CN100415726C - Fluorine-containing chain hydrocarbon melamine derivate with double-key end group and its preparation method - Google Patents
Fluorine-containing chain hydrocarbon melamine derivate with double-key end group and its preparation method Download PDFInfo
- Publication number
- CN100415726C CN100415726C CNB2005100449810A CN200510044981A CN100415726C CN 100415726 C CN100415726 C CN 100415726C CN B2005100449810 A CNB2005100449810 A CN B2005100449810A CN 200510044981 A CN200510044981 A CN 200510044981A CN 100415726 C CN100415726 C CN 100415726C
- Authority
- CN
- China
- Prior art keywords
- chain hydrocarbon
- end group
- reaction
- double
- key end
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paper (AREA)
Abstract
This invention discloses a perfluoro-chain hydrocarbon melamine derivate that has terminal group of double bond and its preparation. The perfluoro-chain hydrocarbon melamine derivate that has terminal group of double bond is produced by condensation reaction with perfluoro-chain hydrocarbon vikane monomer that possesses terminal group of double bond and melamine. This derivate can be used as cross linking agent that contains fluorine, flame retardant, special material assistant, intermedium of organism containing fluorine materials, Its structural formula is formula I, x,p,z=0,1,2;And x+y=2,p+q=2,e+z=2 but x,p,z does not equal 2 at the same time, among them Rf is formula II, n=0-5.
Description
Technical field
The present invention relates to a class and contain perfluoro organic compound of trimeric cyanamide structure and preparation method thereof.Class band double-key end group fluorine-containing chain hydrocarbon melamine derivate and preparation method thereof specifically is by having double-key end group perfluor chain hydrocarbon sulfonyl fluoride monomer and the polycondensation of trimeric cyanamide monomer prepares.
Background technology
Trimeric cyanamide is a kind of broad-spectrum organic chemical industry's intermediates with uniform texture, and topmost purposes is as the raw material of producing melamine formaldehyde resin; Other purposes mainly contains the following aspects: 1, decoration veneer: can be made into fire prevention, antidetonation, heat-stable veneer sheet; 2, coating: trimeric cyanamide is to can be used as linking agent in the coating at acrylic acid series, alkyd system, epoxy; 3, molding powder: can be made into melaminoplast through operations such as mixing, granulations, nontoxic, anti-soil, still can keep good electric property when moist, can be made into the high-grade insulating materials of pure white, anti-daily utensil of beating, sanitary ware and imitative porcelain tableware, electrical equipment etc.; 4, paper treating agent; 5, fire retardant.But also there is its inherent shortcoming in trimeric cyanamide: temperature resistant grade is low, weathering resistance is poor.
Summary of the invention
Technical problem to be solved by this invention provides a kind of new perfluoro organic compound that contains the trimeric cyanamide structure, to be with the double-key end group perfluoro alkane to introduce in the trimeric cyanamide system, make compound have temperature tolerance and antioxidative stabilizer preferably, the present invention provides the preparation method of this compound simultaneously.
The perfluoro organic compound that contains the trimeric cyanamide structure provided by the present invention is a class band double-key end group fluorine-containing chain hydrocarbon melamine derivate, and its general molecular formula is:
In the formula: x, p, z=0,1,2; And x+y=2, p+q=2, e+z=2 but x, p, z do not equal 2 simultaneously
R wherein
fFor:
n＝0～5
Preferred construction is: x, p, z are respectively 0 or 1 derivative that obtains simultaneously in the formula.
This derivative is to obtain by having the reaction of double-key end group perfluor chain hydrocarbon sulfonyl fluoride monomer and trimeric cyanamide monomer condenses, and reaction formula is as follows:
R wherein
fFor:
n＝0～5
Active hydrogen reaction degree in the melamine molecule can be according to the mole control recently of perfluor sulfonyl fluorine and trimeric cyanamide monomer consumption; reactive hydrogen can be from one by the whole acylation reactions of acylation reaction to six hydrogen; when perfluor chain hydrocarbon sulfonyl fluoride monomer and the monomeric mol ratio of trimeric cyanamide greater than 6 the time, the reactive hydrogen complete reaction in the melamine molecule.Be displaced to six hydrogen from a hydrogen and all be substituted, general molecular formula is expressed as: C
3H
(6-d)N
6(R
f)
d, d=1～6 wherein.
