CN101747543A - Styrene-butadiene copolymer chemical foaming composition containing polystyrene micro-blocks, preparation method and application method thereof - Google Patents
Styrene-butadiene copolymer chemical foaming composition containing polystyrene micro-blocks, preparation method and application method thereof Download PDFInfo
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Abstract
The invention discloses a styrene-butadiene copolymer chemical foaming composition containing polystyrene micro-blocks, a preparation method and an application method thereof. The preparation method takes styrene-butadiene copolymer mixing random structure with block structure as base material, and adds flow modifier or softener to regulate the fluidity of rubber. Rubber compositions manufactured by the method have good fluidity and can be molded directly through injection. Chemical foaming agents added reduces product density and effectively achieves the aim of obtaining lightweight material. Post partial chemical crosslinking can be performed so as to improve the stress cracking resistance and wear resistance of the material. Meanwhile, as the partial physical crosslinking of the styrene-butadiene copolymer allows the material to overcome the defect that all-chemical crosslinked rubber cannot be regenerated, the material can be recycled and regenerated.
Description
Technical field
The present invention relates to the synthetic field of chemical industry, be meant a kind of styrene-butadiene copolymer composition and preparation method's and methods for using them especially.
Background technology
As everyone knows, styrene/butadiene block copolymer (SBS) is that industrialized the earliest vinylbenzene belongs to the monomer base thermoplastic elastomer.SBS can be used for for example preparing sole, tackiness agent, daily elastomerics, modifying asphalt and plastics.The Application Areas of SBS maximum is a sole, and sole has accounted for more than 50% of world SBS consumption with SBS.
The lightweight of SBS footwear material is the developing direction of SBS footwear material always, and foaming is the most effective means of footwear material lightweight.SBS footwear material lightweight at present is a main direction of studying to decompose the physical blowing that low-boiling point liquid gasifies in the chemical foaming that produces gas and the foam microspheres by chemical foaming agent (as the AC whipping agent) mainly.
The chemical foaming of SBS footwear material: because traditional SBS is the segmented copolymer that is separated, the shear viscosity of its melt is very insensitive to temperature and shearing rate.SBS cinnamic physical entanglement meeting in the course of processing causes its melt viscosity inequality (PB segment viscosity is low, PB and PS phase interface viscosity height), and it is inhomogeneous to make that the AC whipping agent disperses, and causes the abscess inequality.Therefore the tear strength of SBS foaming back goods, tensile strength, wear resistance etc. can not satisfy the requirement of sole.For the tensile strength that improves foaming product, tear strength, chemically-resistant solvent, performance such as wear-resisting, a method is to add linking agent in foaming process, but there are two difficulties that are difficult to overcome in this: the one, and the adding problem of linking agent, the decomposition temperature of general linking agent is below 140 ℃, and the plasticization temperature of SBS is more than 170 ℃; The 2nd, two key density height of the polyhutadiene phase of traditional SBS " glue burnings " (the chain type thermopositive reaction rapidly of a kind of utmost point) phenomenon can occur under the linking agent effect, and production is difficult to carry out or exists potential safety hazard or product percent of pass low.
The physical blowing of SBS footwear material: owing to can realize injecting continuously foam-in-mould, and obtain controlled foaming thing cortex and improve wear resistance, the SBS physical blowing that adopts foam microspheres or micro mist is the focus of synthetic rubber footwear material research always, but because SBS is a thermoplastic elastomer, therefore, under the effect of foam microspheres long-term tension,, the molecular chain legibility cause footwear material surface be full of cracks even phenomenon of rupture under no luminous environment, also can occur even twining.Therefore, this series products can not get promoting the use of on a large scale all the time.
Because there are above many defectives in the SBS foaming shoe material, cause the sole that SBS makes the density height, wear no resistance, therefore progressively substituted in recent years by other can foam light material such as EVA, urethane (PU) etc.
At present the plastic properties that present such as the tensile strength of the EVA foaming product that uses, tear strength, compression set, wear-resisting, non-skid property can not satisfy the requirement of shoe-making industry fully.Although the wear-resisting excellent property of urethane, also there is shortcoming in foaming raw material at the bottom of the polyurethane shoe, and for example the toxic of heat-curable urethane facility investment height, urethane monomer is big, foam process complexity etc.
