WO2017193762A1 - Rubber composition and application - Google Patents

Abstract

A rubber composition, comprising: 80-120 parts by weight of a raw rubber; 1-5 parts by weight of a peroxide initiator; 2-15 parts by weight of a crossbridging agent; 0.1-1 parts by weight of a free radical-absorbing and releasing modulator; and a strengthening and anti-aging agent. At least 70% by weight of the raw rubber comprises any one or any combination of a polybutadiene rubber, natural rubber, and styrene-butadiene rubber. The invention provides a formulation of a crossbridging and auxiliary agent for an unfinished good of the rubber composition, and offers a technical solution with excellent performance and industrial applicability in representative industries including tires, footwear materials, and wear plates. The invention is also cost effective and friendly to the environment.

Description

Rubber composition and application First, the field of technology

The present invention relates to a cross-linking formulation of a rubber composition, that is, a rubber product, and a preparation method and application.

Second, the background technology

Butadiene rubber (China's production of millions of tons) and natural rubber and styrene-butadiene rubber are general-purpose rubber. The tires, soles, plates and tubes mainly covered by the products are the largest products in rubber. The vulcanization process has been for many years and The history of maturity; the vulcanizing agent is called a bridging agent. In the industry, it is also known as the bridge agent according to HG/T 3060-1988 (1997) "Non-carbon black compounding agent terminology for rubber": vulcanizing agent; curing agent - can cause vulcanization (crosslinking) of rubber substance. Divided into two major categories of inorganic and organic. The former category has sulfur, sulfur monochloride, selenium, tellurium and the like. The latter category contains sulfur-containing accelerators (such as accelerator TMTD), organic peroxides (such as benzoyl peroxide), hydrazine compounds, polysulfide polymers, urethanes, and maleimide derivatives. , amine compounds, metal oxides and isocyanates. The most commonly used are elemental sulfur and sulfur compounds. Common industrial sulfur additives TMTD, TETD, etc. can produce carcinogenic N-nitrosodimethylamine when vulcanized. Sulfur usually accounts for 1.5% of the formula. This kind of substance will produce harmful sulfur-containing compound gas during processing and vulcanization. More fatally, after the end of the rubber product life, it can not be treated by high temperature incineration. Sulfur must become a harmful gas or a toxic residue. Although incineration is sometimes used, the cost is lowest and there is no secondary pollution. Therefore, at present, environmental protection considerations, Western countries put forward a series of environmental protection standards for rubber products, requiring no harmful heavy metals, no nitroso production, no polycyclic aromatic hydrocarbons, low zinc, etc., but no country proposed to ban sulfur, not wanting to But can't do it. From the material performance requirements to the production process requirements, there is no mature alternative technology.

Typical curing systems are as follows:

1, sulfur vulcanization

(1) Conventional vulcanization: It consists of a compounding agent such as sulfur and a small amount of accelerator, and is mainly composed of polysulfide bonds. The high temperature resistance is poor, the compression set is large, and the phenomenon of returning to the original is easy after the sulfur is passed. However, the flexural fatigue resistance is good, the mechanical strength is high, and the rubber and the product are not easy to be sprayed. (2) Effective and semi-effective vulcanization: the amount of sulfur is generally less than 0.5 parts, and the usual amount is 0.35 parts. With a larger amount of accelerator, a longer scorch time is required (super speed accelerator and after-effect combination), active agent A sufficient amount of stearic acid (1-8 parts) should be used. There is almost no vulcanization reversion phenomenon, the vulcanization uniformity is good, the heat resistance is good, the compression deformation is low, and the heat generation is small. The disadvantage is that the flexural fatigue resistance is poor and the blooming phenomenon is easy to occur. Although the formula of the effective vulcanization system using the high TMTD is widely used, the processing stability is poor, and the cut cream is severe. (3) Dynamic equilibrium vulcanization The system, usually a vulcanization system with anti-sulfur reduction properties, has better dynamic performance than an effective semi-effective vulcanization system, but does not achieve the dynamics of conventional vulcanization systems.

2. Resin vulcanization

It is characterized by the formation of a thermally stable C-C bond and an ether bond crosslink. It can improve the heat resistance and flexural resistance of vulcanized rubber, and there is almost no vulcanization and reversion in vulcanization.

Sulfur, D, DM, TMTD, CZ and amine antioxidants all reduce their vulcanization efficiency. The most serious effects are the effects of amine antioxidants and D. A phenolic antioxidant is preferred in the system.

The epoxy resin vulcanizing agent has good vulcanization effect on the carboxyl group-containing rubber and CR. The vulcanized rubber has good flex resistance, low heat generation, good adhesion with brass, but poor aging resistance. When vulcanizing CR, the optimum amount is 8-9 parts, which is activated by ZNO.

CN201510774279 relates to a color base and a vulcanization process thereof, and different color rubber materials are separately prepared, and each color rubber compound is composed of the following raw materials: coloring agent, natural rubber, styrene-butadiene rubber, high styrene, zinc oxide, octadecanoic acid, magnesium oxide , anti-aging agent, reinforcing agent, white smoke, coumarone resin, rubber oil; vulcanizing agent, accelerator.

CN201410218401 relates to an atmospheric pressure vulcanized low calcium magnesium rubber sheet composed of the following parts by weight: 70-90 parts of natural rubber, 10-30 parts of styrene-butadiene rubber, 3-6 parts of zinc oxide, and 0.5 stearic acid. -1.5 parts, 15-25 parts of semi-reinforcing carbon black, 40-60 parts of bakelite powder, 2-4 parts of processing aid, 3-5 parts of tri-line oil, 25-45 parts of sulfur, promoter D0.5-1.5 Parts, accelerator TMTD10-15 parts. Zinc oxide and stearic acid are used as active agents. In the production of tires, the amount of zinc can not be reduced, otherwise there will be cost increases. The existing zinc methacrylate is a rubber-assisted vulcanizing agent and a heat-resistant filler, as used as a sulfur-reducing reducing agent.

Therefore, rubber vulcanization accelerator is an industrial raw material mainly used in the manufacture of tires, tapes, rubber shoes and other industrial rubber products. The current natural rubber and synthetic rubber accelerators have a wide range of vulcanization and can be used alone or in combination with dithiocarbamates, thiurams, terpenes and other alkaline accelerators. Mainly used in the manufacture of tires, tapes, rubber shoes and other industrial rubber products. Rubber vulcanization accelerator M (thiol benzothiazole), rubber vulcanization accelerator ETU (Na-22), rubber vulcanization accelerator DETU, rubber vulcanization accelerator ZDC (EZ), rubber vulcanization accelerator ZDMC (PZ) rubber vulcanization Accelerator ZDBC (BZ), rubber vulcanization accelerator ZMBT (MZ), rubber vulcanization accelerator TMTM, rubber vulcanization accelerator MBT (M), rubber vulcanization accelerator MBTS (DM), new accelerators TDEC, TBzTD, ZBEC, ZBPD Wait.

The vulcanization of rubber is mainly carried out by using sulfur, but the reaction between sulfur and rubber is very slow, so the vulcanization accelerator is born. The addition of the accelerator to the rubber can promote the activation of the vulcanizing agent, thereby accelerating the crosslinking reaction between the vulcanizing agent and the rubber molecule. The effect of shortening the vulcanization time and lowering the vulcanization temperature is achieved. At present, the main vulcanization accelerators used mainly include sulfenamides, thiazoles, thiurams, and some terpenoids, thioureas and dithiocarbamates. Among them, sulfenamides have the best comprehensive performance and are the most widely used, and are the main varieties of current accelerators. In 2004, global rubber consumption was about 19 million t/a. According to rubber additives accounting for 4% of rubber consumption, the annual consumption of rubber additives in the world is about 760,000 tons, of which about 350,000 tons of accelerators. In the production of rubber's main varieties, tires, belts, tubes, plates and other fields dominate the world, can not be moved.

