CN101186722B - Functional rubber strengthening agent and preparation method thereof - Google Patents
Functional rubber strengthening agent and preparation method thereof Download PDFInfo
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- CN101186722B CN101186722B CN2007101591795A CN200710159179A CN101186722B CN 101186722 B CN101186722 B CN 101186722B CN 2007101591795 A CN2007101591795 A CN 2007101591795A CN 200710159179 A CN200710159179 A CN 200710159179A CN 101186722 B CN101186722 B CN 101186722B
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Abstract
Provided is a functionality rubber strengthening agent and a relative preparation method, which relates to a chemical industry auxiliary agent and a preparation method thereof. The preparation method comprises a, under the condition of mechanical agitation, adding starch and initiating agent in a N, N-dimethylformamide solution whose temperature is 70-100DEG C to gelatinize for 0.5-2h, b, under the condition of mechanical agitation, adding hydroxyl protecting agent component A and protonic acid component B in the reactive solution of the first step, and reacting for 0.5-2h under the temperature of 70-100DEG C to prepare starch derivative via scouring, suction, drying and breaking, adding coupling agent to prepare the functionality rubber strengthening agent. The strengthening agent is simple in manufacturing technique, low in cost and comparatively high in environment-friendly extent, which is widely applied in various types of tires and other rubber products.
Description
Technical field
The present invention relates to a kind of auxiliary chemicals and preparation method thereof, particularly relate to a kind of reinforcing rubber that is used for, improve vulcanized rubber elasticity, fall low-heat-generation, reduce functional aid of hysteresis loss and preparation method thereof.
Background technology
Treated starch is the material of a kind of being called as " engineering biopolymerization filler ", is to be obtained by various modifications by common starch.In recent years, the progress aspect starch denaturalization is rapider both at home and abroad, and its product is widely used in fields such as weaving, food, medicine, petrochemical complex, papermaking.Yet starch but seldom is applied in the rubber, with the strengthening agent of starch as rubber, can obtain low-heat-generation, snappiness, the low new type rubber matrix material that lags behind.
Because the restriction of this body structure of starch, it is not ideal that simple starch is made its reinforcing effect of rubber reinforcing filler, therefore starch need be carried out modification and handle.The method of starch conversion is a lot, and wherein chemical modification is the most general.Consider starch and rubber structure, great majority adopt the acid or the acid anhydrides that contain the two keys of c=c that starch is carried out graft modification, but the starch ester of this method preparation, often percentage of grafting is very low, and its condition is difficult to control.
Summary of the invention
The object of the present invention is to provide rubber functional strengthening agent of a kind of starch derivative and preparation method thereof, adopt a kind of hydroxy-protecting agent, make preparation technology simple the starch etherificate, the protection ratio height, obvious as the rubber reinforcing filler reinforcing effect.
The objective of the invention is to be achieved through the following technical solutions:
A kind of functional rubber strengthening agent, it is made by following method:
A. under the mechanical stirring condition, with starch and the initiator N at 70～100 ℃, gelatinization is 0.5～2 hour in the N dimethyl formamide solution;
B. under the mechanical stirring condition, add hydroxy-protecting agent component A and protonic acid B component in the reaction soln in a step, reacted 0.5～2 hour down at 70～100 ℃, washing suction filtration, oven dry, pulverizing make starch derivative; Add composite this functional rubber strengthening agent that makes of coupling agent again.
Aforesaid a kind of functional rubber strengthening agent, described hydroxy-protecting agent component A is dihydropyrane or epoxy alkane.
Aforesaid a kind of functional rubber strengthening agent, described protonic acid B component is tosic acid, aluminum phosphate etc.
The composite interpolation coupling agent of aforesaid a kind of functional rubber strengthening agent composition, described coupling agent is silane coupling agent or titante coupling agent.
A kind of functional rubber strengthening agent preparation method, it prepares as follows:
A. under the mechanical stirring condition, with starch and the initiator N at 70～100 ℃, gelatinization is 0.5～2 hour in the dinethylformamide solution;
B. under the mechanical stirring condition, add hydroxy-protecting agent component A and protonic acid B component in the reaction soln in a step, reacted 0.5～2 hour down at 70～100 ℃, washing suction filtration, oven dry, pulverizing make starch derivative; Add composite this functional rubber strengthening agent that makes of coupling agent again.