Therefore, be desirable to provide novel injectable crosslinkable chemical foaming styrene-butadiene copolymer (SBS) composition that can be used for shoe sole applications.
There have been a large amount of documents and patent to be introduced about styrene-butadiene copolymer, about rubber, thermoplastic elastomer foaming a large amount of introductions arranged also simultaneously.Such as, Chinese patent (CN 101113188A) has been introduced a kind of continuous preparation method of random conjugated diene/vinyl arene copolymers.This patent is defined as vinylbenzene with vinyl-arene, and conjugated diolefine is defined as 1,3 divinyl, and the molecular weight of this multipolymer is 200,000-800, and 000, monodisperse system is counted Mw/Mn=1.6-2.5.This kind multipolymer is designed for the doughnut tyre surface.This copolymer molecule chain is a linear structure, has hinted in the patent that its preparation method can produce the multipolymer with specific degree of branching, and has not carried out the coupling step with close isoelectric substance (as SiCl4).The structure difference of the star structure multipolymer in this and this patent is bigger.Molecular weight of copolymer in the above-mentioned patent is excessive simultaneously, infers because melt viscosity is crossed senior general and can't be foamed according to general knowledge, more can not carry out injection moulding processing.
United States Patent (USP) (USP 4367325) has been introduced a kind of styrene/butadiene random copolymers and production method thereof.The styrene monomer content of this styrene/butadiene random copolymers is 3-30%, and 1,2 paradigmatic structure content of divinylic monomer is 70-90%.This multipolymer is used to produce doughnut, has low rolling resistance and high anti-slippery ability.This multipolymer styrene monomer content lower (being 35-50% in this patent), the melt viscosity height can not carry out injection moulding processing.
Chinese patent (CN 101255242A) has been introduced a kind of butadiene styrene rubber foaming plate and preparation method thereof.The base mateiral that this patent adopts is styrene-butadiene rubber(SBR), natural rubber and cis-1,4-polybutadiene rubber, and the molecular weight of these materials is all excessive, causes the melt viscosity of material big, can't inject processing.This patent adopts sulfur cross-linking system simultaneously, and curing temperature is low, promptly takes place crosslinkedly easily in the injector screw rod, and this formula system also can't be injected processing.
Summary of the invention
First purpose of the present invention is in order to overcome the shortcoming and defect that prior art exists, and a kind of styrene-butadiene copolymer chemical foaming composition that comprises the polystyrene section is provided.
Second purpose of the present invention provides a kind of preparation method who comprises the styrene-butadiene copolymer chemical foaming composition of polystyrene micro-blocks.
The 3rd purpose of the present invention provides a kind of method that is applied to injection moulding production foaming product that comprises the styrene-butadiene copolymer chemical foaming composition of polystyrene micro-blocks.
The 4th purpose of the present invention provides the foaming product that styrene-butadiene copolymer chemical foaming composition that a kind of basis comprises polystyrene micro-blocks makes.
For realizing first purpose of the present invention, technical scheme of the present invention is that each proportioning raw materials is, and is wherein according to the mass fraction raw materials used:
40～70 parts of styrene-butadiene copolymers
9～30 parts of flow ability modifying agents
10～50 parts of tenderizers
0.1～2 part of chemical foaming agent
0～30 part of rubber
0～30 part of filler
0～30 part of reworked material
0.1～1 part of vulcanizing agent
0.1～1 part of vulcanization aid
The molecular structure of described styrene-butadiene copolymer is a linear structure when further being provided with, its molecular structural formula is-and (PSx-PBy) n-, wherein
PS is a styrenic polymer,
PB is a butadiene polymer,
x＝1-300，y＝1-2000，n＝10-3000；
The weight percentage of styrene monomer is 5-80% in the styrene-butadiene copolymer altogether, the number-average molecular weight of multipolymer is 40000-500000, styrene monomer and divinylic monomer are the alternately micro-block structure of the repeatedly block copolymerization formation of complete random copolymerization structure or styrene monomer and divinylic monomer in the molecular chain structure of this polymkeric substance, 1 in the divinylic monomer wherein, the 2-structural content is 10～40%.
