CN1687206A - Technique for producing freerise foaming material of rubber - Google Patents
Technique for producing freerise foaming material of rubber Download PDFInfo
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Abstract
The present invention provides a production process of rubber free foamed material. Said process is characterized by introducing dynamic vulcanization method process of rubber material so as to divide the vulcanization process of rubber into two steps, namely, dynamic prevulcanization can be used for controlling initial point of vulcanization, and addition vulcanization system can be used for controlling vulcanization speed, so that it can high-effectively implement mutual matching of vulcanization and foaming process, and adopt hot air to make vulcanization foaming and can obtain the invented pore-closed foamed material whose apparent density is 0.08-0.65 g/cu.cm.
Description
Technical field the present invention relates to the production technique of a kind of production technique of rubber item, particularly a kind of freerise foaming material of rubber.
The background technology rubber expanded material is porous rubber again, rubber sponge or spongy rubber.The characteristics of rubber expanded material be have light weight, good springiness, vibration damping, sound insulation, heat insulation, the physicals regulation range is big, the cost performance advantages of higher has been widely used in aspects such as aviation, automobile, instrument, instrument, household electrical appliances, packing, shoemaking, sports goods.
The forming method of rubber expanded material has two kinds of moulded from foam method and free foaming methods usually, and these two kinds of methods require different to the prescription of sizing material.Comprise two simultaneous reactions in the foamed forming process of rubber, i.e. the decomposition reaction of the vulcanization reaction of rubber and whipping agent.Vulcanization reaction makes sizing material become thermoset by plasticity-, and the intensity of bubble wall is increased, and modulus increases.The decomposition reaction of whipping agent produces gas, forms abscess and promote abscess to increase, and makes rubber pange.Accurately the speed and the starting point of these two reactions of control are the gordian techniquies that successfully prepare rubber expanded material.
The free foaming method of rubber is meant the method for preformed sizing material direct sulfur foam free expansion moulding in warm air, microwave or salt bath, is used for continuous production rubber pange tubing, sheet material or section bar more.The forming method of this rubber expanded material is that single stage method is finished by sizing material to the foaming finished product.The free foaming method of rubber requires harshness to prescription and processing condition, promptly will reach the mutual coupling of the vulcanization of rubber and two processes of foaming.On the one hand, sizing material must have prevulcanized to a certain degree to make sizing material that certain intensity be arranged before expanding, and could stop the gas leakage of breaking of steeping wall like this; On the other hand, the speed that whipping agent decompose to produce gas will adapt with vulcanization rate, and vulcanization rate crosses that can to cause steeping wall intensity faster than expansion rate too high, and the little or foam of degrees of expansion is split cruelly.
Rubber free foaming method will reach the mutual coupling of the vulcanization of rubber and two processes of foaming, and key is accurately to control speed and the starting point of vulcanizing with these two reactions of foaming.The decomposition reaction of whipping agent at high temperature starts to walk soon, often decomposes immediately after temperature required reaching.The crosslinking reaction of vulcanization system at high temperature has an inductive phase, and promptly the starting of crosslinking reaction is slower than foamable reaction.If do not use ultra-rapid vulcanization promotor and want between multiple promotor and usefulness, often do not reach the purpose of crosslinking reaction fast starting.In addition, the addition of whipping agent is more a lot of greatly than theoretical consumption, and its early stage gas that decomposes is bigger because of bubble wall undercapacity overflows loss.
The free foaming method of rubber is to use multiple ultra-rapid vulcanization promotor to be feature, to make it to produce synergy to reach the fast and fast effect of vulcanization rate of sulfuration starting point on prescription.The usage quantity of whipping agent is also very big, to remedy the loss of gas in foamed forming process.Be the temperature that will stablize control sulfuration and foaming on technology, the fluctuation of temperature tends to cause the fluctuation of product expansion multiplying power and substandard products occur.This rubber foam also has incipient scorch easily takes place, and shortcoming such as should not park for a long time, all will be strict with on producing.
