CN103897333A - Rubber bonding promoter and its preparation method and use - Google Patents
Rubber bonding promoter and its preparation method and use Download PDFInfo
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- CN103897333A CN103897333A CN201210575358.8A CN201210575358A CN103897333A CN 103897333 A CN103897333 A CN 103897333A CN 201210575358 A CN201210575358 A CN 201210575358A CN 103897333 A CN103897333 A CN 103897333A
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Abstract
The invention provides a rubber bonding promoter. The rubber bonding promoter contains cardol shown in the formula (I) and aralkyl resorcinol-aldehyde resin shown in the formula (II). The invention also provides a preparation method of the rubber bonding promoter and a use of the rubber bonding promoter in rubber product preparation. The invention also provides a modified vulcanized rubber composition. The preparation method solves the problem that resorcinol used by the prior art easily produces smoke and releases harmful substances in rubber mixing, greatly reduces content of free resorcinol, obviously improves reaction activity and is conducive to environmental protection.
Description
Technical field
The present invention relates to rubber resin manufacture field, be specifically related to a kind of rubber adhesion accelerating agent and its preparation method and application.
Background technology
Can adopt in rubber item field and in goods, add strongthener and should be able to require to meet the special of rubber item, for example, strongthener is applied in this class rubber item of doughnut.Generally, strongthener has the materials such as steel wire, polymer fiber (artificial silk, nylon, aramid fiber, polyester etc.), carbon fiber, glass fibre.Conventionally between strongthener and rubber, can adopt binding system, for example, binder resin (methylene acceptor).In prior art, more use Resorcinol as methylene acceptor, using vulkacit H (HMT) and HMMM (HMMM) as methylene radical donor compound, promote the bonding of steel cord and rubber/rubber combination.In sulfuration process, methylene radical donor discharges formaldehyde, formaldehyde and Resorcinol reaction in－situ form resorcinol-formaldehyde (RF) network structure, the network structure forming can be improved physicals, mechanical property and the bond properties of vulcanized rubber, and plays good connection and transitional function with sizing material and steel wire tack coat after forming bonding coat.
In prior art often using Resorcinol monomer as methylene acceptor jointing material, but because the smoke point of Resorcinol is lower, in mixing process, (150 ℃～200 ℃) discharge the healthy objectionable impurities of harm, therefore, just little by little by preshrunk and resol replace.In prior art, there is low-down free Resorcinol content (1-5%) through phenylethene modified resorcinol-formaldehyde resin, the difficult phenomenon of smoldering, but, its distinct disadvantage is that its reactive behavior obviously declines, the firm performance of the network that forms is far away from the network with Resorcinol monomer in-situ construction, and product performance obviously decline.In order to make up resin network that resin forms and the difference of original position network, need to be by adding other active substance, for example, in CN 1723224A, disclosed use shale wet goods, on network strength He in density, supplements extraly.
Summary of the invention
The present invention overcomes the above defect of prior art, has proposed a kind of rubber adhesion accelerating agent, and it contains suc as formula the cashew nut diphenol shown in (I) and suc as formula the aralkylation Resorcinol-air aldehyde resin shown in (II);
In described formula (I), n=0-3;
In described formula (II),
M is independent positive integer;
P is independent positive integer or is 0;
m+p≥2；
R
1for H, alkyl, aralkyl, alkylene, fragrant alkylene;
R
2for H, alkyl, aralkyl, alkylene, fragrant alkylene.
Wherein, the mass ratio of described cashew nut diphenol and described aralkylation Resorcinol-air aldehyde resin is 1: 99～30: 70.
Rubber adhesion accelerating agent of the present invention is the resin material that described cashew nut diphenol and described aralkylation Resorcinol-air aldehyde resin physical blending is obtained having more high reactivity reflecting points.The cashew nut diphenol, the aralkylation Resorcinol-air aldehyde resin that in rubber adhesion accelerating agent of the present invention, comprise can mix by arbitrary proportion.Preferably, both mass ratioes are 1: 99～30: 70.Further preferably, both mass ratioes are 1: 99～10: 90.
Formula (I) cashew nut diphenol (cardol), is the resorcinol derivatives chemical that contains two hydroxyls, is to refine and obtain through processes such as decarboxylations from industrial cashew nut oil, and its structure is different from traditional cashew nut oil or cardanol.
