CN1536003A - Superfine starch composite powder filling agent for rubber and its preparation method - Google Patents
Superfine starch composite powder filling agent for rubber and its preparation method Download PDFInfo
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- CN1536003A CN1536003A CNA031091431A CN03109143A CN1536003A CN 1536003 A CN1536003 A CN 1536003A CN A031091431 A CNA031091431 A CN A031091431A CN 03109143 A CN03109143 A CN 03109143A CN 1536003 A CN1536003 A CN 1536003A
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Abstract
The present invention belongs to the field of rubber, specially it relates to a superfine starch composite powder filling agent for rubber and its preparation method. The method includes the following steps: firstly, making thermoplastic starch material or modified starch pass through pulverizer, grinding or ball mill to obtain the superfine starch composite powder whose grain size is hundreds nano to 10-odd microns, then using silane coupling agent or titanate coupling agent and mixing it with the above-mentioned superfine starch composite powder so as to can obtain the invented rubber filling agent. Said invented filling agent can be partially or completely substituted for carbon black or white carbon black, etc. and can be used for producing rubber products including tyre, etc. The superfine starch composite powder contains 5-35 wt% of modifying agent, 0.5-10% of coupling agent and the rest is starch.
Description
Technical field
The invention belongs to rubber materials, particularly be used for ultra-fine composites of starch ground pigment of rubber and preparation method thereof.
Background technology
At present, external relevant for adopting starch/softening agent mixture to be applied in the elastic composition of tire, as U.S. Pat 5,672,639 (Starch composite reinforcedrubber composition and tire with at least one component thereof), US6,269,858 (Rubber containing starch reinforcement and tirehaving component thereof) etc., adopted by it technology that is called " non-manufacturing is mixing ", promptly adopt Banbury mixer 150 ℃～170 ℃ with starch/softening agent mixture and compounding rubber, and then carry out the common complete processing of rubber.Chinese patent application number is that 99121389 (publication number is CN1251374A, the preparation of starch reinforced rubber and the application in tire thereof) document also introduced above-mentioned starch and substituted the method that carbon black and white carbon black prepare rubber as strengthening agent, the processing step of " non-manufacturing is mixing " has also been proposed.
Summary of the invention
One of purpose of the present invention provides the ultra-fine composites of starch ground pigment that is used for rubber, be with thermoplastic starch material, modified starch etc., pass through powder process, as adopt pulverizer, ball mill, shredder etc., the preparation granularity is between hundreds of nanometer to tens micron, be preferably lower than 5 microns ultra-fine composites of starch powder, behind coupling agent and this ultra-fine composites of starch powder thorough mixing, to realize that partly or entirely substituting carbon black, white carbon black etc. is filled in the rubber.
Another object of the present invention provides the preparation method of the ultra-fine composites of starch ground pigment that is used for rubber, promptly utilizes simple method to realize that preparation is used for the ultra-fine composites of starch ground pigment of rubber.
A further object of the present invention provides the application of ultra-fine composites of starch ground pigment in rubber.
The ultra-fine composites of starch ground pigment that is used for rubber of the present invention, its composition and content are:
Properties-correcting agent 5～35wt%
Coupling agent 0.5～10wt%
The starch surplus.
Described ultra-fine composites of starch ground pigment is by thermoplastic starch or modified starch preparation, weighting agent as rubber can partly or entirely substitute carbon black, white carbon black etc., in the preparation process of rubber, adopted traditional rubber processing, wherein need sneak into coupling agent, as silane coupling agent, titanate coupling agent etc., so that starch molecular chain and rubber molecular chain combine closely, rather than exist with isolated particle.
The preparation method who is used for the ultra-fine composites of starch ground pigment of rubber of the present invention, step comprises:
(1) properties-correcting agent and starch are obtained thermoplastic starch, etherification starch or cross-linking starch particle through screw extrusion press or chemical reaction, wherein properties-correcting agent accounts for 5～35wt%, and surplus is a starch.
