CN109609054A - No cobalt composition metal caprate adhesion promoter and preparation method thereof, application - Google Patents
No cobalt composition metal caprate adhesion promoter and preparation method thereof, application Download PDFInfo
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- CN109609054A CN109609054A CN201811432686.6A CN201811432686A CN109609054A CN 109609054 A CN109609054 A CN 109609054A CN 201811432686 A CN201811432686 A CN 201811432686A CN 109609054 A CN109609054 A CN 109609054A
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- acid
- caprate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Abstract
It is to include mixed metal, neodecanoic acid, neopentanoic acid, propionic acid, rosin acid, caprate made of stearic raw material the invention discloses a kind of no cobalt composition metal caprate adhesion promoter and preparation method thereof, application；Caprate is in terms of 100% by quality, includes mixed metal 15%~28%, neodecanoic acid 28%~50%, neopentanoic acid 10%~24%, propionic acid 5%~18%, rosin acid 3%~12%, stearic acid 4%~15%；Mixed metal is in terms of 100% by quality, includes nickel 30%~50%, zinc 15%~35%, rare earth element 30%~50%.It is of the invention with nickel, zinc and a small amount of rare earth metal instead of expensive cobalt, its cement properties of no cobalt composition metal caprate adhesion promoter obtained and former cobalt salt adhesion promoter have peer-level, ageing properties are substantially better than former cobalt salt adhesion promoter, product cost is greatly lowered, with good economic efficiency and social benefit.
Description
Technical field
The present invention relates to no cobalt adhesion promoters and preparation method thereof, application, are especially used for radial wire cord tire, steel
Silk enhancing conveyer belt, the rubber products manufacture such as rubber hose braided with steel wire without cobalt composition metal caprate adhesion promoter and its preparation side
Method, application.
Background technique
It is universal both at home and abroad at present in rubber products industries such as radial wire cord tire, steel wire reinforcement conveyer belt, rubbers hose braided with steel wire
The rubber-metal adhesion promoter used is direct addition type cobalt salt adhesion promoter, and principal item has cobalt decanoate, boron acyl
Change cobalt etc..This kind of direct addition type cobalt salt adhesion promoter, which removes, has high-intensitive cement properties and excellent dynamic mechanical
Outside, also there are the excellent properties such as anti-aging, heat-resisting oxygen, wet-heat resisting, salt tolerant aqueous corrosion.
Cobalt salt adhesion promoter does not participate in reaction directly during the bonding to rubber and metallic framework, only plays bonding
Enhancement effect.For rubber before vulcanization, the coating of sizing material and metallic framework added with cobalt salt adhesion promoter is simple connect
Touching, not any interspersed link；Under conditions of vulcanization, cobalt salt is cracked, and releases active divalent cobalt ion.In activity two
New material layer is formed under the catalytic action of valence cobalt ions, between rubber and coating --- that is, metal sulfide layer cannot
With the cuprous sulfide layer (Cu of stoichiometry2SX) and zinc sulfide layer (ZnSX).It, can be with since they have the activity that the reaction was continued
It is diffused into boundary layer and is chemically bonded by vulcanization bridge and vulcanization of rubber object, that is, produce rubber and reacted with the bonding of coating.?
There is no cobalt atom or carboxyl structures in the bonding chemical bond of rubber and steel wire, that is to say, that rubber and metal are in the process of cohering
Middle organic cobalt salt has only served bonding facilitation, and the only organic cobalt of facilitation is played to the generation of active cuprous sulfide
Active divalent cobalt ion in salt.
After the reaction was completed, cobalt ions is remained in rubber product in the form of cobalt oxide for bonding, and remaining cobalt is used as " rubbish "
It is present in rubber product, these " rubbish " will affect the ageing properties and service life of rubber product.It is anti-in order to reduce bonding
Adverse effect of the remaining cobalt to rubber product performance after answering, in the beginning of this century, international rubber circle just proposes direct addition type
The target that cobalt salt adhesion promoter develops to " low cobalt ", " no cobalt " direction, many countries all open in line with this target development
The direct addition type adhesion promoter of " low cobalt ", " no cobalt " is sent out, to replace the direct addition type cobalt salt generally used now bonding
Promoting agent.But the relevant report that such new product occurs up to the present, is not found also.