This is provided with can also be that the molecular structure of described styrene-butadiene copolymer is the multi-arm star structure, and its molecular structural formula is ((PSx-PBy) n-) mR, wherein
PS is a styrenic polymer,
PB is a butadiene polymer,
R is star structure " nuclear ",
x＝1-300，y＝1-2000，n＝10-3000，m＝3-20；
The weight percentage of styrene monomer is 5-80% in this styrene-butadiene copolymer.The number-average molecular weight of multipolymer is 40000-500000, the alternately micro-block structure that the repeatedly block copolymerization of the complete random copolymerization structure of styrene monomer and divinylic monomer or styrene monomer and divinylic monomer forms in the molecular chain structure of this polymkeric substance, 1 in the divinylic monomer wherein, the 2-structural content is 10～40%.
Described rubber can be selected at least a in natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, polyisoprene rubber, paracril, isoprene-isobutylene rubber, halogenated butyl rubber, ethylene-propylene rubber(EPR), the terpolymer EP rubber for use.This setting is by adding a certain specified property that rubber can improve foam material, can improve tensile strength such as natural rubber, cis-1,4-polybutadiene rubber can improve elasticity and wear resisting property, and paracril can improve oil resistance, and halogenated butyl rubber can improve oil resistant and non-skid property;
Described flow ability modifying agent can be selected at least a in styrene-butadiene-styrene multipolymer, styrene-ethylene-butylene-styrene multipolymer, styrene-ethylene-propylene-styrene multipolymer, ethylene-vinyl acetate copolymer, the ethylene-octene copolymer for use.
Described filler can be selected at least a in carbon black, silicon-dioxide, lime carbonate, talcum powder, the potter's clay for use.
Described reworked material can be selected at least a in regenerated rubber, regnerated rubber powder, EVA regeneration powder sheet or EVA regeneration powder particles, TR or TPR reworked material, PU powder, recycled polyethylene, the polypropene recycled materials for use.This is provided with and adds reworked material and material is not significantly reduced under the prerequisite of performance reduce cost.
Described tenderizer can be selected at least a in naphthenic oil, alkane oil, aromatic hydrocarbon oil, machinery oil, lubricating oil, paraffin, whiteruss, petroleum pitch, Vaseline, coal tar, Viscotrol C, linseed oil, ointment, the atactic polypropylene(APP) for use.
Described vulcanizing agent can be selected benzoyl peroxide, biconjugate benzoyl peroxide, ditertiary butyl peroxide, dicumyl peroxide, hydrogen phosphide cumene, tert-butyl peroxide cumyl, di-t-butyl peroxide-3 for use, 3,5-trimethyl-cyclohexane, 2,5-dimethyl-2, at least a in 5-two (t-butyl peroxy) hexane.
Described vulcanization aid can be selected at least a in sulphur, paraquinonedioxime, dimethacrylate macrogol ester, trimethylolpropane tris (2-methacrylic acid) ester, iso-cyanuric acid triallyl ester, para Toluic Acid's diallyl, the Vinylstyrene for use.
Described chemical foaming agent is sodium bicarbonate, yellow soda ash, bicarbonate of ammonia, volatile salt, ammonium nitrate, N; N '-dimethyl-N; N '-dinitroso pentamethylene tetramine, N, at least a in N '-dinitroso five methyne tetramines, Diisopropyl azodicarboxylate, azo two cyclohexanenitriles, azo diaminobenzene, barium azodicarboxylate, Cellmic C 121, benzol sulfohydrazide, toluene sulfonyl hydrazide, two benzol sulfohydrazide ethers, azide calcium, the azide p-toluenesulfonyl.
Also include the auxiliary agent that adds according to different part performance needs, this auxiliary agent is one or more in frothing aid, softening agent, anti-aging agent, thermo-stabilizer, anti ultraviolet agent, static inhibitor, tinting material, releasing agent, strengthening agent, fire retardant, viscosity increaser, the tack reducing material.This addition that each auxiliary agent is set can be controlled according to actual needs, is limit not damage beneficial effect of the present invention.
