CN106750288A - A kind of anti-preparation method for migrating fire retardant - Google Patents
A kind of anti-preparation method for migrating fire retardant Download PDFInfo
- Publication number
- CN106750288A CN106750288A CN201611173497.2A CN201611173497A CN106750288A CN 106750288 A CN106750288 A CN 106750288A CN 201611173497 A CN201611173497 A CN 201611173497A CN 106750288 A CN106750288 A CN 106750288A
- Authority
- CN
- China
- Prior art keywords
- parts
- fire retardant
- preparation
- migrating
- phosphate
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
-
- 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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Abstract
The invention provides a kind of anti-preparation method for migrating fire retardant：2,4, modified cyanuric acid spiral phosphate is introduced in 6 three (allyloxy) s-triazine polymer beads, and 1 (2,5 dichlorophenyls) pyrazolone of 3 acrylamido 5,2 [4 (ylmethyl of 1,3 benzodioxole 5) base of piperazine 1] pyrimidines, improve to resist and migrate performance.
Description
Technical field
The present invention relates to a kind of preparation method of fire retardant, particularly a kind of anti-preparation method for migrating fire retardant.
Background technology
In recent years, the research and development of flame retardant for plastic towards heat endurance it is high, compatibility is good, it is anti-migrate it is phosphorous poly-
Compound direction is developed.Additive flame retardant is mostly some organic molecules, and these small molecules are easily migrated, oozed out, bloom, no
High temperature resistant has solvent extraction so that Flame Retardancy can gradually be reduced or even lost, and pollution environment.But liquid organophosphorus ester
(such as resorcinol double (diphenyl phosphate) (RDP) or bisphenol-A are double (diphenyl phosphate) (BDP)) are usually used in polymer, to make
Obtain HFFR composites.However, being experienced over time with the product made by the HFFR TPU constituents containing liquid phosphorus acid esters
The migration of phosphate flame retardant.
CN101203558 provides a kind of fire retardant and inorganic/organic composite flame-retardant composition, and it includes inorganic hydrogen
The organic layer of oxide and the carbodiimide base being chemically bonded on the inorganic hydroxide surface.Carbodiimide base has
The example of machine layer includes that any one is the compound layer of the carbodiimide base of representative containing following formula, or even works as to add at high proportion
When, the fire retardant can be highly dispersed in resin, and can obtain the molding system that the deterioration such as electrical property, mechanical performance is suppressed
Product.When this fire retardant is included in organic resin, can suppress by resulting composition obtain moulded products mechanical strength and
Electrical property (for example, resistance to migration) declines.
CN105542229A discloses a kind of many gradient function microcapsules titanium phosphate fire retardants and preparation method thereof, including
The wall material of core and the parcel core, core is titanium phosphate, and wall material is double-deck wall material, and inwall is expansion type flame retardant, by charcoal
The reaction of source modifying agent, acid source modifying agent and source of the gas modifying agent is formed, and outer wall is organosilicon crosslinked polymer.Its preparation method is first
Prepare titanium phosphate powder：Titanium phosphate powder is scattered in solvent again, adds charcoal source modifying agent, acid source modifying agent and source of the gas modified
Agent reaction cladding inwall；Finally by organosilicon crosslinked polymer overmold outer wall, obtain final product.The present invention is so that neat coal amout is high, water-resistance, no
Produce molten drop and heat-resisting organosilicon crosslinked polymer is as outer wall, using expansion type flame retardant as inwall, with catalysis carbon-forming
The titanium phosphate powder of characteristic has more efficient flame-retarding characteristic as the capsule titanium phosphate fire retardant that core is prepared, and is adapted to
Multifunctional gradient flame retardant effect is shown in flame mechanism.Due to the presence of cyclic structure and silicon strand, preparation it is fire-retardant
Agent surface polarity is relatively low, and moisture absorption is very low, and resistance to migration is preferable.
TW201134925A provides a kind of non-migratory, halogen-free fire resistance thermoplastic polyamine formic acid esters constituent, the group
The anti-flammability aromatics organophosphor that does not represent migration is included in molding product such as cable and wire outer skin and insulating barrier into thing
Ester compound.The constituent includes a resin continuous phase, and it includes a kind of thermoplasticity polyamine formic acid esters elastomer, at least one
The aromatics organophosphate ester flame retardant of at least 50 DEG C of fusing point and a kind of inorganic hydrate fire retardant.