Peroxide vulcanization systems are generally not used for general rubber vulcanization. Because traditional peroxide vulcanization, firstly, peroxides are thermally cracked into active free radicals, and some of them directly attack the active hydrogen sites of the polymer to form polymer free radicals. The molecular radicals are coupled in pairs to form a carbon-carbon crosslink bond. This bond type has good heat resistance, but the dynamic properties have poor tear resistance. Another part of the peroxide radical attacks the electrons in the rubber molecule. A group, such as a methyl group, produces a carbon-carbon bond cleavage in the main chain of the molecule, which forms many defects in the rubber crosslinked network and has low performance. There are also some free radicals or quenching or formation of ineffective hooks. In addition, the peroxide will produce a small amount of cracking at normal temperature, and the decomposition will accelerate with the increase of temperature. The degree of controllable scorch during the vulcanization process is low, and there is almost no vulcanization induction period, and the processing adaptability is very poor. It is not uncommon for peroxide cure systems to be used in silicone rubber, fluororubber and nitrile rubber. As a peroxidized sulfide, especially in the vulcanization process of nitrile rubber and ethylene-propylene peroxide peroxide, it can be used as a rubber compound with low compression deformation, fast vulcanization speed and heat-resistant air aging.

Commonly used peroxide DCP produces irritating odor of acetophenone during vulcanization. Commonly used peroxide varieties are BIPB [di(t-butylperoxy) diisopropylbenzene] and bis-five [2,5-di-B Base-2,5-di(t-butylperoxy)hexane], which contains two effective peroxy groups in the molecular structure, and does not produce a pungent odor after vulcanization, and can completely replace DCP in high-grade products. In the peroxide vulcanization system, the addition of the trapping agent TAC or TAIC will slightly delay the scorch time of the vulcanization. As the vulcanization time prolongs, the scaffolding agent will obviously promote the cross-linking effect. Probably because of vulcanization. In the initial stage of the reaction, the self-carrying agent molecule itself undergoes cyclization polymerization and is grafted with rubber molecules to consume some of the rubber molecule radicals. These free radicals should produce normal chemical cross-linking in the absence of a bridging agent. With the prolongation of the vulcanization time, the cross-linking reaction of the allyl double bond with the rubber predominates, forming an active agent bridge bond, thereby improving the crosslinking efficiency.

At present, the development of world accelerators is gradually becoming more environmentally friendly, functional and centralized. From a technical point of view, in recent years, internationally, the toxicity of certain promoters in the rubber processing process, which is prone to harmful nitrosamines, has been paid more and more attention. In view of the fact that many restrictive laws and regulations have been introduced in the world, Germany is early. In 1982, the company promulgated regulations to control nitrosamine content, and the United States, Japan, France, and the United Kingdom also actively developed new vulcanization accelerators that do not produce nitrosamines. Suspension of use will result in a nitrosamine promoter. Therefore, an environmentally friendly vulcanization promotion system has been formed, and some new environmentally friendly varieties have been developed to replace products with carcinogenic risks. In terms of marketing, more emphasis is placed on the application performance research of products, the development of functionalized rubber accelerator masterbatches and predispersions, and the increase in the research and development of compounding has become the main means for foreign major accelerator manufacturers to occupy and expand the market. One. Traditional accelerators such as NOBS have been identified as banned substances that release nitrosamines. After years of use, the global rubber additives have been increasingly concentrated in the production and application of rubber additives. They are mainly concentrated on some varieties with no pollution and good performance. The accelerators are mainly TBBS, CBS and TM'I'D. Wait. In addition, such as zinc oxide in the vulcanization system is indispensable in the form of intermediate ions of complex (or help-crosslinking form), but will return to the form of zinc oxide to discharge rubber products such as tires, zinc oxide is harmful to aquatic organisms. In production, it is often associated with heavy metals, and is also harmful to the human body. At present, Europe and the United States also begin to limit zinc. In addition, the existing vulcanization and accelerator system has certain limitations in the formulation of the filler system, and it is not possible to add more amount to the ideal white carbon black.

In recent years, the international community has paid more and more attention to the toxicity of certain promoters in the rubber processing process, which is prone to harmful nitrosamines. The research on the formation and influence of nitroso compounds has become a global rubber accelerator. Hot topics, so new rubber accelerators are also a substitute for nitrosamine-producing accelerators.

Studies have shown that N-nitrosamines are formed by the reaction of secondary amines with nitrogen oxides. During the vulcanization of rubber compounds, the vulcanization accelerators based on secondary amines (such as morpholine, diisopropylamine, etc.) are decomposed and produced. The secondary amine reacts with nitrogen oxides in the air or with the complexing agent to form N-nitrosamines, while with primary or tertiary amines and nitrogen oxides, it is difficult to form stable nitrosamines. Many countries abroad have long used the main types of vulcanization accelerators, sulfenamides, thiurams, disulfide carbamates and sulfur donors as research objects that may produce nitrosamines. Mechanism and alternative issues.

At present, foreign research indicates that the vulcanization accelerators that may produce nitrosamines are probably amino acid salts such as PZ, ZDC, zDBDC (zinc dibutylsulfurate carbamate), NBC (dibutyl disulfide nickel carbamate), etc.; sulfenyl Secondary amines such as NOBS, DIBS (N,N-diisopropylbenzothiazole-2 sulfonamide), DEBS (N,N-diethyl-2-benzothiazole sulfenamide); thiuram Such as TMTM, TMTD, TETD, tetrabutyl thiuram disulfide (coffee), etc.; --- thioamines such as Yintian M (dithiodimorpholine); - thiocarbamoyl Sulfonamides such as starvation (N-oxydiethylenesulfide carbamoyl-N-oxydiethylenesulfenamide) and the like.

The advanced TBBS is more expensive than the accelerator NOBS due to the price of the raw material tert-butylamine.

In the manufacture of large thick products such as tires and track plates that require fatigue resistance, a sulfur-containing system is usually required. Although the sulfur-containing compound system has good fatigue resistance and tear resistance, the heat and aging resistance is poor, and the processing safety is poor. In the recipe The scorch retarder CTP and the p-phenylenediamine anti-aging agent are almost standard. These materials are harmful or suspected to be harmful.

The existing natural rubber and styrene-butadiene synthetic accelerators have a wide range of vulcanization and can be used alone or in combination with dithiocarbamates, thiurams, guanidines and other alkaline accelerators. Mainly used in the manufacture of tires, tapes, rubber shoes and other industrial rubber products. The main products rubber vulcanization accelerator ETU (Na-22), rubber vulcanization accelerator DETU, rubber vulcanization accelerator ZDC (EZ), rubber vulcanization accelerator ZDMC (PZ) rubber vulcanization accelerator ZDBC (BZ), rubber vulcanization accelerator ZMBT (MZ), rubber vulcanization accelerator TMTM, rubber vulcanization accelerator MBT (M), rubber vulcanization accelerator MBTS (DM) wherein rubber vulcanization accelerator ETU (Na-22) is also called ethylene thiourea. The amount is 0.25-1.5 parts in the general product, 0.2-0.5 parts in the 54-1(W) type neoprene water-resistant product, and 10-20 parts of lead monoxide.

The fluororubber layer and the rubber sheet bonded firmly through the sulfided NBR layer (refer to US19990367502). The fluororubber layer is a fluororubber compound containing a peroxide vulcanizing agent, a polyol vulcanizing agent or a polyamine vulcanizing agent. In the case where the fluororubber composite contains a peroxide vulcanizing agent, it also contains a metal oxide. In the case where the fluororubber composite contains a peroxide vulcanizing agent or a polyol vulcanizing agent, the nitrile rubber compound further contains a metal oxide. The bonding of the two layers is firmly by vulcanization. This rubber laminate is used to compare special automotive fuel hoses and fuel pump diaphragms.

The butyl rubber layer is composed of a functional nitrile rubber having a specific functional group, and according to the fluorine-containing rubber composite vulcanizing agent (refer to US Pat. No. 5,830,946 A, the composition further comprises an organic acid polyvalent salt and a peroxide bridging agent. The material may simultaneously comprise a nitrile rubber mixed with a carboxylated nitrile rubber. The rubber may be hydrogenated. The cured composition made from the crosslinkable composition exhibits improved properties, especially an unexpectedly high modulus).

