with it.
The BET specific surface area that is carried with the silicate granules of zinc oxide fine particles preferably is in 10～55m
2In the scope of/g, more preferably be in 15～50m
2In the scope of/g, further preferably be in 20～45m
2In the scope of/g.
The BET specific surface area that is carried with the silicate granules of alkaline carbonic acid zinc particulate preferably is in 25～90m
2In the scope of/g, more preferably be in 30～85m
2In the scope of/g, further preferably be in 35～80m
2In the scope of/g.
Alkaline carbonic acid zinc particulate is finer than zinc oxide fine particles, can form the higher particulate of BET specific surface area.Therefore, when carrying as stated when holding alkaline carbonic acid zinc particulate, compare when holding zinc oxide fine particles with carrying, the BET specific surface area increases.
If the BET specific surface area is low excessively, then in polymer materials, can not fully contacts, thereby have the situation uneven, that expansion ratio reduces that becomes that foams with whipping agent.
In addition, if the BET specific surface area is too high, is then carried and hold and free zinc oxide or alkaline carbonic acid zinc mixing existence, they form agglutinating particle, thereby have the situation that can not form uniform foam.In addition, because the loading amount of zinc oxide or alkaline carbonic acid zinc is more relatively, there is the situation that is difficult to obtain advantage economically.
As the silicate granules among the present invention, preferably use the aluminium silicate salt mineral grain.In addition, as the silicate granules beyond the aluminium silicate salt mineral grain, can enumerate talcum, mica, feldspar, wilkinite, alkaline magnesium carbonate, silicon-dioxide, Calucium Silicate powder etc.
As the aluminium silicate salt mineral grain among the present invention, for example, can enumerate being selected from least a in kaolinite, halloysite, agalmatolite and the sericite.Among the present invention, the preferred anhydrous aluminium silicate salt of aluminium silicate salt mineral grain mineral grain.As anhydrous aluminium silicate salt mineral grain, for example, can enumerate the particle that is selected from least a the firing in kaolinite, halloysite, agalmatolite and the sericite and obtains.For example, can enumerate being that these clay minerals that the subparticle more than 80% forms are fired the particle that obtains with 500～900 ℃ temperature by the containing ratio below the particle diameter 2 μ m.
Mineral-type foaming of the present invention promotes in the auxiliary agent, with respect to the Al in the aluminium silicate salt mineral grain
2O
3, the ratio (Zn/Al of the Zn in zinc oxide fine particles or the alkaline carbonic acid zinc particulate
2O
3) with molar ratio computing, preferably in 0.2～40.0 scope, more preferably in 0.4～20.0 scope, further preferred in 0.5～10.0 scope.If above-mentioned mol ratio excessively reduces, then exist the quantitative change of contained zinc oxide of holding in surface or alkaline carbonic acid zinc few, the situation of the big or small fine even and higher expansion ratio of the bubble that can not obtain foaming.In addition; If above-mentioned mol ratio excessively increases; Then not carried the fine zinc oxide or the alkaline carbonic acid zinc particulate amount of holding on the aluminium silicate salt mineral grain increases; Operability variation in the manufacturing process, and owing to carried zinc oxide or the alkaline carbonic acid zinc formation agglomeration of holding, so there is the situation that can not be foamed uniformly.
Method of manufacture of the present invention is the method that can make the mineral-type foaming promotion auxiliary agent of the invention described above, it is characterized in that, comprising: the operation of preparing the acidic aqueous solution of zinc salt; With in the presence of silicate granules, thereby the acidic aqueous solution of mixed zinc salts and alkaline aqueous solution are separated out zinc oxide fine particles or alkaline carbonic acid zinc particulate, make zinc oxide fine particles or alkaline carbonic acid zinc particulate carry the lip-deep operation of holding silicate granules.
Through the method for manufacture of the invention described above, can make the silicate granules that is carried with zinc oxide fine particles or alkaline carbonic acid zinc particulate.And then, can handle the silicate granules that is carried with zinc oxide fine particles through utilizing ammonium salt aqueous solution, the contained zinc oxide fine particles of holding is transformed to alkaline carbonic acid zinc particulate, make the silicate granules that is carried with alkaline carbonic acid zinc particulate thus.
Among the present invention, in the presence of silicate granules, the acidic aqueous solution of mixed zinc salts and alkaline aqueous solution, thus zinc oxide fine particles or alkaline carbonic acid zinc are separated out, zinc oxide fine particles or alkaline carbonic acid zinc are carried on the surface of holding silicate granules.
As in the presence of silicate granules, the acidic aqueous solution of mixed zinc salts and alkaline aqueous solution, thereby the method that zinc oxide fine particles or alkaline carbonic acid zinc particulate are separated out, the method that specifically can be listed below.