Existing public technology with the phosphorus over time of product made by the HFFR TPU constituents containing liquid phosphorus acid esters
Ester flame-proof agent is still migrated, although above fire retardant is with certain resistance to migration, however, cannot still meet flexibel polyurethane
The non-migrating demand of foamed plastics.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of anti-preparation method for migrating fire retardant, by following step
It is rapid to realize：
(1) by weight, by 100 parts of pentaerythrite diphosphate ester diacid chlorides;1000-3000 parts of acetone, 10-30 parts of cyanogen
Uric acid, 50-100 parts of triethylamine, 50-80 DEG C of temperature, reaction time 5-10 hours, product was through distillation, washing, the modified trimerization of generation
Cyanic acid spiral phosphate；
（2）By weight, by 100 part 2,4,6- tri- (allyloxy) s-triazine, 20-50 parts of modified cyanuric acid spiral phosphoric acid
Ester, 0.1-1 parts of 1- (2,5- dichlorophenyl) -3- acrylamido -5- pyrazolone, 0.1-1 parts of 2- [4- (dioxies between 1,3- benzo
Heterocyclic pentene -5- ylmethyls) piperazine -1- bases] pyrimidine, 1000-3000 parts of toluene, 2-5 parts of ABVN be polymerized, instead
Should terminate to obtain product.
50-80 DEG C of step 2 reaction temperature.
The step 2 carries out the polymerisation of 15-25 hours.
Described 2,4,6- tri- (allyloxy) s-triazine, pentaerythrite diphosphate ester diacid chloride is commercially available prod.It is described
1- (2,5- dichlorophenyl) -3- acrylamido -5- pyrazolones be commercially available prod, a bio tech ltd is inspired confidence in such as Shanghai
The product of production.2- [4- (1,3- benzodioxole -5- ylmethyls) piperazine -1- bases] pyrimidine, such as Hubei Ju Sheng sections
Skill Co., Ltd produces product.
Beneficial effects of the present invention：
Cyanuric acid spiral phosphate is introduced in 2,4,6- tri- (allyloxy) s-triazine polymer, and containing highly polar group acyl
Amido, 1- (2,5- dichlorophenyl) -3- acrylamido -5- pyrazolones of dioxane, 2- [4- (dioxas between 1,3- benzo
Cyclopentene -5- ylmethyls) piperazine -1- bases] pyrimidine, enhance the interface of fire retardant and the foamed plastics of plastics such as flexibel polyurethane
Effect, while improve the molecular weight of fire retardant, improves fire retardant and interlaminar resin migration resistance, so as to reduce fire retardant
Migrating property.
Specific embodiment
Following examples are only to further illustrate the present invention, are not limitation the scope of protection of the invention.
Embodiment 1
(1) in 3000L reactors, by weight, by 100 parts of pentaerythrite diphosphate ester diacid chlorides;1800 parts of acetone,
19 parts of cyanuric acids, 77 parts of triethylamines, temperature 60 C, 8 hours reaction time, product is washed through purification technique known in the industry, distillation
Wash, dry, the modified cyanuric acid spiral phosphate of generation；
（2）In 3000L reactors, by weight, by 100 part 2,4,6- tri- (allyloxy) s-triazine, 43 parts modified three
Paracyanogen acid spiral phosphate, 0.3 part of 1- (2,5- dichlorophenyl) -3- acrylamido -5- pyrazolones, 0.5 part of 2- [4- (1,3-
Benzodioxole -5- ylmethyls) piperazine -1- bases] pyrimidine, 1800 parts of toluene, 3 parts of ABVNs are warming up to
60 DEG C of polymerisations for carrying out 19 hours, make polymer separate, dry, and obtain product.Numbering is M-1
Embodiment 2
(1) in 3000L reactors, by weight, by 100 parts of pentaerythrite diphosphate ester diacid chlorides;1000 part third
Ketone, 10 parts of cyanuric acids, 50 parts of triethylamines, temperature 50 C, 10 hours reaction time, product steams through purification technique known in the industry
Evaporate, wash, dry, the modified cyanuric acid spiral phosphate of generation；
（2）In 3000L reactors, by weight, by 100 part 2,4,6- tri- (allyloxy) s-triazine, 20 parts modified three
Paracyanogen acid spiral phosphate, 0.1 part of 1- (2,5- dichlorophenyl) -3- acrylamido -5- pyrazolones, 0.1 part of 2- [4- (1,3-
Benzodioxole -5- ylmethyls) piperazine -1- bases] pyrimidine, 1000 parts of toluene, 2 parts of ABVNs are warming up to
