CN107903286B - Fire retardant cyclohexylamine dimethylidene phosphonic acid and preparation method thereof - Google Patents
Fire retardant cyclohexylamine dimethylidene phosphonic acid and preparation method thereof Download PDFInfo
- Publication number
- CN107903286B CN107903286B CN201710960876.4A CN201710960876A CN107903286B CN 107903286 B CN107903286 B CN 107903286B CN 201710960876 A CN201710960876 A CN 201710960876A CN 107903286 B CN107903286 B CN 107903286B
- Authority
- CN
- China
- Prior art keywords
- cyclohexylamine
- phosphonic acid
- fire retardant
- dimethylidene
- preparation
- 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.)
- Active
Links
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 title claims abstract description 88
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003063 flame retardant Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 48
- 239000004033 plastic Substances 0.000 abstract description 16
- 229920003023 plastic Polymers 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 13
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229940074995 bromine Drugs 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940060038 chlorine Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5353—Esters of phosphonic acids containing also nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the field of fire retardant chemicals, and particularly relates to cyclohexylamine dimethylidene phosphonic acid and a preparation method thereof. The preparation method of the fire retardant cyclohexylamine dimethylidene phosphonic acid comprises the following steps: (1) uniformly mixing phosphorous acid and cyclohexylamine; (2) dripping formaldehyde and preserving heat; (3) heating, and dropwise adding the residual formaldehyde to obtain the cyclohexylamine dimethylidephosphonic acid. The invention provides a fire retardant of cyclohexylamine dimethylidene phosphonic acid, which has good fire retardant effect, low solubility and environmental protection, and can be well applied to plastics. The invention also provides a preparation method of the flame retardant cyclohexylamine dimethylidene phosphonic acid, which is simple, convenient to operate, environment-friendly and excellent in performance and is a flame retardant additive for plastics.
Description
Technical Field
The invention belongs to the field of fire retardant chemicals, and particularly relates to a fire retardant cyclohexylamine dimethylidene phosphonic acid and a preparation method thereof.
Background
Most plastics are flammable. With the wide application of plastics in the aspects of buildings, furniture, traffic, aviation, aerospace, electrical appliances and the like, the improvement of the flame retardance of plastics has become a very urgent subject. The flame retardant is an auxiliary agent for inhibiting the combustibility of the polymer, and most of the auxiliary agents are compounds of elements in groups V, VII and III in the periodic table of elements; in particular phosphorus, bromine, chlorine, antimony and aluminium compounds. As a flame retardant with high efficiency, no smoke, low toxicity and no pollution, the phosphorus flame retardant is concerned by researchers and has made remarkable achievement in the aspects of synthesis, application and the like.
However, the raw materials of the common phosphorus flame retardant are most of dangerous and toxic chemicals such as phosphorus oxychloride and the like, and the invention takes the low-toxicity phosphorous acid as a substitute raw material to synthesize the environment-friendly organic phosphine product.
The organic phosphine flame retardant is a flame retardant with better flame retardance, has double functions of flame retardance and plasticization, and can replace halogenated flame retardants. Most of the organic phosphine products are good in water solubility at present, but when the organic phosphine products are used as a flame retardant to be added into plastics, the organic phosphine products are required to have the characteristic of being difficult to dissolve in water, otherwise, the stability of the plastics in water is reduced. Therefore, the development of the fire retardant which is insoluble in water environment and friendly has good economic and social benefits.
Disclosure of Invention
The invention aims to synthesize cyclohexylamine dimethylidene phosphonic acid, has good flame retardant effect and is environment-friendly, and the water solubility of an organic phosphine product applied to a plastic flame retardant is reduced.
The invention also aims to provide a preparation method of the cyclohexylamine dimethylidene phosphonic acid, which has the advantages of good reproducibility, easy operation and environmental protection.
In order to achieve the purpose, the invention adopts the following technical scheme:
a flame retardant cyclohexylamine dimethylidene phosphonic acid having the formula:
the preparation method of the fire retardant cyclohexylamine dimethylidene phosphonic acid comprises the following steps: (1) uniformly mixing phosphorous acid and cyclohexylamine; (2) dripping formaldehyde and preserving heat; (3) raising the temperature, and dripping formaldehyde to obtain the cyclohexylamine dimethylidene phosphonic acid.