(1) silicate granules is dispersed in the acidic aqueous solution of zinc salt, in this dispersion liquid, adds alkaline aqueous solution then.
(2) silicate granules is dispersed in the alkaline aqueous solution, in this dispersion liquid, adds the acidic aqueous solution of zinc salt then.
(3) silicate granules is dispersed in the water, in this dispersion liquid, adds the acidic aqueous solution and the alkaline aqueous solution of zinc salt then simultaneously.
In the method for above-mentioned (1)～(3), especially preferably adopt the method for (1).
The acidic aqueous solution of zinc salt for example, can add zinc oxide, zinc hydroxide, alkaline carbonic acid zinc, zinc sulfate, zinc nitrate etc. and prepares in acidic aqueous solution.As zinc oxide, can use the zinc white that uses as various industrial raw material.As acidic aqueous solution, can enumerate the aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid etc.In addition, also can water-soluble zinc compounds such as zinc chloride be added in the acidic aqueous solution and prepare.
As alkaline aqueous solution, for example, can enumerate the aqueous solution of sodium hydroxide, Pottasium Hydroxide, yellow soda ash etc.Generally speaking, when using sodium hydroxide, Pottasium Hydroxide etc., can make zinc oxide fine particles separate out and carried and hold as alkaline aqueous solution.In addition, when using carbonic acid or when using yellow soda ash etc., can make alkaline carbonic acid zinc separate out and carried and hold as alkaline aqueous solution as acidic aqueous solution.
In addition; The silicate granules that is carried with alkaline carbonic acid zinc can be through following method manufacturing; That is, as stated, through the method for utilizing ammonium salt aqueous solution that the silicate granules that is carried with zinc oxide fine particles is handled; The method that perhaps in the aqueous suspension of the silicate granules that is carried with zinc oxide fine particles, imports carbonic acid gas and carry out carbonating etc. is handled, and the contained zinc oxide fine particles of holding is transformed to alkaline carbonic acid zinc particulate.These methods can be carried out separately, also can be also with two kinds of methods.
As ammonium salt aqueous solution, can enumerate the aqueous solution of volatile caustic, bicarbonate of ammonia, volatile salt etc.These can use separately, also can be also with two or more.
As stated, zinc oxide fine particles is transformed to alkaline carbonic acid zinc particulate, can carries as finer particle and hold through utilizing ammonium salt aqueous solution to handle.
Make zinc oxide fine particles or alkaline carbonic acid zinc particulate the surface of aluminium silicate salt mineral grain separate out and carried hold after, generally fully wash, pulverize after dehydrating.
Polymer compsn of the present invention is characterised in that the mineral-type foaming that contains thermolysis type whipping agent and the invention described above promotes auxiliary agent.
As thermolysis type whipping agent of the present invention, can enumerate organic type of thermolysis type whipping agent and mineral-type thermolysis type whipping agent.
As organic type of thermolysis type whipping agent, so long as the organic type of whipping agent that foams through thermolysis then can use ad lib.As representational organic type of thermolysis type whipping agent, can enumerate ADCA (Cellmic C 121), DPT (dinitrosopentamethylene tetramine), OBSH (p, p '-OBSH), AIBN (Diisopropyl azodicarboxylate) etc.
As mineral-type thermolysis type whipping agent,, for example, can enumerate supercarbonate, carbonate, nitrite etc. so long as the mineral-type whipping agent that foams through thermolysis then can use ad lib.In addition, thermolysis type whipping agent can use separately, also can mix two or more uses.In addition, also can be also with organic type of thermolysis type whipping agent and mineral-type thermolysis type whipping agent.
In the polymer compsn of the present invention, the content that mineral-type foaming promotes auxiliary agent is preferably the scope of 0.5～20 weight part with respect to polymkeric substance 100 weight parts, and the scope of 0.5～15 weight part more preferably further is preferably the scope of 1～10 weight part.If the mineral-type foaming promotes that the content of auxiliary agent is very few, then there is the situation of the big or small fine even and foam that expansion ratio is high that can't form the foaming bubble.In addition, if mineral-type foaming promotes that the content of auxiliary agent is too much, then there are the effect that can't be accompanied with it, the disadvantageous situation that becomes economically.
Thermolysis type whipping agent and mineral-type foaming promote containing of auxiliary agent of proportional not special the qualification; But be preferably with weight ratio (thermolysis type whipping agent: mineral-type foaming promotes auxiliary agent) and count 1: 0.05～3.0 scope, more preferably 1: 0.1～2.6 scope.If the mineral-type foaming promotes that containing of auxiliary agent is proportional very few, then there is the situation that can't make the big or small fine even of foaming bubble and foam with high foamability.In addition, if mineral-type foaming promotes that the content of auxiliary agent is too much, then there are the effect that can't be accompanied with it, the disadvantageous situation that becomes economically.