Although the organic salt of cobalt is bonded with good facilitation for the high intensity of rubber and metal, due to the money of cobalt
Source is rare, expensive, and remaining cobalt will affect the ageing properties and service life of rubber product, therefore, with other metals
The research work of substituting cobalt has begun in developed countries such as Britain, Japan.Preliminary studies have shown that using the single gold in addition to cobalt
Organic salt made of belonging to, cement properties are all less than organic cobalt salt, but are replaced with the compound organic salt that several metals form single
The organic salt of one cobalt is acted on by " concerted catalysis " of several active metallic ions, and the organic salt of composition metal is made to replace cobalt
What organic salt was possible to, the country, China is almost blank about this research work at present.
Summary of the invention
Goal of the invention: in view of the above-mentioned problems, to be to provide a kind of no cobalt composition metal caprate glutinous for an object of the present invention
Promoting agent is closed, had not only been able to maintain the cement properties of cobalt salt adhesion promoter, but also ageing properties can be made to significantly improve, the purpose of the present invention
A kind of two preparation methods for being to provide this no cobalt composition metal caprate adhesion promoter, the third object of the present invention is to mention
For a kind of application of this no cobalt composition metal caprate adhesion promoter.
Technical solution: a kind of no cobalt composition metal caprate adhesion promoter, be with include mixed metal, it is neodecanoic acid, new
Valeric acid, propionic acid, rosin acid, caprate made of stearic raw material；
The caprate is in terms of 100% by quality, comprising mixed metal 15%~28%, neodecanoic acid 28%~50%, new
Valeric acid 10%~24%, propionic acid 5%~18%, rosin acid 3%~12%, stearic acid 4%~15%；
Wherein, the mixed metal is to include nickel 30%~50%, zinc 15%~35%, rare earth member in terms of 100% by quality
Element 30%~50%.
The rare earth element be cerium, praseodymium, neodymium, samarium, lutetium it is at least one of, with nickel, zinc formed " concerted catalysis " effect.
The molecule skeleton symbol of the caprate is NiR2·ZnR2·MeR3, Ni is nickel in formula, and Zn is zinc, and Me is rare earth element,
R is neodecanoic acid, neopentanoic acid, propionic acid, rosin acid, stearic organic acid.Increase compared to existing direct addition type cobalt salt bonding
Into agent, new cobalt decanoate CoR2, by molecule skeleton symbol as it can be seen that no cobalt composition metal caprate adhesion promoter of the invention is due to dilute
Earth elements bring trivalent metal ion, the increase of atomic group volume, can generate bigger steric hindrance in reaction, to complete to synthesize
Reaction needs bigger thermal energy and kinetic energy, this is why to select high-temperature solvent as reaction diluent in preparation method of the present invention
Theoretical foundation.Simultaneously as the characteristic of nickel, zinc organic compound, can make the mobility of product be deteriorated, softening point raising, this
The formula of invention product then can achieve improvement mobility, reduce the purpose of softening point.
A kind of preparation method of above-mentioned no cobalt composition metal caprate adhesion promoter, with the hydroxide of nickel or alkali formula
Carbonate, the hydroxide of zinc or subcarbonate, the raw material that rare earth oxide is mixed metal；It is successively put into reaction kettle
High-temperature solvent, rosin acid, stearic acid, neodecanoic acid, rare earth oxide carry out one section of synthetic reaction in a kettle, slowly heat up
To there is fraction, divide water, solvent refluxing, then proceedes to cooling down after being warming up to 200 DEG C and add neopentanoic acid, nickel to 80 DEG C
Hydroxide or subcarbonate, the hydroxide of zinc or subcarbonate carry out two sections of synthetic reactions again together, slowly rise
Temperature divides water, solvent refluxing, then proceedes to cooling down after being warming up to 200 DEG C and add propionic acid together to 80 DEG C to there is fraction
Three sections of synthetic reactions are carried out again, are to slowly warm up to fraction occur, divide water, solvent refluxing, are then proceeded to be warming up to 200 DEG C, be kept the temperature,
It is warming up to 210 DEG C again, steams solvent and vacuum takes off solvent, carry out melt granulation, obtain capric acid product salt.