Further, the cyclohexylamine dimethylidene phosphonic acid is synthesized by the following formula:
preferably, the specific cyclohexylamine dimethylidene phosphonic acid is prepared by the following specific process:
(1) adding phosphorous acid into a reactor, adding metered cyclohexylamine into the reactor, adjusting the pH value of the system by hydrochloric acid, and uniformly stirring;
(2) controlling the temperature, and dripping 40-90% of the formaldehyde;
(3) slowly cooling to 20-80 deg.C, and keeping the temperature for 1-5 h;
(4) raising the temperature, dropwise adding the residual formaldehyde, and keeping the temperature to continue the reaction to the end point;
(5) cooling to room temperature, stirring and crystallizing;
(6) centrifuging and drying to obtain cyclohexylamine dimethylidene phosphonic acid crystals;
wherein the sum of the formaldehyde amount in the step (2) and the residual formaldehyde amount in the step (4) is the total formaldehyde amount.
Preferably, the molar ratio of the cyclohexylamine to the phosphorous acid to the total formaldehyde is 1: 1.5-2.5.
Preferably, the pH value of the system is adjusted to be less than 2 by using hydrochloric acid in the step (1).
Preferably, the temperature control in the step (2) is 60-120 ℃.
Preferably, the time for dripping 40-90% of the dosage of the formaldehyde in the step (2) is 0.5-2 hours; and (4) dropwise adding the residual formaldehyde for 1-2 h.
Preferably, the temperature increase in the step (4) is 60-120 ℃; and (4) keeping the temperature for 2-5 hours.
Preferably, the dropwise addition of formaldehyde in the step (2) and the step (4) is carried out at a constant speed.
Advantageous effects
The invention provides a fire retardant of cyclohexylamine dimethylidene phosphonic acid, which has good fire retardant effect, low solubility and environmental protection, and can be well applied to plastics. The invention also provides a preparation method of the flame retardant cyclohexylamine dimethylidene phosphonic acid, which is simple, convenient to operate, environment-friendly and excellent in performance and is a flame retardant additive for plastics.
Detailed Description
For a better understanding of the purpose and significance of the present invention, the specific synthetic process of the present invention will now be illustrated by the following specific examples. However, the present invention is not limited to the following examples.
Example 1
The synthesis principle of cyclohexylamine dimethylidene phosphonic acid is as follows:
the specific synthesis process comprises the following steps:
(1) adding 144.3g of phosphorous acid into a reactor, dropwise adding 79.2g of cyclohexylamine into the reactor, regulating the pH value of the system to 2 by using hydrochloric acid, and uniformly stirring;
(2) controlling the temperature to be 120 ℃, dropwise adding 112g of metered formaldehyde solution, finishing dropwise adding for 2 hours, wherein the molar ratio of the reaction material cyclohexylamine to the phosphorous acid to the formaldehyde is 1:2: 2.4;
(3) cooling to 80 ℃, and keeping the temperature for 1 h;
(4) heating to 120 ℃, dropwise adding the residual 39.6g of formaldehyde, keeping the temperature and continuously reacting for 2 hours after 2 hours of dropwise adding;
(5) cooling to room temperature, and centrifuging to obtain cyclohexylamine dimethylidene phosphonic acid crystals.
The activity of the finally obtained cyclohexylamine dimethylidene phosphonic acid crystal is 98.87 percent, and the yield is 84.32 percent.
Example 2
The synthesis principle of cyclohexylamine dimethylidene phosphonic acid is as follows:
the specific synthesis process comprises the following steps:
(1) adding 98.4g of phosphorous acid into a reactor, dropwise adding 79.2g of cyclohexylamine into the reactor, regulating the pH value of the system to 2 by using hydrochloric acid, and uniformly stirring;
(2) controlling the temperature to be 60 ℃, dropwise adding 112g of metered formaldehyde solution, and finishing dropwise adding for 2 hours, wherein the molar ratio of the reaction material cyclohexylamine to the phosphorous acid to the formaldehyde is 1:1.5: 1.5;
(3) cooling to 20 ℃, and preserving heat for 5 hours;
(4) heating to 100 ℃, dropwise adding the rest 10.7g of formaldehyde, keeping the temperature and continuously reacting for 5 hours after 1 hour of dropwise adding;
(5) cooling to room temperature, and centrifuging to obtain cyclohexylamine dimethylidene phosphonic acid crystals.
The activity of the finally obtained cyclohexylamine dimethylidene phosphonic acid crystal is 96.78 percent, and the yield is 82.7 percent.