Polymer compsn of the present invention promotes auxiliary agent owing to contain the mineral-type foaming of the invention described above; So can make the big or small fine of foaming bubble evenly and with higher expansion ratio foams; As purposes, can as the functional porous material with characteristics such as light-duty property, resiliency, heat insulating abilitys, be the expanded plastic that obtains of raw material or the silicon rubber sponge that obtains as raw material with tree elastomer and viton etc. with various Plastic Resins, use in the field according to the various expanded moldings of various raw material institute corresponding method of manufacture, bubble structure, function etc.As typical example, in expanded plastic, can enumerate interior automotive trim material, impact absorbing material, buffer reagent, Perserving materials, insulation wrapping material, ground cushion (mat) material, wrapping material, cushion plate (cushion) material, floating material, epidermis with material, pad (pallet), construction moulding box etc.In rubber sponge, can give an example powder puff, thermal insulation material, packing, heterotypic material, weighting material, submarine armour of shoes materials such as weather strip for automobile and hose protector, various cushion plate, foam sheet, middle level sole and outer shoe, sealing material for building, various filler, various liner (gasket), OA roller, makeup etc.
As polymkeric substance, can enumerate tree elastomer, viton, synthetic resins, thermoplastic elastomer etc.Tree elastomer is meant the polymer substance in the rubber that is obtained by natural phant, as long as have cis-1 on the chemical constitution, 4-TR 301 structure does not then limit shape, tone etc. especially.As viton, can the illustration synthetic polyisoprene, styrene-butadiene rubber(SBR), divinyl rubber, X 050, paracril, butyl rubber, halogenated butyl rubber, ethylene-propylene rubber(EPR), terpolymer EP rubber (EPDM), urethanes, Zylox, viton, chlorosuphonated-polyethylene, ECD, thiorubber etc.As synthetic resins, can use thermoplastic resin and thermosetting resin.As thermoplastic resin; For example, can the illustration Vestolen PP 7052, polyester such as polyamide resin, polycarbonate, polyacetal, PBT, PET, ppe, polyphenylene sulfide, polyetheretherketone, polyaryletherketone, polyamidoimide, polyimide, polyetherimide, polysulfones, polyethersulfone, fluoro-resin, urethane, ionomer, vinylidene chloride, chlorinatedpolyethylenees such as new LDPE (film grade), medium-density polyethylene, high density polyethylene(HDPE), straight chain shape new LDPE (film grade), ultra-low density polyethylene, vinyl-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-propylene copolymer, alfon, ethylene-propylene rubber, polybutylenes, butyl rubber, HIPS, PS, ABS, vinyl chloride resin, methacrylic resin, MMA-styrol copolymer, polyamide 6, polyamide 66, polymeric amide 12, polymeric amide 46, gather Dicyclopentadiene (DCPD), polymethylpentene resin, the plain resin of polyacrylonitrile fibre etc.As thermosetting resin; For example, can illustration resol, epoxy resin such as bisphenol A type epoxy resin, cresols varnish type epoxy resin, phenolic resin varnish type epoxy resin, biphenyl type epoxy resin, naphthalene-ring containing epoxy resin, allyl group phenolic resin varnish type epoxy resin, alicyclic epoxy resin, hetero ring type epoxy resin and their halogenide, urethane (injection molding article with), furane resin, unsaturated polyester, melamine resin, urea resin, allylic resin (DAP), polyimide, silicone resin (containing ambient cure) etc.As thermoplastic elastomer, can the illustration polystyrene-type thermoplastic elastomers, polypropylene-base thermoplastic elastomer, polydiolefin thermoplastic elastomer, chlorine analog thermoplastic elastomer, engineering plastics class elastomerics etc.
The polymer compsn that the present invention put down in writing can carry out crosslinked, also can not carry out crosslinked.When carrying out to use general known materials such as co-crosslinker such as sulphur, organo-peroxide, MOX, resol, zinc oxide, Triple Pressed Stearic Acid, vulcanization accelerator, vulcanization accelerator additive, multi-functional Acrylic Acid Monomer when crosslinked as vulcanization accelerator additive.In the polymer compsn of being put down in writing among the present invention, can use strengthening agent, filling machine, process oil, softening agent, tinting material, antishrinking agent etc. as required.As strengthening agent, can the illustration carbon black, dry type silicon-dioxide, wet silicon dioxide, particulate boehmite etc.As weighting agent, can the illustration water-ground limestone, slight property lime carbonate, colloid lime carbonate, kaolin, talcum, mica, sericite, feldspar, Calucium Silicate powder, alkaline magnesium carbonate, white lake, Marinco H, natural silica, wilkinite, organobentonite etc.They can utilize organic acids such as lipid acid, resinous acid, vinylformic acid, silane coupling agent, titanate coupling agent, aluminum coupling agent etc. to carry out surface treatment.