50 DEG C of polymerisations for carrying out 25 hours, make polymer separate, dry, and obtain product.Numbering is M-2.
Embodiment 3
(1) in 5000 reactors, by weight, by 100 parts of pentaerythrite diphosphate ester diacid chlorides;3000 parts of acetone,
30 parts of cyanuric acids, 100 parts of triethylamines, 80 DEG C of temperature, 5 hours reaction time, product distills through purification technique known in the industry,
Washing, dries, the modified cyanuric acid spiral phosphate of generation；
（2）In 5000 reactors, by weight, by 100 part 2,4,6- tri- (allyloxy) s-triazine, 50 parts modified three
Paracyanogen acid spiral phosphate, 1 part of 1- (2,5- dichlorophenyl) -3- acrylamido -5- pyrazolones, 1 part of 2- [4- (1,3- benzo
Dioxole -5- ylmethyls) piperazine -1- bases] pyrimidine, 3000 parts of toluene, 2-5 parts of ABVN be warming up to 80
The polymerisation of 15 hours DEG C is carried out, polymer separated, dried, obtain product.Numbering is M-3.
Comparative example 1
It is added without modified cyanuric acid spiral phosphate, the other the same as in Example 1.Products obtained therefrom numbering is M-4.
Comparative example 2
It is added without 1- (2,5- dichlorophenyl) -3- acrylamido -5- pyrazolones, the other the same as in Example 1.Products obtained therefrom is numbered
M-5。
Comparative example 3
It is added without 2- [4- (1,3- benzodioxole -5- ylmethyls) piperazine -1- bases] pyrimidine, the other the same as in Example 1.
Products obtained therefrom numbering is M-6.
Embodiment 4
The foamed plastics fire retardant residual volume of flexibel polyurethane P-Mo blue light spectrophotometric determination.
The fire retardant of embodiment 1-3 and comparative example 1-2 is added in the standard recipe of foamed plastics of flexibel polyurethane, made
Into the model of 240mm × 210mm × 97mm, baking oven baking is put into, 120 DEG C of temperature, takes out detection flexibel polyurethane at 15 days time
Foamed plastics fire retardant residual content, numerical value is bigger, and fire retardant is anti-, and to migrate performance bigger, it is known that does not toast preceding flexibel polyurethane
Foamed plastics fire retardant residual content 1.23%, and with conventional three（2- chloropropyls）Phosphate flame retardant is contrasted, and is shown in Table
1。
The detection fire retardant of table 1. is anti-to migrate performance：
| Production code member | Fire retardant residual content % |
| M-1 | 0.96 |
| M-2 | 0.92 |
| M-3 | 0.98 |
| M-4 | 0.52 |
| M-5 | 0.72 |
| M-6 | 0.71 |
| Three（2- chloropropyls）Phosphate flame retardant | 0.23 |
As shown in Table 1, flame retardant products of the invention have it is stronger it is anti-migrate performance, better than three（2- chloropropyls）Phosphate hinders
Combustion agent.
Claims (4)
1. it is a kind of to resist the preparation method for migrating fire retardant, it is characterised in that to be realized by following steps：
By weight, by 100 part 2,4,6- tri- (allyloxy) s-triazine, 20-50 parts of modified cyanuric acid spiral phosphate,
0.1-1 parts of 1- (2,5- dichlorophenyls) -3- acrylamido -5- pyrazolone, 0.1-1 parts of 2- [4- (dioxanes between 1,3- benzos
Amylene -5- ylmethyls) piperazine -1- bases] pyrimidine, 1000-3000 parts of toluene, 2-5 parts of ABVN be polymerized, reaction knot
Beam obtains product.
2. a kind of of claim 1 resists the preparation method for migrating fire retardant, it is characterised in that the modified cyanuric acid spiral phosphorus
The preparation method of acid esters is：
By weight, by 100 parts of pentaerythrite diphosphate ester diacid chlorides;1000-3000 parts of acetone, 10-30 parts of cyanuric acid,
50-100 parts of triethylamine, 50-80 DEG C of temperature, reaction time 5-10 hours, product was washed through purification technique known in the industry, distillation
Wash, dry, generate cyanuric acid spiral phosphate.
3. a kind of of claim 1 resists the preparation method for migrating fire retardant, it is characterised in that 50-80 DEG C of step 2 reaction temperature.