Example 3
The synthesis principle of cyclohexylamine dimethylidene phosphonic acid is as follows:
the specific synthesis process comprises the following steps:
(1) adding 164g of phosphorous acid into a reactor, dropwise adding 79.2g of cyclohexylamine into the reactor, regulating the pH value of the system to 2 by using hydrochloric acid, and uniformly stirring;
(2) controlling the temperature to be 90 ℃, dropwise adding 112g of metered formaldehyde solution, and finishing dropwise adding for 2 hours, wherein the molar ratio of the reaction material cyclohexylamine to the phosphorous acid to the formaldehyde is 1:2.5: 2.5;
(3) cooling to 60 ℃, and preserving heat for 3 h;
(4) heating to 110 ℃, dropwise adding the residual 45.9g of formaldehyde, keeping the temperature and continuously reacting for 3 hours after 1.5 hours of dropwise adding;
(5) cooling to room temperature, and centrifuging to obtain cyclohexylamine dimethylidene phosphonic acid crystals.
The activity of the finally obtained cyclohexylamine dimethylidene phosphonic acid crystal is 96.43 percent, and the yield is 79.31 percent.
Effect test
The cyclohexylamine dimethylidene phosphonic acid obtained in the above examples 1 to 3 can be easily added into plastics due to poor water solubility and has good flame retardant property, the invention tests the oxygen index and the U8594 rating of the cyclohexylamine dimethylidene phosphonic acid prepared in the above examples 1 to 3 after being added into the plastic material, and the specific data are shown in tables 1 and 2.
The blank group is a plastic material to which no cyclohexylamine dimethylidene phosphonic acid crystal is added, and the experimental group 1, the experimental group 2, and the experimental group 3 are plastic materials to which cyclohexylamine dimethylidene phosphonic acid crystals prepared in example 1, example 2, and example 3 are added, respectively.
TABLE 1 oxygen index of plastics
TABLE 2 Plastic U L94
Index calculation method
Activity and yield calculation methods:
a cyclohexylamine dimethylidene phosphonic acid activity test method is formulated by referring to a common organic phosphine product activity test method, and is verified by NMR to determine that the activity test method is effective. The method comprises the following specific steps:
1g (exactly to 0.0001 g) of sample is weighed into a 150m L beaker, 100m L of deionized water is added, the mixture is titrated on a potentiometric titrator, the mutation volumes V1 and V2 are recorded, and the final activity is
Wherein c is NaOH concentration, 1mo L/L, m is the actual mass of the weighed sample, and the content of the phosphorus and the phosphorous is implemented according to the method for measuring the content of the phosphorus and the phosphorous in the scale and corrosion inhibitor for the circulating water of the D L/T806-2013 thermal power plant.
And (3) calculating yield: the theoretical output is calculated by the equation that phosphorous acid or cyclohexylamine is not excessive:
Claims (1)
1. The application of cyclohexylamine dimethylidene phosphonic acid is characterized by being used as a flame retardant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710960876.4A CN107903286B (en) | 2017-10-17 | 2017-10-17 | Fire retardant cyclohexylamine dimethylidene phosphonic acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710960876.4A CN107903286B (en) | 2017-10-17 | 2017-10-17 | Fire retardant cyclohexylamine dimethylidene phosphonic acid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107903286A CN107903286A (en) | 2018-04-13 |
| CN107903286B true CN107903286B (en) | 2020-08-04 |
Family
ID=61841306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710960876.4A Active CN107903286B (en) | 2017-10-17 | 2017-10-17 | Fire retardant cyclohexylamine dimethylidene phosphonic acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107903286B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276441A (en) * | 2018-01-31 | 2018-07-13 | 山东大学 | The preparation method of two methylenephosphonic acid of cyclohexylamine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891685A (en) * | 2015-05-19 | 2015-09-09 | 山东省泰和水处理有限公司 | A synthesis process of 1,3-cyclohexanebis(methylamine) tetra(methylenephosphonic acid) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL285361A (en) * | 1961-11-13 | 1900-01-01 | ||
| CN103130832B (en) * | 2011-11-24 | 2015-11-25 | 上海雅运纺织助剂有限公司 | The improvement preparation method of fire-retardant N-methylol di alkyl phosphonic acid (methyl) propionic acid amide |
| CA2900282C (en) * | 2013-02-19 | 2016-07-26 | Nano Safe Coatings Incorporated (A Florida Corporation 3 P 14000024914) | Phosphorus functional antimicrobial coatings for metal surfaces |
| CN104975497B (en) * | 2015-06-30 | 2017-03-22 | 西南大学 | Flame retardant, preparation method and applications thereof |