Find that through the inventor's years of researches styrene-butadiene copolymer composition that comprises the little block of vinylbenzene has good injectable chemical foaming performance, this is because this styrene-butadiene copolymer that comprises polystyrene micro-blocks has suitable molecular weight and styrene monomer content, therefore under hot-work, have lower melt viscosity, can inject processing easily.And lower melt viscosity makes chemical foaming agent be uniformly dispersed easily and even foaming.Under the chemical cross-linking agent effect by these cross-linking set formed copolymer molecule network can finely avoid under the effect of chemical foaming agent long-term tension the styrene-butadiene copolymer molecular chain to separate twining check surface of footwear material even the footwear material phenomenon of rupture that is caused.Because the little block of polyhutadiene hydrocarbon is evenly distributed in the polystyrene micro-blocks, fundamentally avoided because polyhutadiene is assembled the crosslinked thermopositive reaction of quick chain type that causes, so also can not produce SBS " glue burning " phenomenon.This copolymer structure design not only guarantees to adopt the foam material of this multipolymer production to have the elasticity of enough rubber like materials, and the polystyrene of part belongs to physical crosslinking that the little block of monomer forms and gives this material and still keep the renewable processing characteristics of conventional SBS, has environmental protection characteristic.Therefore this kind multipolymer can be used for shoe sole production.And described multipolymer can adopt existing foam-injection production equipment to produce at low cost.Whipping agent adopts general chemical foaming agent, compares with the physical blowing that contains foam microspheres, has lower-cost advantage.
For realizing second purpose of the present invention; technical scheme of the present invention is may further comprise the steps; wherein raw materials used proportioning preparation: at first with styrene-butadiene copolymer by claim 1; flow ability modifying agent; rubber; filler; reworked material; tenderizer; and auxiliary agent is put into the Banbury mixer banburying simultaneously; mixed 5～30 minutes; add vulcanizing agent then; vulcanization aid; chemical foaming agent; mixed 2～5 minutes; 60～120 ℃ of Banbury mixer temperature; sizing material after the banburying is mixed with mill; sheet down after the thin-pass 5～20 times is used sizing material the forcing machine extruding pelletization at last, and extruder temperature is 60～110 ℃; by vane pelletizing or water ring pelletizing.
For realizing second purpose of the present invention; technical scheme of the present invention can also be may further comprise the steps; wherein raw materials used proportioning preparation: at first will be by the flow ability modifying agent of the described proportioning of claim 1 by claim 1; tenderizer is put into the Banbury mixer banburying; mixed 2～15 minutes; add styrene-butadiene copolymer then; rubber; filler; reworked material and auxiliary agent; mixed 3～15 minutes; add vulcanizing agent again; vulcanization aid; chemical foaming agent; mixed 2～5 minutes; 60～120 ℃ of Banbury mixer temperature; sizing material after the banburying is mixed with mill; sheet down after the thin-pass 5～20 times; at last sizing material is used the forcing machine extruding pelletization, extruder temperature is 60～110 ℃, by vane pelletizing or water ring pelletizing.
For realizing second purpose of the present invention; technical scheme of the present invention can also be may further comprise the steps; wherein raw materials used proportioning preparation by claim 1: at first with the styrene-butadiene copolymer of certain proportioning; flow ability modifying agent; rubber; filler; reworked material; tenderizer; and auxiliary agent is put into the Banbury mixer banburying simultaneously; mixed 5～30 minutes; 100～160 ℃ of Banbury mixer temperature; sizing material after the banburying is in blocks with mill; add vulcanizing agent; vulcanization aid; chemical foaming agent; sheet down after the thin-pass 10～30 times; at last sizing material is used the forcing machine extruding pelletization; 60～110 ℃ of extruder temperatures are by vane pelletizing or water ring pelletizing.Because reworked material is that the higher material of some melt temperature is as regeneration PP, PE, during banburying temperature is improved, if in Banbury mixer, add vulcanizing agent, vulcanization aid, chemical foaming agent, vulcanizing agent, vulcanization aid, chemical foaming agent will be decomposed, therefore sizing material is put in the mill of normal temperature and adds vulcanizing agent, vulcanization aid, chemical foaming agent again after the cooling in flakes.
