CN104448390A - Green tire functional master batch and preparation method thereof - Google Patents
Green tire functional master batch and preparation method thereof Download PDFInfo
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- CN104448390A CN104448390A CN201410818158.XA CN201410818158A CN104448390A CN 104448390 A CN104448390 A CN 104448390A CN 201410818158 A CN201410818158 A CN 201410818158A CN 104448390 A CN104448390 A CN 104448390A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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Abstract
The invention discloses a green tire functional master batch and a preparation method thereof. The green tire functional master batch comprises the following substances in parts by weight: 29-35 parts of a carbon black mixture with high radical content, 6-8 parts of a modified boric acid ester interfacial active agent and 50-70 parts of a rubber modifier, wherein the carbon black mixture with high radical content is a residue obtained by cracking a rubber part after sorting waste full-steel tires and comprises more than 70% of carbon black by mass and the rest part mainly being SiO2; and the main technical indexes are as follows: the fineness is more than 2000 meshes, the oil factor is 50-100cm<3>/100g, the low volatile matters are less than 2%, and the pH value is 7-8. The invention also discloses the preparation method of the green tire functional master batch. The product disclosed by the invention is applied to preparation of tires and replaces high-dispersity white carbon black or carbon black of same or proper weight parts, the low rolling resistance and slippery resistance of the master batch are 15-20% superior to those of an original material on the basis of a green tire and can be improved by more than 30% on the basis of a half green tire, and the processing difficulty is greatly reduced.
Description
Technical field
The present invention relates to a kind of green tire functional master batch and preparation method thereof, belong to tire manufacturing art.
Background technology
According to country " ten two-five " planning, in the middle of tire, development field given special assistance to by function novel material, and through the develop rapidly of decades, the production of Chinese half steel, all steel, giant-scale engineering tyre obtains develop rapidly.Close to the throughput in the whole world 50%.But the development of the various materials of corresponding supporting development particularly functional novel material is not enough, also gap is larger to comprise the ability of introducing and employment.In November, 2012, European Union's labeling acts passed through of making laws formally was implemented, detailed requirement is proposed to the environmental protection (fuel-economizing) of tire, security (dry, wet and slippery performance) and low noise, and other developed economies also proposes similar technical requirements, this creates considerable influence to the Tire production industry of China, i.e. technology barriers.That to challenge also be opportunity, corresponding enterprise all going into overdrive to introduce and use novel material, new formula produces the high-performance tire of meeting the need of market, be called for short green tire, but also run into considerable difficulty in production implementation process:
1, complete green tire formula is the white carbon black+coupling agent of solution polymerized butylbenzene+high dispersive, and implementation cost is higher.
2, green tire is produced because of the white carbon black about 80 parts using high structure a large amount of in formula, and conventional tyre only about 10 ~ 20 parts.The difficulty of processing of white carbon black is large, and low to roll resistance bad; The heat-dissipating of carbon black is high, and wet-sliding resistant performance is not good, and rolling resistance is large.So technique execution and difficulty of processing are very large in tire production process, product homogeneity and poor stability.
3, existing domestic tire enterprise will reach the higher level that labeling acts specifies, as two B level tire (rolling resistance and anti-slippery all reach B level) is still difficult to.
Summary of the invention
Technical problem to be solved by this invention is to provide that a kind of preparation cost is low, and difficulty of processing is low, green tire functional master batch that can substitute white carbon black and preparation method thereof.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of green tire functional master batch, comprises the material of following parts by weight: the carbon black mixt of the high group content of 29-35 part; 6-8 part modified boric acid ester interface activating agent; Rubber modified dose of 50-70 part.