Tradition cashew nut oil mainly contains cardanol, and the cashew nut diphenol of herein mentioning is the chemical that contains high-content cashew nut diphenol obtaining after special processing, and wherein the content of cashew nut diphenol at least reaches 20%.
According to the Rate Relationship of phenols alkyl the position of substitution and relative response, formula (I) structure has very high phenols reactive behavior, has the activity that can well with methylene radical donor react identical with other alkylation Resorcinol class monomers.In formula (I) structure, there are longer alkene and alkyl chain, are conducive to the fusion of bonding coat network and rubber network, thereby make bonding coat firmer.Formula (I) cashew nut diphenol itself is a kind of liquid of very thickness, cannot accurately join in rubber in actual use, therefore, the present invention mixes described formula (I) cashew nut diphenol with olefin-modified Resorcinol-air aldehyde resin, thereby the resin material that obtains solid state is rubber adhesion accelerating agent of the present invention, in this solid resin, there is the free highly active material reacting with methylene radical donor, and the similar Resorcinol monomer phenomenon of " being fuming " can not occur in mixing process.
Wherein, described aralkylation Resorcinol-air aldehyde resin is by preparing with aldehyde compound condensation reaction after alkene and Resorcinol alkanisation by resorcinol compound, vinyl compound, aldehyde compound.Wherein, the mol ratio of described resorcinol compound and described vinyl compound is 1: 0.1～1: 1; The mol ratio of described resorcinol compound and described aldehyde compound is 1: 0.1～1: 0.7.
Wherein, described vinyl compound is ethene, propylene, butylene, amylene, hexene, heptene, octene, nonene, limonene, cyclopentadiene, isoprene, divinyl, vinylbenzene, alpha-methyl styrene, p-methylstyrene, divinylbenzene ethene, vinyl naphthalene, Vinyl toluene or the arbitrary combination more than both.
Wherein, described aldehyde compound is formaldehyde, paraformaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, phenyl aldehyde, furfural, crotonic aldehyde or the arbitrary combination more than both.
The present invention also provides a kind of preparation method of rubber adhesion accelerating agent, it comprises the steps, using acid as catalyzer, alkene and Resorcinol are carried out to alkylated reaction, then prepare described aralkylation Resorcinol-air aldehyde resin with the condensation reaction of aldehydes, then add described cashew nut diphenol, finally neutralization obtains rubber adhesion accelerating agent described in product, this rubber adhesion accelerating agent has the feature of low free Resorcinol, compared with traditional alkylation Resorcinol air aldehyde resin, there is better reactive behavior.
Preparation method of the present invention adopts has the cashew nut diphenol of high reaction activity as the properties-correcting agent of alkylation Resorcinol air aldehyde resin, mix with this alkylation Resorcinol air aldehyde resin, keeping under glue furnacing temperature in this resinoid low feature of being fuming, improve the crosslinking reaction density of resin network in sulfidation, thereby obviously improved the performance of alkylation Resorcinol air aldehyde resin of the prior art.
The present invention also provides a kind of modification vulcanizate compositions, and it contains described rubber adhesion accelerating agent, methylene radical donor and rubber components.Wherein, the weight ratio of described methylene radical donor and described rubber adhesion accelerating agent is 1: 10～10: 1.Conventionally, methylene radical donor in building rubber compound composition formula and the weight ratio of methylene receptor can change, but generally speaking, the weight ratio of methylene radical donor and methylene receptor (for example, rubber adhesion accelerating agent of the present invention) is between 1: 10～10: 1.Preferably, in specific embodiment both weight ratios between 1: 3～3: 1.
Wherein, described methylene radical donor is melamine methylol, 2-nitro-2-methyl isophthalic acid-propyl alcohol, the yuban of vulkacit H, HMMM, pentamethoxyl methyl melamine, six ethoxyl methyl trimeric cyanamides, esterification or the arbitrary combination that both are above.
Wherein, described rubber components is the multipolymer of multipolymer, isobutene rubber, vinyl-acrylic rubber, vinylbenzene and divinyl of multipolymer, vinylbenzene, divinyl and the isoprene of multipolymer, vinyl cyanide and the isoprene of multipolymer, the acrylonitrile and butadiene of cis-Isosorbide-5-Nitrae-polyisoprene, polyhutadiene, sovprene, isoprene and divinyl or the arbitrary combination that both are above.The vulcanization reaction of rubber components needs the existence of sulfur vulcanizing agent conventionally, and applicable sulfur sulfurizing agent comprises: elementary sulfur (free sulphur) or sulfur donor are as curing ammonium, poly sulfide or sulphur olefin adducts.Vulcanizing agent is preferably selected elementary sulfur.The consumption of sulfur sulfurizing agent is generally between 0.5～10phr.
