CN106147106A - A kind of styrene-ethylene-ethylene-propylene-based block copolymer modified foaming body and preparation method and application - Google Patents
A kind of styrene-ethylene-ethylene-propylene-based block copolymer modified foaming body and preparation method and application Download PDFInfo
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- CN106147106A CN106147106A CN201510138851.7A CN201510138851A CN106147106A CN 106147106 A CN106147106 A CN 106147106A CN 201510138851 A CN201510138851 A CN 201510138851A CN 106147106 A CN106147106 A CN 106147106A
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Abstract
The present invention is a kind of soft low compression deformation, and stretching resistance is big, high bounce-back, can be with the styrene-ethylene-ethylene of recycling-propylene-based block copolymer foaming body and preparation method and application.The mass ratio of described styrene-ethylene-ethylene-propylene-based block copolymer, ethylene ethyl acetate copolymer, softening oil, rubber, described foaming agent, described bridging agent, described activating agent and described zinc oxide is 30-60:10-50:10-110:5-35:1-12: 0.5-1.5:0.5-2.2:1-2.3, the soft high bounce-back of the foaming product that is made from, compression resistant are askew, good endurance, are applicable to as the higher foaming product of the askew performance requirement of compression resistant.
Description
Technical field
The present invention relates to a kind of styrene-ethylene-ethylene-propylene-based block copolymer foaming body and preparation method and application.
Background technology
Ethylene ethyl acetate copolymer (being called for short EVA) is uniformly to mix EVA raw material, prepare foaming master batch through banburying unit high pressure banburying granulation, inject to mould by pipeline, then sulfuration on the product obtaining and vulcanizing press of foaming outside mould obtains goods, known general ethene and acetate ethylene copolymer (EVA) foam material are at the middle end of most footwear material especially sport footwears or shoe-pad, the auxiliary material of sports goods, the industrial production such as box material have a wide range of applications, what this had benefited from them has good plasticity, elastic, machinability, after foaming, density of material is little, the advantages such as mechanical property is good.
There is not on-slip and the shortcoming such as compression is big in general EVA product, high bounce-back not, has very big obstacle and limitation to follow-up production and use, accessory during foam production is many, it is therefore contemplated that a kind of on-slip and compression diminish, stretching resistance is big, bounce-back height, foam performance and mechanical property are excellent, and expansion ratio is high, bubble is uniform, and light weight is heat-resist, excellent in durability, tensile property is good, and shock resistance is excellent, can be with recycling.The present invention provides on-slip and compression little, and stretching resistance is big, and rebound high a kind of styrene-ethylene-ethylene-propylene-based block copolymer foaming body.
Content of the invention
It is an object of the invention to provide a kind of soft low compression deformation, stretching resistance is big, high bounce-back, can be with the styrene-ethylene-ethylene of recycling-propylene-based block copolymer foaming body and preparation method and application.
A kind of styrene-ethylene-ethylene-propylene-based block copolymer foaming body that the present invention provides includes styrene-ethylene-ethylene-propylene-based block copolymer, ethylene ethyl acetate copolymer, softening oil, rubber, foaming agent, bridging agent, activating agent and zinc oxide.
Above-mentioned a kind of styrene-ethylene-ethylene-propylene-based block copolymer modified foaming body includes said components.
Wherein, described styrene-ethylene-ethylene-propylene-based block copolymer is the polymer of the block being made up of the styrene monomer hydrogenating and rubber monomer, and it shows the feature of rubber within the scope of wider temperature；
The weight/mass percentage composition of ethyl acetate in described ethylene ethyl acetate copolymer (being called for short EVA) ethylene ethyl acetate copolymer；For 9-55%, preferably 18-26%；
Described rubber is ethylene propylene diene rubber, natural rubber, polyisoprene rubber, nitrile rubber, neoprene, butadiene-styrene rubber, butadiene rubber, chlorosulfonation rubber, silicon rubber, at least one in polyurethane rubber, preferably ethylene propylene diene rubber；
Described softening oil is paraffin oil, White Mineral Oil, naphthenic oil, liquid polyisoprene, vegetable oil preferred liquid polyisoprene；
Described foaming agent be azodicarbonamide, 4, in 4'-OBSH, unifor, sodium acid carbonate one or more mixing, preferably azodicarbonamide；
Described bridging agent is selected from least one in cumyl peroxide (DCP) the 2nd, sulphur and dual-tert-butyl peroxide diisopropyl benzene, preferably cumyl peroxide；
At least one in stearic acid, magnesium carbonate and calcium stearate, zinc stearate for the described activating agent,
At least one in activated zinc oxide mesh number 800--3500 mesh, zinc carbonate for the described zinc oxide, preferably zinc oxide.
