CN1188460C - Granular nano material as rubber stuffing and its prepn - Google Patents

Granular nano material as rubber stuffing and its prepn Download PDF

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CN1188460C
CN1188460C CN 02110498 CN02110498A CN1188460C CN 1188460 C CN1188460 C CN 1188460C CN 02110498 CN02110498 CN 02110498 CN 02110498 A CN02110498 A CN 02110498A CN 1188460 C CN1188460 C CN 1188460C
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nano material
granular
rubber
dispersion
agent
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CN1388156A (en
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骆天荣
任真
于泳
赵永红
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骆天荣
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Abstract

The present invention introduces a granular nanometer material for the rubber addition and a preparation method thereof. The present invention belongs to the technical field of the nanometer material. The present invention is characterized in that a set of complete technological methods for preparing the granular nanometer material comprises the following steps of adding a surface modifier and a dispersion adhesive in the nanometer material, heating and mixing the surface modifier, dispersion adhesive and the nanometer material, and manufacturing granules with 1 to 50mm of grain diameter by using a granulating machine or a tabletting machine. The granular nanometer material prepared by the present invention can greatly lighten the aggregation phenomenon of the nanometer powder and extend the shelf life. Moreover, the flying phenomenon of the nanometer powder can be avoided in the process of packing and using so that a user can conveniently pack, store, transport and weigh the nanometer material. Simultaneously, the damage to the operating staff's health and the environmental pollution can be reduced, and the present invention can be rapidly and evenly dispersed in the process of the rubber adding operation so as to enhance the responsive operation of the granular nanometer material. The granular nanometer material for the rubber addition has wide market prospect so that the present invention can be widely popularized.

Description

Granular nano material that rubber is dosed and preparation method thereof
One, technical field
Granular nano material that rubber disclosed by the invention is dosed and preparation method thereof, the metal nanometer material technical field, be specifically related to a kind of Rubber processing compound-a kind of and be used for the granular nano material that rubber is dosed, also related to this preparation method who is used for the granular nano material that rubber doses.
Two, background technology
As everyone knows, mineral powder uses mainly as compound in the Rubber processing prescription, it is indispensable auxiliary agent, in recent years, because new technology, developing rapidly of novel material, nano material is with its unique nano effect, as: 1. small-size effect, 2. surface interface effect, 3. quantum size effect, 4. tunnel effect etc., thereby nano material gains great popularity in recent years, and many Application Areass have been developed, dosing use in rubber item is exactly one of its purposes, and it can improve the mechanical property of rubber item greatly, as: wear-resisting, intensity, ageing-resistant etc., because nano material is used the excellent properties that is showed in rubber item, will more and more become the leading role of the inorganic kind of dosing.
The tradition mineral powder is because the characteristics of self, it exists in rubber mixing process that dispersing property is poor, roll banding, dust from flying, the harm employee is healthy and problem such as environment, nano material is because particle diameter is littler, and specific surface area is bigger, and this problem is more apparent outstanding.
In order to overcome the above problems, both at home and abroad in succession dispersing property and the problems such as dust from flying, roll banding, environmental protection of mineral powder in the Rubber processing process have been launched research in recent years, as Chinese patent CN1130154A, provide a kind of, made the particulate state high-active zinc oxide by screw extrusion press by bonding dispersion agent or tensio-active agent; Provide a kind of zinc oxide dispersion as U.S. Pat 6046260, mainly be to be binding agent with petroleum pitch or terpenes, lipid acid is tensio-active agent, and synthetic rubber, natural rubber are carrier, zinc oxide is scattered in made the zinc oxide dispersion in the carrier rubber; The zinc oxide of commercially available Baeyer-TUV-80 product and for example, it is that carrier makes predispersion with the ethylene-propylene diene copolymer; Though above example has solved the problems such as roll banding, dust from flying, environmental protection and harm person health of traditional mineral powder in Rubber processing, for novel replacement nano material, does not still have good terms of settlement at present.
The nano-material surface particle is more than common material in addition, surface energy is very big, be very easy between the particle reunite, in air, store and very easily absorb moisture and carbonic acid gas, these can have influence on the use properties and the effect of nano material, this makes packing, storing, the quality guaranteed period of nano material all be affected, and with traditional mineral powder relatively, in use, the dispersion of nano material is more difficult, directly use nano material, its dispersed being difficult to guarantees that this can cause the instability of rubber item quality.Therefore research and development are used for the easy dispersed particles shape nano material that rubber is dosed, and to improve the rubber item performance, are that people expect.