Compound thermolysis type whipping agent of the present invention is characterised in that the mineral-type foaming of mixture heat decomposition-type foaming agent and the invention described above promotes auxiliary agent.
Compound thermolysis type whipping agent of the present invention promotes auxiliary agent owing to be pre-mixed the foaming of thermolysis type whipping agent and mineral-type, therefore can be more prone to interpolation in polymkeric substance etc.In addition, promote auxiliary agent, therefore can more effectively obtain to make the big or small fine even of foaming bubble and make the effect of the present invention of its foaming with higher multiplying power owing to can be pre-mixed mineral-type foaming with optimum proportion to thermolysis type whipping agent.
Thermolysis type whipping agent in the compound thermolysis type whipping agent and mineral-type foaming promote the blending ratio of auxiliary agent, are preferably the weight ratio of explaining in the ratio that contains in the polymer compsn of the invention described above (thermolysis type whipping agent: the mineral-type foaming promotes auxiliary agent).
The effect of invention
The mineral-type foaming of the application of the invention promotes auxiliary agent, can promote the decomposition of whipping agent with a spot of zinc amount, can make the big or small fine of foaming bubble evenly and with higher expansion ratio make its foaming.
Manufacturing method according to the invention can promote auxiliary agent with the mineral-type foaming of good efficient manufacturing the invention described above.
Polymer compsn of the present invention promotes auxiliary agent owing to contain the mineral-type foaming of the invention described above, therefore can make the big or small fine of foaming bubble evenly and with higher expansion ratio make its foaming.
Description of drawings
Fig. 1 is the photo of expression use according to the cross section of the expanded moldings of the embodiment 8 of the mineral-type foaming promotion auxiliary agent of embodiments of the invention 1.
Fig. 2 is that expression uses the foaming of comparative example 1 to promote the photo in cross section of expanded moldings of the comparative example 2 of auxiliary agent.
Embodiment
Below, utilize embodiment to specify the present invention, still, the present invention does not receive the qualification of following examples.
(embodiment 1)
In having the aggregation container of impeller, add the hydrochloric acid 2025.6g of 36 weight %, add after the ion exchanged water 2.0kg, add zinc oxide (zinc oxide for rubber: 813.9g and dissolving 2 kinds of zinc white).Then, add after the ion exchanged water 15.0kg, the 45.0 weight % that add preparation in advance fire kaolinic slurry 740g, stir to make it in 20 minutes to disperse.Then, under agitation through adding the aqueous sodium hydroxide solution 5.0kg of 16.0 weight % in 60 minutes, add the end back and stirred 60 minutes.Afterwards, dilute, leave standstill, remove the washing step of supernatant repeatedly, wash fully, obtain being carried with the kaolinic suspension liquid of firing of zinc oxide fine particles.
Fire kaolinic suspension liquid and add and have in the aggregation container of impeller resulting, the ammonium bicarbonate aqueous solution 3.20kg that under high-speed stirring, adds 10 weight % stirred 10 minutes.Afterwards, begin to heat up, remain on 70 ℃ and stirred 60 minutes with 1 ℃/minute heat-up rate.
With the dilution of the water of 5 times of amounts, the washing step of supernatant is further diluted, leaves standstill, removed to hold over night and after the slaking, remove supernatant repeatedly, washes fully with resulting resultant.Afterwards, dewater, resulting thickener with 105 ℃ of dryings, is pulverized it with pulverizer, what obtain being carried with alkaline carbonic acid zinc particulate fires the kaolin powder.
(embodiment 2)
Except adding the kaolinic slurry 2714.9g of firing of 45.0 weight % and adding beyond the aqueous sodium hydroxide solution with 1 minute, operate equally with embodiment 1, obtain being carried with the kaolinic suspension liquid of firing of zinc oxide fine particles.This suspension liquid is dewatered, resulting thickener with 105 ℃ of dryings, and is pulverized it with pulverizer, what obtain being carried with zinc oxide fine particles fires the kaolin powder.
(embodiment 3)
Except adding the kaolinic slurry 2714.9g of firing of 45.0 weight %; With added beyond the aqueous sodium hydroxide solution with 1 minute; Operate equally with embodiment 1, preparation is carried with the kaolin of firing of zinc oxide fine particles, and itself and embodiment 1 are operated equally; Utilize ammonium bicarbonate aqueous solution to handle, what obtain being carried with alkaline carbonic acid zinc particulate fires the kaolin powder.
(embodiment 4)
Except adding the kaolinic slurry 4936.2g of firing of 45.0 weight % and adding beyond the aqueous sodium hydroxide solution with 1 minute, operate equally with embodiment 1, obtain being carried with the kaolinic suspension liquid of firing of zinc oxide fine particles.This suspension liquid is dewatered, resulting thickener with 105 ℃ of dryings, and is pulverized it with pulverizer, what obtain being carried with zinc oxide fine particles fires the kaolin powder.