The carbon black mixt of described high group content, it is the resistates after useless all steel tire sorting after rubber section cracking, and comprising carbon black more than 70% mass parts, rest part is mainly sio
2; The key technical indexes: fineness > 2000 order, oil-absorption(number) 50-100cm
3/ 100g, low-volatile < 2%, pH value 7-8.In this process of producing product, the process of its internal cleavage produces a lot of air vent channel, be rich in abundant all kinds of functional groups in the channel, as-oH,-cooH etc., so temperature very easily more than 100 DEG C and interfacial agent combine, participate in crosslinked in the tire refining glue course of processing, positive-effect is produced to caoutchouc elasticity, low-heat-generation etc.The carbon black mixt manufacturer of the described high group content of In The Area of Qingdao comprises the good chemical company of Qingdao Jin Run.Described modified boric acid ester interface activating agent is the product that applicant produces and sells, related application number: 2010102976566.The described rubber modified dose of product produced and sold for applicant, Patents number is ZL 2010102976481.
Optimize, in the formula of above-mentioned green tire functional master batch, the parts by weight of rubber modified dose are 57-67 parts.
Preferably, described green tire functional master batch comprises the material of following parts by weight: the carbon black mixt of 29 parts of high group contents; 8 parts of modified boric acid ester interface activating agents; 63 parts rubber modified dose.
Preferably, described green tire functional master batch comprises the material of following parts by weight: the carbon black mixt of 30 parts of high group contents; 6 parts of modified boric acid ester interface activating agents; 64 parts rubber modified dose.
The present invention also provides a kind of method preparing above-mentioned green tire functional master batch, comprises the steps:
1) by formula, the carbon black mixt of high group content is added micronizer mill grinding, fineness is separated by cyclonic separator after reaching 2000 orders;
2) carbon black mixt after trapping is added in bacterium activation reaction kettles, and the modified boric acid ester interface activating agent of formula ratio reacts between 60-140 DEG C, carries out activation coupling, time 30-60 minute, increases the active site of carbon black mixt outside, becomes activated grafting thing, then blowing, cooling; To strengthen product when tire applications and the large pendant groups crosslinked action of rubber, improve its bonding force when compounding rubber and processing viscosity;
3) at normal temperatures, activated grafting thing is composite with rubber modified dose of mechanically mixing in proportion, metering packing evenly.
Step 1) in micronizer mill grinding rotating speed be 5000-15000 rev/min.
Step 2) in activation coupling process be 60 minutes, activation temperature is 100-140 DEG C.
The invention has the beneficial effects as follows:
1) tire formulation cost reduces relatively;
2) Rubber processing difficulty has and reduces by a relatively large margin, and mooney viscosity reduces by 20 ~ 30%;
3) by test film: add functional master batch of the present invention 20 parts and replace 20 parts of high-dispersion white carbon blacks in formula, on the basis of green tire, low rolling is hindered and is anti-slipperyly all better than original 15 ~ 20%, and the basis of half green tire can improve more than 30%.
By green tire functional master batch of the present invention, use suitable in different tire formulation systems, especially to the use of the tire of different varieties and the different sites of tire, can play a significant role, can improve the quality and performance of tire, reduce costs.The market capacity of this product and development prospect are very wide.
Embodiment
Embodiment 1
Film is tested
The application experiment of functional master batch of the present invention in green tire
The green tire functional master batch that the present embodiment provides, comprises the material of following parts by weight: the carbon black mixt of 29 parts of high group contents; 8 parts of modified boric acid ester interface activating agents; 63 parts rubber modified dose.
Prepare the method for above-mentioned green tire functional master batch, comprise the steps:
1) by formula, the carbon black mixt of high group content is added micronizer mill grinding, fineness is separated by cyclonic separator after reaching 2000 orders, and the rotating speed of micronizer mill grinding is 15000 revs/min.
2) carbon black mixt after trapping is added in bacterium activation reaction kettles, and the modified boric acid ester interface activating agent of formula ratio reacts between 100 DEG C, carries out activation coupling, 60 minutes time, increase the active site of carbon black mixt outside, become activated grafting thing, then blowing, cooling; To strengthen product when tire applications and the large pendant groups crosslinked action of rubber, improve its bonding force when compounding rubber and processing viscosity.