Wherein, promotor is improved curability by controlling vulcanization reaction time or temperature, and the kind that is applicable to the promotor using comprises amine, disulphide, guanidine, thiocarbamide, thiazole, thiuram, sulphenamide, dithiocar-bamate and sulfonate.The first promotor is preferably selected sulphenamide.If use the second promotor, preferably select guanidine, dithio amino methyl salt or thiuram compound.
In modification vulcanizate compositions of the present invention, further can also add additive, comprise sulphur, carbon black, cobalt salt, stearic acid, silicon-dioxide, filler, zinc oxide, promotor, antioxidant, softening oil, softening agent, wax, antiozonidate etc., and other analogous products.
Modification vulcanizate compositions of the present invention comprises: (i) be selected from natural rubber or elastomeric rubber components; (ii) methylene radical donor; (iii) described rubber adhesion accelerating agent, that is, the blend of cashew nut diphenol and aralkyl Resorcinol-aldehydes compound resin is as methylene receptor.Wherein, the blend of this cashew nut diphenol and aralkyl Resorcinol-aldehydes compound resin can make by aralkyl Resorcinol-air aldehyde resin melting of cashew nut diphenol and preparation is mixed.Methylene receptor component of the present invention, compares with existing aralkyl Resorcinol-aldehydes compound resin, has higher hardness, modulus, the more excellent vulcanization of rubber, stretching and steel wire bond properties, has outstanding ageing-resistant performance.
The present invention also provides described rubber adhesion accelerating agent and modified rubber composition in the application of preparing in rubber item.Wherein, described rubber item comprises tire, transmission/moving band, truck mud guard, rubber soles and heel, inner liner of bowl mill, print roller.
The resin material rubber adhesion accelerating agent of the present invention that resorcinol formaldehyde resin physical blending after cashew nut diphenol and vinylbenzene is obtained has more high reactivity reflecting points.Rubber adhesion accelerating agent of the present invention and modified rubber composition can be used as producing the rubber compounding resin of tire, flexible pipe, conveying belt, can be used for the preparation of modified rubber composition.Further, rubber adhesion accelerating agent of the present invention and modified rubber composition can be used for preparing rubber item, can also be used for the production of composite prod, for example, tire, travelling belt, conveying belt, print roller, rubber boots are followed and sole, rubber dish-cloth wringers, car mat, truck mud guard, inner liner of bowl mill and analogous products etc.Further, rubber adhesion accelerating agent of the present invention and modified rubber composition can be used for steel wire and cover the product such as body cord or rubber cover and the manufacture of glue, tire.
Embodiment
In conjunction with following specific embodiment, the present invention is described in further detail, and protection content of the present invention is not limited to following examples.Do not deviating under the spirit and scope of inventive concept, variation and advantage that those skilled in the art can expect are all included in the present invention, and take appending claims as protection domain.Implement process of the present invention, condition, reagent, experimental technique etc., except the content of mentioning specially below, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
The preparation of embodiment 1-6 rubber adhesion accelerating agent
In embodiment 1-6, take in the four-hole boiling flask that 110g Resorcinol is added to 500mL, be warming up to 130 ℃ of stirrings and dissolve.Add 0.35g p-methyl benzenesulfonic acid.Then drip appropriate vinylbenzene.After, at 130 ℃, keep 10min, be then warming up to 150-155 ℃, keep 15min.Be cooled to 130 ℃, drip 46.6g liquid formaldehyde (37%).After being added dropwise to complete, backflow 30min, adds appropriate cashew nut diphenol, stirs, then drips 0.18g NaOH (50%) neutralization.First air distillation, then continues underpressure distillation; Inclining, synthetic resin be rubber adhesion accelerating agent, and cooling retention is stand-by.Wherein, the add-on of cashew nut diphenol (purity 40%) can be suitable any dosage.Following table 1 is listed content, the softening temperature etc. of the free Resorcinol in the vinylbenzene, cashew nut diphenol, synthetic product of embodiment 1-6.