The foam material that Chinese patent CN98122899 provides the free foaming method of a kind of paracril and polyvinyl chloride blend to make, the consumption of its whipping agent and vulcanization system is big, and vulcanization system is a feature with multiple ultra-rapid vulcanization accelerator combination.Chinese patent CN 02132013 provides the free method foaming of a kind of terpolymer EP rubber material, and the vulcanization accelerator in its vulcanization system is wanted multiple class and usefulness, and consumption is big.These patents all are mixing with sizing material, extrude premolding, at last with the free foaming method production technique of hot-air vulcanization foaming, thereby very high to the requirement of prescription.
At present, the formulating of recipe of traditional rubber free foaming method often all be by virtue of experience with a large amount of tests, by regulating the type and the consumption of whipping agent, regulate the kind and the consumption of vulcanization system, make expansion rate and vulcanization rate reach coupling and prepare rubber expanded material.Its difficult point is also to exist between whipping agent and the vulcanization system and influences each other, thereby requires a great deal of time and financial resources are tested just and can be found out the prescription that is suitable for producing.In addition, the change of the manufacturer of raw material and production batch also exerts an influence to the vulcanization rate of rubber and the expansion rate of whipping agent in process of production, thereby cause the fluctuation of producing, influence the production stability of rubber expanded material, this has further increased the production cost of preparation rubber expanded material.
Summary of the invention the object of the present invention is to provide a kind of production technique of new freerise foaming material of rubber, when this production technique will reduce the rubber free foaming to the prescription and the harsh requirement of technology, simplify the prescription of rubber pange sizing material, reduce material cost, production stability is improved.Can produce volume density with this novel process can be at 0.08～0.65g/cm
3Between foaming plate, tubing or section bar that regulate, unicellular structure.
The production technique of a kind of freerise foaming material of rubber of the present invention is as follows, and following consumption is a mass parts:
(1) dynamic vulcanization: with 100 parts of rubber, 0～250 part of weighting agent, 0～100 part of tenderizer, vulcanization system adds in Banbury mixer or the mill for 0.1～10 part successively, and mixing processing is 5～30 minutes under 100～200 ℃ temperature, makes the prevulcanized sizing material;
(2) add vulcanization system and whipping agent: the prevulcanized sizing material is added 1～20 part of 1～5 part of vulcanization system and whipping agent in Banbury mixer or mill, mixing processing is 5～15 minutes under the temperature of room temperature to 100 ℃, and the thin-pass slice makes rubber unvulcanizate;
(3) premolding: rubber unvulcanizate being lower than in temperature under 100 ℃ the condition with the Rubber Extruder extrusion moulding is sheet material, tubing or section bar, or uses the mould compression molding, makes the premolding sizing material;
(4) sulfur foam: the premolding sizing material is put into baking oven or draw to drying tunnel, hot air temperature is controlled at 150～230 ℃, and sulfuration is carried out simultaneously with foaming, finishes in 3-30 minute, takes out cooling, makes freerise foaming material of rubber.
The rubber that the present invention uses has natural rubber or synthetic rubber, and wherein synthetic rubber has terpolymer EP rubber, paracril, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, silicon rubber or chloroprene rubber.The rubber that the present invention uses also comprises the blend between these rubber, the blend of these rubber and plastics.
The weighting agent that the present invention uses has carbon black, white carbon black, lime carbonate, talcum powder, potter's clay, Calucium Silicate powder, aluminium hydroxide or magnesium hydroxide.
The tenderizer that the present invention uses has fatty hydrocarbon ils, naphthenic oil, fragrant hydrocarbon ils or ester plasticizer.
The vulcanization system that the present invention uses has sulfur sulfide system, peroxide vulcanizing system or resin cure system.Sulfur sulfide system is made up of Sulfur, vulcanization leveller and vulcanization accelerator, vulcanization leveller has zinc oxide, zinc carbonate, stearic acid or glycol ether, and vulcanization accelerator has thiazoles, guanidine class, sulfenamide, polythio amido formiate, thiurams, Thiourea or xanthogenic acid salt.Peroxide vulcanizing system has dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butyl peroxy hexane or dibenzoyl peroxide etc.The resin cure system has tert.-butylbenzene fluosite or brominated phenolic resin.