3) at normal temperatures, activated grafting thing is composite with rubber modified dose of mechanically mixing in proportion, metering packing evenly.
The functional master batch provided by the present embodiment carries out the film test of tire, replaces 20 parts of carbon blacks, compare the performance of conventional tyre formula and test recipe with the functional master batchs of 20 parts.Conventional tyre film formula and experimental wheel fetus film formula are in table 1:
Table 1 is filled a prescription
| Material/formula | Regular convention formula | Test recipe |
| SSBR | 0 | 0 |
| NR | 80 | 80 |
| BR | 20 | 20 |
| N234 | 20 | 0 |
| 1165MP | 45 | 45 |
| The present embodiment masterbatch | 0 | 20 |
| NAP10 | 20 | 20 |
| Other are same | Slightly | Slightly |
| S | 1.8 | 1.8 |
Test the tyre film of above-mentioned two kinds of formulas, concrete test-results is in table 2, table 3 and table 4:
Table 2 processing performance compares
Table 3 cross-linked rubber shore hardness (shoreA) compares
Table 4-1 tg δ compares (DMA test)
Table 4-2 tg δ compares (DMA test)
Embodiment 2
Comparison study experiment in different kinds of tyre formula
A kind of green tire functional master batch that the present embodiment provides, comprises the material of following parts by weight: the carbon black mixt of 30 parts of high group contents; 6 parts of modified boric acid ester interface activating agents; 64 parts rubber modified dose.
Prepare the method for above-mentioned green tire functional master batch, comprise the steps:
1) to be added after micronizer mill mesh-of-grind reaches 2000 orders by the carbon black mixt of high group content by formula and be separated by cyclonic separator, the rotating speed of micronizer mill grinding is 15000 revs/min.
2) carbon black mixt after trapping is added in bacterium activation reaction kettles, and the modified boric acid ester interface activating agent of formula ratio reacts between 100 DEG C, carries out activation coupling, 60 minutes time, increase the active site of carbon black mixt outside, become activated grafting thing, then blowing, cooling; To strengthen product when tire applications and the large pendant groups crosslinked action of rubber, improve its bonding force when compounding rubber and processing viscosity.
3) at normal temperatures, activated grafting thing is composite with rubber modified dose of mechanically mixing in proportion, metering packing evenly.
The functional master batch provided by the present embodiment is applied in the formula of snowfield tire, half green tire and green tire and carries out simultaneous test.Wherein, L3-1 and L3-2 is two groups of simultaneous test numberings of snowfield tire, L3-3 and L3-4 is two groups of simultaneous test numberings of half green tire, L3-5 and L3-6 is two groups of simultaneous test numberings of green tire.
In this experiment, the formula rate of six groups of experiment tires is in table 5:
Table 5 is filled a prescription list:
The quantitative measurement of six groups of experiment tires the results are shown in Table 6:
Table 6 quantitative measurement result
In the present embodiment, in the formula of L3-4, L3-6, replace 5 parts of N220 carbon blacks by 9 parts of functional master batchs.The quantitative measurement result listed as can be seen from table 6, the tire of using function masterbatch is compared to contrast tire, and its multiple key property is all significantly improved, can the result of use of direct functions masterbatch.
The DMA of six groups of experiments tests deciphering and the results are shown in Table 7:
Table 7 DMA tests and understands the results list
At low temperatures, the peak value of-30 DEG C ~ 0 DEG C of tg δ is higher, and anti-slippery is better, and vehicle safety is better; At high temperature, 40 DEG C ~ 60 DEG C tg δ are lower, and rolling resistance is less, more fuel-economizing.Result is understood in the DMA test listed from table 7, and the tire of using function masterbatch is compared to contrast tire, and it is anti-slippery, low rolls resistive can being all significantly improved, and proves the result of use of functional master batch.
Embodiment 3
Present embodiments provide a kind of green tire functional master batch, comprise the material of following parts by weight: the carbon black mixt of 29 parts of high group contents; 6 parts of modified boric acid ester interface activating agents; 65 parts rubber modified dose.