US2010190895A1 discloses a crosslinked rubber composition comprising 100 parts by weight of EPDM EPDM, 5120 parts by weight of carbon black, 70-150 parts by bituminous fines, weight and 0.28 from obtained parts by weight organic Peroxide, with outstanding temperature resistance and sealing properties.

For example, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is a peroxide which can be used as a vulcanizing agent for synthetic rubber.

Therefore, it is a goal of the rubber industry to invent a harmless, environmentally friendly vulcanization system capable of satisfying the cost, from the performance to the industrial adaptability represented by tires, shoe materials and wear plates.

Third, the content of the invention

The object of the present invention is to provide a rubber composition, that is, a formulation of an auxiliary agent such as cross-linking of a product, which can meet the technical solutions of performance, industrial adaptability represented by tires, shoe materials and wear plates, and can Taking into account cost and environmental protection, The invention proposes a cross-linking or vulcanization system of a general rubber product, and a preparation application of the rubber composition.

The technical proposal of the present invention is a rubber composition comprising raw rubber, the mass part is 80-120 parts; the peroxide initiator, the mass part is 1-5 parts; the bridging agent, the mass part is 2-15 parts Free radical absorption and release modifier, the mass part is 0.1-1 part; reinforcing agent and anti-aging agent; the raw rubber includes one to three of polybutadiene rubber, natural rubber and styrene-butadiene rubber, and the quality of the raw rubber More than 70%. Of course, other additives such as tackifiers, dispersants and the like which are used in the existing formulations may be added. The ratios of the present invention are all by weight.

The peroxide initiator is one of the following materials:

(1) di-tert-butyl peroxide, benzoyl peroxide, lauroyl peroxide);

(2) hydroperoxide (cumene hydroperoxide, t-butyl hydroperoxide);

(3) a dialkyl peroxide (di-tert-butyl peroxide, dicumyl peroxide);

(4) an ester peroxide (tert-butyl peroxybenzoate, tert-butyl peroxy-t-pentanoate);

(5) ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide);

(6) a dicarbonate peroxide (diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate);

The bridging agent is a salt containing an allyl double bond, an organic acid within 7 carbon and a magnesium, zinc, aluminum, calcium or iron, one to three; an organic acid within 7 carbon Including acrylic acid, crotonic acid, methacrylic acid, methoxybenzene acrylic acid, 4-pentenoic acid and the like.

The radical absorption release modifier comprises a metal salt such as ferric chloride, copper chloride or sodium nitrite; an organic valence metal such as copper alkylthiocarbamate or N-nitroso-N-phenylhydroxylamine aluminum. Salt; hydroquinone and derivatives of HQHQ, DTBHQ and other HQ; 616, 1076 and other multi-hindered phenols; BHT, di-tert-butyl cresol; 626 diphosphite, 2,6 dithiobis (6-tert-butyl) 3-methylphenol), 2,6 di-tert-butyl-a-dimethylamino-p-cresol, nitroxide piperidinol. Nitroxide piperidinal aldehyde, 4-acetamido-2,2,6,6-tetramethylpiperidine-1-1 nitroxide, 705 phosphite, phenoxazine, and the like.

The polybutadiene rubber, natural rubber and styrene-butadiene rubber account for more than 85% by weight of the raw rubber, and the other components are polymer materials containing an olefin bond; the antioxidant is an aldehyde amine or an imidazole.

The bridging agent is a single or more pure product, or Ethylene-propylene rubber as a carrier containing more than 65% bridging agent and containing appropriate amount of regulating agent for storage and transportation of safe and stable film and rubber particles.

The amount of the reinforcing agent added is added according to the requirements of the product, and is basically the same as the prior art. However, the reinforcing agent of the present invention is especially white carbon black, and the amount of addition can be one to several times higher than that of the prior art, and is a reinforcing agent which is more environmentally friendly and improves the performance of the product. Other reinforcing agents include carbon black, rubber powder, and other commonly used reinforcing additives; the material used in the present invention requires PH6-8 Left and right, carbon black produced using high aromatic oil should pay attention to remove surface aromatic residues.

The invention has strong selectivity for the anti-aging agent, and it is not suitable to use some common diamine and polyphenol anti-aging agents, and the use of environmentally friendly and inexpensive aldehyde amines or imidazoles has a good effect.

The application of the invention may be directly selecting a suitable variety of bridging agent, initiator, and free radical absorption release modifier, or preparing a semi-finished rubber mixture together with the reinforcing agent raw rubber to be used. The amount of white carbon black added is one to several times higher than that of the prior art, and reaches 15 to 50% by weight of the raw rubber.

The invention is directed to the bridging system proposed by the largest rubber: natural rubber is the most traditional rubber variety, and a series of products with good physical and mechanical properties and excellent process performance can be obtained by a suitable compounding method.

Styrene-butadiene rubber is a synthetic rubber in which butadiene and styrene are copolymerized in a certain ratio. Because it is rich in benzene ring side chains, it has better heat resistance and wet skid resistance than natural rubber and butadiene rubber.

Polybutadiene rubber, according to the different catalytic system, the structure of the obtained polymer material is also different, high-cis type 1,4 structure polybutadiene rubber, commonly known as butadiene rubber, compared with natural rubber and styrene-butadiene rubber, It has the characteristics of high elasticity, good wear resistance, good cold resistance, low heat generation, flex resistance and good dynamic performance. The main disadvantages are poor wet skid resistance, low tear strength and tensile strength, large cold flow, and poor processing performance. Generally, it must be used in combination with other rubber types. Medium and high 1,2 structural content polybutadiene rubber, is a new type of rubber with low dynamic heat generation, improved wet skid resistance, heat resistance, Langsheng has a medium content of goods, Qilu Petrochemical and other units have In the development of high content products.

The polybutadiene rubber includes not only cis-1,4-polybutadiene rubber but also polybutadiene rubber having a trans and 1,2 structure. The trans type may have better hysteresis heat generation performance, and the 1,2 structure has low heat generation, good heat resistance, and good wet skid resistance, but has poor sensitivity to the sulfur vulcanization system and is highly sensitive to the peroxide system. It is common to use butadiene rubber, and it is not excluded to use an appropriate ratio of trans and 1,2 structured polybutadiene rubber. All of the above three rubbers have been applied to the proportioning system of the present invention, and both have superior effects to the prior art.

The invention generally prepares an initiator to be blended into a weight ratio of less than 40% and a free radical absorption release modifier from the viewpoints of safety and stability of raw material storage and transportation, industrial hygiene of product production, and comprehensive environmental protection; and further with high temperature ester and paraffin Oil; whitening black, calcium carbonate and other desensitizing agent adsorption desensitizing agent together pre-formulated into a desensitized safely transportable non-flying powder, as a safe and stable initiation system, used in the practical examples of the present invention SK8713D40F is a compound-initiated bridging system for the current tire soles and other fields. Its ratio is dicumyl peroxide 40, white carbon black 25, paraffin oil 10, high temperature ester 21, 2, 6 di-tert Base-a-dimethylamino-p-cresol 3, nitroxide piperidinol 0.5, 2.4% di-tert-butyl cresol 0.5. When blended with ethylene propylene rubber, paraffin oil, high temperature ester, free radical absorption release modifier And the bridging agent accounts for more than 65% by weight, and prepares a uniform strip or rubber pellet; as a stable triggering bridge body The verification formula of the present invention is the use of the safe composition SK8954EP70, which is zinc methacrylate or zinc acrylate 70 ethylene propylene rubber 2; paraffin oil 3 parts 2,6 di-tert-butyl-a-dimethylamino-p-cresol 2.4, Di-tert-butyl cresol 0.4, Nitroxide piperidinol 0.2.

When the product is produced, the raw rubber system and the reinforcing (and anti-aging system if necessary) system and the vulcanization system of the invention are combined, not only can ensure the formula of the product is simple and accurate, the production control is easy, and the peroxide initiator, Highly active substances such as bridging agents, even dangerous goods, have become a common chemical with very stable storage and transportation through the combination of free radical absorption and release modifiers and other desensitizers, ensuring long-term stability of use performance. effective.