The whipping agent that the present invention uses has Cellmic C 121 (blowing agent AC), p, the chemical foaming agent of types such as p '-OBSH (whipping agent OBSH), N-N '-dinitrosopentamethylene tetramine (blowing agent H), sodium bicarbonate or bicarbonate of ammonia, or the activation modification thing of these whipping agents or the mixture between them.
Can also add use properties and the processing performance that a spot of other auxiliary agent improves material in the starting material that the present invention uses, as adding anti-aging agent, modifier, tinting material or moisture adsorbent etc.
The production technique of a kind of freerise foaming material of rubber provided by the invention has following two big characteristics:
(1) dynamic vulcanization process is introduced in the production technique of freerise foaming material of rubber: the dynamic vulcanization complete processing is a method commonly used in the rubber plastic blend type thermoplastic elastomer processing technology, it is a kind of in the process of mixing processing, and rubber is also carrying out the reactive working method of crosslinking reaction simultaneously.The present invention introduces dynamic vulcanization process in the production technique of freerise foaming material of rubber, at first adds a small amount of vulcanization system in rubber mixing process, at high temperature carries out dynamic vulcanization, makes sizing material that certain precrosslink degree be arranged, and makes the prevulcanized sizing material.
The described dynamic vulcanization process of production technique provided by the invention is with rubber, weighting agent, tenderizer, vulcanization system adds mixing processing in Banbury mixer or the mill successively, this consumption of crossing the range request vulcanization system will lack as far as possible, when particularly using sulfur sulfide system, the sulfury consumption will lack, and is advisable to be no more than 0.5 part of consumption.In the mixing course of processing, vulcanization system makes rubber generation crosslinking reaction, has realized the prevulcanization of sizing material.Its target is to make sizing material that prevulcanized to a certain degree be arranged and keep plasticity-to get final product, and too much vulcanization system consumption can cause prevulcanized undue, makes sizing material lose plasticity-, is unfavorable for the processing in later stage on the contrary.Dynamic vulcanization carries out more than need being controlled at the required temperature of vulcanization reaction, is generally 100 ℃～200 ℃, and optimum temps is 150～180 ℃.Dynamic vulcanization can Banbury mixer or mill on carry out, required time is a principle with the dynamic vulcanization sufficient reacting, is generally 5～30 minutes.
(2) the total process of the sulfuration of rubber was divided into for two steps: adding whipping agent and vulcanization system at normal temperatures in the prevulcanized sizing material becomes the foaming rubber unvulcanizate, extrude with forcing machine and to be pre-formed as sheet material, tubing or section bar, with the hot-air vulcanization foaming, thereby prepare rubber expanded material.This foaming forming technique was divided into for two steps with the total process of the sulfuration of rubber, and the first step dynamic vulcanization has satisfied the fast requirement of the crosslinked starting point of sizing material, had promptly realized the purpose of precrosslink; The vulcanization system control that the second step vulcanization rate was added by the later stage can be synchronous with the decomposition rate of whipping agent easily.This two-step approach production technique has realized the requirement that the rubber free foaming mates mutually to sulfidation and foaming process equally, but easier than traditional single stage method.
Production technique provided by the invention is described adds vulcanization system and the whipping agent process is carried out in Banbury mixer or mill, melting temperature is controlled at below 100 ℃ in case the generation of vulcanization reaction and whipping agent decomposition reaction.Mixing 5～15 minutes, Synergist S-421 95 is uniformly dispersed, thin-pass is 1 to 3 time then, and slice makes the foaming rubber unvulcanizate.The vulcanization system kind that the vulcanization system of adding adds in the time of can be with the first step dynamic vulcanization is identical or different, its consumption rubber compounding consumption routinely gets final product, and also unnecessaryly uses polythio amido formiate ultra fast accelerator as traditional free foaming prescription.The consumption of whipping agent can be less than the consumption of traditional free foaming prescription, because through the existing certain melt strength of the prevulcanized sizing material of dynamic vulcanization, effectively stoped the early stage gas that foams to overflow, has improved the utilising efficiency of whipping agent.