For realizing the 3rd purpose of the present invention, the method of foaming product is produced in composition injection moulding of the present invention, it is characterized in that: the styrene-butadiene copolymer chemical foaming composition that will contain polystyrene micro-blocks mixes and granulation under the temperature below 120 ℃ with processing aid, linking agent and whipping agent, then the pellet that obtains is injected mould and carries out foam-injection therein through injection moulding machine, obtain foaming product.
For realizing the 4th purpose of the present invention, the density of this foaming product of the present invention: 0.2～1.0 (g/cm3).This foaming product can be used for making at the bottom of beach shoes, slippers, sneakers, the sports shoes and the big end of leather shoes, perhaps is used for automobile interior trim material and lagging material
Beneficial effect of the present invention
1) compare with this styrene-butadiene copolymer physical blowing composition that contains foam microspheres, the foam-in-mould difficulty, but this styrene-butadiene copolymer chemical foaming composition has the low advantage of cost, and the mould that is fit to high foamability foams outward.
2) this styrene-butadiene copolymer composition foaming product can adopt on existing EVA foam-injection equipment and the rubber plate vulcanization equipment and produce, and production unit need not to transform.
3) this styrene-butadiene copolymer has suitable molecular weight and styrene monomer content, therefore has lower melt viscosity under hot-work, can make this styrene-butadiene copolymer composition inject processing easily.And lower melt viscosity makes chemical foaming agent be uniformly dispersed easily and even foaming.
4) this styrene-butadiene copolymer composition under the chemical cross-linking agent effect by these cross-linking set formed copolymer molecule network can finely avoid under the effect of foam microspheres long-term tension the styrene-butadiene copolymer molecular chain to separate twining check surface of footwear material even the footwear material phenomenon of rupture that causes as conventional SBS.
5) foam material of this styrene-butadiene copolymer composition still keeps rubber property, excellent wet-sliding resistant performance, and compression set is low, and elastic recovery is good, and wear resistance, tensile strength at yield and tear strength all are better than the EVA foam material.
6) foamed products of this styrene-butadiene copolymer composition can be used to make beach shoes and slippers, can also be used for making at the bottom of sneakers, the sports shoes and the big end of leather shoes, also can be used for the lagging material of automobile interior trim material and various occasions.
Below in conjunction with embodiment the present invention is done further introduction.
Embodiment
Below by embodiment the present invention is carried out concrete description; only be used for the present invention is further specified; can not be interpreted as the qualification to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Embodiment 1
By following component and content (mass parts)
50 parts of styrene-butadiene copolymers
10 parts of cis-1,4-polybutadiene rubbers
5 parts of styrene-butadiene-styrene multipolymers
4 parts of silica 1s
10 parts of regenerated rubbers
10 parts of naphthenic oils
0.4 part of dicumyl peroxide
0.3 part of iso-cyanuric acid triallyl ester
0.3 part of Cellmic C 121
At first styrene-butadiene copolymer, styrene-butadiene-styrene multipolymer, cis-1,4-polybutadiene rubber, silicon-dioxide, regenerated rubber, the naphthenic oil of said ratio are put into the Banbury mixer banburying simultaneously, mixed 5 minutes.Add dicumyl peroxide, iso-cyanuric acid triallyl ester, Cellmic C 121 then, mixed 2 minutes, 100 ℃ of Banbury mixer temperature are mixed the sizing material after the banburying with mill, sheet down after the thin-pass 10 times.At last sizing material is used the forcing machine extruding pelletization, extruder temperature is 80 ℃, by the vane pelletizing.
Embodiment 2
By following component and content (mass parts)
40 parts of styrene-butadiene copolymers
10 parts of terpolymer EP rubbers
15 parts of ethylene-vinyl acetate copolymers
13.5 parts of talcum powder
10 parts in regeneration EVA powder
10 parts in machinery oil
0.2 part of tert-butyl peroxide cumyl
0.3 part of trimethylolpropane tris (2-methacrylic acid) ester
1 part of Cellmic C 121
At first styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, terpolymer EP rubber, talcum powder, regeneration EVA powder, the machinery oil of said ratio are put into the Banbury mixer banburying simultaneously, mixed 5 minutes.Add tert-butyl peroxide cumyl, trimethylolpropane tris (2-methacrylic acid) ester, Cellmic C 121 then, mixed 2 minutes, 100 ℃ of Banbury mixer temperature are mixed the sizing material after the banburying with mill, sheet down after the thin-pass 10 times.At last sizing material is used the forcing machine extruding pelletization, extruder temperature is 80 ℃, by the vane pelletizing.