The cross-linking system of the present invention comprises a peroxide initiator, a bridging agent and a radical absorption-release modifier, and the main components of the vulcanization system composed of all the vulcanizing agents and the accelerator and the active agent are replaced by three components. To: The peroxide initiator produces the reactive radicals required for crosslinking.

Peroxide bridging agent is an important auxiliary agent for cross-linking raw rubber materials, forming an ion-bond bridge with high heat resistance and low hysteresis. At the same time, under the initiation of free radicals, the bridging agent is activated, in addition to being a polymer chain. The high-quality bridge between the two can be self-assembled into a high-modulus hard segment, which realizes the separation of the soft and hard phases in the material system, and improves the physical and mechanical properties of the material while maintaining the flexibility of the material.

The peroxide absorption release modifier is essentially a heat-sensitive free radical capture and release system. The free radicals generated in the material storage and processing temperature (depending on the material system, such as below 50-60 ° C) are all captured, and the use thereof. Related to the process conditions of vulcanization cross-linking, such as the use of such free radical absorption and release modifiers when controlling to a processing temperature below 120 ° C, mainly exhibits free radicals released by the absorption of peroxides and bridging agents, when the temperature rises to 140 °C (generally, also related to the material system) above, the initiator emits a large amount of free radicals, when the temperature reaches the half-life temperature of the initiator used for 1 minute, the initiator and regulator free radical release rate will be quite fast, this temperature condition It is very suitable for rapid vulcanization of small products. The vulcanization temperature is selected between the decomposition temperature of the regulator and the half-life temperature of the initiator for 1 minute. It is sure to find a vulcanization condition suitable for large and thick products. After the regulator is completely consumed, the bridging agent and the rubber have begun to be induced to form free radical crosslinks. At the same time, the regulator that absorbs a large amount of free radicals also begins to crack rapidly, releasing a large amount of active free radicals, causing the crossover. The coupling reaction proceeds at a much faster rate than peroxide cracking. Through the increase or decrease of the amount of initiator and regulator, and the adjustment of the vulcanization temperature, the cross-linking effect comparable to that of the sulfur vulcanization system can be achieved: processing at 120 ° C for more than one hour without scorching, and sufficient at the vulcanization (crosslinking) temperature During the vulcanization induction period, there is a fast cross-linking kinetics and a perfect cross-linking kinetics during the vulcanization flattening period.

The beneficial effects: the process conditions of the product of the invention can be adjusted mainly by the components of the three materials such as the peroxide initiator and the vulcanization working temperature, and can be completely compatible with the existing vulcanization process conditions or even completely the same. However, cross-linking is more efficient and more efficient. It is therefore possible to use the control conditions of the existing optimized vulcanization process.

The invention discards the old concept that the peroxide is generally not used for the general rubber, and the formula of the general rubber article which replaces the butadiene rubber, the natural rubber and the styrene-butadiene rubber and the mixture thereof by providing a simple and efficient cross-linking formula system, the invention The system can completely prepare tire, shoe material and track shoe wear plate products, and has already tested the main performance of the model, which can be applied to tires, shoe materials and track shoes, bridges on the crosslinked network of the products of the invention. The keys are both CC bond and C-Me ion bond. The bond can be much higher than the polysulfide bond monosulfide bond. The use temperature can be increased or increased by about 20 °C compared with the prior art, and the corresponding degree of aging resistance is increased, especially the tire. The important index - improved lag angle index, good wear resistance, good cutting resistance, high tensile strength, flexural fatigue resistance of various products (more than 300,000 times of the existing flexing, the invention has 300,000 There are revolutionary improvements in the above-mentioned flexing), and the mechanical strength is also fully achieved and exceeds the level of the existing formula. The relevant basic data of the present invention are as follows, the formulations of Examples 1-13, 16-20, 22-27 module Basically able to achieve:

If the performance requirements of automotive tread rubber based on black carbon black are used, the process and physical and mechanical properties of the conventional sulfur vulcanization system, the dynamic equilibrium vulcanization system and the sulfur-free vulcanization system of the present invention are respectively compared as follows:

A, typical formula table

NR170BM masterbatch (parts by weight)

3# tobacco sheet glue 60.0 1502 butyl benzene rubber 15.0 9100 cis butyl rubber 25.0 C5 resin 3 dispersant 2.0 cleaning high wear-resistant carbon black 55.0 220 white carbon black 15.0 anti-RD 1.0 anti-MB 1.0 paraffin oil 5.0 total: 182.0

NR170B01 conventional vulcanization system:

NR170BM masterbatch 182.0 zinc oxide 5.0 stearic acid 2.5 accelerator CZ 0.8 scorch retarder CTP 0.3 sulfur 2.2 total: 192.8

NR170B02 Dynamic Balanced Vulcanization System:

NR170BM 182.0 zinc oxide 5.0 stearic acid 2.5 accelerator CZ 1.0 accelerator DPTT 1.5 silicon 69 2.5 sulfur 1.0 total: 200.5

NR170B03 The vulcanization system of the invention:

NR170BM masterbatch 182.0 SK8954EP70 13.0 SK8713D40F 4.0 Total: 199.0

B, performance table

Vulcanizer 120 degrees * 30 minutes rubber torque

C. Brief analysis, it can be seen from the above comparison test results that the vulcanization system of the present invention is used in the case where the composition is completely identical except for the vulcanization system:

1. The viscosity of the semi-finished rubber compound is low, which is conducive to processing and forming.

2. The anti-scorch performance of the rubber material is much better than the dynamic equilibrium vulcanization system. It is equivalent to the conventional vulcanization system and can be directly implemented in the current tire production without special process measures.

3. The material exhibits excellent resistance to sulfuration and reduction, far superior to conventional vulcanization systems, and even superior to dynamic equilibrium vulcanization systems.

4. Wear and other physical and mechanical properties are also superior to the other two systems.

5, the product does not have the risk of blooming.

Based on the NR170B03 formula, the fineness adjustment and optimization of the rubber produced by the industrial mixer is commissioned by Shandong Linglong Tire:

A, formula table

3# tobacco sheet glue 60.0 1502 butyl benzene rubber 15.0 9100 butyl rubber 25.0 C5 resin 3 dispersant 2.0 cleaning high wear-resistant carbon black 50.0 220 white carbon black 15.0 anti-RD 1.0 anti-MB 1.0 SK8954EP70 13.0 SK8713D40F 4.0 total: 189.0

B performance table

C brief analysis

It can be seen from the above test results that the vulcanization system of the present invention exhibits excellent physical and mechanical properties, aging resistance, and abrasion resistance even in the case where the formulation is not optimized for actual use and there is no fine handling of the bicycle trial. And the winding resistance and the loss tangent are also relatively low. This system provides a very large space for the wear-rolling resistance-ground grip, the so-called magic triangle performance coordination optimization. In fact, the system we invented has a very large adjustment range. Now it is only a ratio that we have initially optimized to be practical, which shows a huge advantage over the conventional system. The amount of white carbon black added is one to several times higher than that of the prior art, and reaches 15 to 50% by weight or more of the raw rubber amount. Can be added to dissolve, improve product performance.

Fourth, the specific implementation

The general application of the invention: butadiene rubber, natural rubber and styrene-butadiene rubber account for 70-85% by weight of the rubber (green rubber), 100% of course is more suitable, other components are generally polymer materials containing olefin bonds; other ingredients Such as a small amount of binary or EPDM, polypropylene, maleic anhydride binary or ethylene propylene diene rubber (EPDM is a copolymer of ethylene, propylene or / and a small amount of non-conjugated diene, or other low olefins) Polymer), it is not excluded to use other recycled rubber, secondary rubber powder (also can be classified into the filler system).