Vinylbenzene, the cashew nut diphenol of table 1 embodiment 1-6, content, the softening temperature of the Resorcinol that dissociates
| Embodiment | Vinylbenzene (g) | Cashew nut diphenol (g) | Free Resorcinol (%) | Softening temperature (℃) |
| 1 | 58.2 | 0 | 3.7 | 110 |
| 2 | 58.2 | 11 | 3.45 | 105 |
| 3 | 58.2 | 22 | 3.1 | 99 |
[0037]
| 4 | 69.7 | 0 | 2.1 | 110 |
| 5 | 69.7 | 11 | 1.98 | 105 |
| 6 | 69.7 | 22 | 1.8 | 101 |
Problem about product:
Embodiment 7-12
Take in the four-hole boiling flask that 110g Resorcinol is added to 500mL, be warming up to 130 ℃ of stirrings and dissolve.Add 0.35g p-methyl benzenesulfonic acid.Then drip appropriate alpha-methyl styrene.After, at 130 ℃, keep 10min, be then warming up to 150-155 ℃, keep 15min.Be cooled to 130 ℃, drip 46.6g liquid formaldehyde (37%).After being added dropwise to complete, backflow 30min, adds appropriate cashew nut diphenol, stirs, then drips 0.18g NaOH (50%) neutralization.Then underpressure distillation of first air distillation; It is rubber adhesion accelerating agent that hypsokinesis goes out synthetic resin, and cooling retention is stand-by.Wherein, the add-on of cashew nut diphenol (purity 40%) can be suitable any dosage.Following table 1 is listed content, the softening temperature etc. of the free Resorcinol in the vinylbenzene, cashew nut diphenol, synthetic product of embodiment 7-12.
Alpha-methyl styrene, the cashew nut diphenol of table 2 embodiment 7-12, content, the softening temperature of the Resorcinol that dissociates
| Embodiment | Alpha-methyl styrene | Cashew nut diphenol (g) | Free Resorcinol (%) | Softening temperature (℃) |
| 7 | 66.2 | 0 | 4.0 | 110 |
| 8 | 66.2 | 11 | 3.69 | 108 |
| 9 | 66.2 | 22 | 3.2 | 102 |
| 10 | 82.7 | 0 | 2.5 | 115 |
| 11 | 82.7 | 11 | 2.0 | 108 |
| 12 | 82.7 | 22 | 1.88 | 103 |
The analysis of the thermal weight loss of embodiment 13 rubber adhesion accelerating agents
In prior art, if the adhesion promotor adding in rubber combination mixing process is Resorcinol or derivatives thereof, because Resorcinol is to exist with free state, its volatility easily causes the generation of " smoldering " phenomenon.Under the prerequisite of the outstanding performance of maintenance, the rubber adhesion accelerating agent of invention has overcome this technical problem.
In the present embodiment, adopting thermogravimetry (TGA) to measure the volatility of resin material, is the cashew nut diphenol recording under condition of nitrogen gas, the product of R-80, embodiment 1-6, the thermal weight loss data of B-20-S shown in table 2.
Table 3 thermogravimetric (TGA) analytical data
Note: B-20-S is from INDSPEC Chemical Corporation, Pittsburg, PENACOLITE resin B-20-S that PA obtains, the FD110 that being of cashew nut diphenol contest high (Beijing) Science and Technology Co., Ltd. provides
R-80 is commercially available 80% pre-dispersed Resorcinol and the blend of 20%EPDM (ethylene-propylene diene copolymer), commercially available obtaining, and Jinhua Rake chemical company provides.
As seen from Table 2, compared with commercially available R-80, at high temperature, the volatility of rubber adhesion accelerating agent of the present invention reduces greatly, be on close level with commercially available B20-S, can effectively reduce and even can eliminate because of the Resorcinol disadvantageous effect producing of " smoldering " thereupon.Its major cause is that added cashew nut diphenol at high temperature there will not be the phenomenon of smoldering, so the phenomenon that the resin finally obtaining is not also smoldered.
Embodiment 14 rubber combination applicating evaluatings
The rubber adhesion accelerating agent that embodiment 1-12 is made respectively with market on Resorcinol and resin like product compare, to evaluate its effect in rubber and the impact on rubber performance.The composition of detected object rubber combination is in table 3.