Condensation reaction between the monomer both can be that body carries out condensation reaction, also can be that body carries out condensation reaction in solution, and concrete preparation method is as follows:
1, carries out the body condensation reaction at 40～160 ℃ and obtain by containing double-key end group perfluor chain hydrocarbon sulfonyl fluoride monomer and trimeric cyanamide.
2, by organic solvent dissolution double-key end group perfluor chain hydrocarbon sulfonyl fluoride monomer and trimeric cyanamide monomer, the solution polycondensation reaction obtains, and the solid content of reactant is preferably 25%～30% in the solution, and temperature of reaction is 40～160 ℃, and the reaction times is 6～12h.The solvent that is adopted in the reaction can be: acetonitrile, pyridine, dimethyl formamide (DMF), N-Methyl pyrrolidone (NMP) etc.
The gas HF that produces in the above-mentioned reaction process can utilize alkali lye to absorb and remove.
Institute of the present invention synthetic band double-key end group fluorine-containing chain hydrocarbon melamine derivate, the carbon that fluorine element, the bond energy of strong electronegativity is big-fluorine bond is introduced temperature tolerance and the antioxidative stabilizer that the trimeric cyanamide system can effectively be improved this class material.With contain trimeric cyanamide alkyl material equally and compare: long and two keys of part cause crosslinkedly anti-ultraviolet lamp according to the time, further give material heatproof, weathering resistance.Institute of the present invention synthetic band double-key end group fluorine-containing chain hydrocarbon melamine derivate can be used as the fluorine material intermediate of a class excellent performance, can be further two keys by end group carry out copolymerization, prepare the melamine derivative that contains long-chain high molecular perfluoroalkyl, by institute of the present invention synthetic derivative and tetrafluoroethylene copolymerization, the fluorine material thermostability that obtains is up to more than 500 ℃.The present invention utilizes simple raw material monomer, by condensation polymerization prepare a class formation clear and definite contain functional double-key end group perfluor chain hydrocarbon compound, the molecular weight of this compounds can be controlled by controlling monomeric molar ratio, have very high using value, can be used as fluorine-containing linking agent, high grade paint, fire retardant, special material auxiliary agent, organic fluoride-containing material intermediate.
Embodiment
The present invention is described by the following examples, but does not limit the present invention.
Embodiment 1:
12.6g (0.1mol) trimeric cyanamide placed be furnished with heating; mechanical stirring; in three mouthfuls of round-bottomed flasks of the 500ml of nitrogen protection device; add 280ml～330ml anhydrous acetonitrile dissolution with solvents; make the solid content of reactant in the solution 25%～30%; at elevated temperature to 60 ℃; remain under this temperature and drip perfluoroolefine (3-oxa-penta-4-alkene) sulfonic acid fluoride 84.3g (0.3mol) by constant pressure funnel; reaction keeps 5～8h; after reaction finishes; with the product cooling, filter, after repeatedly washing with methyl alcohol; adopt deionized water repeatedly to wash again; 100 ℃ of dryings of vacuum obtain the brown viscous liquid product, productive rate 95%.
Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 19.88 | 0.33 | 44.02 | 15.89 | 9.27 |
| Measured value (%) | 19.81 | 0.36 | 44.01 | 15.89 | 9.23 |
The structure of this material is:
Embodiment 2:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating, three mouthfuls of round-bottomed flasks of 500ml of mechanical stirring, nitrogen protection device; add 250ml anhydrous acetonitrile dissolution with solvents; elevated temperature to 80 ℃; remain under this temperature and drip perfluoroolefine (3-oxa-penta-4-alkene) sulfonic acid fluoride 84.3g (0.3mol) by constant pressure funnel; reaction keeps 8～12h; after reaction finishes; product is cooled off; filter; after repeatedly washing with methyl alcohol, use the deionized water repetitive scrubbing again, 100 ℃ of dryings of vacuum; obtain the thick liquid product, productive rate 91%.Product is tested through ultimate analysis:
| C | F | O | N | |
| Theoretical value (%) | 19.23 | 47.31 | 17.07 | 4.98 |
| Measured value (%) | 19.19 | 47.33 | 17.13 | 4.96 |
The structure of this material is:
Embodiment 3:
In three mouthfuls of round-bottomed flasks of the 500ml that is equipped with heating, mechanical stirring, nitrogen protection device; add liquid perfluoroolefine (3-oxa-penta-4-alkene) sulfonic acid fluoride 84.3g (0.3mol); elevated temperature to 50 ℃ remains under this temperature and by casing drum 6.3g (0.05mol) trimeric cyanamide is added in the reaction system, keeps reaction 6～12h; after reaction finishes; with the product cooling, repeatedly wash 100 ℃ of dryings of vacuum with deionized water; obtain the thick liquid product, productive rate 92%.