Each component raw material of the present invention selects industrial raw material.Nickel content is not less than 55% in the nickel hydroxide, alkali formula
Nickel content is not less than 45% in nickelous carbonate, and Zn content is not less than 64% in the zinc hydroxide, and Zn content is not in basic zinc carbonate
Lower than 50%, the rare earth oxide purity is not less than 99.5%, and the above percentage is mass percent.
The high-temperature solvent is D40 of the boiling range at 175~210 DEG C.
The hydroxide or subcarbonate of the nickel, the hydroxide of zinc or subcarbonate, rare earth oxide are with powder
Shape, which is added, to be used.
A kind of application of above-mentioned no cobalt composition metal caprate adhesion promoter is binded for rubber and metallic framework.
The utility model has the advantages that the invention has the advantages that being made with nickel, zinc and a small amount of rare earth metal instead of expensive cobalt
There is peer-level, aging without cobalt its cement properties of composition metal caprate adhesion promoter and former cobalt salt adhesion promoter
It can be substantially better than former cobalt salt adhesion promoter, the use longevity for being conducive to the ageing properties for improving rubber product and improving rubber product
Life, realizes direct target of the addition type cobalt salt adhesion promoter product without cobalt；The price of nickel is only cobalt in product of the present invention
1/3, the price of zinc is only the 1/20 of cobalt, and also below the price of cobalt, they make to produce the price of the less rare earth metal of usage amount
Product cost is greatly lowered, and not only reduces the use cost of user, improves the profit of manufactory, while also saving in short supply
Cobalt metal resource, with good economic efficiency and social benefit.
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated, these embodiments are merely to illustrate the present invention and do not have to
In limiting the scope of the invention.
A kind of no cobalt composition metal caprate adhesion promoter, be with include mixed metal, neodecanoic acid, neopentanoic acid, propionic acid,
Caprate made of rosin acid, stearic raw material.
Caprate is in terms of 100% by quality, includes mixed metal 15%~28%, neodecanoic acid 28%~50%, neopentanoic acid
10%~24%, propionic acid 5%~18%, rosin acid 3%~12%, stearic acid 4%~15%；Wherein, mixed metal is with quality
For 100% meter, include nickel 30%~50%, zinc 15%~35%, rare earth element 30%~50%, rare earth element be cerium, praseodymium,
Neodymium, samarium, lutetium it is at least one of.
Table 1 is the mixed metal component proportion table (being in terms of 100% by mixed metal amount) of three kinds of different formulations:
The ratio between molar ratio, pure metal that mass ratio is each metallic element in table 1, reality uses the hydrogen-oxygen of nickel when preparing
Compound or subcarbonate, the hydroxide of zinc or subcarbonate, rare earth oxide.
Table 2 is that the caprate component of three kinds of different formulations prepares fertilizer charge ratio table:
The above-mentioned preparation process without cobalt composition metal caprate adhesion promoter is: (1) prepared by mixed metal powder: by matching
Side weighs hydroxide powder or basic carbonate salt fines, the hydroxide powder of zinc or basic carbonate salt fines, rare-earth oxidation of nickel respectively
Object powder is spare；(2) one sections of synthetic reactions: putting into the high-temperature solvent of half or so of material total volume in a kettle, then according to
Secondary investment rosin acid, stearic acid, neodecanoic acid, rareearth oxidate powder, are to slowly warm up to fraction occur, divide water, solvent refluxing, then
Cooling down is to 80 DEG C after being continuously heating to 200 DEG C；(3) two sections of synthetic reactions: add neopentanoic acid, nickel hydroxide powder or
Basic carbonate salt fines, the hydroxide powder of zinc or basic carbonate salt fines, are to slowly warm up to fraction occur, divide water, solvent refluxing, so
After be continuously heating to 200 DEG C after cooling down to 80 DEG C；(4) three sections of synthetic reactions: propionic acid is added, is to slowly warm up to evaporate
Point, divide water, solvent refluxing, then proceed to be warming up to 200 DEG C, heat preservation, then be warming up to 210 DEG C, steam solvent and vacuum take off it is molten
Agent carries out melt granulation, obtains capric acid product salt.