Described styrene-ethylene-ethylene-propylene-based block copolymer, ethylene ethyl acetate copolymer, softening oil, ethylene propylene diene rubber, the mass ratio of foaming agent, bridging agent, activating agent and zinc oxide be 5-50:10-60:20-150:5-30,2-12:0.5-1.3:0.5-2.2:1-2.6, preferably 30-65:20-50:10-110:10-25: 3-18:0.7-1.2:0.7-1.4, more preferably 20-55:25-45:80-100:15-30: 1.5-8:0.65-1.3:0.5-2.5:1.7-2.5.
The present invention provide method prepare described foaming body, plasticate after comprising the steps: to mix aforementioned each component granulate or slice standby, sulfidization molding, obtain described foaming body.
In vulcanisation step described in the method, temperature is 155-190 DEG C, preferably 165-180 DEG C, and more preferably 175 DEG C, the time is 3-22min, preferably 5-10min, more preferably 6min.
nullAdditionally，In order to make each component mix more uniform，The described method preparing foaming body，Also comprise the steps: that the mode of mixing in described blend step can knead step by step，Can comprise the steps: softening oil、Styrene-ethylene-ethylene-propylene-based block copolymer，First knead with ethylene propylene diene rubber，Mixing time 2-5 min，In this step, temperature is less than 60 DEG C，Ethylene ethyl acetate copolymer is added after above-mentioned material mixing，Simultaneously by foaming agent、Bridging agent、Activating agent and zinc oxide one remove and continue mixing in banbury，Banbury temperature 115-135 DEG C，Banburying time 8-13min，Double roller mills，Temperature 80-100 DEG C rolling 5-8 min，Play triangle bag 2-6 time，Granulation or to be pressed into sheet stock standby，155 DEG C-190 DEG C times are 4-18 min，Inject in mould at vulcanizer or by pipeline，Then mould outgoing brewed foaming body.
The foaming body that the invention described above provides is used for preparing footwear material, slippers, case and bag, car and boat material, aircraft materials, space material, furniture material, health medical material, floating material, packing material, building and ornament materials, foam tire, foam tubing, insulation material, heat-barrier material, acoustic material, show and colour, outdoor goods, packaging material, dress materials, decoration material, cap material, vibration-absorptive material, toy for children, instrumental music assistant product, small stores, the goods such as the various auxiliary materials of sports goods, in the sole that foaming body is the end, also tool is widely used, wherein said sole is midsole or the footwear big end, slippers.
A kind of styrene-ethylene-ethylene-propylene-based block copolymer modified foaming body of the present invention, not only has that on-slip is good and compression diminishes, and stretching resistance is big, soft bounce-back height, foam performance and mechanical property are excellent, bubble is uniform, light weight, expansion ratio is high, and heat-resist, tensile property is good, shock resistance is excellent, can be with recycling.Gently compressed by its product weight diminish, heat-resist, applicable make softness bounce-back height, on-slip, compression diminish the higher goods of requirement.
It is main body sizing material that the present invention uses styrene-ethylene-ethylene-propylene-based block copolymer, ethylene ethyl acetate copolymer, softening oil, ethylene propylene diene rubber, makes through mixing, granulation, injection sulfur foam.The proportion of this styrene-ethylene-ethylene-propylene-based block copolymer modified foaming body is below 0.178, light weight, this product compression resistant is askew below≤37%, high bounce-back≤58%, performance stable homogeneous, compression resistant deformation, performance ageing-resistant, pressure are excellent, have good elasticity, can stand to use for a long time.The midsole compression prepared with this modified foaming body diminishes, soft bounce-back height, light weight, endurance quality are good, at the midsole of class and leisure of racing, instep formation part, slippers, shoe-pad etc., has important using value.The present invention relates to foaming body simultaneously and be applicable to various footwear material, Mature Audiences, health medical material case and bag, car and boat material, packaging material, aircraft materials, space material, furniture material, foam tire, floating material, packing material, building and ornament materials, foam tubing, insulation material, heat-barrier material, acoustic material, show and colour, outdoor goods, dress materials, decoration material, cap material, vibration-absorptive material, toy for children, instrumental music assistant product, small stores, the application of various auxiliary materials of sports goods etc..