Embodiment 3
By following component and content (mass parts)
49 parts of styrene-butadiene copolymers
10 parts of paracrils
5 parts of styrene-ethylenes-propylene-styrene multipolymer
3.5 parts of silica 1s
10 parts of regnerated rubber powders
10 parts of aromatic hydrocarbon oil
0.2 part of tert-butyl peroxide cumyl
0.3 part of trimethylolpropane tris (2-methacrylic acid) ester
2 parts of Cellmic C 121s
At first styrene-ethylene-propylene-styrene multipolymer, the aromatic hydrocarbon oil of said ratio are put into the Banbury mixer banburying, mixed 3 minutes, add styrene-butadiene copolymer, paracril, silicon-dioxide, regnerated rubber powder then, mixed 8 minutes, add tert-butyl peroxide cumyl, trimethylolpropane tris (2-methacrylic acid) ester, Cellmic C 121 again, mixed 100 ℃ of Banbury mixer temperature 2 minutes, sizing material after the banburying is mixed sheet down after the thin-pass 10 times with mill.At last sizing material is used the forcing machine extruding pelletization, extruder temperature is 70 ℃, by the vane pelletizing.
Embodiment 4
By following component and content (mass parts)
70 parts of styrene-butadiene copolymers
9 parts of styrene-ethylenes-propylene-styrene multipolymer
0 part of silica 1
10 parts of aromatic hydrocarbon oil
0.2 part of dicumyl peroxide
0.3 part of trimethylolpropane tris (2-methacrylic acid) ester
0.5 part in two benzol sulfohydrazide ethers
At first styrene-butadiene copolymer, styrene-ethylene-propylene-styrene multipolymer, silicon-dioxide, the aromatic hydrocarbon oil of said ratio are put into the Banbury mixer banburying simultaneously, mixed 8 minutes.Add dicumyl peroxide, trimethylolpropane tris (2-methacrylic acid) ester, two benzol sulfohydrazide ethers then, mixed 2 minutes, 100 ℃ of Banbury mixer temperature are mixed the sizing material after the banburying with mill, sheet down after the thin-pass 10 times.At last sizing material is used the forcing machine extruding pelletization, extruder temperature is 80 ℃, by the vane pelletizing.
Embodiment 5
By following component and content (mass parts)
53.5 parts of styrene-butadiene copolymers
10 parts of cis-1,4-polybutadiene rubbers
5 parts of styrene-butadiene-styrene multipolymers
0 part of silica 1
10 parts of regenerating polypropylenes
10 parts of alkane oil
0.2 part of dicumyl peroxide
0.3 part of iso-cyanuric acid triallyl ester
1 part in two benzol sulfohydrazide ethers
At first with the styrene-butadiene copolymer of said ratio, styrene-butadiene-styrene multipolymer, cis-1,4-polybutadiene rubber, silicon-dioxide, regenerating polypropylene, alkane oil, put into the Banbury mixer banburying simultaneously, mixed 10 minutes, 160 ℃ of Banbury mixer temperature, sizing material after the banburying is in blocks with mill, add dicumyl peroxide, iso-cyanuric acid triallyl ester, two benzol sulfohydrazide ethers, sheet down after the thin-pass 10 times, at last sizing material is used the forcing machine extruding pelletization, 90 ℃ of extruder temperatures are by the water ring pelletizing.
The foaming product performance test
The rubber particles that embodiment is made passes through injector injection molding, makes foam sheet.The injection mould has heating unit, can be heated to 200 ℃ mould is the highest.