The peroxide initiator is (1) di-tert-butyl peroxide, benzoyl peroxide, lauroyl peroxide; (2) hydroperoxide (cumene hydroperoxide, t-butyl hydroperoxide); (3) Dialkyl peroxide (di-tert-butyl peroxide, dicumyl peroxide); (4) tert-butyl peroxybenzoate, tert-butyl peroxy-t-pentanoate; (5) Methyl ethyl ketone oxide, cyclohexanone peroxide; (6) diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate; the amount is 1-5 parts (all parts by weight, the same below);

Commonly used are di-tert-butyl peroxide, 2,5-dimethyl-2-5-bis(tert-butylperoxy)hexane, tert-butyl peroxybenzoate, 2,1-bis(tert-butyl) Peroxy)cyclohexane, 2,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, dicumyl peroxide, t-butylperoxy cumene 2,5-Dimethyl-2-5-bis(peroxy-tert-butyl)-3-hexyne and the like.

There are also many types of free radical absorption and release modifiers, in an amount of 0.1-1 parts; typically, metal salts such as ferric chloride, copper chloride, sodium nitrite; copper alkylthiocarbamate, N- Organic valence metal salts such as nitroso-N-phenylhydroxylamine aluminum; hydroquinones such as hydroquinone and MTBHQ, DTBHQ, etc.; multi-hindered phenols such as 616, 1076; BHT, di-tert-butyl cresol; 626 diphosphite , 2,6 dithiobis(6-tert-butyl-3-methylphenol), 2,6 di-tert-butyl-a-di Methylamino-p-cresol, nitroxide piperidinol; nitroxide piperidinaldehyde, 4-acetamido-2,2,6,6-tetramethylpiperidine-1-1 nitroxide, 705 phosphite, phenoxazine and the like. The dosage is 1-5 parts;

The bridging agent contains an allyl double bond, and the organic acid within 7 carbon includes zinc, magnesium, zinc, aluminum, calcium, etc. of acrylic acid, crotonic acid, methacrylic acid, methoxybenzene acrylic acid, 4-pentenoic acid, and the like. Or iron salt; the amount is 2-10 parts;

The invention has strong selectivity for the anti-aging agent, and it is not suitable to use some commonly used p-phenylenediamine and polyphenol anti-aging agents, and the use of environmentally-friendly and inexpensive aldehyde amines or imidazoles has good effects, and 1-10 parts are used.

The application of the invention is to directly select a bridging agent, an initiator or a free radical absorption release modifier, or to prepare a semi-finished rubber mixture for use together with a reinforcing agent raw rubber.

Examples of specific formulations, applications and processes (both in parts by weight):

1. Rubber composition, raw rubber is one of butadiene rubber, natural rubber or styrene-butadiene rubber, 100 parts, 35 parts of reinforcing system, especially white carbon black (hydrated silica); anti-aging agent imidazole 5 parts; As a light sole material.

The initiator, di-tert-butyl peroxide, cumene peroxide or lauroyl peroxide, in an amount of 5 parts; the bridging agent is zinc dimethacrylate or calcium acrylate, a total of 5 parts;

A free radical absorption release modifier, in an amount of 0.7 parts, using hydroquinone, MTBHQ, DTBHQ, 616, 1076 or tert-butylaminophenol. The performance is basically the same.

Using the existing vulcanization process, the vulcanization temperature is controlled at 120-150 °C. The measurement of the prepared spline is similar to the basic data performance index.

2, rubber composition, raw rubber is butadiene rubber, natural rubber or styrene-butadiene rubber in any two ratios, 90 parts; reinforcing system white carbon black (hydrated silica) 20 parts; 120 degrees foaming microspheres 4 Part of paraffin oil 20 parts of light calcium carbonate 30 parts of antioxidant aldehyde amine 1 part; bridging agent is zinc dimethacrylate or calcium acrylate, a total of 13 parts, initiator, 2,5 dimethyl-2-5-double (tert-Butylperoxy)hexane, in an amount of 6 parts; a free radical absorption release modifier, in an amount of 0.5 part, using hydroquinone, MTBHQ, DTBHQ, 616, 1076 or tert-butylaminophenol. The performance is basically the same.

Using the existing vulcanization process, the vulcanization temperature is controlled at 149 °C. The measurement of the prepared spline is similar to the performance data of the basic data, and the foaming midsole of the sports shoe can be made.

3, rubber composition, raw rubber is butadiene rubber, natural rubber or styrene-butadiene rubber in any two ratios, 90 parts; reinforcing system white carbon black (hydrated silica) 60 parts; anti-aging agent 3 parts, aldimine Or imidazole; the bridging agent is 30 parts of zinc dimethacrylate and calcium acrylate, the initiator, 2,5 dimethyl-2-5-bis(tert-butylperoxy)hexane, the amount is 2.5 parts; a free radical absorption release modifier, in an amount of 0.2 parts, using hydroquinone, MTBHQ, DTBHQ, 616, 1076 or tert-butylaminophenol. The performance is basically the same. With the existing vulcanization process, the vulcanization temperature is controlled at 145 °C. The measurement of the prepared spline is similar to the performance data of the basic data, and a high-hardness light-colored rubber roller can be produced.

4, rubber composition, raw rubber is butadiene rubber, natural rubber or styrene-butadiene rubber in any two ratios, 90 parts; reinforcing system high wear-resistant carbon black, 45 parts of white carbon black (hydrated silica) 25 parts 1 part of antioxidant, aldehyde amine or imidazole; bridging agent is zinc dimethacrylate and zinc acrylate, a total of 1.6 parts; initiator, 2,5 dimethyl-2-5-bis (tert-butyl) Peroxy)hexane, in an amount of 5 parts; a free radical absorption release modifier in an amount of 1 part, using BHT or di-tert-butylcresol.

Using the existing vulcanization process (preparing the tire), the vulcanization temperature was controlled at 149 °C. The tire's lag angle index is significantly improved, the elongation is high, and the flexural fatigue resistance is more than 350,000 times.

5, rubber composition, raw rubber is cis-butadiene rubber, natural rubber or styrene-butadiene rubber in any two ratios, 120 parts; reinforcing system white carbon black (hydrated silica) 30 parts; light magnesium oxide 25 parts anti-aging 10 parts, aldehyde amines or imidazole; bridging agent is magnesium dimethacrylate, 15 parts of calcium acrylate; initiator, 2,1-bis(tert-butylperoxy)cyclohexane, 2, 1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, dicumyl peroxide, t-butylperoxy cumene or 2,5-dimethyl-2- 5-bis(tert-butylperoxy)hexane, in an amount of 3 parts; free radical absorption release modifier, in an amount of 0.5 parts, using 626 diphosphite, 2,6 dithiobis (6-tert-butyl) 3-methylphenol), 2,6-di-tert-butyl-a-dimethylamino-p-cresol, nitroxide piperidinol, nitroxide piperidinaldehyde or tert-butylaminophenol. Using the existing vulcanization process, the vulcanization temperature is controlled at 152 °C. The light-colored transportation belt has obvious improvement in heat-resistance and wear-resistance index, high elongation and flexural fatigue resistance of more than 330,000 times.

6, rubber composition, raw rubber is butadiene rubber, natural rubber or styrene-butadiene rubber in any two ratios, 90 parts; reinforcing system white carbon black (hydrated silica) 30 parts; anti-aging agent, 1 part, aldehyde Amines or imidazoles; bridging agent is magnesium dimethacrylate or magnesium acrylate, a total of 5 parts; initiator, 2,5 dimethyl-2-5-bis(peroxy-tert-butyl)-3- Hexyne, in an amount of 9 parts; a radical absorption and release modifier, in an amount of 0.5 parts, using 626 diphosphite, 2,6 dithiobis(6-tert-butyl-3-methylphenol), 2, 6 di-tert-butyl-a-dimethylamino-p-cresol, nitroxide piperidinol, nitroxide piperidinaldehyde or tert-butylaminophenol. The existing vulcanization process is used, and the vulcanization temperature is controlled at 165 ° C to produce a heat-resistant low-deformation seal.