(embodiment 5)
Except adding the kaolinic slurry 4936.2g of firing of 45.0 weight %; With added beyond the aqueous sodium hydroxide solution with 1 minute; Operate equally with embodiment 1, preparation is carried with the kaolin of firing of zinc oxide fine particles, and itself and embodiment 1 are operated equally; Utilize ammonium bicarbonate aqueous solution to handle, what obtain being carried with alkaline carbonic acid zinc particulate fires the kaolin powder.
(embodiment 6)
Except adding the steatitic slurry 1110.0g of 30.0 weight %; With added beyond the aqueous sodium hydroxide solution with 40 minutes; Operate equally with embodiment 1, preparation is carried with the talcum of zinc oxide, and itself and embodiment 1 are operated equally; Utilize ammonium bicarbonate aqueous solution to handle, obtain being carried with the talcum powder of alkaline carbonic acid zinc particulate.
(embodiment 7)
In having the aggregation container of high speed agitator, add the aqueous sodium hydroxide solution 10.0kg of 8.0 weight %, add wollastonite powder 333.0kg, stir and made its dispersion in 20 minutes, the slurry of preparation wollastonite.Then, dissolved oxygen zinc 813.9kg in the hydrochloric acid 2025.6kg of 36.0 weight %, it is 6.0kg that the interpolation ion exchanged water makes total amount, and the acidic aqueous solution for preparing is in advance under agitation added in the slurry with 15 fens clockwise wollastonites.In addition, operate equally with embodiment 1, preparation is carried with the wollastonite of zinc oxide, and itself and embodiment 1 are operated equally, utilizes ammonium bicarbonate aqueous solution to handle, and obtains being carried with the wollastonite powder of alkaline carbonic acid zinc particulate.
(comparative example 1)
In having the aggregation container of impeller, add the hydrochloric acid 2025.6g of 36 weight %, add after the ion exchanged water 2.0kg, add zinc oxide (zinc oxide for rubber: 813.9g and dissolving 2 kinds of zinc white).Then, add after the ion exchanged water 15.0kg dilution,, add the end back and stirred 60 minutes through adding the aqueous sodium hydroxide solution 5.0kg of 16.0 weight % in 1 minute.Afterwards, dilute, leave standstill, remove the washing step of supernatant repeatedly, wash fully, dewater then, resulting thickener with 105 ℃ of dryings, is pulverized it with pulverizer, obtain the zinc oxide end.
As stated, here, do not add and fire kaolinic slurry and the acidic aqueous solution and the alkaline aqueous solution of mixed zinc salts, the preparation zinc oxide fine particles.
[mensuration of BET specific surface area]
The mineral-type foaming of the embodiments of the invention 1～7 that obtain as above operating promotes the zinc oxide of auxiliary agent and comparative example 1, measures the BET specific surface area.The flowing-type specific area measuring device that the BET specific surface area utilizes Micromeritics company to produce is measured.
In addition, as relatively, following commercially available Zinc oxide powder is also measured the BET specific surface area.
2 kinds of zinc white: the commercially available zinc oxide for rubber that makes by method national law (indirect method)
Compound zinc white: the commercially available article of the lime carbonate that coats with zinc oxide
Active zinc white: the commercially available zinc oxide fine particles that latex product that makes with damp process or transparent rubber are used
In addition, represent in the lump that in table 1 Zn in weight, zinc oxide fine particles or the alkaline carbonic acid zinc particulate of Zn converted weight, anhydrous aluminium silicate salt mineral grain of contained zinc oxide fine particles of holding or alkaline carbonic acid zinc particulate is with respect to the Al in the anhydrous aluminium silicate salt mineral grain
2O
3Ratio (Zn/Al
2O
3) the loading amount that converts of mol ratio and Zn.
Embodiment 1, embodiment 3 and embodiment 5 are the kaolin particles of firing that are carried with alkaline carbonic acid zinc particulate.Can know that its BET specific surface area is higher than the embodiment 2 and embodiment 4 that is carried with zinc oxide fine particles.
Can know that in addition mineral-type foaming of the present invention promotes auxiliary agent, compare with the compound zinc white of the lime carbonate of zinc oxide coating to have higher BET specific surface area with conduct.