(2) thermoplastic starch, etherification starch or the cross-linking starch particle of step (1) are pulverized through mechanical means such as pulverizing or grinding, obtain particle diameter and be hundreds of nanometer to tens micron, be preferably lower than 5 microns thermoplastic starch, etherification starch or cross-linking starch particle, and then mix with coupling agent, obtain being used for the ultra-fine composites of starch ground pigment of rubber, the coupling agent that contains 0.5～10wt% in the wherein ultra-fine composites of starch powder, the properties-correcting agent of 5～35wt%, surplus is a starch.
The ultra-fine composites of starch ground pigment of rubber that is used for of the present invention is when using, be ultra-fine composites of starch ground pigment is added separately or and carbon black, white carbon black together joins in the rubber, at 70 ℃～100 ℃, preferably carry out mixing at 80 ℃～90 ℃, also need add vulcanizing agent simultaneously (as Sulfur, tolylene diisocyanate etc.), vulcanization accelerator is (as N cyclohexyl 2 benzothiazole sulfenamide, N, N-di-isopropyl-2-[4-morpholinodithio sulphenamide, N-oxy-diethlene-2-henzothiazole-sulfenamide etc.) etc. need the auxiliary agent that adds in the common rubber mixing process.Wherein rubber can be natural rubber, synthetic rubber etc., as polyhutadiene, polyisoprene, paracril or styrene-butadiene rubber(SBR) etc.
Described properties-correcting agent comprises softening agent, as water, ethylene glycol, glycerol, sorbyl alcohol, polyvinyl alcohol or their any mixture etc.; Etherifying agent is as benzyl chloride or monochloroethane etc.; Linking agent is as epoxy chloropropane, dicarboxylic acid compound or their any mixture etc.
Described starch comprises etherification starch, cross-linking starch or thermoplastic starch etc., and etherification starch comprises benzyl substituted starch or ethyl starch etc., and cross-linking starch comprises Epicholorohydrin or with the cross-linking starchs such as carboxylic acid of two functional groups.
Described coupling agent comprises silane coupling agent or titanate coupling agent etc., these coupling agents also are often to adopt in the rubber industry, as γ-aminocarbonyl propyl triethoxyl silane, γ-hydroxypropyl triethoxyl silane, γ-sulfydryl propyl-triethoxysilicane or 3,3 '-two (propyl-triethoxysilicane) tetrasulfide etc.
The preparation of thermoplastic starch material is existing narration in a lot of documents, in starch, add water, ethylene glycol, glycerol, sorbyl alcohol, polyvinyl alcohol or their any mixture etc. as softening agent, adopt forcing machine, extrude at 90 ℃～180 ℃ and to obtain the thermoplastic starch flour complexes, drying is removed low molecular compound, obtain ultrafine powder through grinding and processing again, ultra-fine composites of starch powder and coupling agent are mixed the back use as rubber filler.Wherein starch can adopt the relatively abundant and more cheap W-Gum of China, wheat starch etc.; Forcing machine preferably adopts twin screw extruder (length-to-diameter ratio is not less than 25); The total amount of softening agent is preferably in 20%～30% 5%～35%; Extrusion temperature is preferably at 90 ℃～160 ℃.
The modified starch that is adopted comprises that a kind of benzyl substituted starch is [referring to document Starch, 1998,50 (6): 250～257], cross-linking starch (make as the carboxylic acid that adopts Epicholorohydrin, two functional groups etc., referring to document " chemistry of starch and technology ", RL Whistler, JN Bemiller, EF Paschll published in 1988) etc., the substitution value maximum can reach DS=1 (DS is the substitution value shorthand notation), generally 0.1～0.5, the preparation of modified starch has narration in some open source literatures.Benzyl starch has certain water-repellancy, has reduced the hydroxy radical content on the starch molecular chain, strengthens the consistency with rubber molecule; Cross-linking starch is mainly crosslinked by the hydroxyl on the starch molecular chain, reduce the gelatinization characteristic of starch, the starch granules not gelatinization in hot water as high-crosslinking-degree obtains non-crystalline state starch, help preparing thinner starch powder, increase the dispersive ability in rubber mixing process.The modified starch that makes is pulverized through ball mill, obtained the ultra-fine starch powder of particle diameter below 5 μ m; Mix the weighting agent use of back with coupling agent again as rubber.