The formula of table 4 detected object rubber combination
| Sequence number | Title | Mass fraction |
[0056]
| 1 | Natural rubber | 100 |
| 2 | Carbon black (N375) | 42 |
| 3 | Silicon-dioxide | 10 |
| 4 | Zinc oxide | 8 |
| 5 | Sulphur (80%) (OT20) | 5 |
| 6 | Cobalt (CN 20.5%) | 1 |
| 7 | The N-tertiary butyl-benzothiazole-sulphenamide (TBBS) | 1.2 |
| 8 | 1 of polymerization, 2-dihydro-2,2,4-trimethylquinoline (TMQ) | 0.5 |
| 9 | N-(1,2-, bis-fourth methyl)-N '-phenyl-p-phenylene diamines [6PPD (4020)] | 1.5 |
| 10 | One of R-80 or B-20-S or embodiment 1-12 product | 1.5 |
| 11 | Methylene acceptor-HMMM (65%) | 3.5 |
The first step is mixed rubber components the mixing master batch (master batch) that makes with Banbury Banbury mixer at approximately 150 ℃.
Second step, the rubber adhesion accelerating agent of respectively being prepared by embodiment 1-12 or comparative sample R-80 or B-20-S (being methylene receptor), add cobalt salt, at approximately 145 ℃ of temperature, sneaks in the master batch that Banbury mixer mixing obtains.The 3rd step adds insoluble sulfur listed in table 3, promotor, HMMM mixingly at 90～100 ℃, and the product of mixing gained is placed and spent the night in the environment of approximately 23 ℃ of steady temperatures and relative humidity 50%.Then, at 150 ℃, measure its sulphur and become instrument sulfuration, shape, optimum cure degree, to evaluate its mechanical property, test data as shown in table 4.
Wherein tensile property adopts GB/T 528-2009 to test; Hardness adopts GB/T 531.1-2008 to test; Curability is to adopt Alpha Technologies MDR sulphur to become instrument, adopts by reference standard: GB/T 16584-1996 and GB/T 1233-2008 standard, under 150 ℃, 1 ° radian and 1.67 hertz of conditions, measure.Become in instrument at vibration disk sulphur, sizing material sample is subject to the oscillatory shear power of uniform amplitude, measures the moment of torsion that embeds the vibration net dish in glue sample under curing temperature; The cure conditions that steel wire cord bond properties (N) adopts: 155 ℃ × 40min, steel cord specification: 3+9+15*0.22+1, tests with standard A STM D1871-2004.
Table 4 rubber size performance
Visible according to table 4, in embodiment 2,3,5,6,8,9,11,12 because having added appropriate cashew nut diphenol, thereby show the performance that exceedes other several comparative sample.The content that is mainly wherein vinylbenzene or alpha-methyl styrene and cashew nut diphenol is higher, and modulus and extraction performance are more excellent, and wherein the Performance Ratio R-80 of salt solution after aging is well a lot, and other performance also reaches or exceeded the level of B-20-S.Table 4 illustrates, carrying out the existing phenylethene modified Resorcinol air aldehyde resin of modification with cashew nut diphenol has remarkable good result, has good market outlook.
Claims (16)
1. a rubber adhesion accelerating agent, is characterized in that, it contains suc as formula the cashew nut diphenol shown in (I) and suc as formula the aralkylation Resorcinol-air aldehyde resin shown in (II);
In described formula (I), n=0-3;
In described formula (II),
M is independent positive integer;
P is independent positive integer or is 0;
m+p≥2；
R
1for H, alkyl, aralkyl, alkylene, fragrant alkylene;
R
2for H, alkyl, aralkyl, alkylene, fragrant alkylene.
2. rubber adhesion accelerating agent as claimed in claim 1, is characterized in that, the mass ratio of described cashew nut diphenol and described aralkylation Resorcinol-air aldehyde resin is 1: 99～30: 70.
3. rubber adhesive as claimed in claim 1, the purity of its cashew nut diphenol is from 20%～99%, preferred purity is 40-80%.
4. the rubber adhesion accelerating agent as described in claim 1-2, it is characterized in that, described aralkylation Resorcinol-air aldehyde resin is by preparing with aldehyde compound condensation reaction after alkene and Resorcinol alkanisation by resorcinol compound, vinyl compound, aldehyde compound; Wherein, the mol ratio of described resorcinol compound and described vinyl compound is 1: 0.1～1: 1; The mol ratio of described resorcinol compound and described aldehyde compound is 1: 0.1～1: 0.7.
5. rubber adhesion accelerating agent as claimed in claim 3, it is characterized in that, described vinyl compound is ethene, propylene, butylene, amylene, hexene, heptene, octene, nonene, limonene, cyclopentadiene, isoprene, divinyl, vinylbenzene, alpha-methyl styrene, p-methylstyrene, divinylbenzene ethene, vinyl naphthalene, Vinyl toluene or the arbitrary combination more than both.