The described premolding process of production technique provided by the invention can be lower than that extrusion moulding is a sheet material under 100 ℃ the temperature with Rubber Extruder in material temperature, tubing or section bar, or use the mould compression molding.To control the temperature of sizing material in the premolding process, prevent the vulcanization reaction of rubber and the generation in advance of whipping agent decomposition reaction, the required shape of sizing material before obtaining foaming.
Described sulfuration of production technique provided by the invention and foaming process are preformed sizing material is put into baking oven or to draw to drying tunnel, hot air temperature is controlled at more than the initial decomposition temperature of used whipping agent, be generally 150～230 ℃, foaming is carried out synchronously with sulfuration under this temperature, finishes in 3-30 minute.Take out postcooling, make freerise foaming material of rubber.Sizing material has been because of the process that has experienced dynamic vulcanization has had certain melt strength, is enough to resist the bulging force that gas that whipping agent decomposes produces, and seals up bubble effectively.Along with the carrying out of expansion process, sulfuration takes place simultaneously and is improving the intensity of steeping wall, and this matching process has suppressed overflowing of gas, thereby realizes high efficiency foaming.By regulating foaming agent consumption, can easily prepare volume density at 0.08～0.65g/cm
3Between rubber expanded material.
The present invention introduces dynamic vulcanization process in the production technique of freerise foaming material of rubber, realizes the pre-vulcanization process of sizing material, thereby the sulfidation of rubber was divided into for two steps, be i.e. dynamic vulcanization control sulfurized starting point, the vulcanization system of adding control vulcanization rate.Compare with a traditional step sulfuration method, production technique provided by the invention has realized the mutual coupling of sulfidation and foaming process very effectively, and is easy to regulate, and makes the sulfurized starting point stable, the foaming favorable reproducibility.The vulcanization system consumption that the present invention adopts is little, uses MC medium curing promotor to get final product, and does not need to use special ultra-rapid vulcanization promotor.The utilization ratio height of whipping agent just can be prepared the foam material of high foamability under the few situation of consumption.Prescription of the present invention is simple, and material cost is low, the production stability height, and suitability is wide, needs special rubber tooling can realize the production of the freerise foaming material of rubber hurriedly.
Embodiment
Following examples are explained the present invention, but do not limit the scope of the invention.
The starting material that use in following examples and the trade mark thereof are: terpolymer EP rubber (EPDM, Keltan 4703 types, DSM N. V. produces), semi-reinforcing hydrocarbon black (N770 type), talcum powder (1250 orders sieve), paraffin oil (Sunpar 2280), zinc oxide (rubber industry level), stearic acid, calcium oxide, Sulfur, accelerator M (2-benzothiazolyl mercaptan), accelerator D (vulkacit D), blowing agent AC (Cellmic C 121, faint yellow fines).
Embodiment 1-4: the sulfury consumption is to the influence of rubber free foaming when comparing dynamic vulcanization.
Press raw material ratio in the table 1, in volume is 3 liters rubber internal mixer, add terpolymer EP rubber, semi-reinforcing hydrocarbon black, talcum powder, paraffin oil, zinc oxide, stearic acid, calcium oxide, Sulfur and captax successively and carry out mixing and dynamic vulcanization, banburying chamber's temperature is controlled to be 170 ℃, the reinforced back that finishes continues mixing 15 minutes, discharging makes the prevulcanized sizing material; After treating prevulcanized sizing material cooling, again in the roller temperature be in 10 inches two roller mills of 40 ℃ with prevulcanized sizing material bag roller, add blowing agent AC, vulkacit D and Sulfur successively and carry out mixingly, continue mixing 10 minutes, thin-pass 3 times, slice makes rubber unvulcanizate; With the pole shape mouth mould that internal diameter is 5mm is housed, screw diameter is that the Rubber Extruder of 30mm is extruded above-mentioned rubber unvulcanizate, and mouthful mould and barrel temperature are controlled at below 50 ℃, extrude pole shape preform, put into temperature and be 190 ℃ convection oven and carry out free foaming, under the effect of warm air, sulfuration and foaming are carried out synchronously, continue 10 minutes, take out cooling, make bar-shaped freerise foaming material of rubber, the smooth epidermis of its outside surface knot skim, an inner hole is even, and foam elasticity is good.As can be seen from Table 1, dynamically the sulphur dosage of using during prevulcanized is related to the prevulcanized degree, thereby has influence on the multiplying power of foaming, makes the volume density difference of foam.