7. Rubber composition, raw rubber is a combination of three ratios of butadiene rubber, natural rubber or styrene-butadiene rubber (any combination may be more than 10 parts per component) 100 parts; reinforcing system white carbon black (hydration oxidation) Silicon) 30 parts; aluminum hydroxide 60 parts coupling agent 2 parts anti-aging agent 1 part; bridging agent zinc dimethacrylate or aluminum acrylate, 8 parts, initiator, methyl ethyl ketone peroxide, cyclohexanone peroxide , diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate or t-butyl peroxy cumene, the amount is 3 parts; free radical absorption and release modifier, the amount is 0.7 parts, using 626 Diphosphite, 2,6-dithiobis(6-tert-butyl-3-methylphenol), 2,6-di-tert-butyl-a-dimethylamino-p-cresol, nitroxide piperidine Alcohol, nitroxide piperidinal or tert-butylaminophenol. Using the existing vulcanization process, the vulcanization temperature is controlled at 150 °C. The measurement results of the above prepared splines are similar to the basic data performance indexes, and the flame retardant rubber sheet and the fireproof sole can be produced.

Based on the performance requirements of transparent and color macrosole for advanced sports shoes using silica, the conventional sulfur vulcanization system and the sulfur-free vulcanization system of the present invention are compared with the physical and mechanical properties.

A, NR160WM formula table:

3# tobacco sheet glue 60.0 1502 butyl benzene glue 25.0 9100 butyl butyl rubber 15.0 C5 resin 3 dispersant 2.0 175 white carbon black 50.0 sulfur-free grease 7 paraffin oil 10 anti-RD 1.0 anti-MB 1.0 KH570 1.5 total: 175.5

NR1W01 conventional vulcanization system:

NR170WM masterbatch 175.5 zinc oxide 5.0 stearic acid 2.5 accelerator CZ 0.8 accelerator TT 0.3 sulfur 2.2 total: 185.8

NR170WO2 sulfur-free vulcanization system:

NR170WM masterbatch 175.5.0 SK8954EP70 10.0 SK8713D40F 4.0 Total: 189.5

B performance table:

C, brief analysis

The sulfur vulcanization system is difficult to make a light-colored transparent rubber compound, and the odor is heavy, and the abrasion and strength cannot be made very high. The vulcanization system of the present invention can be obviously improved to make up for these deficiencies.

8. Rubber composition, raw rubber is high-cis type 1,4 structure polybutadiene rubber and styrene-butadiene rubber in any ratio (such as 8:2 mass ratio) 100 parts, secondary rubber powder 15 parts; high resistance Charcoal black 20 reinforcement system at least 30 parts of white carbon black (hydrated silica); anti-aging agent aldehyde amine 2 parts; bridging agent, zinc dimethacrylate or calcium acrylate, 5 parts; initiator, methyl ethyl ketone peroxide, Oxidized cyclohexanone, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, t-butylperoxy cumene or 2,5-dimethyl-2-5-bis(tert-butylperoxy) Hexane, in an amount of 5 parts; a free radical absorption release modifier, in an amount of 0.7 parts, using 626 diphosphite, 2,6 dithiobis(6-tert-butyl-3-methylphenol), 2,6 di-tert-butyl-a-dimethylamino-p-cresol, nitroxide piperidinol, nitroxide piperidinaldehyde or tert-butylaminophenol.

With the existing vulcanization process, the vulcanization temperature is controlled at 150-160 °C.

The above 1-8 is used to prepare the vulcanized tape to prepare the tire and the sole, and the data index of the tape test is obviously improved. The working temperature of the product is increased by 20 °C.

Binary or EPDM rubber and the like are mixed with a peroxide initiator and a bridging agent to prepare a rubber strip or a rubber particle; or a radical absorption and release modifier is added together to prepare a rubber strip or a rubber particle. The weight ratio of initiator and bridging agent accounts for 60%. When the product is produced, the raw rubber system and the reinforcing filler (anti-aging system) system and the above-mentioned rubber strip or rubber pellet are directly prepared by the existing vulcanization process (including Conventional processes such as mixing and mixing) semi-finished or finished products. Even so, binary or EPDM rubber is a small amount in the rubber system, and it has a greater advantage as a premix.

9. Rubber composition, raw rubber is a combination of any combination of butadiene rubber and styrene-butadiene rubber, 90 parts; reinforcing system white carbon black (hydrated silica) 30 parts, plus secondary glue 25 parts; anti-aging agent, aldehyde 1 part of amine; bridging agent, magnesium dimethacrylate or zinc acrylate or zinc 4-pentenoate 15 parts; initiator, 2,1-bis(tert-butylperoxy)-3,3,5-three Methylcyclohexane or 2,5-dimethyl-2-5-bis(tert-butylperoxy)hexane in an amount of 5 parts; a free radical absorption release modifier in an amount of 0.7 parts, using 2,6 Dithiobis(6-tert-butyl-3-methylphenol), 2,6-di-tert-butyl-a-dimethylamino-p-cresol, nitroxide piperidinol, nitroxide piperidine Aldehyde or tert-butylaminophenol. Using the existing vulcanization process, the vulcanization temperature is controlled at 150 °C.

This ratio is used to prepare shoe materials and the like. Resistant to fatigue performance. With more than 300,000 times of flexing, there has been a revolutionary improvement, and the mechanical strength has fully reached and exceeded the level of existing formula products.

10, rubber composition, raw rubber is natural rubber, styrene-butadiene rubber in two arbitrary ratios, 110 parts; reinforcing system white carbon black (hydrated silica) 40 parts, plus 15 parts of carbon black, 20 parts of rubber powder; Antioxidant, 0.8 parts of imidazole; bridging agent, zinc methacrylate 10 parts; initiator, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate or t-butyl peroxidation Propylene, 2 parts; free radical absorption and release modifier, 0.7 parts, with 2,6 dithiobis(6-tert-butyl-3-methylphenol), 2,6 di-tert-butyl- A-dimethylamino-p-cresol, nitroxide piperidinol or tert-butylaminophenol.

Using the existing vulcanization process, the vulcanization temperature is controlled at 155 °C.

This ratio is used to prepare shoe materials and the like. Resistant to fatigue performance. With more than 300,000 times of flexing, there has been a revolutionary improvement, and the mechanical strength has fully reached and exceeded the level of existing formula products.

11. Rubber composition, the raw rubber is a combination of butylbenzene and butadiene rubber in any ratio (such as 8:2 mass ratio) of 100 parts; the reinforcing system is at least 30 parts of white carbon black (hydrated silica), and another carbon black 10 Parts; anti-aging agent, 2 parts of aldehyde amine; bridging agent, magnesium dimethacrylate or magnesium acrylate, 9 parts; initiator, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, peroxidation Dicyclohexyl dicarbonate, t-butylperoxy cumene or 2,5-dimethyl-2-5-bis(tert-butylperoxy)hexane or di-tert-butyl peroxide, in an amount of 4 a free radical absorption and release modifier in an amount of 0.7 parts using 626 diphosphite, 2,6 dithiobis(6-tert-butyl-3-methylphenol), 2,6 di-tert-butyl- A-dimethylamino-p-cresol, nitroxide piperidinol, nitroxide piperidinaldehyde or tert-butylaminophenol.

Using the existing vulcanization process, the vulcanization temperature is controlled at 120-130 °C.

12, rubber composition, raw rubber is a combination of any of the three ratios of butadiene rubber, natural rubber or styrene butadiene rubber, 90 parts (such as 30:30:40); 10 parts of binary or EPDM rubber; reinforcing system 30 parts of white carbon black (hydrated silica), 10 parts of asphalt; 1 part of anti-aging agent; bridging agent, zinc acrylate, 13 parts; initiator, dicumyl peroxide, 5 parts; free radical absorption and release The regulator is used in an amount of 0.7 part by weight of t-butylaminophenol.

Using the existing vulcanization process, the vulcanization temperature is controlled at 150 °C. Suitable for making tire bonding layer and high speed tape string glue.