In the preparation process of caprate, there is reaction water discharge.
Table 3 is the quality and technical index of caprate obtained above:
| Project | Index |
| Appearance | Yellow green is granular |
| Tenor % | 20.0±1 |
| Heating loss (105 DEG C) %≤ | 1.0 |
| Softening point DEG C | 80~110 |
The molecule skeleton symbol of caprate is NiR2·ZnR2·MeR3, Ni is nickel in formula, and Zn is zinc, and Me is rare earth element, and R is
Neodecanoic acid, neopentanoic acid, propionic acid, rosin acid, stearic organic acid.Promote compared to existing direct addition type cobalt salt bonding
Agent, new cobalt decanoate CoR2, by molecule skeleton symbol as it can be seen that no cobalt composition metal caprate adhesion promoter of the invention is due to rare earth
Element brings trivalent metal ion, the increase of atomic group volume, can generate bigger steric hindrance in reaction, and it is anti-to complete synthesis
In requisition for bigger thermal energy and kinetic energy, this is why to select high-temperature solvent as reaction diluent in preparation method of the present invention
Theoretical foundation.Simultaneously as the characteristic of nickel, zinc organic compound, can make the mobility of product be deteriorated, softening point increases, this hair
The formula of bright product then can achieve improvement mobility, reduce the purpose of softening point.Each component raw material used selects industry
With raw material, nickel content is not less than 55% in nickel hydroxide, and nickel content is not less than 45% in basic nickel carbonate, and zinc contains in zinc hydroxide
Amount is not less than 64%, and Zn content is not less than 50% in basic zinc carbonate, and rare earth oxide purity is not less than 99.5%, the above percentage
Number is mass percent.
According to the theoretical research both at home and abroad to cobalt salt adhesion promoter, prevailing at present is catalytic theory, by urging
The adhesion mechanism of cobalt salt adhesion promoter can be illustrated by changing theory.Cobalt salt adhesion promoter is in heated (100 DEG C~200 DEG C) condition
Under, cracking releases active divalent cobalt ion, and under the catalysis of active cobalt ions, the metals such as copper, zinc and sulphur are chemically reacted,
Cu cannot be generated with the metal sulfide of stoichiometry, such as copper by generating2SX, reaction equation are as follows:
Cu+XS=Cu2SX
Cu2SXIn the S atom other end then enter on the net structure node of rubber, that is, it is intermediate in metal and rubber
Formation " sulphur bridge ", sulphur and metal are combined into ionic bond, and the bond energy of ionic bond is in 586kJ/mol~1047kJ/mol；Sulphur atom
Between combination and the combination of sulphur and rubber be covalent bond, the bond energy of covalent bond is in 63kJ/mol~712kJ/mol, this is just
Rubber and metal is set to carry out high-tenacity bonding by chemical bond completely.
It is of the invention without cobalt composition metal caprate adhesion promoter and existing direct addition type cobalt salt adhesion promoter
With similar catalytic mechanism, under heating condition, product of the present invention is in addition to releasing active nickelous, zinc ion, simultaneously also
Release amount of activated rare earth ion.Under " concerted catalysis " effect of various active metal ion, keep catalytic capability big
It is big to increase, to reach horizontal with the comparable bonding of cobalt salt adhesion promoter.Simultaneously as being remained without cobalt ions, substantially improve
The ageing properties and service life of rubber product, realize direct target of the addition type adhesion promoter without cobalt.