Product is tested through ultimate analysis:
| C | F | O | N | |
| Theoretical value (%) | 19.23 | 47.31 | 17.07 | 4.98 |
| Measured value (%) | 19.20 | 47.31 | 17.11 | 4.99 |
The structure of preparing by solution reaction among the structure that this compound is known in analysis and the embodiment 2 is consistent, is that six ripple hydrogen alive in the trimeric cyanamide all participate in reaction equally.
Embodiment 4:
6.2g (0.05mol) trimeric cyanamide placed be furnished with heating, mechanical stirring, in three mouthfuls of round-bottomed flasks of the 500ml of nitrogen protection device, add 350ml anhydrous acetonitrile dissolution with solvents, make the solid content of reactant in the solution 20%～25%, at elevated temperature to 60 ℃, remain under this temperature and drip perfluoroolefine (3-oxa-penta-4-alkene) sulfonic acid fluoride by constant pressure funnel, after adding 2.81g (0.01mol), stop to drip, reaction keeps 3h, extract 0.5ml solution with syringe, know by nucleus magnetic hydrogen spectrum and flying time mass spectrum analysis: the product major part is that a hydrogen replaces; Continue to drip perfluoroolefine (3-oxa-penta-4-alkene) sulfonic acid fluoride before 0.15mol, measuring product is a hydrogen, two hydrogen, three mix products that hydrogen replaces, be sulfonic acid fluoride: trimeric cyanamide≤3: 1 o'clock, product are a hydrogen, two hydrogen, three mix products that hydrogen replaces; Adding perfluoroolefine (3-oxa-penta-4-alkene) sulfonic acid fluoride 0.15～0.3mol, measuring product is four hydrogen, five hydrogen, six mix products that hydrogen replaces, and sulfonic acid fluoride: trimeric cyanamide 〉=6: 1 o'clock, product are that acylation reaction all takes place six hydrogen.
Embodiment 5:
12.6g (0.1mol) trimeric cyanamide placed be furnished with heating; mechanical stirring; in three mouthfuls of round-bottomed flasks of the 500ml of nitrogen protection device; add 280ml anhydrous dimethyl formamide dissolution with solvents; elevated temperature to 65 ℃; remain under this temperature conditions and drip perfluoroolefine (4-methyl-3 by constant pressure funnel; 6-two oxa-s-7-octene) sulfonic acid fluoride 133.9g (0.3mol); reaction keeps 6～9h; after reaction finishes; with the product cooling, filter, after repeatedly washing with methyl alcohol; adopt deionized water repeatedly to wash again; 100 ℃ of dryings of vacuum obtain the brown viscous liquid product, productive rate 90%.Product is tested through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 21.25 | 0.22 | 54.62 | 10.62 | 6.20 |
| Measured value (%) | 21.21 | 0.24 | 54.61 | 10.59 | 6.23 |
The accurate structure of this material is:
Embodiment 6:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating; mechanical stirring; in three mouthfuls of round-bottomed flasks of the 500ml of nitrogen protection device; add 240ml anhydrous dimethyl formamide dissolution with solvents; elevated temperature to 80 ℃; remain under this temperature and drip perfluoroolefine (4-methyl-3 by constant pressure funnel; 6-two oxa-s-7-octene) sulfonic acid fluoride 133.9g (0.3mol); reaction keeps 8～12h; after reaction finishes; with the product cooling, filter, after repeatedly washing with methyl alcohol; adopt deionized water repeatedly to wash again; 100 ℃ of dryings of vacuum obtain the thick liquid product, productive rate 89%.
Product is tested through ultimate analysis:
| C | F | O | N | |
| Theoretical value (%) | 20.89 | 57.29 | 11.13 | 3.25 |
| Measured value (%) | 20.85 | 57.23 | 11.15 | 3.26 |
The structure of this material is:
Embodiment 7:
In three mouthfuls of round-bottomed flasks of the 500ml that is equipped with heating, mechanical stirring, nitrogen protection device; add liquid perfluoroolefine (4-methyl-3,6-two oxa-s-7-octene) sulfonic acid fluoride 133.9g (0.3mol), elevated temperature to 90 ℃; remain under this temperature and 6.3g (0.05mol) trimeric cyanamide is added in the reaction system by casing drum; keep reaction 8～12h, reaction after finishing is cooled off product; repeatedly wash with deionized water; 100 ℃ of dryings of vacuum obtain the thick liquid product, productive rate 88%.