13. Rubber composition, raw rubber is high cis type 1,4 structure polybutadiene rubber and styrene-butadiene rubber in any ratio (such as 5:5 mass ratio) 100 parts, secondary rubber powder 15 parts; The system is at least 30 parts of white carbon black (hydrated silica), another 10 parts of carbon black; 2 parts of anti-aging agent aldehyde amine; bridging agent, dimethacrylate or zinc acrylate, 5 parts; initiator, methyl ethyl ketone peroxide, Cyclohexanone oxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, Tert-butylperoxy cumene or 2,5-dimethyl-2-5-bis(tert-butylperoxy)hexane, in an amount of 5 parts; free radical absorption release modifier, in an amount of 0.7 parts, using 626 diphosphite, 2,6 dithiobis(6-tert-butyl-3-methylphenol), 2,6 di-tert-butyl-a-dimethylamino-p-cresol, nitroxide Pyridinol, nitroxide piperidinal or tert-butylaminophenol.

Using the existing vulcanization process, the vulcanization temperature is controlled at 130-140 °C.

14. Rubber composition, raw rubber is high-cis type 1,4 structure polybutadiene rubber and styrene-butadiene rubber in any ratio (such as 8:2 mass ratio) 100 parts, secondary rubber powder 15 parts; The system is at least 30 parts of white carbon black (hydrated silica), another 10 parts of carbon black; the antioxidant is 2 parts of aldehyde amine; the bridging agent, dimethacrylate or zinc acrylate, 5 parts; initiator, methyl ethyl ketone peroxide, Cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, t-butylperoxy cumene or 2,5-dimethyl-2-5-bis(tert-butyl Oxy) hexane, in an amount of 5 parts; a free radical absorption release modifier in an amount of 0.7 parts, using 626 diphosphite, 2,6 dithiobis(6-tert-butyl-3-methylphenol) 2,6 di-tert-butyl-a-dimethylamino-p-cresol, nitroxide piperidinol, nitroxide piperidinaldehyde or tert-butylaminophenol.

With the existing vulcanization process, the vulcanization temperature is controlled at 150-160 °C.

15. Rubber composition, raw rubber is a combination of any two ratios of butadiene rubber, natural rubber or styrene-butadiene rubber, 90 parts; binary or ternary rubber of ethylene-propylene, polypropylene, 10 parts; white carbon of reinforcing system 30 parts of black (hydrated silica); 1 part of antioxidant; bridging agent, magnesium dimethacrylate or aluminum acrylate, 3 parts; initiator, dicumyl peroxide, 5 parts; free radical absorption The regulator is released in an amount of 0.7 parts, using an organic valence metal salt such as copper alkylthiocarbamate, N-nitroso-N-phenylhydroxylamine aluminum or hydroquinone.

Using the existing vulcanization process, the vulcanization temperature is controlled at 150 °C.

16. Rubber composition, raw rubber is a combination of any two ratios of butadiene rubber, natural rubber or styrene-butadiene rubber, 110 parts; high-cis type 1,4 structure polybutadiene rubber and styrene-butadiene rubber can be any two ratios Combination (such as 8:2 mass ratio) 100 parts; reinforcing system at least 30 parts of white carbon black (hydrated silica), another 10 parts of carbon black; 2 parts of anti-aging agent aldehyde amine; bridging agent, zinc dimethacrylate or Zinc acrylate, 5 parts; initiator, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, t-butyl peroxy cumene or 2, 5 Methyl-2-5-bis(tert-butylperoxy)hexane, in an amount of 5 parts; a radical absorption and release modifier, in an amount of 0.7 parts, using 626 diphosphite, 2,6 dithio double (6-tert-Butyl-3-methylphenol), 2,6-di-tert-butyl-a-dimethylamino-p-cresol, nitroxide piperidinol, nitroxide piperidinal or tert-butyl Aminophenol. The magnesium salt is replaced by a salt of acrylic acid, crotonic acid, calcium methoxybenzoate or aluminum; the quality index of the prepared sample is not large (the friction resistance is slightly difference).

With the existing vulcanization process, the vulcanization temperature is controlled at 150-160 °C.

17. Rubber composition, raw rubber is 100 parts of any combination of cis-butadiene rubber and styrene-butadiene rubber (10:90); polypropylene, 10 parts; 40 parts of reinforcing system white carbon black (hydrated silica); anti-aging 1 part; bridging agent, zinc dimethacrylate and zinc acrylate, a total of 3 parts; initiator, 2,5 dimethyl-2-5-bis(tert-butylperoxy) hexane, the amount is 5 parts; free radical absorption and release regulator, the amount of 0.7 parts, using copper chloride, sodium nitrite and other metal salts; the quality index of the prepared samples is not large.

18. Rubber composition, raw rubber is 100 parts of any combination of 40% (40:10:50) of butadiene rubber, natural rubber or styrene-butadiene rubber; binary or EPDM rubber, polypropylene, 10 parts; Reinforcing system white carbon black (hydrated silica) 50 parts; anti-aging agent 1 part; bridging agent, dimethacrylic acid or with aluminum acrylate, 5 parts; initiator, dicyclohexyl peroxydicarbonate or 2,5 Dimethyl-2-5-bis(tert-butylperoxy)hexane in an amount of 5 parts; free radical absorption release modifier in an amount of 0.5 part, using alkylthiocarbamate or N-nitrous oxide Base-N-phenylhydroxylamine aluminum.

Using the existing vulcanization process and temperature profile, the maximum vulcanization temperature is controlled at 150 °C. The quality indicators of the prepared samples are not much different.

19, rubber composition, raw rubber is cis-butadiene rubber, natural rubber or styrene-butadiene rubber in any combination of any three ratios, 90 parts; ethylene-propylene binary or ternary glue, 10 parts; reinforcing system white carbon black (hydration Silica) 30 parts; antioxidant 1 part; bridging agent, zinc dimethacrylate or zinc acrylate, 10 parts; initiator, 2,5 dimethyl-2-5-bis(tert-butylperoxy) Hexane, in an amount of 5 parts; a free radical absorption release modifier in an amount of 1 part, using alkyl thiocarbamate, N-nitroso-N-phenylhydroxylamine aluminum tert-butylaminophenol.

Using the existing vulcanization process and temperature profile, the maximum vulcanization temperature is controlled at 155 °C. The quality indicators of the prepared samples are not much different.

20, rubber composition, raw rubber is cis-butadiene rubber, natural rubber or styrene-butadiene rubber in any combination of any ratio (20:40:20), 80 parts; polypropylene 10 parts, reinforcing system white carbon black (hydration oxidation Silicon) 30 parts; 1 part antioxidant; bridging agent calcium dimethacrylate or calcium acrylate, 8 parts; initiator, tert-butyl peroxybenzoate, 2,1-bis(tert-butylperoxy) Cyclohexane or 2,5-dimethyl-2-5-bis(tert-butylperoxy)hexane in an amount of 5 parts; free radical absorption release modifier in an amount of 1 part, using tert-butylaminophenol .

Using the existing vulcanization process, the vulcanization temperature is controlled at 135 °C. At the same time, it is better to add magnesium or zinc dimethacrylate.

21, rubber composition, raw rubber is a combination of natural rubber and styrene-butadiene rubber in any ratio of 105 (such as 60:30); Polyethylene, 10 parts, reinforcing system white carbon black (hydrated silica) 45 parts; anti-aging agent 1 part; bridging agent, dimethacrylate or calcium acrylate, 3 parts; initiator, methyl ethyl ketone peroxide, The dosage is 5 parts; the free radical absorption release modifier is used in an amount of 0.5 part, and t-butylaminophenol is used.

Using the existing vulcanization process and temperature profile, the maximum vulcanization temperature is controlled at 148 °C. The quality indicators of the prepared samples are not much different.

22, rubber composition, raw rubber is a combination of butadiene rubber, natural rubber in any ratio (10:80) 90 parts; polyethylene, 10 parts; reinforcing system white carbon black (hydrated silica) 30 parts; anti-aging agent 1 part; bridging agent, dimethacrylic acid or aluminum acrylate, 5 parts; initiator, methyl ethyl ketone peroxide, 3 parts; free radical absorption and release modifier, 0.3 parts, with tert-butylaminophenol.

With the existing vulcanization process, the vulcanization temperature is controlled at 125 °C.

23, rubber composition, raw rubber is butadiene rubber, natural rubber or styrene-butadiene rubber in any two ratios, 80 parts; polypropylene, 10 parts of reinforcing system white carbon black (hydrated silica) 30 parts; anti-aging agent 1 part; bridging agent, aluminum dimethacrylate or aluminum acrylate, 3 parts; initiator, t-butyl hydroperoxide, 2 parts; free radical absorption and release modifier, 1 part, with uncle Butylaminophenol.