It is produced in the rubber products industries such as radial wire cord tire, steel wire reinforcement conveyer belt, rubber hose braided with steel wire using the present invention
When product substitute existing cobalt decanoate adhesion promoter, equipment, technique and operating condition are not necessarily to change, bonding level and other objects
Reason index can reach or more than the peer-level for using cobalt decanoate product, rubber product ageing properties and service life are mentioned
It is high.Product of the present invention not only reduces the use cost of user, improves the profit of manufactory, while also saving cobalt in short supply
Metal resource.
Product of the present invention is glutinous with existing commercially available cobalt decanoate through units such as the applicant, macromolecule institutes, Qingdao University of Science and Technology
It closes promoting agent and product of the present invention has carried out contrast and application test, under same dosage, identical conditions of vulcanization, achieve good
Effect, especially 2# formula, should be optimum formula.
Table 4 is that the applicant is general without cobalt composition metal caprate adhesion promoter and present rubber industry to the present invention
The test data of direct addition type cobalt salt adhesion promoter (cobalt decanoate) compares list:
Table 5 is that Qingdao University of Science and Technology is logical without cobalt composition metal caprate adhesion promoter and present rubber industry to the present invention
The test data of direct addition type cobalt salt adhesion promoter (cobalt decanoate) compares list:
In terms of the test data listed by table 4, the table 5, under same dosage, identical conditions of vulcanization, the bonding of product of the present invention
Level is parity with or superiority over former commercial product, and the ageing properties of rubber product and other physical properties significantly improve.Due to using
Cheap metal reduces the manufacturing cost of product of the present invention to only the 1/ of cobalt salt adhesive product instead of expensive cobalt
3 or so, meanwhile, the precious metal cobalt that a large amount of almost all rely on import is saved, this not only substantially increases the warp of manufactory
Ji benefit, has been greatly reduced the use cost of user, while improving the ageing properties and service life of rubber product.Cause
This, the present invention was not only with good economic efficiency without cobalt composition metal caprate adhesion promoter product, but also had good society
Meeting benefit, and have a vast market foreground.
Claims (8)
1. a kind of no cobalt composition metal caprate adhesion promoter, it is characterised in that: be with include mixed metal, it is neodecanoic acid, new
Valeric acid, propionic acid, rosin acid, caprate made of stearic raw material；
The caprate is in terms of 100% by quality, includes mixed metal 15%~28%, neodecanoic acid 28%~50%, neopentanoic acid
10%~24%, propionic acid 5%~18%, rosin acid 3%~12%, stearic acid 4%~15%；
Wherein, the mixed metal is in terms of 100% by quality, includes nickel 30%~50%, zinc 15%~35%, rare earth element
30%~50%.
2. no cobalt composition metal caprate adhesion promoter according to claim 1, it is characterised in that: the rare earth element
For cerium, praseodymium, neodymium, samarium, lutetium it is at least one of.
3. no cobalt composition metal caprate adhesion promoter according to claim 1, it is characterised in that: the caprate
Molecule skeleton symbol is NiR2·ZnR2·MeR3, Ni is nickel in formula, and Zn is zinc, and Me is rare earth element, and R is neodecanoic acid, neopentanoic acid, third
Acid, rosin acid, stearic organic acid.
4. a kind of preparation method of no cobalt composition metal caprate adhesion promoter described in claim 1, it is characterised in that: with
The hydroxide or subcarbonate of nickel, the hydroxide of zinc or subcarbonate, the raw material that rare earth oxide is mixed metal；
High-temperature solvent, rosin acid, stearic acid, neodecanoic acid, rare earth oxide are successively put into reaction kettle, carry out one section in a kettle
Synthetic reaction is to slowly warm up to fraction occur, divides water, solvent refluxing, then proceedes to after being warming up to 200 DEG C cooling down to 80
DEG C, it adds neopentanoic acid, the hydroxide of nickel or subcarbonate, the hydroxide of zinc or subcarbonate and carries out two again together
Section synthetic reaction, is to slowly warm up to fraction occur, divides water, solvent refluxing, then proceedes to after being warming up to 200 DEG C cooling down to 80
DEG C, it adds propionic acid and carries out three sections of synthetic reactions again together, be to slowly warm up to fraction occur, divide water, solvent refluxing, then proceed to
200 DEG C are warming up to, is kept the temperature, then be warming up to 210 DEG C, solvent is steamed and vacuum takes off solvent, carry out melt granulation, obtain caprate
Product.