Product is tested through ultimate analysis:
| C | F | O | N | |
| Theoretical value (%) | 20.89 | 57.29 | 11.13 | 3.25 |
| Measured value (%) | 20.87 | 57.26 | 11.17 | 3.27 |
The structure of preparing by solution reaction among the structure that this compound is known in analysis and the embodiment 6 is consistent, is that six ripple hydrogen alive in the trimeric cyanamide all participate in reaction equally.
Embodiment 8:
12.6g (0.1mol) trimeric cyanamide placed be furnished with heating; mechanical stirring; in three mouthfuls of round-bottomed flasks of the 500ml of nitrogen protection device; add the anhydrous N-Methyl pyrrolidone dissolution with solvents of 300ml; elevated temperature to 100 ℃; remain under this temperature and drip perfluoroolefine (4 by constant pressure funnel; 7-dimethyl-3; 6,9-trioxa-10-hendecene) sulfonic acid fluoride 183.6g (0.3mol), reaction keeps 6～9h; after reaction finishes; with the product cooling, filter, after repeatedly washing with methyl alcohol; adopt deionized water repeatedly to wash again; 100 ℃ of dryings of vacuum obtain the brown viscous liquid product, productive rate 77%.
Product is through ultimate analysis:
| C | H | F | O | N | |
| Theoretical value (%) | 20.83 | 0.16 | 56.92 | 12.61 | 4.42 |
| Measured value (%) | 20.79 | 0.19 | 56.95 | 12.62 | 4.42 |
The structure of this material is:
Embodiment 9:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating; mechanical stirring; in three mouthfuls of round-bottomed flasks of the 500ml of nitrogen protection device; add the anhydrous N-Methyl pyrrolidone dissolution with solvents of 250ml; elevated temperature to 100 ℃; remain under this temperature and drip perfluoroolefine (4 by constant pressure funnel; 7-dimethyl-3; 6,9-trioxa-10-hendecene) sulfonic acid fluoride 183.6g (0.3mol), reaction keeps 6～9h; after reaction finishes; with the product cooling, filter, after repeatedly washing with methyl alcohol; adopt deionized water repeatedly to wash again; 100 ℃ of dryings of vacuum obtain the brown viscous liquid product, productive rate 75%.
Product is through ultimate analysis:
| C | F | O | N | |
| Theoretical value (%) | 20.57 | 58.87 | 13.05 | 2.28 |
| Measured value (%) | 20.55 | 58.88 | 13.06 | 2.30 |
The accurate structure of this material is:
Embodiment 10:
In three mouthfuls of round-bottomed flasks of the 500ml that is equipped with heating, mechanical stirring, nitrogen protection device; add liquid perfluoroolefine (4; 7-dimethyl-3; 6; 9-trioxa-10-hendecene) sulfonic acid fluoride (n=2) 183.6g (0.3mol); elevated temperature to 100 ℃; remain on and by casing drum 6.3g (0.05mol) trimeric cyanamide is added 1 under this temperature conditions and go in the reaction system; keep reaction 9～12h, reaction after finishing is cooled off product; repeatedly wash with deionized water; 100 ℃ of dryings of vacuum obtain the thick liquid product, productive rate 74%.
Product is tested through ultimate analysis:
| C | F | O | N | |
| Theoretical value (%) | 20.57 | 58.87 | 13.05 | 2.28 |
| Measured value (%) | 20.52 | 58.84 | 13.08 | 2.32 |
The structure of preparing by solution reaction among the structure that this compound is known in analysis and the embodiment 9 is consistent, is that six ripple hydrogen alive in the trimeric cyanamide all participate in reaction equally.
Embodiment 11:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating; mechanical stirring; in three mouthfuls of round-bottomed flasks of the 1000ml of nitrogen protection device; add the anhydrous N-Methyl pyrrolidone dissolution with solvents of 450ml; elevated temperature to 100 ℃; remain under this temperature by constant pressure funnel drip perfluoroolefine (4,7,10-trimethylammonium-3; 6; 9,12-four oxa-s-13-tetradecene) sulfonic acid fluoride (n=3) 233.4g (0.3mol), reaction keeps 6～9h; after reaction finishes; with the product cooling, filter, after repeatedly washing with methyl alcohol; adopt deionized water repeatedly to wash again; 100 ℃ of dryings of vacuum obtain the brown viscous liquid product, productive rate 65%.