Using the existing vulcanization process, the vulcanization temperature is controlled at 150 °C.

24, rubber composition, raw rubber is 100 parts of butadiene rubber; reinforcing system white carbon black (hydrated silica) 20 parts; calcium acrylate or zinc acrylate 40 parts of aldehyde amine antioxidant 1 part; dispersant, 3 parts; The agent is tert-butyl peroxybenzoate or t-butylperoxybenzene, and the amount is 2 parts; the free radical absorption release regulator is used in an amount of 0.2 part, and t-butylaminophenol is used.

The golf ball core was produced by using an existing vulcanization process and controlling the vulcanization temperature at 148 °C.

The above 19-24 vulcanized rubber is used to prepare a track shoe. Achieving significantly improved data indicators for rubber testing.

25, rubber composition, raw rubber is 100 parts of butadiene rubber, ethylene or propylene binary or ternary glue, 10 parts; reinforcing system white carbon black (hydrated silica) 30 parts; aldehyde amine antioxidant 1 part; Aqueous agent, magnesium crotonate, magnesium 4-pentenoate, 4 parts; initiator, t-butyl peroxy cumene, 7 parts; free radical absorption and release modifier, 0.1 part, with tert-butyl Aminophenol. Using the existing vulcanization process, the vulcanization temperature is controlled at 120 °C.

26, rubber composition, raw rubber is natural rubber or styrene-butadiene rubber in any two ratios, 90 parts; ethylene-propylene binary or ternary glue, 15 parts; reinforcing system white carbon black (hydrated silica) 30 2 parts; aldehyde amine anti-aging agent; bridging agent, zinc dimethacrylate or zinc acrylate, 6 parts; initiator, 5 parts of dicumyl peroxide; free radical absorption and release regulator, the amount is One part is made of copper alkylthiocarbamate or N-nitroso-N-phenylhydroxylamine aluminum. Using the existing vulcanization process (control program), the vulcanization temperature is controlled at 140 °C.

27. In the rubber composition, the raw rubber and the reinforcing anti-aging system material is a mixing component, and the binary or EPDM rubber is prepared by mixing a peroxide initiator and a bridging agent into a rubber particle. The composition; the weight ratio of the second mixing component initiator and the bridging agent accounts for more than 50%, and the two mixing components are required to enter the existing vulcanization process when the product is produced. The second mixing component uses the above ratio of 1-26. The composition of binary or EPDM is less than 50%.

28. On the basis of 27, the initiator, the bridging agent, the initiator are prepared to have a weight ratio of 40% or less, the bridging agent accounts for more than 60% by weight, and is blended with a radical absorption release modifier. When the above three components are 100 parts; the second compounding which is pre-formulated with ethylene propylene rubber, high temperature ester, paraffin oil, and a small amount of white carbon black, calcium carbonate and other desensitizing agent desensitizing agents Ingredients, ethylene propylene rubber, high temperature ester, paraffin oil, white carbon black, calcium carbonate are within 100 parts (including ethylene propylene rubber, high temperature ester, paraffin oil accounted for more than 60 parts); the second mixing component can be safely stored Transport, the powder does not fly, as a safe and stable initiation system; when blended with ethylene propylene rubber, paraffin oil, high temperature ester, free radical absorption and release modifier and bridging agent are evenly prepared into strips or colloidal particles; as stable Vulcanization system.

While the invention has been described above in the preferred embodiments, it is not intended to limit the invention. A person skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

Claims (9)

1. A rubber composition comprising a raw rubber, a mass fraction of 80-120 parts; a peroxide initiator, a mass fraction of 1-5 parts; a bridging agent, a mass fraction of 2-15 parts; a radical absorption The release regulator, the mass part is 0.1-1 part; the reinforcing agent and the anti-aging agent; the raw rubber comprises one to three of polybutadiene rubber, natural rubber and styrene-butadiene rubber, and accounts for more than 70% of the quality of the raw rubber. .
2. The rubber composition according to claim 1, wherein said bridging agent is a salt containing an allyl group, a salt of an organic acid within 7 carbons and magnesium, zinc, aluminum, calcium or iron, wherein One to three kinds; the organic acid within 7 carbon includes one of acrylic acid, crotonic acid, methacrylic acid, methoxybenzene acrylic acid or 4-pentenoic acid.
3. The rubber composition according to claim 1 or 2, wherein the peroxide initiator is one of the following materials:

   (1) di-tert-butyl peroxide, benzoyl peroxide, lauroyl peroxide;

   (2) a hydroperoxide comprising cumene hydroperoxide or t-butyl hydroperoxide;

   (3) a dialkyl peroxide, including di-tert-butyl peroxide or dicumyl peroxide;

   (4) ester peroxides, including tert-butyl peroxybenzoate or tert-butyl peroxy-t-pentanoate;

   (5) ketone peroxides, including methyl ethyl ketone peroxide or cyclohexanone peroxide;

   (6) Dicarbonate peroxides, including diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate.
4. The rubber composition according to claim 2, wherein said radical absorbing release modifier comprises ferric chloride, copper chloride, a metal salt of sodium nitrite, copper alkylthiocarbamate, N- nitroso-N-phenylhydroxylamine aluminum organic variable price metal salt, hydroquinone, MTBHQ or MTBHQ derivative, DTBHQHQ or DTBHQHQ derivative, 616 polyh hindered phenol, 1076 polyh hindered phenol, BHT, di-tert-butyl cresol, 626 Diphosphite, 2,6-dithiobis(6-tert-butyl-3-methylphenol), 2,6-di-tert-butyl-a-dimethylamino-p-cresol, nitroxide piperidine Alcohol, nitroxide piperidinaldehyde, 4-acetamido-2,2,6,6-tetramethylpiperidine-1-1 nitroxide, 705 phosphite or phenol.
5. The rubber composition according to claim 2 or 4, wherein the polybutadiene rubber, natural rubber and styrene-butadiene rubber account for more than 85% by weight of the raw rubber, and the other components are polymer materials containing an ethylenic bond; The antioxidants use aldehydes and imidazoles.
6. The rubber composition according to claim 2 or 4, wherein the bridging agent is a single or more pure product, or ethylene-propylene rubber is used as a carrier bridging agent, and the carrier bridging agent accounts for 70% or more. The free radical absorption and release modifier is 2.5% or more and the dispersant is more than 2% to prepare a film or colloidal film which is safe and stable for storage and transportation.
7. The rubber composition according to claim 1, wherein white carbon black is added in an amount of up to the amount of raw rubber 15-50%.
8. The rubber composition according to claim 2 or 4, wherein the raw rubber and the reinforcing anti-aging system material are the first mixing component, and the white carbon black, calcium silicate, diatomaceous earth, calcium carbonate, dispersing agent , paraffin oil, high temperature ester and peroxide initiator, free radical absorption and release modifier prepared as a non-flying powder as a second mixing component; the weight ratio of the initiator in the second mixing component is less than 40%, The weight ratio of the radical absorption and release modifier is 2.5% or more, and the two kinds of kneading components are required to enter the existing vulcanization process when the product is produced; the composition of the adsorption desensitizer including silica is 50% or less.
9. The rubber composition according to claim 2 or 4, wherein when the initiator and the bridging agent are blended, the initiator is prepared to have a weight ratio of 40% or less, and the bridging agent accounts for more than 60% by weight; the initiator, The bridging agent is further blended with a free radical absorption release modifier; the above initiator, bridging agent and free radical absorption release modifier are further adsorbed with ethylene propylene rubber, high temperature ester, paraffin oil, and a small amount of white carbon black and calcium carbonate. The desensitizing agent is pre-formulated into a second desensitizing component; in the second mixing component, when 100 parts of ethylene-propylene rubber, high-temperature ester, paraffin oil, white carbon black and calcium carbonate are used, Ethylene propylene rubber, high temperature ester and paraffin oil account for more than 50 parts.