4. a kind of anti-preparation method for migrating fire retardant of claim 1, it is characterised in that step 2 gather for 15-25 hour
Close reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611173497.2A CN106750288B (en) | 2016-12-19 | 2016-12-19 | A kind of anti-preparation method for migrating fire retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611173497.2A CN106750288B (en) | 2016-12-19 | 2016-12-19 | A kind of anti-preparation method for migrating fire retardant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106750288A true CN106750288A (en) | 2017-05-31 |
| CN106750288B CN106750288B (en) | 2019-03-19 |
Family
ID=58891163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611173497.2A Active CN106750288B (en) | 2016-12-19 | 2016-12-19 | A kind of anti-preparation method for migrating fire retardant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106750288B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1414000A (en) * | 2002-09-26 | 2003-04-30 | 东北林业大学 | Sythetic method of pentaerythrite diphosphate ester diacid chlorine |
| CN101157839A (en) * | 2006-10-02 | 2008-04-09 | 信越化学工业株式会社 | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same |
| CN104448555A (en) * | 2014-11-21 | 2015-03-25 | 济南泰星精细化工有限公司 | Preparation method of novel halogen-free fire retardant for polypropylene |
-
2016
- 2016-12-19 CN CN201611173497.2A patent/CN106750288B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1414000A (en) * | 2002-09-26 | 2003-04-30 | 东北林业大学 | Sythetic method of pentaerythrite diphosphate ester diacid chlorine |
| CN101157839A (en) * | 2006-10-02 | 2008-04-09 | 信越化学工业株式会社 | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same |
| CN104448555A (en) * | 2014-11-21 | 2015-03-25 | 济南泰星精细化工有限公司 | Preparation method of novel halogen-free fire retardant for polypropylene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106750288B (en) | 2019-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Recent developments in the flame-retardant system of epoxy resin | |
| Liang et al. | Recent developments in flame retardant polymeric coatings | |
| KR101424596B1 (en) | Preparation method of flame retardant using melaminephosphate | |
| Schartel | Phosphorus-based flame retardancy mechanisms—old hat or a starting point for future development? | |
| Shen et al. | The flame-retardant mechanisms and preparation of polymer composites and their potential application in construction engineering | |
| Hörold | Phosphorus-based and intumescent flame retardants | |
| CN107207779B (en) | The flame retardant compositions of phosphorus compound and melam comprising heat treatment | |
| CN107075378A (en) | Fire retardant combination and flame-retarded synthetic resin composition | |
| CN107108984A (en) | Fire-retardant polyolefin based resin composition | |
| CN107109236A (en) | Fire retardant combination and flame-retarded synthetic resin composition | |
| KR20180104280A (en) | Thermoplastic polyester resin composition and molded article | |
| WO2006039299A1 (en) | Halogen-free flame retardant polyester | |
| Fink | Flame retardants | |
| CN102503982A (en) | Phosphonitrilic chloride trimer epoxy compound with flame-retardant property and preparation and application thereof | |
| CN109694568A (en) | A kind of High glow wire halogen-free flame retardant polyamide compound and the preparation method and application thereof | |
| Ray et al. | Halogen-free flame-retardant polymers | |
| Xiang et al. | A novel halogen‐free intumescent flame retardant containing phosphorus and nitrogen and its application in polypropylene systems | |
| Kukla et al. | Novel phosphorus-containing silazanes as flame retardants in epoxy resins | |
| CN103270093A (en) | Fireproof polyamide article including a coating formed by plasma treatment | |
| Bifulco et al. | In situ P-modified hybrid silica–epoxy nanocomposites via a green hydrolytic sol–gel route for flame-retardant applications | |
| Wu et al. | Recent progress of DOPO-containing compounds as flame retardants for versatile polymeric materials | |
| Aljamal et al. | Improving thermal and flame retardant properties of sorbitol‐based bioepoxy systems by phosphorus‐based flame retardants | |
| Yang et al. | A smart DOPO‐containing decoration armed on Salen‐polyphosphazene toward high‐efficient flame retardancy for epoxy thermoset | |
| CN106750288A (en) | A kind of anti-preparation method for migrating fire retardant | |
| CN110283359A (en) | A kind of N- phosphorus compound replaces phosphinimine type fire retardant and preparation method thereof |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180823 Address after: 200433 C149 64, 1426 military industrial road, Yangpu District, Shanghai. Applicant after: Shanghai Pu Xin polymer materials Co., Ltd. Address before: 324000 8-1 Donggang eight road, Kecheng District, Quzhou, Zhejiang Applicant before: Quzhou universal New Material Co., Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200727 Address after: No. 109 Yunhe Road, Yunlong Town, Yinzhou District, Ningbo City, Zhejiang Province Patentee after: NINGBO JINSHAN NEW MATERIAL Co.,Ltd. Address before: 200433 C149 64, 1426 military industrial road, Yangpu District, Shanghai. Patentee before: Shanghai Pu Xin polymer materials Co.,Ltd. |