Prepare the method for above-mentioned green tire functional master batch, comprise the steps:
1) by formula the carbon black mixt of high group content added after micronizer mill mesh-of-grind reaches 2000 orders and be separated by cyclonic separator; The rotating speed of micronizer mill grinding is 10000 revs/min.
2) carbon black mixt after trapping is added in bacterium activation reaction kettles, and the modified boric acid ester interface activating agent of formula ratio reacts between 100 DEG C, carries out activation coupling, 60 minutes time, increase the active site of carbon black mixt outside, become activated grafting thing, then blowing, cooling; To strengthen product when tire applications and the large pendant groups crosslinked action of rubber, improve its bonding force when compounding rubber and processing viscosity.
3) at normal temperatures, activated grafting thing is composite with rubber modified dose of mechanically mixing in proportion, metering packing evenly.
Embodiment 4
A kind of green tire functional master batch, comprises the material of following parts by weight: the carbon black mixt of 35 parts of high group contents; 8 parts of modified boric acid ester interface activating agents; 57 parts rubber modified dose.
Prepare the method for above-mentioned green tire functional master batch, comprise the steps:
1) by formula the carbon black mixt of high group content added after micronizer mill mesh-of-grind reaches 2000 orders and be separated by cyclonic separator; The rotating speed of micronizer mill grinding is 10000 revs/min.
2) carbon black mixt after trapping is added in bacterium activation reaction kettles, and the modified boric acid ester interface activating agent of formula ratio reacts between 140 DEG C, carries out activation coupling, 60 minutes time, increase the active site of carbon black mixt outside, become activated grafting thing, then blowing, cooling; To strengthen product when tire applications and the large pendant groups crosslinked action of rubber, improve its bonding force when compounding rubber and processing viscosity.
3) at normal temperatures, activated grafting thing is composite with rubber modified dose of mechanically mixing in proportion, metering packing evenly.
Embodiment 5
A kind of green tire functional master batch, comprises the material of following parts by weight: the carbon black mixt of 30 parts of high group contents; 8 parts of modified boric acid ester interface activating agents; 50 parts rubber modified dose.
Prepare the method for above-mentioned green tire functional master batch, comprise the steps:
1) by formula the carbon black mixt of high group content added after micronizer mill mesh-of-grind reaches 2000 orders and be separated by cyclonic separator; The rotating speed of micronizer mill grinding is 10000 revs/min.
2) carbon black mixt after trapping is added in bacterium activation reaction kettles, and the modified boric acid ester interface activating agent of formula ratio reacts between 140 DEG C, carries out activation coupling, 60 minutes time, increase the active site of carbon black mixt outside, become activated grafting thing, then blowing, cooling; To strengthen product when tire applications and the large pendant groups crosslinked action of rubber, improve its bonding force when compounding rubber and processing viscosity.
3) at normal temperatures, activated grafting thing is composite with rubber modified dose of mechanically mixing in proportion, metering packing evenly.
The examination and test of products result prepared in above-described embodiment 1-5 and applied code see the following form:
Table 8 examination and test of products result and applied code
| Outward appearance | Black powder | Operative norm |
| Oil number ml/100g | 55±10 | GB/T 3780.2 |
| 105 DEG C of weight loss on heating % | ≤5 | GB/T 5211.3 |
| PH value | 8±1 | GB/T 1717 |
Product property is: black powder, nontoxic, free from environmental pollution.
Claims (7)
1. a green tire functional master batch, is characterized in that, comprises the material of following parts by weight: the carbon black mixt of the high group content of 29-35 part; 6-8 part modified boric acid ester interface activating agent; Rubber modified dose of 50-70 part;
The carbon black mixt of described high group content, it is the resistates after useless all steel tire sorting after rubber section cracking, and composition comprises: carbon black more than 70% mass parts, rest part is mainly sio
2; Carbon black mixt the key technical indexes: fineness > 2000 order, oil-absorption(number) 50-100cm
3/ 100g, low-volatile < 2%, pH value 7-8.