In the process of preparation rubber, use the consistency between coupling agent enhancing starch molecule and the rubber molecule, promote the connection between the two molecule, guarantee that starch is not to be present in the rubber external phase with isolated particle, and act on mutually in conjunction with forming cross-linked structure with rubber molecular chain.Native starch is made up of amylose starch and amylopectin, and amylose content is at 0～40% (mass ratio), and molecular weight necessarily, is polymerized by glucose unit from millions of to several.Therefore, a lot of hydroxyls are arranged on the starch molecular chain, form very strong hydrogen bond action, exist with the inflexible double-spiral structure.Rubber, especially natural rubber are to exist with the apolar chain molecule that the C-C key links to each other, and consistency is poor between the starch.This just causes the structure properties and the mechanical property of starch granules filled rubber gained material relatively poor.For this reason, the coupling agent that the present invention adopts, both had hydroxyl, amido, sulfydryl isopolarity functional group, has nonpolar alkane molecule chain again, polar functional group and starch molecular chain effect, and apolar chain and rubber molecular chain consistency are good, cross connection forms hydrogen bond and chemical bond at starch and rubber molecule interchain, material is played good enhancement, obtain cross-linked network structure.Adopting modified starch also mainly is in order to reduce the hydroxy radical content on the starch molecular chain, to weaken the polarity of starch molecule, increasing the consistency with rubber molecule.
The ultra-fine composites of starch ground pigment that is used for rubber of the present invention can partly or entirely substitute carbon black, white carbon black etc. as the weighting agent of rubber; The processing step that is adopted is simple, does not change simultaneously the complete processing of rubber, can be used for comprising the manufacturing of the rubber item of tire.
Embodiment
Embodiment 1
W-Gum makes moisture below 0.5% at 110 ℃ of dry 4h.Get this W-Gum 1000g and (also can adopt moisture W-Gum, the corresponding minimizing of following amount of water), add entry 150g, glycerine 50g, sorbyl alcohol 50g, polyvinyl alcohol 50g, after mixing evenly, in twin screw extruder, 90 ℃～180 ℃ following extruding pelletizations are pulverized after drying and are prepared into the thermoplastic starch ultrafine powder of granularity in hundreds of nanometer to tens micron.Add 0.5%～10% coupling agent, mixed evenly back is stand-by.Get this ultra-fine composites of starch powder 10g, 20g, 30g, 40g, with corresponding carbon black 30g, 20g, 30g, 0g, respective sample is numbered 1,2,3,4, and white carbon black 1.0g～10g, mixing at 70 ℃～100 ℃ jointly with the 100g natural rubber, add vulcanizing agent 1.0g simultaneously, the auxiliary agent of vulcanization accelerator 1.0g and other variable quantitys.This mixing process needs 5～15min approximately, and the rubber that makes vulcanizes 15～20min under 145 ℃～150 ℃ conditions, and this elastomeric material is used for the tread rubber of tire or the rubber item of other purposes.
Embodiment 2
In the 5L there-necked flask, add W-Gum 1000g (starch oven dry weight), add 2000ml water, splash into 15% aqueous sodium hydroxide solution and Epicholorohydrin in batches, the ratio of the amount of substance of the two is 2.5: 1, according to different substitution values, need to add the Epicholorohydrin of different amounts.Add 45 ℃～50 ℃ reactions of back intensification 8h, use 1molL
-1Sulfuric acid neutralization, 70% washing with alcohol is used in washing more then, 90 ℃ of vacuum-drying 4h then obtain the cross-linking starch of moisture＜0.5%, substitution value is 0.1～0.3 to be advisable.At grinding in ball grinder 8h, obtain the ultra-fine composites of starch powder that particle diameter is lower than 5 μ m, with standby behind the silane coupling agent mixing.The reinforced condition identical with embodiment 1, same carbon black, Sulfur, N-oxy-diethlene-2-henzothiazole-sulfenamide additive are mixing with natural rubber together, 70 ℃～80 ℃ of temperature, time 5～10min, make rubber and vulcanize 15min down at 150 ℃, this rubber can be used for the tread rubber of tire or uses as other possible rubber item.
Embodiment 3
In the 5L there-necked flask of taking back the stream prolong, add W-Gum 1000g (starch oven dry weight), water 2000ml, the sodium sulfate that adds starch weight 10%, heat up 50 ℃, add 15% aqueous sodium hydroxide solution and benzyl chloride in batches, the ratio of the amount of substance of the two is 2.5: 1～4: 1, be warming up to 65 ℃～70 ℃ after adding, reaction 5h, cooling then, incline the stillness of night, add 50% alcohol-pickled spending the night, filter then, washing is dry, ball mill grinding makes the ultra-fine modified starch powder of etherification starch, and following condition is with embodiment 1.
Table 1 has been listed the performance that adopts the elastomeric material that ultra-fine composites of starch powder makes
| Project | ????1 | ????2 | ????3 | ????4 |
| Curing temperature/℃ | ????151 | ????151 | ????151 | ????151 |
| Curing time/min | ????15 | ????15 | ????15 | ????15 |
| Shao Er A type hardness tester | ????43 | ????47 | ????52 | ????44 |
| 100% stress at definite elongation/MPa | ????0.7 | ????0.6 | ????0.8 | ????0.6 |
| 300% stress at definite elongation/MPa | ????2.8 | ????3.2 | ????4.0 | ????2.7 |
| Breaking tenacity/Mpa | ????8.5 | ????7.0 | ????10.1 | ????8.5 |
| Tensile yield/% | ????520 | ????470 | ????530 | ????540 |
| Setafter break/% | ????14 | ????14 | ????20 | ????18 |
Annotate: 1,2,3, No. 4 sample is a sample prepared among the embodiment 1
Claims (10)
1. ultra-fine composites of starch ground pigment that is used for rubber, it is characterized in that: the composition of described weighting agent and content are:
Properties-correcting agent 5～35wt%
Coupling agent 0.5～10wt%
Ultra-fine starch surplus.
2. weighting agent as claimed in claim 1 is characterized in that: described properties-correcting agent comprises softening agent, etherifying agent and linking agent.
3. weighting agent as claimed in claim 2 is characterized in that: described softening agent is water, ethylene glycol, glycerol, sorbyl alcohol, polyvinyl alcohol or their any mixture; Described etherifying agent is benzyl chloride or monochloroethane; Described linking agent is epoxy chloropropane, dicarboxylic acid compound or their any mixture.
4. weighting agent as claimed in claim 1 is characterized in that: described coupling agent comprises silane coupling agent or titanate coupling agent.
5. weighting agent as claimed in claim 4, it is characterized in that: described silane coupling agent is γ-aminocarbonyl propyl triethoxyl silane, γ-hydroxypropyl triethoxyl silane, γ-sulfydryl propyl-triethoxysilicane or 3,3 '-two (propyl-triethoxysilicane) tetrasulfide.
6. weighting agent as claimed in claim 1 is characterized in that: described starch comprises etherification starch, cross-linking starch or thermoplastic starch; The particle diameter of described starch is a hundreds of nanometer to tens micron.
7. weighting agent as claimed in claim 6 is characterized in that: described etherification starch comprises benzyl substituted starch or ethyl starch; Cross-linking starch comprises Epicholorohydrin or with the carboxylic acid cross-linking starch of two functional groups.
8. preparation method as any described weighting agent of claim 1～7, it is characterized in that: step comprises:
(1) properties-correcting agent and starch are obtained thermoplastic starch, etherification starch or cross-linking starch particle through screw extrusion press or chemical reaction, wherein properties-correcting agent accounts for 5～35wt%, and surplus is a starch;
(2) with thermoplastic starch, etherification starch or the cross-linking starch particle of step (1) through pulverizing or grinding, obtain particle diameter and be thermoplastic starch, etherification starch or the cross-linking starch particle of hundreds of nanometer to tens micron, and then mix with coupling agent, obtain being used for the ultra-fine composites of starch ground pigment of rubber, the coupling agent that contains 0.5～10wt% in the wherein ultra-fine composites of starch powder, the properties-correcting agent of 5～35wt%, surplus are starch.