Annotate: 1. the melting index test condition is 200 ℃, 5Kg; Do not add vulcanizing agent during the melting index test
2. specimen preparation condition: 70 ℃ of injection temperatures, 170 ℃ of die temperatures, 300 seconds dwell times of heating
Claims (10)
1. styrene-butadiene copolymer chemical foaming composition that contains polystyrene micro-blocks,
It is characterized in that each proportioning raw materials is, wherein according to the mass fraction raw materials used:
40～70 parts of styrene-butadiene copolymers
9～30 parts of flow ability modifying agents
10～50 parts of tenderizers
0.1～2 part of chemical foaming agent
0～30 part of rubber
0～30 part of filler
0～30 part of reworked material
0.1～1 part of vulcanizing agent
0.1～1 part of vulcanization aid
2. the styrene-butadiene copolymer chemical foaming composition that contains polystyrene micro-blocks according to claim 1, it is characterized in that: the molecular structure of described styrene-butadiene copolymer is a linear structure, its molecular structural formula is-(PSx-PBy) n-, wherein
PS is a styrenic polymer,
PB is a butadiene polymer,
x＝1-300，y＝1-2000，n＝10-3000；
The weight percentage of styrene monomer is 5-80% in the styrene-butadiene copolymer altogether, the number-average molecular weight of multipolymer is 40000-500000, styrene monomer and divinylic monomer are the alternately micro-block structure of the repeatedly block copolymerization formation of complete random copolymerization structure or styrene monomer and divinylic monomer in the molecular chain structure of this polymkeric substance, 1 in the divinylic monomer wherein, the 2-structural content is 10～40%.
3. the styrene-butadiene copolymer chemical foaming composition that contains polystyrene micro-blocks according to claim 1, it is characterized in that: the molecular structure of described styrene-butadiene copolymer is the multi-arm star structure, its molecular structural formula is ((PSx-PBy) n-) mR
Wherein
PS is a styrenic polymer,
PB is a butadiene polymer,
R is star structure " nuclear ",
x＝1-300，y＝1-2000，n＝10-3000，m＝3-20；
The weight percentage of styrene monomer is 5-80% in this styrene-butadiene copolymer, the number-average molecular weight of multipolymer is 40000-500000, the alternately micro-block structure that the repeatedly block copolymerization of the complete random copolymerization structure of styrene monomer and divinylic monomer or styrene monomer and divinylic monomer forms in the molecular chain structure of this polymkeric substance, 1 in the divinylic monomer wherein, the 2-structural content is 10～40%.
4. according to claim 1 or 2 or 3 described a kind of SB chemical foaming compositions that contain polystyrene micro-blocks; It is characterized in that: described rubber can be selected natural rubber; Butadiene-styrene rubber; Butadiene rubber; Polyisoprene rubber; Acrylonitrile-butadiene rubber; Butyl rubber; Halogenated butyl rubber; EP rubbers; At least a in the ethylene propylene diene rubber; Described flow ability modifying agent can be selected styrene-butadiene-styrene; The styrene-ethylene-butylene-styrene copolymer; Styrene-ethylene-propylene-styrene copolymer; Ethylene-vinyl acetate copolymer; At least a in the ethylene-octene copolymer; Described filler can be selected carbon black; Silica; Calcium carbonate; Talcum powder; At least a in the potter's clay; Described reworked material can be selected reclaimed rubber; Regnerated rubber powder; EVA regeneration powder sheet or EVA regeneration powder particles; TR or TPR reworked material; The PU powder; Recycled polyethylene; At least a in the polypropene recycled materials; Described softening agent can be selected naphthenic oil; Alkane oil; Aromatic naphtha; Machinery oil; Lubricating oil; Paraffin; Atoleine; Asphalt; Vaseline; Coal tar; Castor oil; Linseed oil; Ointment; At least a in the atactic polypropylene; Described vulcanizing agent can be selected benzoyl peroxide; The biconjugate benzoyl peroxide; Di-tert-butyl peroxide; Cumyl peroxide; Hydrogen phosphide cumene; The tert-butyl peroxide cumyl; Di-t-butyl peroxide-3; 3; The 5-trimethyl-cyclohexane; 2; 5-dimethyl-2; The 5-(t-butyl peroxy) at least a in the hexane; Described vulcanization aid can be selected sulphur; Paraquinonedioxime; PEGDMA-400; Trimethylolpropane tris (2-methacrylic acid) ester; Iso-cyanuric acid triallyl ester; Para Toluic Acid's diallyl; At least a in the divinylbenzene; Described CBA is sodium acid carbonate; Sodium carbonate; Carbonic hydroammonium; Ammonium carbonate; Ammonium nitrate; N; N '-dimethyl-N; N '-dinitroso pentamethylene tetramine; N, N '-dinitrosopentamethlyene tetramine; Azodiisobutyronitrile; Azo two cyclohexanenitriles; The azo diaminobenzene; Barium azodicarboxylate; Celogen Az; Benzene sulfonyl hydrazide; Toluene sulfonyl hydrazide; Two benzene sulfonyl hydrazide ethers; Azide calcium; At least a in the Azide p-toluenesulfonyl.