2. green tire functional master batch according to claim 1, is characterized in that, functional master batch comprises rubber modified dose of 57-67 part.
3. green tire functional master batch according to claim 1, is characterized in that, comprises the material of following parts by weight: the carbon black mixt of 29 parts of high group contents; 8 parts of modified boric acid ester interface activating agents; 63 parts rubber modified dose.
4. green tire functional master batch according to claim 1, is characterized in that, comprises the material of following parts by weight: the carbon black mixt of 30 parts of high group contents; 6 parts of modified boric acid ester interface activating agents; 64 parts rubber modified dose.
5. the method for the green tire functional master batch of preparation described in above-mentioned any one claim, is characterized in that, comprise the steps:
1) by formula, the carbon black mixt of high group content is added micronizer mill grinding, fineness is separated by cyclonic separator after reaching 2000 orders;
2) carbon black mixt after trapping is added in bacterium activation reaction kettles, and the modified boric acid ester interface activating agent of formula ratio reacts between 60-140 DEG C, carries out activation coupling 30-60 minute, increase the active site of carbon black mixt outside, become activated grafting thing, then blowing, cooling; To strengthen product when tire applications and the large pendant groups crosslinked action of rubber, improve its bonding force when compounding rubber and processing characteristics;
3) at normal temperatures, activated grafting thing is composite with rubber modified dose of mechanically mixing in proportion, metering packing evenly.
6. the preparation method of green tire functional master batch according to claim 3, is characterized in that, in step 1), the rotating speed of micronizer mill grinding is 5000-15000 rev/min.
7. the preparation method of green tire functional master batch according to claim 3, is characterized in that, step 2) in activation coupling process be 60 minutes, activation temperature is 100-140 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844863A (en) * | 2014-08-01 | 2015-08-19 | 青岛四维化工有限公司 | High-performance environment-friendly half-green tire formula |
| CN104844864A (en) * | 2014-08-01 | 2015-08-19 | 青岛四维化工有限公司 | High-performance environment-friendly green tire formula |
| CN112143099A (en) * | 2020-09-09 | 2020-12-29 | 烟台融晟新材料有限公司 | Formula and method for preparing black master batch by adopting self-made modified pyrolytic carbon black |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000527A (en) * | 2010-09-30 | 2011-04-06 | 青岛四维化工有限公司 | Modified boric acid ester interface activating agent and preparation method thereof |
| CN103059340A (en) * | 2012-12-27 | 2013-04-24 | 青岛四维化工有限公司 | A functional master batch for green tires and a preparation method thereof |
| CN104177671A (en) * | 2014-08-13 | 2014-12-03 | 青岛四维化工有限公司 | Radial tire steel wire rubber and preparation method thereof |
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2014
- 2014-12-24 CN CN201410818158.XA patent/CN104448390A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000527A (en) * | 2010-09-30 | 2011-04-06 | 青岛四维化工有限公司 | Modified boric acid ester interface activating agent and preparation method thereof |
| CN103059340A (en) * | 2012-12-27 | 2013-04-24 | 青岛四维化工有限公司 | A functional master batch for green tires and a preparation method thereof |
| CN104177671A (en) * | 2014-08-13 | 2014-12-03 | 青岛四维化工有限公司 | Radial tire steel wire rubber and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844863A (en) * | 2014-08-01 | 2015-08-19 | 青岛四维化工有限公司 | High-performance environment-friendly half-green tire formula |
| CN104844864A (en) * | 2014-08-01 | 2015-08-19 | 青岛四维化工有限公司 | High-performance environment-friendly green tire formula |
| CN112143099A (en) * | 2020-09-09 | 2020-12-29 | 烟台融晟新材料有限公司 | Formula and method for preparing black master batch by adopting self-made modified pyrolytic carbon black |
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