Embodiment 5-7: relatively foaming agent consumption is to the influence of rubber free foaming.
Its dynamic vulcanization technology, add auxiliary agent technology and the sulfur foam processing step identical with embodiment 2, its material fiting ratio example and foaming the results are shown in Table 1.The bar-shaped foamed rubber that makes, the smooth epidermis of its outside surface knot skim, an inner hole is even, springiness.As can be seen from Table 1, foaming agent consumption is big more, and expansion ratio is big more, and the volume density of foam is more little.Among the embodiment 7,12 parts of blowing agent ACs volume density that just can foam out is 0.09g/cm
3Foam.When so high expansion ratio foamed with traditional single stage method, under the situation that adds complicated vulcanization system cooperation, the consumption of whipping agent was usually more than 18 parts.
Embodiment 8: relatively without the influence of dynamic vulcanization technology to the rubber free foaming.
Press the source material mixture ratio example of embodiment 8 in the table 1, adding terpolymer EP rubber, semi-reinforcing hydrocarbon black, talcum powder, paraffin oil, zinc oxide, stearic acid, calcium oxide in volume is 3 liters rubber internal mixer successively carries out mixing, banburying chamber's temperature is controlled to be 170 ℃, the reinforced back that finishes continues mixing 15 minutes, discharging.After treating sizing material cooling, again in the roller temperature be in 10 inches two roller mills of 40 ℃ with sizing material bag roller, add blowing agent AC, captax, vulkacit D and Sulfur successively and carry out mixingly, continue mixing 10 minutes, thin-pass 3 times, slice makes rubber unvulcanizate.After this extrude premolding, the technology of sulfur foam is identical with embodiment 2, volume density is 0.82g/cm behind the free foaming
3Therefore present embodiment does not have the dynamic vulcanization process owing to do not add vulcanization system in the high-temperature mixing process.Although after adding auxiliary agent, the cooperation population proportion of rubber unvulcanizate is identical with embodiment 2, and its expansion ratio is little more a lot of than embodiment 2, makes the foam volume density very big, fails to realize effectively foaming effect.Present embodiment has compared the bad result of the free foaming that technological process caused of dynamic vulcanization for want of, and is similar with traditional rubber free foaming production technique.
Table 1
| Embodiment | ??1??????2??????3??????4 | ??5??????6??????7 | ??8 |
| Dynamic vulcanization proportioning ethylene propylene diene rubber semi-reinforcing hydrocarbon black talcum powder paraffin oil zinc oxide stearic acid calcium oxide captax Sulfur | ? ??100????100????100????100 ??60?????60?????60?????60 ??50?????50?????50?????50 ??50?????50?????50?????50 ??5??????5??????5??????5 ??3??????3??????3??????3 ??3??????3??????3??????3 ??0.5????0.5????0.5????0.5 ??0.025??0.05???0.075??0.1 | ? ??100????100????100 ??60?????60?????60 ??50?????50?????50 ??50?????50?????50 ??5??????5??????5 ??3??????3??????3 ??3??????3??????3 ??0.5????0.5????0.5 ??0.05???0.05???0.05 | ? ??100 ??60 ??50 ??50 ??5 ??3 ??3 ??- ??- |
| Add auxiliary agent proportioning Sulfur vulkacit D captax blowing agent AC | ? ??1.475??1.45???1.425??1.4 ??1.5????1.5????1.5????1.5 ??-??????-??????-??????- ??6??????6??????6??????6 | ? ??1.45???1.45???1.45 ??1.5????1.5????1.5 ??-??????-???????- ??3??????9??????12 | ? ??1.5 ??1.5 ??0.5 ??6 |
| Foaming is volume density as a result, g/cm 3 | ? ??0.25???0.30???0.34???0.38 | ? ??0.57???0.14???0.09 | ? ??0.82 |
Annotate: proportioning unit is a mass parts
Claims (6)
1. the production technique of a freerise foaming material of rubber is characterized in that its production technique is as follows:
(1) dynamic vulcanization: with 100 parts of rubber, 0～250 part of weighting agent, 0～100 part of tenderizer, vulcanization system adds in Banbury mixer or the mill for 0.1～10 part successively, and mixing processing is 5～30 minutes under 100～200 ℃ temperature, makes the prevulcanized sizing material;
(2) add vulcanization system and whipping agent: the prevulcanized sizing material is added 1～20 part of 1～5 part of vulcanization system and whipping agent in Banbury mixer or mill, mixing processing is 5～15 minutes under the temperature of room temperature to 100 ℃, and the thin-pass slice makes rubber unvulcanizate;
(3) premolding: rubber unvulcanizate being lower than in temperature under 100 ℃ the condition with the Rubber Extruder extrusion moulding is sheet material, tubing or section bar, or use the mould compression molding, make the premolding sizing material;
(4) sulfur foam: the premolding sizing material is put into baking oven or draw to drying tunnel, hot air temperature is controlled at 150～230 ℃, and sulfuration is carried out simultaneously with foaming, finishes in 3-30 minute, takes out cooling, makes freerise foaming material of rubber.
2. according to the production technique of right 1 described a kind of freerise foaming material of rubber, it is characterized in that rubber has the blend between natural rubber, terpolymer EP rubber, paracril, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, silicon rubber, chloroprene rubber or these rubber and the blend of these rubber and plastics.
3. according to the production technique of right 1 described a kind of freerise foaming material of rubber, it is characterized in that weighting agent has carbon black, white carbon black, lime carbonate, talcum powder, potter's clay, Calucium Silicate powder, aluminium hydroxide or magnesium hydroxide.
4. according to the production technique of right 1 described a kind of freerise foaming material of rubber, it is characterized in that tenderizer has fatty hydrocarbon ils, naphthenic oil, fragrant hydrocarbon ils or ester plasticizer.
5. according to the production technique of right 1 described a kind of freerise foaming material of rubber, it is characterized in that vulcanization system has sulfur sulfide system, peroxide vulcanizing system or resin cure system; Sulfur sulfide system is made up of Sulfur, vulcanization leveller and vulcanization accelerator, vulcanization leveller has zinc oxide, zinc carbonate, stearic acid or glycol ether, and vulcanization accelerator has thiazoles, guanidine class, sulfenamide, polythio amido formiate, thiurams, Thiourea or xanthogenic acid salt; Peroxide vulcanizing system has dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butyl peroxy hexane or dibenzoyl peroxide; The resin cure system has tert.-butylbenzene fluosite or brominated phenolic resin.
6. according to the production technique of right 1 described a kind of freerise foaming material of rubber, it is characterized in that whipping agent has Cellmic C 121, p, p '-OBSH, N-N '-dinitrosopentamethylene tetramine, sodium bicarbonate or bicarbonate of ammonia.
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2005
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Owner name: SHANGHAI JIAOTONG UNIV.; JIANGYIN HAIDA RUBBER AN Free format text: FORMER OWNER: SHANGHAI JIAOTONG UNIV.; JIANGYIN HAIDA RUBBER AND PLASTIC PRODUCTS CO., LTD. Effective date: 20081010 |
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Effective date of registration: 20081010 Address after: No. 800, Dongchuan Road, Shanghai, Minhang District: 200240 Co-patentee after: Jiangyin Haida Rubber & Plastic Co., Ltd. Patentee after: Shanghai Jiao Tong University Address before: No. 800, Dongchuan Road, Shanghai, Minhang District: 200240 Co-patentee before: Jiangyin Haida Rubber and Plastic Production Co., Ltd. Patentee before: Shanghai Jiao Tong University |
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