5. according to claim 4 one contains the styrene-butadiene copolymer chemical foaming composition of polystyrene micro-blocks, it is characterized in that: also include the auxiliary agent that adds according to different part performance needs, this auxiliary agent is one or more in frothing aid, softening agent, anti-aging agent, thermo-stabilizer, anti ultraviolet agent, static inhibitor, tinting material, releasing agent, strengthening agent, fire retardant, viscosity increaser, the tack reducing material.
6. method for preparing the styrene-butadiene copolymer chemical foaming composition that contains polystyrene micro-blocks; it is characterized in that may further comprise the steps; wherein raw materials used proportioning preparation: at first with styrene-butadiene copolymer by claim 1; flow ability modifying agent; rubber; filler; reworked material; tenderizer; and auxiliary agent is put into the Banbury mixer banburying simultaneously; mixed 5～30 minutes; add vulcanizing agent then; vulcanization aid; chemical foaming agent; mixed 2～5 minutes; 60～120 ℃ of Banbury mixer temperature; sizing material after the banburying is mixed with mill; sheet down after the thin-pass 5～20 times; at last sizing material is used the forcing machine extruding pelletization; extruder temperature is 60～110 ℃; by vane pelletizing or water ring pelletizing.
7. method for preparing the styrene-butadiene copolymer chemical foaming composition that contains polystyrene micro-blocks; it is characterized in that may further comprise the steps; wherein raw materials used proportioning preparation: at first will be by the flow ability modifying agent of the described proportioning of claim 1 by claim 1; tenderizer is put into the Banbury mixer banburying; mixed 2～15 minutes; add styrene-butadiene copolymer then; rubber; filler; reworked material and auxiliary agent; mixed 3～15 minutes; add vulcanizing agent again; vulcanization aid; chemical foaming agent; mixed 2～5 minutes; 60～120 ℃ of Banbury mixer temperature; sizing material after the banburying is mixed with mill; sheet down after the thin-pass 5～20 times; at last sizing material is used the forcing machine extruding pelletization, extruder temperature is 60～110 ℃, by vane pelletizing or water ring pelletizing.
8. method for preparing the styrene-butadiene copolymer chemical foaming composition that contains polystyrene micro-blocks; it is characterized in that may further comprise the steps; wherein raw materials used proportioning preparation by claim 1: at first with the styrene-butadiene copolymer of certain proportioning; flow ability modifying agent; rubber; filler; reworked material; tenderizer; and auxiliary agent is put into the Banbury mixer banburying simultaneously; mixed 5～30 minutes; 100～160 ℃ of Banbury mixer temperature; sizing material after the banburying is in blocks with mill; add vulcanizing agent; vulcanization aid; chemical foaming agent; sheet down after the thin-pass 10～30 times; at last sizing material is used the forcing machine extruding pelletization; 60～110 ℃ of extruder temperatures are by vane pelletizing or water ring pelletizing.
9. one kind is applied to the method that foaming product is produced in injection moulding according to the described composition of one of claim 1-5, it is characterized in that: the styrene-butadiene copolymer chemical foaming composition that will contain polystyrene micro-blocks mixes and granulation under the temperature below 120 ℃ with processing aid, linking agent and whipping agent, then the pellet that obtains is injected mould and carries out foam-injection therein through injection moulding machine, obtain foaming product.
10. the foaming product that method according to claim 9 obtains is characterized in that: the density of this foaming product: 0.2～1.0 (g/cm
3).
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