Product is through ultimate analysis:
| C | F | O | N | |
| Theoretical value (%) | 20.81 | 60.96 | 12.32 | 1.80 |
| Measured value (%) | 20.85 | 60.88 | 12.36 | 1.73 |
The structure of this material is:
Embodiment 12:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating; mechanical stirring; in three mouthfuls of round-bottomed flasks of the 1000ml of nitrogen protection device; add the anhydrous N-Methyl pyrrolidone dissolution with solvents of 500ml, elevated temperature to 130 ℃ remains under this temperature and drips perfluoroolefine (4 by constant pressure funnel; 7; 10,13-tetramethyl--3,6; 9; 12,15-five oxa-s-16-17 alkene) sulfonic acid fluoride (n=4) 283.2g (0.3mol), reaction keeps 10～12h; after reaction finishes; with the product cooling, filter, after repeatedly washing with methyl alcohol; adopt deionized water repeatedly to wash again; 100 ℃ of dryings of vacuum obtain the brown viscous liquid product, productive rate 61%.
Product is through ultimate analysis:
| C | F | O | N | |
| Theoretical value (%) | 20.97 | 62.31 | 11.85 | 1.48 |
| Measured value (%) | 20.95 | 62.28 | 11.86 | 1.43 |
The structure of this material is:
Embodiment 13:
6.3g (0.05mol) trimeric cyanamide placed be furnished with heating; mechanical stirring; in three mouthfuls of round-bottomed flasks of the 1000ml of nitrogen protection device, add the anhydrous N-Methyl pyrrolidone dissolution with solvents of 600ml, elevated temperature to 160 ℃; remain under this temperature and drip perfluoroolefine (4,7,10 by constant pressure funnel; 13; 16-pentamethyl--3,6,9; 12; 15,18-six oxa-s-19-icosa alkene) sulfonic acid fluoride (n=5) 333.1g (0.3mol), reaction keeps 12～14h; after reaction finishes; with the product cooling, filter, after repeatedly washing with methyl alcohol; adopt deionized water repeatedly to wash again; 100 ℃ of dryings of vacuum obtain the brown viscous liquid product, productive rate 56%.
Product is through ultimate analysis:
| C | F | O | N | |
| Theoretical value (%) | 21.08 | 63.26 | 11.52 | 1.26 |
| Measured value (%) | 21.05 | 63.28 | 11.56 | 1.23 |
The structure of this material is:
Claims (5)
1. be with the double-key end group fluorine-containing chain hydrocarbon melamine derivate for one kind, its general structure is expressed as:
In the formula: x, p, z=0,1,2, and x+y=2, p+q=2, e+z=2, but x, p, z do not equal 2 simultaneously, wherein R
fFor:
n＝0～5。
2. derivative according to claim 1 is characterized in that x, p, z are respectively 0 or 1 simultaneously in the described general structure.
3. the preparation method of the described band double-key end group of claim 1 fluorine-containing chain hydrocarbon melamine derivate, it is characterized in that it being to obtain carrying out the body condensation reaction under 40～160 ℃ or carry out solution condensation reaction in the presence of organic solvent by containing double-key end group perfluor chain hydrocarbon sulfonyl fluoride monomer and trimeric cyanamide, the described structural formula that contains double-key end group perfluor chain hydrocarbon sulfonyl fluoride monomer is:
4. preparation method according to claim 3 is characterized in that described organic solvent is acetonitrile, pyridine, dimethyl formamide or N-Methyl pyrrolidone.