[mensuration of decomposition temperature and dissolving gas generation]
Use powdered sample as test; Use is with respect to organic type of thermolysis type whipping agent ADCA (Cellmic C 121) powder 1.0g; Add the powder and 2 kinds of zinc white, compound zinc white and the active zinc white powder 0.83g that obtain in embodiment 1～7 and the comparative example 1, thorough mixing and the mixed powder for preparing.In firing boat, take by weighing this mixed powder of about 1g, insert test tube shape Glass tubing and be installed in the tube furnace central part of the heating part that forms dissolving gas generating capacity determinator.Then, connect Glass tubing and take place and heat with 5 ℃/minute heat-up rates after the gas vol measurement section, measure the temperature variation of sample portion and the volume change in the Glass tubing, obtain the decomposition temperature and the dissolving gas generating capacity (ml/g, whipping agent) of sample.Table with test results is shown in Table 2.
[table 2]
| Sample | Decomposition temperature (℃) | Dissolving gas generating capacity (ml/g.ADCA) |
| Embodiment 1 | 147 | 320 |
| Embodiment 2 | 147 | 260 |
| Embodiment 3 | 147 | 300 |
| Embodiment 4 | 147 | 250 |
| Embodiment 5 | 147 | 270 |
| Embodiment 6 | 153 | 300 |
| Embodiment 7 | 153 | 280 |
| Comparative example 1 | 160 | 240 |
| 2 kinds of zinc white | 160 | 200 |
| Compound zinc white | 160 | 220 |
| Active zinc white | 160 | 230 |
| ADCA is independent | 203 | 250 |
Can know that embodiment 1～7 compares with active zinc white with comparative example 1,2 kinds of zinc white, compound zinc white, decomposition temperature reduces, and the dissolving gas generating capacity improves.
[EVA compatibility test]
In EVA (ethylene-vinyl acetate copolymer resin), cooperate the foregoing description 1～5 and comparative example 1,2 kinds of zinc white, compound zinc white and active zinc white.
Use ADCA as whipping agent.Shown in proportioning is for example following, specifically expression in table 3.
EVA resin [Tosoh (strain) produces, ウ Le ト ラ セ Application 630] 100.0 weight parts
Whipping agent ADCA [three associations change into (strain) and produce セ Le マ イ Network one C] 4.0 weight parts
Foaming promotes auxiliary agent 0.5～2.0 weight part
Triple Pressed Stearic Acid (1 grade of reagent) 1.0 weight parts
Linking agent [three new chemistry (strain) are produced Perhexa 3M] 1.0 weight parts
Weighting agent [(strain) Tokuyama produces, magnesiumcarbonate TT] 10.0 weight parts
The limit is with the mixing EVA resin of roller, and above-mentioned various compounding ingredient is added on the limit, adds the mixing dispersion in back and cooperates.Resulting foamed body composition is placed mould, carry out 30 minutes press foamings with 160 ℃, obtain expanded moldings.
To resulting foaming body measurement proportion, its result is shown in the table 3.
In addition, utilize following formula to obtain the volume expansion ratio to resulting expanded moldings.
Volume expansion ratio=[(the volume cm of foam
3Volume=the 93.6cm of)/(mould
3)] * 100
In addition, resulting expanded moldings is observed its cross section, measure the every 1cm in cross section
2In the above bubble quantity and bubble of diameter 0.2mm that exists, this number is estimated as the homogeneity in foam cross section.
Fig. 1 is the photo in cross section of the expanded moldings of expression embodiment 8, and Fig. 2 is the photo in cross section of the expanded moldings of expression comparative example 2.As shown in Figure 2, it is inhomogeneous to foam in the expanded moldings of comparative example 2, so can discern big bubble.Relative therewith, as shown in Figure 1, in the expanded moldings of embodiment 8, there is not the air pocket that can discern as among Fig. 2, and even foaming.
As shown in table 3ly know that use the foaming of embodiments of the invention 1～5 to promote that foam cross section homogeneity is 0 among the embodiment 8～12 of auxiliary agent, it foams equably.Relative therewith, in the comparative example 2～5, can not be foamed uniformly.Particularly use in the comparative example 2 of zinc oxide of comparative example 1, obtain higher relatively expansion ratio, but it is inhomogeneous to foam.Use 2 kinds of commercially available zinc white comparative example 3, use commercially available compound zinc white comparative example 4, use in the comparative example 5 of commercially available active zinc white, expansion ratio is low or foam inhomogeneous.
[EPDM compatibility test]
As shown in table 4, use the foaming of the present invention of embodiment 1, embodiment 4 and embodiment 5 to promote auxiliary agent, and the zinc oxide of comparative example 1,2 kinds of zinc white, compound zinc white and active zinc white, carry out the test that cooperates with EPMD.
The limit is with the mixing EPMD of roller (terpolymer EP rubber), the compounding ingredient except foaming promotes auxiliary agent shown in the limit interpolation table 4 and prepare masterbatch.
Then, with respect to the masterbatch that is equivalent to 100 weight part EPDM, add the foaming shown in the table 4 with the use level shown in the table 4 and promote auxiliary agent down the mixing of roller, preparation rubber foams sheet material.