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following example.Described method is conventional method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.
Embodiment 1 prepares a kind of styrene-ethylene-ethylene-propylene-based block copolymer modified foaming body；
nullBy the trade name styrene-ethylene-ethylene-propylene-based block copolymer of 40-60 weight portion、The naphthenic oil of 30-100 weight portion，The trade name ethylene ethyl acetate copolymer EVA7350 of 30-45 weight portion、Number-average molecular weight is 800-2000 (wherein the weight/mass percentage composition of ethyl acetate (VA) is 18%)、Mixing in the trade name ethylene propylene diene rubber of 25-35 weight portion and input banbury，Foaming agent azodicarbonamide by trade name AC6000 of 3-15% weight portion simultaneously、Dual-tert-butyl peroxide diisopropyl benzene (BIPB) of 0.5-1.1% weight portion、The activated zinc oxide of the activating agent stearic acid of 0.5-0.9 % weight portion and 1.2-1.8% weight portion puts into mixing in banbury，In mixing process，Melting temperature is 105-130 DEG C，Mixing time is 8-16 min；Mill temperature plays triangle bag 2-6 time less than 90 DEG C of mills, begins to pratise, after finishing, in mill, all raw materials is carried out discharge in 80 DEG C-90 DEG C, restraints thin, then after slice cooling, standby；
By vulcanizing press, if curing temperature is 155-190 DEG C, cure time is 6-35 min in a mold, obtains the styrene-ethylene-ethylene-propylene-based block copolymer modified foaming body of the various multiplying powers of the present invention after opening mould at the outer immediate effervescence of mould.
Embodiment 2 prepares a kind of styrene-ethylene-ethylene-propylene-based block copolymer modified foaming body；
nullBy the trade name styrene-ethylene-ethylene-propylene-based block copolymer of 35-65 weight portion、The trade name ethylene ethyl acetate copolymer EVA7470 of 30-40 weight portion、Number-average molecular weight is 800-2000 (wherein the weight/mass percentage composition of ethyl acetate (VA) is 18%)、The trade name ethylene-propylene-diene monomer of 15-30 weight portion、Put into mixing in banbury with the liquid polyisoprene of 30-90 weight portion，Foaming agent azodicarbonamide by trade name AC6000 of 2.4% weight portion simultaneously、Dual-tert-butyl peroxide diisopropyl benzene (BIPB) of 0.5-1.2% weight portion、The activated zinc oxide of the activating agent stearic acid of 0.5-0.10 % weight portion and 1.3-2% weight portion puts into mixing in banbury，In mixing process，Melting temperature is 100-125 DEG C，Mixing time is 8-15 min；Mill temperature plays triangle bag 3-7 time less than 95 DEG C of mills, begins to pratise, after finishing, in mill, all raw materials is carried out discharge in 90 DEG C-100 DEG C, restraints thin, then after granulating and drying, standby；
Injecting mould after cure by ejaculator, curing temperature is 170 DEG C-190 DEG C, and the time is 6min, after sulfuration is molded in shaping baking oven, obtains the various body styrene-ethylene-ethylene-propylene-based block copolymer modified foaming body of the present invention.
According to upper identical step, parts by weight listed by embodiment 2 are carried out, and obtain the real a kind of styrene-ethylene-ethylene-propylene-based block copolymer modified foaming body preparing gained.