Three, summary of the invention
The objective of the invention is provides granular nano material that a kind of rubber doses and preparation method thereof to society, for improving the rubber item quality, alleviate environmental pollution and do some contribution.
Technical scheme of the present invention comprises the technical scheme of the granular nano material that this rubber is dosed and the technical scheme of its preparation method.
The present invention is directed to the variety of problems that nano material exists in rubber materials uses; adopt a whole set of preparation method of granules and technology; according to different nano materials and environment for use; at first utilize high performance mixing equipment with nano material and different surface-modifying agent mixing; nano material is carried out surface modification; and then under heating condition, mix with the organic dispersion binding agent of fused; mixed dispersion is carried out granulation with tablets press or tabletting machine, and making the footpath that rubber doses is the granular nano material of 1mm-50mm.Granular nano material with the present invention's preparation, alleviated the agglomeration of nano-powder greatly, prolonged the quality guaranteed period, avoided nano-powder in packing and use, to fly upward phenomenon, be convenient to packing, storing, weighing, alleviated, in addition the granular nano material dosed of the rubber of the present invention's preparation to the harm of operator ' s health and to the pollution of environment, dose process and disperse fast, evenly being used for rubber, can give full play to the nano effect of nano material.This granular nano material each component ratio prescription is: nano material: surface-modifying agent: disperse binding agent=40-95%: 1-20%: 4-40%, wherein each component ratio summation must satisfy 100% (weight percent).The granular nano material that this rubber is dosed is that main body is made with the nano material, and described nano material comprises: nano level lime carbonate, zinc oxide, graphite, magnesium oxide, silicon-dioxide; Described addible surface-modifying agent is positively charged ion, nonionogenic tenside, at least a in the titanate coupling agent; Described addible dispersion binding agent is at least a in aliphatic alcohols in 50-150 ℃ organism of fusing point or softening temperature, fatty amine, fatty acid, the resene.
The granular nano material that aforesaid rubber is dosed, its detailed technical essential has: a, described nano material are meant: in nano level lime carbonate, zinc oxide, graphite, magnesium oxide, the silicon-dioxide any; The surface-modifying agent of b, described interpolation comprises: the quaternary ammonium salts of cats product, imidazolines, silicone based, the fatty alcohol-polyoxyethylene ether of the TX-10-polyoxyethylene nonylphenol ether of nonionogenic tenside, the fatty alcohol-polyoxyethylene ether of the AE0-9-polymerization degree 9, the AE0-10-polymerization degree 10, titanate coupling agent; Can add wherein at least a in the preparation;
The preparation method of the granular nano material that rubber of the present invention is dosed; it is based on nano material; adopt a whole set of preparation method of granules and technology; according to different service requirementss; in preparation process, add different surfaces properties-correcting agent, disperse binding agent; through heating, being mixed and made into dispersion, with tablets press or tabletting machine dispersion is carried out granulation again.Its technical characterstic is: a.This granular nano material each component ratio prescription is: nano material: surface-modifying agent: disperse binding agent=40-95%: 1-20%: 4-40%, each component ratio summation must satisfy 100% (weight percent), and wherein: described nano material comprises: nanometer grade calcium carbonate, zinc oxide, magnesium oxide, graphite, silicon-dioxide; The surface-modifying agent of described interpolation is positively charged ion, nonionogenic tenside, titanate coupling agent at least a; Described dispersion binding agent is that fusing point or aliphatic alcohols, fatty amine, fatty acid, the resene of softening temperature in 50-150 ℃ organism are at least a; B. the preparation method of this granular nano material: according to different nano materials and environment for use, by necessary requirement each component is weighed up standbyly, earlier the nano material powder is added mixing tank, be heated to 50-180 ℃, start mixing tank, add surface-modifying agent; To disperse binding agent to be heated to 50-180 ℃, make its fusion, add mixing tank, mix 30-120 minute, obtain dispersion, again with dispersion with tablets press or tabletting machine granulation, make the particle that particle diameter is 1mm-50mm.
The preparation method of the granular nano material that aforesaid rubber is dosed, technical essential has: a, described nano material are: nano level lime carbonate, zinc oxide, in graphite, magnesium oxide, the silicon-dioxide any; B, surface-modifying agent comprise: the quaternary ammonium salts of cats product, imidazolines, silicone based, the fatty alcohol-polyoxyethylene ether of the TX-10-polyoxyethylene nonylphenol ether of nonionogenic tenside, the fatty alcohol-polyoxyethylene ether of the AE0-9-polymerization degree 9, the AE0-10-polymerization degree 10, titanate coupling agent; Can add wherein at least a in the preparation.
The present invention is directed to nano material, to exist dispersing property in rubber mixing process poor, roll banding, dust from flying, the harm employee is healthy and problem such as environment, a whole set of preparation method of granules and technology have been adopted, according to different nano materials and environment for use, at first nano material is carried out surface modification, and then mix with organic dispersion binding agent, with the dispersion granulation, make particle.Practical, high in technological content, the easy handling of this cover particle preparation of nanomaterials is convenient to promote.Prepare the granular nano material that rubber is dosed with the present invention, alleviated the agglomeration of nano-powder greatly, and in air, do not absorb moisture and carbonic acid gas, prolonged the quality guaranteed period, avoided nano-powder in packing and use, to fly upward phenomenon simultaneously, be convenient to packing, storing, weighing, alleviated to the harm of operator ' s health and to the pollution of environment, the granular nano material dosed of the rubber of the present invention preparation in addition, owing to added surface-modifying agent and disperseed binding agent, in rubber mixing process, disperse fast, evenly, can give full play to the nano effect of nano material.
Four, description of drawings
Fig. 1 is preparation method's schema of the granular nano material dosed of rubber.
In Fig. 1: 1, nano material; 2, surface-modifying agent; 3, disperse binding agent; 4, heating; 5, fusion; 6, mix; 7, granulation; 8, check.
Five, concrete implementing method
Particulate calcium carbonate nano material that embodiment one rubber is dosed and preparation method thereof:
1, the particulate calcium carbonate nano material dosed of rubber: its each component is: a, nano material: nano-calcium carbonate; B, surface-modifying agent: nonionogenic tenside AE0-9-fatty alcohol-polyoxyethylene ether (polymerization degree 9) and positively charged ion tetrahydroglyoxaline; C, dispersion binding agent are paraffin and petroleum resin; The concrete ratio of each component is: nano-calcium carbonate: AE0-9-fatty alcohol-polyoxyethylene ether (polymerization degree 9): positively charged ion tetrahydroglyoxaline: paraffin: petroleum resin=65%: 5%: 5%: 15%: 10%, (weight percent).
2, the particulate calcium carbonate preparation of nanomaterials that rubber is dosed: the component of the granular nano material that this example rubber is dosed and ratio thereof with this example 1 described in, earlier each component is weighed up standby, then nano-calcium carbonate is added mixing tank, be heated to 180 ℃, start mixing tank, add surface-modifying agent AE0-9-fatty alcohol-polyoxyethylene ether (polymerization degree 9) and positively charged ion tetrahydroglyoxaline; To disperse binding agent paraffin and petroleum resin to be heated to 180 ℃ in addition, make its fusion; Fused is disperseed binding agent to add mixing tank again, mixed 30 minutes, obtain dispersion, dispersion is carried out granulation with tablets press or tabletting machine, particle diameter is 1mm.
Granular graphite nano material that embodiment two rubber are dosed and preparation method thereof:
1, the granular graphite nano material dosed of rubber: its each component is: a, nano material: nano level graphite; B, surface-modifying agent: titanate coupling agent; C, dispersion binding agent: primary octadecylamine; The concrete ratio of each component is: nano level graphite: titanate coupling agent: primary octadecylamine=95%: 1%: 4% (weight percent).
2, the granular graphite preparation of nanomaterials dosed of rubber: the component of the granular nano material that this example rubber is dosed and ratio thereof with this example 1 described in, earlier each component is weighed up standby, then nano level graphite is added mixing tank, be heated to 50C, start mixing tank, add titanate coupling agent; To disperse the binding agent primary octadecylamine to be heated to 50 ℃ in addition, make its fusion; Fused is disperseed binding agent to add mixing tank again, mixed 60 minutes, obtain dispersion, dispersion is carried out granulation with tablets press or tabletting machine, particle diameter is 50mm.
Particulate state nano zinc oxide material that embodiment three rubber are dosed and preparation method thereof:
1, the particulate state nano zinc oxide material dosed of rubber: its each component is: a, nano material: nano zine oxide, b, surface-modifying agent: nonionogenic tenside TX-10-polyoxyethylene nonylphenol ether (epoxide polymerization degree 10), titanate coupling agent, hydroxy silicon oil, c, dispersion binding agent: paraffin and petroleum resin; The concrete ratio of each component is: nano zine oxide: TX-10-polyoxyethylene nonylphenol ether (epoxide polymerization degree 10): titanate coupling agent: hydroxy silicon oil: paraffin: petroleum resin=40%: 10%: 5%: 5%: 10%: 30% (weight percent).
2, the preparation method of the particulate state nano zinc oxide material dosed of rubber: the component of the granular nano material that this example rubber is dosed and ratio thereof with this example 1 described in, earlier each component is weighed up standby, then the nano material nano zine oxide is added mixing tank, be heated to 100 ℃, start mixing tank, add surface-modifying agent TX-10-polyoxyethylene nonylphenol ether (epoxide polymerization degree 10), titanate coupling agent, hydroxy silicon oil; To disperse binding agent paraffin and petroleum resin to be heated to 100 ℃ in addition, make its fusion; Fused is disperseed binding agent to add mixing tank again, mixed 120 minutes, obtain dispersion, dispersion is carried out granulation with tablets press or tabletting machine, particle diameter is 10mm.
Particulate state bitter earth nano material that embodiment four rubber are dosed and preparation method thereof:
1, the particulate state bitter earth nano material dosed of rubber: its each component is: a, nano material: nano magnesia; B, surface-modifying agent: nonionogenic tenside AE0-10-fatty alcohol-polyoxyethylene ether (polymerization degree is 10) and cationic quaternary ammonium salt, c, dispersion binding agent are stearic acid and Shi Di resin; The concrete ratio of each component is: nano magnesia: AE0-10-fatty alcohol-polyoxyethylene ether: cationic quaternary ammonium salt: stearic acid: petroleum resin=70%: 8%: 2%: 10%: 10%, (weight percent).
2, the particulate state bitter earth nano preparation methods dosed of rubber: the component of the granular nano material that this example rubber is dosed and ratio thereof with this example 1 described in, earlier each component is weighed up standby, then nano magnesia is added mixing tank, be heated to 150 ℃, start mixing tank, add surface-modifying agent AE0-10-fatty alcohol-polyoxyethylene ether (polymerization degree is 10) and cationic quaternary ammonium salt; To disperse binding agent stearic acid and petroleum resin to be heated to 150 ℃ in addition, make its fusion; Fused is disperseed binding agent to add mixing tank again, mixed 90 minutes, obtain dispersion, dispersion is carried out granulation with tablets press or tabletting machine, particle diameter is 6mm.
Particulate silica nano material that embodiment five rubber are dosed and preparation method thereof:
1, the particulate silica nano material dosed of rubber: its each component is: a, nano material: nano silicon; B, surface-modifying agent: titanate coupling agent and amido silicon oil; C, dispersion binding agent are resol and octadecanol; The concrete ratio of each component is: nano silicon: titanate coupling agent: amido silicon oil: resol: octadecanol=55%: 6%: 4%: 20%: 15% (weight percent).
2, the particulate silica preparation of nanomaterials dosed of rubber: the component of the granular nano material that this example rubber is dosed and ratio thereof with this example 1 described in, earlier each component is weighed up standby, then nano silicon is added mixing tank, be heated to 80 ℃, start mixing tank, add titanate coupling agent and amido silicon oil; To disperse adhesive phenolic resin and octadecanol to be heated to 120 ℃ in addition, make its fusion; Will fusion disperses binding agent to add mixing tank again, mixes 60 minutes, obtains dispersion, and dispersion is carried out granulation with tablets press or tabletting machine, and particle diameter is 15mm.

Claims (4)

1, the granular nano material dosed of a kind of rubber, it is based on nano material, adopt a whole set of preparation method of granules and technology, according to different service requirementss, in preparation process, add different surfaces properties-correcting agent, disperse binding agent, through heating, be mixed and made into dispersion, with tablets press or tabletting machine dispersion is carried out granulation again, be characterised in that: this granular nano material each component and part by weight prescription are: nano material: surface-modifying agent: disperse binding agent=40-95%: 1-20%: 4-40%, each component ratio summation must satisfy 100%; Wherein: described nano material is: nano level lime carbonate, zinc oxide, graphite, magnesium oxide, silicon-dioxide; The surface-modifying agent of described interpolation is: at least a in positively charged ion, nonionogenic tenside, the titanate coupling agent; The dispersion binding agent of described interpolation is at least a in aliphatic alcohols in 50 1 150 ℃ organism of its fusing point or softening temperature, fatty amine, fatty acid, the resene.
2, the granular nano material dosed of rubber according to claim 1 is characterised in that:
A. described nano material is meant: in nano level lime carbonate, zinc oxide, graphite, magnesium oxide, the silicon-dioxide any;
B. surface-modifying agent comprises: the quaternary ammonium salts of cats product, imidazolines, silicone based, the fatty alcohol-polyoxyethylene ether of the TX-10-polyoxyethylene nonylphenol ether of nonionogenic tenside, the fatty alcohol-polyoxyethylene ether of the AE0-9-polymerization degree 9, the AE0-10-polymerization degree 10, titanate coupling agent; Add wherein at least a.
3, the preparation method of the granular nano material dosed of a kind of rubber; it is based on nano material; adopt a whole set of preparation method of granules and technology; according to different service requirementss; in preparation process, add different surfaces properties-correcting agent, disperse binding agent; through heating, being mixed and made into dispersion, with tablets press or tabletting machine dispersion is carried out granulation again, be characterised in that:
A. this granular nano material each component and part by weight prescription are: nano material: surface-modifying agent: disperse binding agent=40-95%: 1-20%: 4-40%, wherein each component ratio summation must satisfy 100%; Described nano material comprises: nanometer grade calcium carbonate, zinc oxide, magnesium oxide, graphite, silicon-dioxide; The surface-modifying agent of described interpolation is at least a in positively charged ion, nonionogenic tenside, the titanate coupling agent; Described dispersion binding agent is at least a in aliphatic alcohols in 50-150 ℃ organism of fusing point or softening temperature, fatty amine, fatty acid, the resene;
B. the preparation method of this granular nano material: on request the each component branch is weighed up standbyly, at first the nano material powder is added mixing tank, be heated to 50-180 ℃, start mixing tank, add surface-modifying agent; To disperse binding agent to be heated to 50-180 ℃, make its fusion, add mixing tank, mix 30-120 minute, obtain dispersion, again with dispersion with tablets press or tabletting machine granulation, make the particle that particle diameter is 1mm-50mm.
4, the preparation method of the granular nano material dosed of rubber according to claim 3 is characterised in that:
A, described nano material are meant: in nanometer grade calcium carbonate, zinc oxide, graphite, magnesium oxide, the silicon-dioxide any;
B, surface-modifying agent comprise: the quaternary ammonium salts of cats product, imidazolines, silicone based, the fatty alcohol-polyoxyethylene ether of the TX-10-polyoxyethylene nonylphenol ether of nonionogenic tenside, the fatty alcohol-polyoxyethylene ether of the AE0-9 polymerization degree 9, the AE0-10-polymerization degree 10, titanate coupling agent; Add wherein at least a.
CN 02110498 2002-06-03 2002-06-03 Granular nano material as rubber stuffing and its prepn Expired - Fee Related CN1188460C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100343326C (en) * 2004-11-26 2007-10-17 华南热带农业大学 Method for preparing nano calcium carbonate/rubber composite materials
CN101077914B (en) * 2007-06-27 2013-02-06 骆天荣 Nano zinc oxide particle added to rubber and preparation method thereof
DE102008054967A1 (en) * 2008-12-19 2010-06-24 Evonik Degussa Gmbh Silatran-containing particles
CN107602917A (en) * 2017-08-31 2018-01-19 贺州钟山县双文碳酸钙新材料有限公司 A kind of modified calcium carbonate for cable rubber sheath
CN111825916A (en) * 2019-04-15 2020-10-27 呈和科技股份有限公司 Composite auxiliary agent and preparation method thereof
CN113150391A (en) * 2021-03-19 2021-07-23 安徽瑞邦橡塑助剂集团有限公司 Spherical graphite filler for rubber and preparation method thereof

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