Resulting rubber foams sheet material is carried out compacting sulfuration in 30 minutes at 170 ℃, obtain EPDM bipeltate sheet material.
Resulting EPDM bipeltate sheet material is measured proportion, and its result is shown in the table 4.
In addition, with the above-mentioned volume expansion ratio of likewise obtaining resulting EPDM bipeltate sheet material, its result is shown in the table 4.
In addition, resulting EPDM bipeltate sheet material is measured compression set.Compression set is obtained as follows, that is, at normal temperatures, be the expanded moldings boil down to thickness 7.62mm of 9.53mm with thickness, keeps decontroling after 10 hours, measures the thickness of decontroling after 1 hour.Measuring the result representes in table 4.
Can know that from the result shown in the table 4 cooperate the foaming of embodiments of the invention 1,4 and 5 to promote that proportion is little among the embodiment 13～15 of auxiliary agent, the volume expansion ratio is high.In addition, know, can access uniform foam according to the compression set I.
Relative therewith, can know that in comparative example 6～9 it is than great, the volume expansion ratio is low.In addition, in the comparative example 10, the amount of the active zinc white that is cooperated is less than comparative example 9, but the proportion of foam diminishes, and it is big that the volume expansion ratio becomes.This thinks owing to the amount that reduces as the zinc oxide of vulcanization accelerator is suppressed sulfuration.But can know that its compression set becomes bigger value, foaming unevenly with the state that contains air pocket.
Relative therewith, but in the knowledge capital inventive embodiment 13～15, make its foaming with volume expansion ratio height and the little state of compression set, and the big or small fine of foaming bubble evenly and with high foamability makes its foaming.
In addition, according to embodiment 14 and 15 and the comparison of comparative example 10 can know, in the embodiments of the invention, even Zn conversion amount is few, also can tight cure, but the mineral-type foaming of knowledge capital invention promotes that auxiliary agent also is effective as vulcanization accelerator.
In addition; In the foregoing description; In rubber, add the foaming of thermolysis type whipping agent and mineral-type of the present invention respectively and promote auxiliary agent; But be pre-mixed that the foaming of thermolysis type whipping agent and mineral-type of the present invention promotes auxiliary agent and when in rubber, adding, also can confirm and likewise or better to obtain effect of the present invention with above-mentioned each embodiment as compound thermolysis type whipping agent.
As stated, the mineral-type of the application of the invention foams and promotes auxiliary agent, can promote the decomposition of whipping agent with a spot of zinc amount, and the big or small fine of foaming bubble evenly and with higher expansion ratio foamed.
Claims (10)
1. a mineral-type foaming that promotes thermolysis type whipping agent to decompose promotes auxiliary agent, it is characterized in that: be carried with zinc oxide fine particles or alkaline carbonic acid zinc particulate on the surface of silicate granules,
The loading amount of zinc oxide fine particles or alkaline carbonic acid zinc particulate converts with metallic zinc, is in the scope of 6～75 weight %,
The BET specific surface area that is carried with the silicate granules of zinc oxide fine particles is in 10～55m
2In the scope of/g,
The BET specific surface area that is carried with the silicate granules of alkaline carbonic acid zinc particulate is in 25～90m
2In the scope of/g.
2. mineral-type foaming as claimed in claim 1 promotes auxiliary agent, and it is characterized in that: silicate granules is the aluminium silicate salt mineral grain.
3. mineral-type foaming as claimed in claim 2 promotes auxiliary agent, it is characterized in that:
The aluminium silicate salt mineral grain is an anhydrous aluminium silicate salt mineral grain.
4. mineral-type foaming as claimed in claim 3 promotes auxiliary agent, it is characterized in that:
Anhydrous aluminium silicate salt mineral grain is with the particle that is selected from least a the firing in kaolinite, halloysite, agalmatolite and the sericite and obtains.
5. promote auxiliary agent like each described mineral-type foaming in the claim 1～4, it is characterized in that: thermal decomposition of blowing agent is an organic type of thermal decomposition of blowing agent.
6. a method of making each described mineral-type foaming promotion auxiliary agent in the claim 1～5 is characterized in that, comprising:
Prepare the operation of the acidic aqueous solution of zinc salt; With
In the presence of silicate granules, the acidic aqueous solution of the mixed-alkali aqueous solution and said zinc salt, thus zinc oxide fine particles or alkaline carbonic acid zinc particulate are separated out, make zinc oxide fine particles or alkaline carbonic acid zinc particulate carry the lip-deep operation of holding said silicate granules.
7. mineral-type foaming as claimed in claim 6 promotes the method for manufacture of auxiliary agent; It is characterized in that: also comprise and utilize ammonium salt aqueous solution that the silicate granules that is carried with zinc oxide fine particles is handled; The contained zinc oxide fine particles of holding is transformed to alkaline carbonic acid zinc particulate, forms the operation of the silicate granules that is carried with alkaline carbonic acid zinc particulate thus.