5. the preparation method of no cobalt composition metal caprate adhesion promoter according to claim 4, it is characterised in that: institute
It states nickel content in nickel hydroxide and is not less than 55%, nickel content is not less than 45% in basic nickel carbonate, and zinc contains in the zinc hydroxide
Amount is not less than 64%, and Zn content is not less than 50% in basic zinc carbonate, and the rare earth oxide purity is above not less than 99.5%
Percentage is mass percent.
6. the preparation method of no cobalt composition metal caprate adhesion promoter according to claim 4, it is characterised in that: institute
Stating high-temperature solvent is D40 of the boiling range at 175~210 DEG C.
7. the preparation method of no cobalt composition metal caprate adhesion promoter according to claim 4, it is characterised in that: institute
It states hydroxide or subcarbonate, the hydroxide of zinc or subcarbonate, rare earth oxide of nickel and use is added with powdery.
8. a kind of application of no cobalt composition metal caprate adhesion promoter described in claim 1, it is characterised in that: be used for rubber
Glue and metallic framework bind.
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| CN201811432686.6A CN109609054B (en) | 2018-11-28 | 2018-11-28 | Cobalt-free composite metal caprate adhesion promoter and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030036596A1 (en) * | 1998-02-19 | 2003-02-20 | Toru Imori | Adhesion accelerator for bonding rubber to metal and rubber composition |
| CN101962522A (en) * | 2010-10-27 | 2011-02-02 | 镇江泛华新材料科技发展有限公司 | Cobalt salt adhesive for adhering ethylen e-propylene-diene mischpolymere and bare steel framework and preparation method thereof |
| CN103183845A (en) * | 2013-03-15 | 2013-07-03 | 陕西煤业化工技术研究院有限责任公司 | Fluorine-containing cobalt neocaprate and cobalt borate salt-mixture and preparation method thereof |
| CN106832401A (en) * | 2017-02-20 | 2017-06-13 | 镇江泛华新材料科技发展有限公司 | Direct addition type high-performance cobalt salt adhesion promoter and preparation method thereof |
-
2018
- 2018-11-28 CN CN201811432686.6A patent/CN109609054B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030036596A1 (en) * | 1998-02-19 | 2003-02-20 | Toru Imori | Adhesion accelerator for bonding rubber to metal and rubber composition |
| CN101962522A (en) * | 2010-10-27 | 2011-02-02 | 镇江泛华新材料科技发展有限公司 | Cobalt salt adhesive for adhering ethylen e-propylene-diene mischpolymere and bare steel framework and preparation method thereof |
| CN103183845A (en) * | 2013-03-15 | 2013-07-03 | 陕西煤业化工技术研究院有限责任公司 | Fluorine-containing cobalt neocaprate and cobalt borate salt-mixture and preparation method thereof |
| CN106832401A (en) * | 2017-02-20 | 2017-06-13 | 镇江泛华新材料科技发展有限公司 | Direct addition type high-performance cobalt salt adhesion promoter and preparation method thereof |
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Denomination of invention: Cobalt free composite metal decanoate adhesive promoter and its preparation method and Application Effective date of registration: 20210319 Granted publication date: 20201120 Pledgee: Shanghai Qixiang New Material Technology Co.,Ltd. Pledgor: JIANGSU CHEESHINE PERFORMANCE MATERIALS Co.,Ltd. Registration number: Y2021980001841 |
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Date of cancellation: 20230615 Granted publication date: 20201120 Pledgee: Shanghai Qixiang New Material Technology Co.,Ltd. Pledgor: JIANGSU CHEESHINE PERFORMANCE MATERIALS Co.,Ltd. Registration number: Y2021980001841 |