| CN105777805A (en) * | 2016-04-06 | 2016-07-20 | 山东泰和水处理科技股份有限公司 | Synthetic method and application of dimethylphosphinic acid glutamate |
| CN106046049B (en) * | 2016-07-01 | 2018-04-27 | 武汉科技大学 | Benzylamine-N, N- dimethylene phosphonic acids melamine salt and preparation method and application |
| CN106751380A (en) * | 2016-11-25 | 2017-05-31 | 重庆市优合新型材料有限公司 | A kind of halogen-free flame retardants and flame-proof ABS plastics and preparation method thereof |
| CN106958143A (en) * | 2017-04-06 | 2017-07-18 | 天津工业大学 | A kind of preparation method of antiflaming finishing agent and its fire-retardant Lyocell fiber fabric |
-
2017
- 2017-10-17 CN CN201710960876.4A patent/CN107903286B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891685A (en) * | 2015-05-19 | 2015-09-09 | 山东省泰和水处理有限公司 | A synthesis process of 1,3-cyclohexanebis(methylamine) tetra(methylenephosphonic acid) |
Non-Patent Citations (1)
| Title |
|---|
| "Design, synthesis and anticholinesterase activity of some new α-aminobisphosphonates";Khodayar G. et al;《Journal of Enzyme Inhibition and Medicinal Chemistry》;20101231;第25卷(第6期);第828页左栏第3段、第829页左栏第5段、第833页Scheme2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107903286A (en) | 2018-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020132075A3 (en) | Method of preparing phosphorus-containing flame retardants and their use in polymer compositions | |
| PH12022550935A1 (en) | Method of preparing phosphorus-containing flame retardants and their use in polymer compositions | |
| CN101376665A (en) | Phosphaphenanthrene flame-retardant compound containing s-triazine structure, and preparation and use thereof | |
| CN107189098A (en) | A kind of additive and its preparation method for polymer and application and the flame-retardant polymer moulding compound being made from it | |
| CN102924521A (en) | Silicon-containing expansive flame retardant and preparation method and application thereof | |
| CN104478934B (en) | Containing a fire retardant for the ring three phosphonitrile phenanthrene of oneself interior phosphoric acid ester of two oxygen heterocycle, preparation method and application | |
| CN105017525B (en) | A kind of branched modification agent and corresponding fire-retardant nylon resin | |
| CN104558684A (en) | DOPO-containing dioxacaprophosphate flame retardant as well as preparation method and application thereof | |
| CN111116987B (en) | Method for synthesizing fine-grained aluminum hypophosphite composite flame retardant | |
| CN107903286B (en) | Fire retardant cyclohexylamine dimethylidene phosphonic acid and preparation method thereof | |
| CN104262680B (en) | Hyperbranched intumescent flame retardant and preparation method thereof | |
| CN110066384A (en) | The preparation method of single-component flame-retardant epoxy resin system, imidazoles latent curing agent and preparation method thereof | |
| CN103509052B (en) | A kind of preparation method of high-purity amino trimethylene phosphonic acid | |
| CN105295092B (en) | A kind of phosphorous, nitrogen luxuriant molysite fire retardant and its preparation method and application | |
| CN103804692B (en) | A kind of preparation method being applied in the phosphonate fire retardant of the high content of phosphorus of polyurethane foam | |
| CN104693770A (en) | Halogen-free expansion type flame-retardant polycarbonate composite material and preparation method thereof | |
| CN107337691B (en) | A kind of new phosphorus-containing flame retardant and preparation method thereof | |
| CN100500800C (en) | 2-Carboxyethylphenylphosphinate pentaerythritol flame retardant and preparation method thereof | |
| CN106995535A (en) | A kind of preparation method and applications of the bis phosphoric acid phenyl ester phosphorus nitrogen synergistic fire retardant of the phosphonitrile containing ring three | |
| CN110092944A (en) | The preparation method and applications of diphenyl sulphone (DPS) nitrogen phosphorus sulphur synergistic flame retardant containing DOPO | |
| CN109233046A (en) | A kind of preparation method of phosphor-containing flame-proof poly-ethylene cable material | |
| CN104370967A (en) | Polymer-type nitrogen-phosphorus-containing flame retardant and preparation method thereof | |
| CN108570073A (en) | A kind of novel phosphorus-silicon fire retardant preparation method and applications containing adamantane ring | |
| CN109319951B (en) | Environment-friendly circulating water scale inhibitor | |
| CN105502326A (en) | Method for producing aluminum triphosphate by utilizing methyl phosphorus dichloride production waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No.1, Shiliquan East Road, Shizhong District, Zaozhuang City, Shandong Province 277100 Patentee after: Shandong Taihe Technology Co.,Ltd. Address before: 277000 No.1, Shiliquan East Road, Shizhong District, Zaozhuang City, Shandong Province Patentee before: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES Co.,Ltd. |