Aforesaid a kind of functional rubber strengthening agent preparation method, its described hydroxy-protecting agent component A with the starch quality ratio is: component A: starch=1: 3～1: 7.
Aforesaid a kind of functional rubber strengthening agent preparation method, its described protonic acid B component with the starch quality ratio is: B component: starch=0.5: 100～2.0: 100.
Advantage of the present invention and effect are:
1. the present invention adopts a kind of hydroxy-protecting agent with the starch etherificate, has overcome existing preparation treated starch working condition harshness, and prepared product percentage of grafting is low, as the unfavorable shortcoming of rubber reinforcing filler reinforcing effect.
2. to prepare the technology of starch ethers simple in the present invention, and protection ratio, percentage of grafting height have good reinforcing effect as rubber item strengthening agents such as tires, realize snappiness, low-heat-generation and the low hysteresis loss function of rubber composite simultaneously.
Description of drawings
Fig. 1 is the infrared spectrogram of W-Gum of the present invention and starch ethers;
Fig. 2 is the SEM photo figure of W-Gum of the present invention;
Fig. 3 is the SEM photo figure of starch ethers of the present invention.
Embodiment
The present invention is described in detail with reference to the accompanying drawings.
Embodiment 1
Dihydropyrane (liquid state) 20ml/ protonic acid 0.05g/ stirs 1 hour/B component of 0.5 hour/reaction at 95 ℃: starch (mass ratio)=1: 100.
Embodiment 2
Applicating example
The starch ethers compound that utilizes institute's application method to make carries out the cross-linked rubber test according to following rubber compounding scheme.
Table 1: scheme 1 (part)
Table 3: the vulcanized rubber physicals relatively
| Scheme 1 | Scheme 2 | |
| Treated starch | 0 part | 8 parts |
| 143 ℃ of test piece cure conditions * | 30min | 30min |
| Hardness (Shao Er A) | 64 | 65 |
| 300% stress at definite elongation MPa | 12.1 | 11.7 |
| Tensile strength MPa | 25.0 | 20.6 |
| Tensile yield % | 522 | 462 |
| Setafter break % | 28 | 22 |
| Tear strength kN/m | 57 | 55 |
| Density Mg/m 3 | 1.12 | 1.12 |
| Elasticity % | 35 | 46 |
| Constant load compression heat generation ℃ | 39 | 35 |
| The flex crack number of times | 60,000 times be full of cracks does not appear | 60,000 times be full of cracks does not appear |
| Dynamic tgd value | -20 ℃ is 0.62; + 60 ℃ is 0.15 | -20 ℃ is 0.48; + 60 ℃ is 0.07 |
Fig. 2, Fig. 3 are photo figure, the unintelligible the understanding of the present invention that do not influence of the literal among the figure;
The structural analysis of the starch ethers of this method preparation is as follows:
1. graft product Infrared spectroscopy
The infrared spectrogram of starch and starch ethers as shown in Figure 1.
Among Fig. 1, A is a W-Gum, and B is a starch ethers, 1701cm in B
-1There is tangible ehter bond absorption peak at the place, and 1653 cm
-1The hydroxyl absorption peak die down.
2. the scanning electron microscope analysis of W-Gum and starch ethers
In order to observe the variation of surface topography, with W-Gum and carry out the sign that modification W-Gum has later carried out scanning electronic microscope respectively.
Can see that by Fig. 2 the particle of corn ative starch is filled circles and polygon, smooth surface, surface tissue is tight, and corner angle are smooth.
Fig. 3 is the SEM figure of starch ethers; certain variation has taken place in its face shaping of starch of comparing with the scanning electron microscope of W-Gum after the modification as can be seen, and as rough, the outside has been subjected to certain " corrosion "; loosely organized, reaction has taken place in this explanation starch and hydroxy-protecting agent.
Claims (5)
1. functional rubber strengthening agent is characterized in that it is made by following method:
A. under the mechanical stirring condition, with starch and the initiator N at 70～100 ℃, gelatinization is 0.5～2 hour in the N dimethyl formamide solution;
B. under the mechanical stirring condition, add hydroxy-protecting agent component A---dihydropyrane and protonic acid B component---tosic acid or aluminum phosphate in the reaction soln in a step, reacted 0.5～2 hour down at 70～100 ℃, washing suction filtration, oven dry, pulverizing make starch derivative; Add composite this functional rubber strengthening agent that makes of coupling agent again.