6. rubber adhesion accelerating agent as claimed in claim 3, is characterized in that, described aldehyde compound is formaldehyde, paraformaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, phenyl aldehyde, furfural, crotonic aldehyde or the arbitrary combination more than both.
7. the preparation method of the rubber adhesion accelerating agent as described in claim 1-6, it is characterized in that, using acid as catalyzer, alkene and Resorcinol are carried out to alkylated reaction, then prepare described aralkylation Resorcinol-air aldehyde resin with the condensation reaction of aldehydes, then add described cashew nut diphenol, finally neutralization obtains rubber adhesion accelerating agent described in product.
8. the acid using in preparation method as claimed in claim 7 is selected from tosic acid, sulfuric acid, hydrochloric acid, the combination of one or any two kinds in oxalic acid.
9. a modification vulcanizate compositions, is characterized in that, it contains just like the rubber adhesion accelerating agent described in claim 1-6, methylene radical donor and rubber components.
10. modification vulcanizate compositions as claimed in claim 9, is characterized in that, the weight ratio of described methylene radical donor and described rubber adhesion accelerating agent is 1: 10～10: 1, and its preferred ratio is 1: 3～3: 1.
11. modification vulcanizate compositions as claimed in claim 9, it is characterized in that, described methylene radical donor is melamine methylol, 2-nitro-2-methyl isophthalic acid-propyl alcohol, the yuban of vulkacit H, HMMM, pentamethoxyl methyl melamine, six ethoxyl methyl trimeric cyanamides, esterification or the arbitrary combination that both are above.
12. modification vulcanizate compositions as claimed in claim 9, it is characterized in that, described rubber components is the multipolymer of multipolymer, isobutene rubber, vinyl-acrylic rubber, vinylbenzene and divinyl of multipolymer, vinylbenzene, divinyl and the isoprene of multipolymer, vinyl cyanide and the isoprene of multipolymer, the acrylonitrile and butadiene of cis-Isosorbide-5-Nitrae-polyisoprene, polyhutadiene, sovprene, isoprene and divinyl or the arbitrary combination that both are above.
13. modification vulcanizate compositions as claimed in claim 9, it is characterized in that, described modification vulcanizate compositions further comprises additive, comprises sulphur, carbon black, cobalt salt, stearic acid, silicon-dioxide, filler, zinc oxide, promotor, antioxidant, softening oil, softening agent, wax, antiozonidate.
14. rubber adhesion accelerating agents as claimed in claim 1 and modification vulcanizate compositions as claimed in claim 8 are in the application of preparing in rubber item.
15. application as claimed in claim 14, is characterized in that, described rubber item comprises tire, transmission/moving band, truck mud guard, rubber soles and heel, inner liner of bowl mill, print roller.
16. application as claimed in claim 14, is characterized in that, can be used for steel wire and cover glue, tire body cord, tyre surface or rubber cover.
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| CN112521666A (en) * | 2020-12-15 | 2021-03-19 | 北京彤程创展科技有限公司 | Rubber composition, preparation method thereof and rubber product |
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| CN114671741A (en) * | 2020-12-24 | 2022-06-28 | 彤程新材料集团股份有限公司 | Resorcinol oligomeric derivative for rubber tire and preparation and application of masterbatch particle of resorcinol oligomeric derivative |
| CN115594896A (en) * | 2022-11-03 | 2023-01-13 | 北京彤程创展科技有限公司（Cn） | Rubber composition, rubber product and application |
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| CN110678322A (en) * | 2017-02-15 | 2020-01-10 | Vf亚洲有限公司 | Method for manufacturing an article of footwear |
| CN107383924A (en) * | 2017-09-03 | 2017-11-24 | 安徽天裕汽车零部件制造有限公司 | A kind of fender material and preparation method thereof |
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Address after: 215635 Jiangsu, Jiangsu, Yangtze River, Yangtze River International Chemical Industrial Park, Tian Ba Road, No. 99, No., Suzhou Patentee after: SINO LEGEND (ZHANGJIAGANG) CHEMICAL CO., LTD. Address before: 215635 Jiangsu, Jiangsu, Yangtze River, Yangtze River International Chemical Industrial Park, Tian Ba Road, No. 99, No., Suzhou Patentee before: Sino Legend Zhangjiagang Chemi |