9. purposes as any described weighting agent of claim 1～7, it is characterized in that: the described ultra-fine composites of starch ground pigment of rubber that is used for is when using, be ultra-fine composites of starch ground pigment is added separately or together to join in the rubber with carbon black, white carbon black, carry out mixingly at 70 ℃～100 ℃, in mixing process, also need add simultaneously rubber with vulcanizing agent, vulcanization accelerator auxiliary agent.
10. purposes as claimed in claim 9 is characterized in that: described rubber is natural rubber, polyhutadiene, polyisoprene, paracril or styrene-butadiene rubber(SBR).
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| CN 03109143 CN1273527C (en) | 2003-04-04 | 2003-04-04 | Superfine starch composite powder filling agent for rubber and its preparation method |
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| CN 03109143 CN1273527C (en) | 2003-04-04 | 2003-04-04 | Superfine starch composite powder filling agent for rubber and its preparation method |
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| CN1536003A true CN1536003A (en) | 2004-10-13 |
| CN1273527C CN1273527C (en) | 2006-09-06 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519510B (en) * | 2009-03-20 | 2011-04-20 | 沈阳化工学院 | Method for preparing low-heat-generation fatigue-resistant vulcanized rubber |
| CN103554586A (en) * | 2013-09-29 | 2014-02-05 | 安徽同丰橡塑工业有限公司 | Tire production process |
| CN104861219A (en) * | 2014-02-25 | 2015-08-26 | 淮安智祥科技有限公司 | Rubber composite material and preparation method thereof |
| WO2016097151A1 (en) * | 2014-12-19 | 2016-06-23 | Novamont S.P.A. | Destructured starch derivatives and elastomer compositions containing them |
| CN106146906A (en) * | 2016-06-29 | 2016-11-23 | 广西大学 | A kind of preparation method and application of natural emulsion filler |
| JP2018503718A (en) * | 2014-12-19 | 2018-02-08 | ノバモント・ソシエタ・ペル・アチオニＮｏｖａｍｏｎｔ Ｓｏｃｉｅｔａ Ｐｅｒ Ａｚｉｏｎｉ | Use of broken starch derivatives as hysteresis reducing additives for elastomer compositions. |
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2003
- 2003-04-04 CN CN 03109143 patent/CN1273527C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519510B (en) * | 2009-03-20 | 2011-04-20 | 沈阳化工学院 | Method for preparing low-heat-generation fatigue-resistant vulcanized rubber |
| CN103554586A (en) * | 2013-09-29 | 2014-02-05 | 安徽同丰橡塑工业有限公司 | Tire production process |
| CN104861219A (en) * | 2014-02-25 | 2015-08-26 | 淮安智祥科技有限公司 | Rubber composite material and preparation method thereof |
| WO2016097151A1 (en) * | 2014-12-19 | 2016-06-23 | Novamont S.P.A. | Destructured starch derivatives and elastomer compositions containing them |
| CN107108760A (en) * | 2014-12-19 | 2017-08-29 | 诺瓦蒙特股份公司 | Converted starch derivative and the elastic composition containing them |
| US20170362344A1 (en) * | 2014-12-19 | 2017-12-21 | Novamont S.P.A. | Destructured starch derivatives and elastomer compositions containing them |
| JP2018503718A (en) * | 2014-12-19 | 2018-02-08 | ノバモント・ソシエタ・ペル・アチオニＮｏｖａｍｏｎｔ Ｓｏｃｉｅｔａ Ｐｅｒ Ａｚｉｏｎｉ | Use of broken starch derivatives as hysteresis reducing additives for elastomer compositions. |
| US10889655B2 (en) | 2014-12-19 | 2021-01-12 | Novamont S.P.A. | Destructured starch derivatives and elastomer compositions containing them |
| CN107108760B (en) * | 2014-12-19 | 2021-05-11 | 诺瓦蒙特股份公司 | Modified starch derivatives and elastomer compositions containing them |
| CN106146906A (en) * | 2016-06-29 | 2016-11-23 | 广西大学 | A kind of preparation method and application of natural emulsion filler |
| CN106146906B (en) * | 2016-06-29 | 2019-04-02 | 广西大学 | A kind of preparation method and application of natural emulsion filler |
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| CN1273527C (en) | 2006-09-06 |
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