2. a kind of functional rubber strengthening agent according to claim 1 is characterized in that described coupling agent is silane coupling agent or titante coupling agent.
3. functional rubber strengthening agent preparation method is characterized in that preparing as follows:
A. under the mechanical stirring condition, with starch and the initiator N at 70～100 ℃, gelatinization is 0.5～2 hour in the dinethylformamide solution;
B. under the mechanical stirring condition, add hydroxy-protecting agent component A---dihydropyrane and protonic acid B component---tosic acid or aluminum phosphate in the reaction soln in a step, reacted 0.5～2 hour down at 70～100 ℃, washing suction filtration, oven dry, pulverizing make starch derivative; Add composite this functional rubber strengthening agent that makes of coupling agent again.
4. a kind of functional rubber strengthening agent preparation method according to claim 3 is characterized in that described hydroxy-protecting agent component A and starch quality ratio are: component A: starch=1: 3～1: 7.
5. a kind of functional rubber strengthening agent preparation method according to claim 3 is characterized in that described protonic acid B component and starch quality ratio are: B component: starch=0.5: 100～2.0: 100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101591795A CN101186722B (en) | 2007-12-25 | 2007-12-25 | Functional rubber strengthening agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101591795A CN101186722B (en) | 2007-12-25 | 2007-12-25 | Functional rubber strengthening agent and preparation method thereof |
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| Publication Number | Publication Date |
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| CN101186722A CN101186722A (en) | 2008-05-28 |
| CN101186722B true CN101186722B (en) | 2010-11-24 |
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| CN2007101591795A Expired - Fee Related CN101186722B (en) | 2007-12-25 | 2007-12-25 | Functional rubber strengthening agent and preparation method thereof |
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Families Citing this family (2)
| 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 |
| CN111115782B (en) * | 2020-01-09 | 2022-05-20 | 江西省地质环境监测总站(鄱阳湖生态环境研究所) | Sewage treatment flocculant and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5672639A (en) * | 1996-03-12 | 1997-09-30 | The Goodyear Tire & Rubber Company | Starch composite reinforced rubber composition and tire with at least one component thereof |
| US6273163B1 (en) * | 1998-10-22 | 2001-08-14 | The Goodyear Tire & Rubber Company | Tire with tread of rubber composition prepared with reinforcing fillers which include starch/plasticizer composite |
| CN1854175A (en) * | 2005-04-27 | 2006-11-01 | 住友橡胶工业株式会社 | Starch composite and rubber composite including same |
| CN1970609A (en) * | 2006-12-07 | 2007-05-30 | 沈阳化工学院 | Rubber reinforcing agent and its preparation method |
-
2007
- 2007-12-25 CN CN2007101591795A patent/CN101186722B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5672639A (en) * | 1996-03-12 | 1997-09-30 | The Goodyear Tire & Rubber Company | Starch composite reinforced rubber composition and tire with at least one component thereof |
| US6273163B1 (en) * | 1998-10-22 | 2001-08-14 | The Goodyear Tire & Rubber Company | Tire with tread of rubber composition prepared with reinforcing fillers which include starch/plasticizer composite |
| CN1854175A (en) * | 2005-04-27 | 2006-11-01 | 住友橡胶工业株式会社 | Starch composite and rubber composite including same |
| CN1970609A (en) * | 2006-12-07 | 2007-05-30 | 沈阳化工学院 | Rubber reinforcing agent and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 齐卿等.偶联剂对淀粉/丁苯橡胶复合材料性能的影响.合成橡胶工业29 5.2006,29(5),351-355. |
| 齐卿等.偶联剂对淀粉/丁苯橡胶复合材料性能的影响.合成橡胶工业29 5.2006,29(5),351-355. * |
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Owner name: SHENYANG UNIVERSITY OF CHEMICAL TECHNOLOGY Free format text: FORMER OWNER: SHENYANG INSTITUTE OF CHEMICAL TECHNOLOGY Effective date: 20111229 |
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Assignee: Liaoning Shuangqiang Plastic Technology Development Co.,Ltd. Assignor: Shenyang University of Chemical Technology Contract record no.: 2012990000058 Denomination of invention: Functional rubber strengthening agent and preparation method thereof Granted publication date: 20101124 License type: Exclusive License Open date: 20080528 Record date: 20120222 |
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