A kind of styrene-ethylene-ethylene prepared by table the 1st, embodiment 26-27-propylene-based block copolymer modified foaming body physical property table:
Foaming product 1:1.60 multiplying power
Form 1
From form 1, a kind of styrene-ethylene-ethylene-propylene-based block copolymer modified foaming body that the present invention provides not only has the performance of lighter weight, also there is preferably softness, the soft high bounce-back of the foaming product that is made from, compression resistant are askew, good endurance, are applicable to as the higher foaming product of the askew performance requirement of compression resistant.
nullThe above，It is only detailed description of the invention and the application of the present invention，But protection scope of the present invention is not limited only to this，Any foaming body comprising styrene-ethylene-ethylene-propylene-based block copolymer foaming and foamed plastics，Foaming body is preparing footwear material，Case and bag，Mature Audiences，Vibration-absorptive material acoustic material，Car and boat material，Aircraft materials，Space material，Furniture material，Health medical material，Floating material，Packing material，Building and ornament materials，Foam tire，Foam tubing，Insulation material，Heat-barrier material，Show and colour，Outdoor goods，Packaging material，Dress materials，Decoration material，Cap material，，Toy for children，Instrumental music assistant product，Small stores，The application of the various auxiliary materials of sports goods etc.，And the sole that described foaming body is the end，At slippers，Shoe-pad，Application in instep formation part falls within protection scope of the present invention.Other any under without departing from spirit of the invention and principle in the technical scope of patent diselosesll of the present invention, the change that readily occurs in, modification, combination, replacement, simplify the substitute mode that all should be equivalence, all should cover in scope.
Claims (6)
1. styrene-ethylene-ethylene-propylene-based block copolymer foaming body, including styrene-ethylene-ethylene-propylene-based block copolymer, ethylene ethyl acetate copolymer, softening oil, rubber, foaming agent, bridging agent, activating agent and zinc oxide.
2. the co-polymer foamed body according to claim 1, it is characterised in that: described styrene-ethylene-ethylene-propylene-based block copolymer is the polymer of the block being made up of the styrene monomer hydrogenating and rubber monomer,
In described ethylene ethyl acetate copolymer, the weight/mass percentage composition of ethyl acetate is 9-55%;
Described softening oil is paraffin oil, White Mineral Oil, naphthenic oil, liquid polyisoprene, vegetable oil；
Described rubber is ethylene propylene diene rubber, natural rubber, polyisoprene rubber, nitrile rubber, neoprene, butadiene-styrene rubber, butadiene rubber, chlorosulfonation rubber, silicon rubber, at least one in polyurethane rubber,；
Described foaming agent is azodicarbonamide, 4,4'
One or more mixing in-OBSH, unifor, sodium acid carbonate；
At least one in cumyl peroxide, sulphur and dual-tert-butyl peroxide diisopropyl benzene for the described bridging agent；
At least one in stearic acid, magnesium carbonate and calcium stearate, zinc stearate for the described activating agent.
3. the co-polymer foamed body according to claim 1-2 is arbitrary, it is characterised in that: the mass ratio of described styrene-ethylene-ethylene-propylene-based block copolymer, ethylene ethyl acetate copolymer, softening oil, rubber, described foaming agent, described bridging agent, described activating agent and described zinc oxide is 30-60:10-50:10-110:5-35:1-12: 0.5-1.5:0.5-2.2:1-2.3.
4. the method preparing the arbitrary described co-polymer foamed body of claim 3, comprises the steps: to carry out granulating after described in claim 3, component mixing is plasticated or slice is standby, and sulfuration obtains described foaming body.
5. method according to claim 4, it is characterised in that: in described vulcanisation step, temperature is 150-201 DEG C, and the time is 3～30 minutes.
6. the arbitrary described foaming body of claim 1-2 is used as footwear material in preparation, case and bag, adult toy, car and boat material, aircraft materials, space material, furniture material, health medical material, floating material, packing material, building and ornament materials, foam tire, foam tubing, insulation material, heat-barrier material, acoustic material, show and colour, outdoor goods, packaging material, dress materials, decoration material, cap material, vibration-absorptive material, toy for children, instrumental music assistant product, small stores, the auxiliary material of various sports goods, sole, slippers, application in instep formation part and shoe-pad.
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| CN107584832A (en) * | 2017-09-12 | 2018-01-16 | 滁州远方车船装备工程有限公司 | A kind of honeycomb aluminum plate of high sound insulation and preparation method thereof |
| CN114921048A (en) * | 2022-03-17 | 2022-08-19 | 三六一度(中国)有限公司 | Cold-resistant midsole material, preparation method thereof and shoes |
| CN114921048B (en) * | 2022-03-17 | 2023-06-13 | 三六一度(中国)有限公司 | Cold-resistant midsole material, preparation method thereof and shoes |
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Application publication date: 20161123 |