5. preparation method according to claim 3 is characterized in that in the reaction system solution in the presence of organic solvent, the reactant solid content is 20%～35%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100449810A CN100415726C (en) | 2005-10-24 | 2005-10-24 | Fluorine-containing chain hydrocarbon melamine derivate with double-key end group and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100449810A CN100415726C (en) | 2005-10-24 | 2005-10-24 | Fluorine-containing chain hydrocarbon melamine derivate with double-key end group and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1955168A CN1955168A (en) | 2007-05-02 |
| CN100415726C true CN100415726C (en) | 2008-09-03 |
Family
ID=38062752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100449810A Expired - Fee Related CN100415726C (en) | 2005-10-24 | 2005-10-24 | Fluorine-containing chain hydrocarbon melamine derivate with double-key end group and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100415726C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5034525A (en) * | 1988-09-19 | 1991-07-23 | Takateru Dekura | Synthetic lubricant |
| US5225549A (en) * | 1988-10-08 | 1993-07-06 | Takateru Dekura | Perfluoropolyether lubricants for electromagnetic recording media |
| JP2001247981A (en) * | 2000-03-07 | 2001-09-14 | Fuji Photo Film Co Ltd | Metal surface treating agent |
-
2005
- 2005-10-24 CN CNB2005100449810A patent/CN100415726C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5034525A (en) * | 1988-09-19 | 1991-07-23 | Takateru Dekura | Synthetic lubricant |
| US5225549A (en) * | 1988-10-08 | 1993-07-06 | Takateru Dekura | Perfluoropolyether lubricants for electromagnetic recording media |
| JP2001247981A (en) * | 2000-03-07 | 2001-09-14 | Fuji Photo Film Co Ltd | Metal surface treating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1955168A (en) | 2007-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100540540C (en) | Contain fluorine-containing chain hydrocarbon melamine derivate of functional end group and preparation method thereof | |
| CN103328538B (en) | A kind of method for preparing polycondensation product | |
| CN105418865A (en) | Novel high-molecular-block dispersing agent, preparation method and application thereof | |
| CN105175786B (en) | A kind of Montmorillonite composite fire retardant and preparation method thereof | |
| CN103012297B (en) | Cyanate ester and polymer containing s-triazine structure and preparation methods of cyanate ester and polymer | |
| CN109467690A (en) | A kind of flame-retardant polyether glycol and its preparation method and application | |
| BR102013009283A2 (en) | Composition, and methods for forming a coating, and for improving the freeze / thaw stability of an aqueous composition. | |
| CN105199146B (en) | A kind of hydrotalcite composite flame-retardant agent and preparation method thereof | |
| US8268931B2 (en) | Process for cleaner production of chlorinated rubber without using carbon tetrachloride and water | |
| CN104262628A (en) | Organo-siloxane polyethersulfone resin with linear and cage-like main chains and preparation method thereof | |
| CN100415726C (en) | Fluorine-containing chain hydrocarbon melamine derivate with double-key end group and its preparation method | |
| CN100488953C (en) | Perfluor chain hydrocarbon melamine derivative and its preparation method | |
| CN103951794A (en) | Low-foam polycarboxylate dispersant and its preparation method | |
| CN111019128A (en) | Polytriazole resin toughened by alkynyl polyethylene glycol and preparation method thereof | |
| CN100448851C (en) | Fluorine-containing chain hydrocarbon melamine derivate with ester-base alkyl ether and carboxylic end group and its preparation method | |
| CN102432436A (en) | Poly-fluorophenyl-substituted aromatic diphenol and synthesis method and application thereof | |
| CN105130819B (en) | Fluorinated aromatic tetrone compound and polyphenyl based quinoxaline | |
| CN104710457B (en) | Three [2- (dimethyl chloride propoxyl group silicon acyloxy) ethyl] isocyanurate compounds and preparation method thereof | |
| CN100480244C (en) | Perfluoro propionyl tripolycyanamide derivate and preparation process thereof | |
| Nakano et al. | Synthesis and properties of α‐substituted benzylpyridinium salts as cationic initiators | |
| CN100532423C (en) | Plastic of polyester ketone containing fluorin, and preparation method | |
| CN106588723A (en) | Preparation method of pentaerythritol tris(3-mercaptopropionate) | |
| CN105664784B (en) | fluorine-containing surfactant and preparation method thereof | |
| Wang et al. | Synthesis and the effects of new melamine superplasticizer on the properties of concrete | |
| CN105061754A (en) | Polyarylether polymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SHANDONG HUAXIA SHENZHOU NEW MATERIAL CO., LTD. Free format text: FORMER NAME: DONGGUE SHENZHOU NEW MATERIAL CO., LTD., SHANDONG |
|
| CP03 | Change of name, title or address |
Address after: 256401 Tangshan Town, Huantai County, Zibo Patentee after: Shandong Dongyue Shenzhou New Material Co., Ltd. Address before: 256400 Tangshan Town, Huantai County, Zibo, Shandong Patentee before: Donggue Shenzhou New Material Co., Ltd., Shandong |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080903 Termination date: 20171024 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |