CN109161054A - A kind of preparation method of imitative mussel phosphorus flame retardant - Google Patents
A kind of preparation method of imitative mussel phosphorus flame retardant Download PDFInfo
- Publication number
- CN109161054A CN109161054A CN201810789120.2A CN201810789120A CN109161054A CN 109161054 A CN109161054 A CN 109161054A CN 201810789120 A CN201810789120 A CN 201810789120A CN 109161054 A CN109161054 A CN 109161054A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- phosphorus flame
- parts
- imitative mussel
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The present invention discloses a kind of preparation method of imitative mussel phosphorus flame retardant; including following operating procedure: (1) mixing pentaerythritol diphosphate, phosphenylic acid dichloro ester, methyl-silicone oil, anhydrous calcium chloride with after; under nitrogen protection effect; it reacts and phosphorus flame retardant crude product is made, after then being dissolved using 1,2- dichloroethanes; remove anhydrous calcium chloride; 1,2- dichloroethanes is removed in evaporation, obtains phosphorus flame retardant sterling；(2) phosphorus flame retardant sterling is added into tannic acid solution, after being mixed evenly, ferric trichloride, lutecium chloride is then added thereto, after being mixed evenly, is filtered using vacuum filtration machine, complete primary cladding；(3) after repeating step (2), remaining substance drying will be filtered for the last time, is crushed, imitative mussel phosphorus flame retardant is made.Imitative mussel phosphorus flame retardant produced by the present invention, excellent fireproof performance is excellent in compatibility with matrix resin, and will not influence the original every mechanical property of matrix resin.
Description
Technical field
The invention belongs to technical field of flame retardant agent preparation, and in particular to a kind of preparation method of imitative mussel phosphorus flame retardant.
Background technique
Organic phosphorus flame retardant mostly has many advantages, such as low cigarette, nontoxic, low halogen, Halogen, meets the developing direction of fire retardant,
With good development prospect.Organic phosphorus flame retardant includes phosphate, phosphite ester, phosphate, organophosphorated salt, and there are also phosphas
Cycle compound and polymer phosphorus (phosphine) acid esters etc., but most widely used is phosphate and phosphonate ester.Phosphorus flame retardant is directly applied
When, there is the technological deficiencies poor with the compatibility of matrix, therefore in the prior art, mostly using phosphorus flame retardant it
Before, processing is modified to its surface, wherein imitative mussel material cladding processing is research hot topic in recent years, it not only can be real
The surface of existing fire retardant is modified, can also improve the compatibility with material, moreover it is possible to be the fire-retardant increase charcoal source of fire retardant, improve resistance
Fuel efficiency fruit.
Summary of the invention
It is more excellent the object of the present invention is to provide a kind of flame retardant property and can guarantee one kind of mechanical properties of polymer
The preparation method of imitative mussel phosphorus flame retardant.
The present invention is achieved by the following technical solutions.
A kind of preparation method of imitative mussel phosphorus flame retardant, including following operating procedure:
(1) by weight, by 34-39 parts of pentaerythritol diphosphates, 41-45 parts of phosphenylic acid dichloro esters, 3-6 parts of methyl silicon
Oil, 11-15 parts of anhydrous calcium chloride mixing under nitrogen protection effect, are reacted 4-5 hours at 210-220 DEG C, are cooled to after
After room temperature, phosphorus flame retardant crude product is made, after then being dissolved using 1,2- dichloroethanes, removes anhydrous calcium chloride, is removed in evaporation
1,2- dichloroethanes is removed, phosphorus flame retardant sterling is obtained；
(2) by weight, 1 part of phosphorus flame retardant sterling is added into 15-17 parts of tannic acid solutions, is mixed evenly
Afterwards, 3-4 parts of ferric trichlorides, 2-3 parts of lutecium chlorides are then added thereto, after being mixed evenly, are carried out using vacuum filtration machine
It filters, completes primary cladding；
(3) after repetition step (2) 4-5 times, remaining substance drying will be filtered for the last time, and after crushing, imitative mussel phosphorus system is made
Fire retardant.
Specifically, in above-mentioned steps (1), temperature when evaporation removes 1,2- dichloroethanes is 88-92 DEG C.
Specifically, in above-mentioned steps (2), in tannic acid solution, the mass fraction of tannic acid is 45-55%.
Specifically, in above-mentioned steps (3), temperature when drying and processing is 78-86 DEG C, and the time of drying and processing is that 1-2 is small
When.
From the above technical scheme, it can be seen that the beneficial effects of the present invention are:
A kind of preparation method of imitative mussel phosphorus flame retardant provided by the invention, easy to operate, low in cost, imitative mussel obtained
Phosphorus flame retardant, excellent fireproof performance is excellent in compatibility with matrix resin, and will not influence the original items of matrix resin
Mechanical property.Wherein, phosphorus flame retardant sterling made from step (1) of the present invention, purity is high, excellent fireproof performance, while surface
Active group it is more, be conducive to the cladding of imitative mussel；Imitative mussel material in the present invention has ferric tannate and tannic acid lutetium mixed
It is combined into, after the two synergistic effect, can effectively enhance its compatibility with matrix resin, and will not influence matrix resin
Mechanical property.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
A kind of preparation method of imitative mussel phosphorus flame retardant, including following operating procedure:
(1) by weight, by 34 parts of pentaerythritol diphosphates, 41 parts of phosphenylic acid dichloro esters, 3 parts of methyl-silicone oils, 11 parts
Anhydrous calcium chloride mixes with after, under nitrogen protection effect, reacts 4 hours at 210 DEG C, and after being cooled to room temperature, phosphorus system is made
Fire retardant crude product after then dissolving using 1,2- dichloroethanes, removes anhydrous calcium chloride, removes 1,2- dichloroethanes in evaporation,
Obtain phosphorus flame retardant sterling；
(2) by weight, 1 part of phosphorus flame retardant sterling is added into 15 parts of tannic acid solutions, after being mixed evenly, so
3 parts of ferric trichlorides, 2 parts of lutecium chlorides are added thereto afterwards, after being mixed evenly, are filtered using vacuum filtration machine, complete
Primary cladding；
(3) after repeating step (2) 4 times, remaining substance drying will be filtered for the last time, and after crushing, imitative mussel phosphorus system resistance is made
Fire agent.
Specifically, in above-mentioned steps (1), temperature when evaporation removes 1,2- dichloroethanes is 88 DEG C.
Specifically, in above-mentioned steps (2), in tannic acid solution, the mass fraction of tannic acid is 45%.
Specifically, in above-mentioned steps (3), temperature when drying and processing is 78 DEG C, and the time of drying and processing is 1 hour.
Embodiment 2
A kind of preparation method of imitative mussel phosphorus flame retardant, including following operating procedure:
(1) by weight, by 36 parts of pentaerythritol diphosphates, 43 parts of phosphenylic acid dichloro esters, 5 parts of methyl-silicone oils, 13 parts
Anhydrous calcium chloride mixes with after, under nitrogen protection effect, reacts 4.5 hours at 215 DEG C, and after being cooled to room temperature, phosphorus is made
Flame retardant crude product after then dissolving using 1,2- dichloroethanes, removes anhydrous calcium chloride, removes 1,2-, bis- chloroethene in evaporation
Alkane obtains phosphorus flame retardant sterling；
(2) by weight, 1 part of phosphorus flame retardant sterling is added into 16 parts of tannic acid solutions, after being mixed evenly, so
3 parts of ferric trichlorides, 2 parts of lutecium chlorides are added thereto afterwards, after being mixed evenly, are filtered using vacuum filtration machine, complete
Primary cladding；
(3) after repeating step (2) 4 times, remaining substance drying will be filtered for the last time, and after crushing, imitative mussel phosphorus system resistance is made
Fire agent.
Specifically, in above-mentioned steps (1), temperature when evaporation removes 1,2- dichloroethanes is 90 DEG C.
Specifically, in above-mentioned steps (2), in tannic acid solution, the mass fraction of tannic acid is 50%.
Specifically, in above-mentioned steps (3), temperature when drying and processing is 82 DEG C, and the time of drying and processing is 1.5 hours.
Embodiment 3
A kind of preparation method of imitative mussel phosphorus flame retardant, including following operating procedure:
(1) by weight, by 39 parts of pentaerythritol diphosphates, 45 parts of phosphenylic acid dichloro esters, 6 parts of methyl-silicone oils, 15 parts
Anhydrous calcium chloride mixes with after, under nitrogen protection effect, reacts 5 hours at 220 DEG C, and after being cooled to room temperature, phosphorus system is made
Fire retardant crude product after then dissolving using 1,2- dichloroethanes, removes anhydrous calcium chloride, removes 1,2- dichloroethanes in evaporation,
Obtain phosphorus flame retardant sterling；
(2) by weight, 1 part of phosphorus flame retardant sterling is added into 17 parts of tannic acid solutions, after being mixed evenly, so
4 parts of ferric trichlorides, 3 parts of lutecium chlorides are added thereto afterwards, after being mixed evenly, are filtered using vacuum filtration machine, complete
Primary cladding；
(3) after repeating step (2) 5 times, remaining substance drying will be filtered for the last time, and after crushing, imitative mussel phosphorus system resistance is made
Fire agent.
Specifically, in above-mentioned steps (1), temperature when evaporation removes 1,2- dichloroethanes is 92 DEG C.
Specifically, in above-mentioned steps (2), in tannic acid solution, the mass fraction of tannic acid is 55%.
Specifically, in above-mentioned steps (3), temperature when drying and processing is 86 DEG C, and the time of drying and processing is 2 hours.
Comparative example 1
Step does not add lutecium chloride in (2), remaining operating procedure is identical with embodiment 1.
Imitative mussel phosphorus flame retardant is made with the method for each embodiment and comparative example respectively, is then sliced it with PET mixed
After conjunction, blending extrusion is added twin-screw extrude, cooling, sample is made in pelletizing, wherein the addition of imitative mussel phosphorus flame retardant
Amount is the 10% of PET chipping qualities, and then the properties of test sample, test result are as shown in table 1:
The performance test of 1 sample of table
| Project | Oxygen index (OI) (%) | Tensile strength, M/Kpa |
| Pure PET sample | 21.5 | 26.4 |
| Embodiment 1 | 32.3 | 26.0 |
| Comparative example 1 | 27.9 | 22.8 |
| Embodiment 2 | 32.5 | 26.2 |
| Embodiment 3 | 32.8 | 26.3 |
As shown in Table 1, mussel phosphorus flame retardant, excellent fireproof performance, the compatibility with matrix resin are imitated made from the present embodiment
Can be excellent, it will not influence the mechanical property of matrix resin.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (4)
1. a kind of preparation method of imitative mussel phosphorus flame retardant, which is characterized in that including following operating procedure:
(1) by weight, by 34-39 parts of pentaerythritol diphosphates, 41-45 parts of phosphenylic acid dichloro esters, 3-6 parts of methyl silicon
Oil, 11-15 parts of anhydrous calcium chloride mixing under nitrogen protection effect, are reacted 4-5 hours at 210-220 DEG C, are cooled to after
After room temperature, phosphorus flame retardant crude product is made, after then being dissolved using 1,2- dichloroethanes, removes anhydrous calcium chloride, is removed in evaporation
1,2- dichloroethanes is removed, phosphorus flame retardant sterling is obtained；
(2) by weight, 1 part of phosphorus flame retardant sterling is added into 15-17 parts of tannic acid solutions, is mixed evenly
Afterwards, 3-4 parts of ferric trichlorides, 2-3 parts of lutecium chlorides are then added thereto, after being mixed evenly, are carried out using vacuum filtration machine
It filters, completes primary cladding；
(3) after repetition step (2) 4-5 times, remaining substance drying will be filtered for the last time, and after crushing, imitative mussel phosphorus system is made
Fire retardant.
2. a kind of preparation method of imitative mussel phosphorus flame retardant according to claim 1, which is characterized in that above-mentioned steps
(1) in, temperature when evaporation removes 1,2- dichloroethanes is 88-92 DEG C.
3. a kind of preparation method of imitative mussel phosphorus flame retardant according to claim 1, which is characterized in that above-mentioned steps
(2) in, in tannic acid solution, the mass fraction of tannic acid is 45-55%.
4. a kind of preparation method of imitative mussel phosphorus flame retardant according to claim 1, which is characterized in that above-mentioned steps
(3) in, temperature when drying and processing is 78-86 DEG C, and the time of drying and processing is 1-2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810789120.2A CN109161054B (en) | 2018-07-18 | 2018-07-18 | Preparation method of mussel-like phosphorus flame retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810789120.2A CN109161054B (en) | 2018-07-18 | 2018-07-18 | Preparation method of mussel-like phosphorus flame retardant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109161054A true CN109161054A (en) | 2019-01-08 |
| CN109161054B CN109161054B (en) | 2020-10-16 |
Family
ID=64897762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810789120.2A Active CN109161054B (en) | 2018-07-18 | 2018-07-18 | Preparation method of mussel-like phosphorus flame retardant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109161054B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734377A (en) * | 2019-01-31 | 2019-05-10 | 商丘市睢阳区水务局 | A kind of energy saving and environment friendly construction material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07157617A (en) * | 1993-12-08 | 1995-06-20 | Asahi Denka Kogyo Kk | Vinyl chloride resin composition for agricultural use |
| CN106565959A (en) * | 2016-11-07 | 2017-04-19 | 常州大学 | Macromolecule phosphorus-nitrogenous flame retardant in cage cyclic phosphonate ester structure and preparation method |
| CN106883601A (en) * | 2017-03-06 | 2017-06-23 | 华北科技学院 | A kind of preparation method of imitative mussel fire proofing |
| CN107778530A (en) * | 2017-10-27 | 2018-03-09 | 华北科技学院 | A kind of preparation method of imitative mussel material microcapsule surface modified flame-retardant agent |
-
2018
- 2018-07-18 CN CN201810789120.2A patent/CN109161054B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07157617A (en) * | 1993-12-08 | 1995-06-20 | Asahi Denka Kogyo Kk | Vinyl chloride resin composition for agricultural use |
| CN106565959A (en) * | 2016-11-07 | 2017-04-19 | 常州大学 | Macromolecule phosphorus-nitrogenous flame retardant in cage cyclic phosphonate ester structure and preparation method |
| CN106883601A (en) * | 2017-03-06 | 2017-06-23 | 华北科技学院 | A kind of preparation method of imitative mussel fire proofing |
| CN107778530A (en) * | 2017-10-27 | 2018-03-09 | 华北科技学院 | A kind of preparation method of imitative mussel material microcapsule surface modified flame-retardant agent |
Non-Patent Citations (2)
| Title |
|---|
| 石延超 等: ""有机磷阻燃剂的合成及在阻燃高分子材料中的应用研究进展"", 《高分子材料科学与工程》 * |
| 赵伟: ""聚合型磷基阻燃剂合成及对环氧树脂的阻燃机理研究"", 《中国优秀博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734377A (en) * | 2019-01-31 | 2019-05-10 | 商丘市睢阳区水务局 | A kind of energy saving and environment friendly construction material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109161054B (en) | 2020-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106243385B (en) | A kind of DOPO based flameproofings and preparation method thereof | |
| CN104140559A (en) | Application of cyclophosphazene compound in preparation of resin as fire retardant | |
| KR20090045407A (en) | Oligomeric bis-phosphate flame retardants and compositions containing the same | |
| CN108610510A (en) | Phospho hetero phenanthrene phosphonitrile compound flame retardant, composite material and preparation method and application | |
| CN105669760A (en) | Organic phosphaphenanthrene derivatives, and preparation method and application thereof | |
| CN111484732B (en) | Phytate composite flame retardant for polyamide and preparation method thereof | |
| CN105085984B (en) | A kind of halogen-free flame retardants and the flame retarded polymeric material containing the halogen-free flame retardants | |
| CN102775442A (en) | Oligomer phosphonate and preparation method and application thereof | |
| CN111139548A (en) | High-flame-retardant polyester PET and fiber thereof | |
| CN112480166A (en) | Preparation method of nitrogen-phosphorus flame retardant | |
| CN108440731B (en) | Preparation method of lignin-based intumescent flame retardant | |
| CN104479350A (en) | Halogen-free flame-retarded polycaprolactam compound with low smoke and extremely low odor | |
| CN111116987A (en) | Method for synthesizing fine-grained aluminum hypophosphite composite flame retardant | |
| CN105175785A (en) | Phosphorus-nitrogen compound intercalated hydrotalcite and preparation method thereof | |
| CN109161054A (en) | A kind of preparation method of imitative mussel phosphorus flame retardant | |
| CN110283359A (en) | A kind of N- phosphorus compound replaces phosphinimine type fire retardant and preparation method thereof | |
| CN111285990A (en) | Preparation of melamine ring-containing triphosphonic acid and derivative compounded high-performance reactive polyurethane flame retardant | |
| CN103194048A (en) | Flame retardant compositions, molded products and fiber matrixes | |
| CN109517188A (en) | A kind of biology base composite flame-retardant agent and its application | |
| CN107129595A (en) | A kind of hyperbranched expandable type fire retardant and preparation method thereof | |
| CN106317804B (en) | A kind of high grade of transparency bittern-free flame-proof material | |
| CN100500800C (en) | 2-Carboxyethyl phenyl pentaerythritol hypophosphite combustion inhibitor and preparing method thereof | |
| CN110845529B (en) | Phosphorus-containing polyethylene polyamine flame retardant and preparation method thereof | |
| KR100483652B1 (en) | Process for the preparation of condensed phosphoric acid esters | |
| CN103660306A (en) | Method for molding halogen-free flame-retardant thermoplastic polyester composition |
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 |