8. compound thermolysis type whipping agent is characterized in that:
It promotes that through each described mineral-type foaming in mixture heat decomposition-type foaming agent and the claim 1～5 auxiliary agent obtains.
9. polymer compsn is characterized in that:
Contain each described mineral-type foaming promotion auxiliary agent in thermolysis type whipping agent and the claim 1～5.
10. polymer compsn as claimed in claim 9 is characterized in that:
Said mineral-type foaming promotes that the content of auxiliary agent is 0.5～20 weight part with respect to polymkeric substance 100 weight parts.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007-332108 | 2007-12-25 | ||
| JP2007332108 | 2007-12-25 | ||
| PCT/JP2008/003861 WO2009081560A1 (en) | 2007-12-25 | 2008-12-19 | Inorganic foaming accelerator, process for producing the inorganic foaming accelerator, and polymer composition |
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| Publication Number | Publication Date |
|---|---|
| CN101910264A CN101910264A (en) | 2010-12-08 |
| CN101910264B true CN101910264B (en) | 2012-08-29 |
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| CN2008801228728A Active CN101910264B (en) | 2007-12-25 | 2008-12-19 | Inorganic foaming accelerator, process for producing the inorganic foaming accelerator, and polymer composition |
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| Country | Link |
|---|---|
| JP (1) | JP4332587B2 (en) |
| CN (1) | CN101910264B (en) |
| TW (1) | TWI425036B (en) |
| WO (1) | WO2009081560A1 (en) |
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| WO2012108386A1 (en) * | 2011-02-07 | 2012-08-16 | ダイソー株式会社 | Composition for sportswear and foam thereof |
| US10138360B2 (en) * | 2015-01-27 | 2018-11-27 | Toyo Tire & Rubber Co., Ltd. | Rubber composition for vibration damping rubbers, and vibration damping rubber |
| JP7411400B2 (en) * | 2019-12-13 | 2024-01-11 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition for anti-vibration rubber and anti-vibration rubber |
| CN111849032B (en) * | 2020-06-29 | 2022-09-27 | 江苏索普化工股份有限公司 | Low-ammonia foaming promoter and preparation method thereof, foaming material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1357346A (en) * | 1970-07-15 | 1974-06-19 | Ici Ltd | Foams |
| CN1618875A (en) * | 2004-10-09 | 2005-05-25 | 中国科学院长春应用化学研究所 | Peroxide crosslinking poly epsilon caprolactone foam plastic and its preparation method |
| CN101031611A (en) * | 2004-07-13 | 2007-09-05 | 英尼奥斯欧洲有限公司 | Expandable polystyrene composition and process for making same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4444679A (en) * | 1982-07-19 | 1984-04-24 | Uniroyal, Inc. | Blowing agent compositions |
| JPH0565361A (en) * | 1990-11-05 | 1993-03-19 | Kanegafuchi Chem Ind Co Ltd | Foamable composition, rigid foam prepared therefrom, and preparation of rigid foam |
| JPH0699023A (en) * | 1992-09-24 | 1994-04-12 | Fuji Kagaku Kogyo Kk | Granular deodorant composition |
| JP2001303434A (en) * | 2000-04-24 | 2001-10-31 | Lion Corp | Slurry containing photocatalyst |
| JP4664571B2 (en) * | 2002-06-06 | 2011-04-06 | 丸尾カルシウム株式会社 | Foam stabilizer and foam-molded product comprising the same |
-
2008
- 2008-12-18 JP JP2008321846A patent/JP4332587B2/en active Active
- 2008-12-19 CN CN2008801228728A patent/CN101910264B/en active Active
- 2008-12-19 WO PCT/JP2008/003861 patent/WO2009081560A1/en active Application Filing
- 2008-12-25 TW TW97150730A patent/TWI425036B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1357346A (en) * | 1970-07-15 | 1974-06-19 | Ici Ltd | Foams |
| CN101031611A (en) * | 2004-07-13 | 2007-09-05 | 英尼奥斯欧洲有限公司 | Expandable polystyrene composition and process for making same |
| CN1618875A (en) * | 2004-10-09 | 2005-05-25 | 中国科学院长春应用化学研究所 | Peroxide crosslinking poly epsilon caprolactone foam plastic and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| JP昭59-30834A 1984.02.18 |
| JP特开平5-65361A 1993.03.19 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009081560A1 (en) | 2009-07-02 |
| JP4332587B2 (en) | 2009-09-16 |
| TW200948873A (en) | 2009-12-01 |
| JP2009173885A (en) | 2009-08-06 |
| TWI425036B (en) | 2014-02-01 |
| CN101910264A (en) | 2010-12-08 |
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